WO2016140251A1 - Composition de caoutchouc réticulable au silane ainsi que corps moulé en caoutchouc réticulé au silane, procédé de fabrication de ceux-ci, et article moulé en caoutchouc réticulé au silane - Google Patents

Composition de caoutchouc réticulable au silane ainsi que corps moulé en caoutchouc réticulé au silane, procédé de fabrication de ceux-ci, et article moulé en caoutchouc réticulé au silane Download PDF

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WO2016140251A1
WO2016140251A1 PCT/JP2016/056386 JP2016056386W WO2016140251A1 WO 2016140251 A1 WO2016140251 A1 WO 2016140251A1 JP 2016056386 W JP2016056386 W JP 2016056386W WO 2016140251 A1 WO2016140251 A1 WO 2016140251A1
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Prior art keywords
rubber
silane
parts
mass
coupling agent
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English (en)
Japanese (ja)
Inventor
宏樹 千葉
西口　雅己
有史 松村
晃一 水野
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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Priority to JP2017503677A priority Critical patent/JP6706870B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethylene-propylene or ethylene-propylene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes

Definitions

  • the present invention relates to a silane cross-linkable rubber composition, a silane cross-linked rubber molded product, a production method thereof, and a silane cross-linked rubber molded product.
  • Rubber products such as coating materials for various industrial cables (including electric wires) and rubber molding materials (for example, glass run channels for automobiles, weather strips, rubber hoses, wiper blade rubbers, gaskets and vibration-proof rubbers) have compression set. It is required to be small.
  • sheath materials jacketet materials
  • insulating materials for example, glass run channels for automobiles, weather strips, rubber hoses, wiper blade rubbers, gaskets and vibration-proof rubbers
  • rubber mold materials for example, weather strips, gaskets
  • crosslinked EP rubber obtained by vulcanizing (crosslinking) ethylene-propylene rubber has been used as a product used for applications requiring small compression set.
  • the crosslinked EP rubber had to be vulcanized after the EP rubber was molded.
  • Patent Document 1 in the method of injection molding a rubber composition containing ethylene-propylene rubber as a main component, the propylene content as the ethylene-propylene rubber is 30 to 55% by weight, Mooney viscosity (ML (1 + 4) It has been proposed to use an organic peroxide having a temperature of 100 ° C.) of 20 to 80 and adding an organic peroxide as a vulcanizing agent.
  • Patent Document 2 it has been proposed to further subject a vulcanized rubber product to a thermal history treatment under atmospheric pressure or vacuum pressure.
  • the rubber contains 100 parts by mass of rubber and 30 parts by mass to 150 parts by mass of metal hydroxide, and the rubber is ethylene-propylene rubber 1 having an ethylene ratio of 60% to 64% and an ethylene ratio of 66% to A non-halogen flame retardant rubber composition in which 70% ethylene-propylene rubber 2 is mixed at a mass ratio of 70:30 to 30:70 has been proposed.
  • JP-A-8-66931 Japanese Patent Laid-Open No. 11-302415 JP 2012-241041 A
  • Patent Documents 1 to 3 since a process for vulcanizing rubber is necessary in production, a vulcanization facility that can be heated to a temperature at which the rubber is vulcanized is necessary. In addition to this, the vulcanization time is long, and there is a problem in terms of productivity. Further, when a general EP rubber is used to obtain a molded article having a high tensile strength, a material having a high viscosity is often used. However, a material with high viscosity is inferior in fluidity, and for example, it has been difficult to produce extrusion molding at a high linear velocity with high productivity.
  • the present invention overcomes the above-mentioned problems of the prior art, and is a silane-crosslinked rubber molded article that has both a small compression set and a high tensile strength and is excellent in appearance even when extruded at a high linear velocity, and a method for producing the same It is an issue to provide.
  • the present invention also provides a silane crosslinkable rubber composition and a method for producing the same, which can produce the silane crosslinked rubber molded product having the above-mentioned characteristics with high productivity without requiring a vulcanization facility. Let it be an issue.
  • this invention makes it a subject to provide the silane crosslinked rubber molded article containing the silane crosslinked rubber molded object which has said outstanding characteristic.
  • the rubber silane cross-linking method refers to a silanol condensation catalyst after a hydrolyzable silane coupling agent having an unsaturated group is grafted to rubber in the presence of an organic peroxide to obtain a silane-grafted rubber.
  • the silane graft rubber is brought into contact with moisture to obtain a crosslinked rubber in which the silane graft rubber is crosslinked through a silane coupling agent.
  • the silane crosslinkable rubber composition comprises 0.3 to 400 parts by weight of an inorganic filler, 1 to 15 parts by weight of a silane coupling agent, and 100 parts by weight of the base rubber.
  • Adult obtained by melt-mixing 0.01 to 0.6 parts by mass of a peroxide and 0.0001 to 0.5 parts by mass of a silanol condensation catalyst.
  • [4] The silane crosslinkable rubber composition according to any one of [1] to [3], wherein the base rubber contains 1 to 30% by mass of a polypropylene resin.
  • [5] The silane crosslinkable rubber composition according to any one of [1] to [4], wherein the content of the silane coupling agent is 3 to 15 parts by mass with respect to 100 parts by mass of the base rubber. .
  • [6] A silane-crosslinked rubber molded article obtained by molding the silane-crosslinkable rubber composition according to any one of [1] to [5] and then bringing it into contact with water.
  • [7] A silane-crosslinked rubber molded product comprising the silane-crosslinked rubber molded product according to [6].
  • 0.3 to 400 parts by weight of the inorganic filler 1 to 15 parts by weight of the silane coupling agent, 0.01 to 0.6 parts by weight of the organic peroxide, and 0.0001 to 0.001 of the silanol condensation catalyst.
  • a method for producing a silane crosslinkable rubber composition comprising a step (1) of melt-mixing 5 parts by mass to obtain a silane crosslinkable rubber composition,
  • the step (1) includes the following step (a) and step (c).
  • Step (b) for preparing a silane masterbatch Step (c) for preparing a catalyst masterbatch by melt-mixing the remainder of the base rubber and the silanol condensation catalyst (c): the silane masterbatch and the silanol
  • Step (c) for preparing a catalyst masterbatch by melt-mixing the remainder of the base rubber and the silanol condensation catalyst (c): the silane masterbatch and the silanol A step of melt-mixing a condensation catalyst or the catalyst master batch.
  • a method for producing a silane crosslinkable rubber composition A method for producing a silane crosslinkable rubber composition.
  • Step (1) Base rubber 100 containing 61 to 100% by mass of ethylene- ⁇ olefin rubber having a Mooney viscosity (ML (1 + 4) 125 ° C.) measured in accordance with JIS K 6300-1: 2013 of more than 40 and not more than 90 0.3 to 400 parts by mass of an inorganic filler, 1 to 15 parts by mass of a silane coupling agent, 0.01 to 0.6 parts by mass of an organic peroxide, and 0.0001 to Step (2) of obtaining 0.5 parts by mass of melt-mixed to obtain a silane crosslinkable rubber composition: Step of obtaining a molded body by molding the silane crosslinkable rubber composition obtained in the step (1) (3): A method for producing a silane-crosslinked rubber molded body, comprising a step of bringing the molded body obtained in the step (2) into contact with water to obtain a silane-crosslinked rubber molded body.
  • Mooney viscosity ML (1 + 4) 125 ° C.
  • the step (1) includes the following step (a) and step (c). However, when a part of the base rubber is melt-mixed in the following step (a), the following step (a) and step (b) And step (c), Step (a): Melting and mixing all or part of the base rubber, the inorganic filler, the silane coupling agent, and the organic peroxide at a temperature equal to or higher than the decomposition temperature of the organic peroxide.
  • Step (b) for preparing a silane masterbatch Step (c) for preparing a catalyst masterbatch by melt-mixing the remainder of the base rubber and the silanol condensation catalyst (c): the silane masterbatch and the silanol
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • a silane-crosslinked rubber molded article that overcomes the above-described conventional problems, achieves both a small compression set and a high tensile strength, and has an excellent appearance, without requiring an EP rubber vulcanization facility, is necessary. Can be manufactured at high speed and with high productivity. Therefore, according to the present invention, even when extrusion molding is performed at a high linear velocity, the silane cross-linking has both a small compression set (hereinafter sometimes referred to as excellent compression set) and a high tensile strength, and also has an excellent appearance.
  • a rubber molded body and a method for producing the same can be provided.
  • silane cross-linkable rubber composition that can produce a silane cross-linked rubber molded article having such excellent characteristics without vulcanization equipment and with high productivity, and a method for producing the same. Furthermore, a silane cross-linked rubber molded article including the silane cross-linked rubber molded article having such excellent characteristics can be provided.
  • the silane crosslinkable rubber composition of the present invention comprises an ethylene- ⁇ olefin rubber having a Mooney viscosity (ML (1 + 4) 125 ° C.) measured in accordance with JIS K 6300-1: 2013 of more than 40 and 90 or less.
  • This silane crosslinkable rubber composition has an inorganic filler of 0.3 to 400 parts by weight, a silane coupling agent of 1 to 15 parts by weight, and an organic peroxide of 0.01 to 0. 6 parts by mass and 0.0001 to 0.5 parts by mass of a silanol condensation catalyst can be prepared by melt mixing. Thereby, as will be described later, the silane coupling agent is grafted to the base rubber to form a silane crosslinkable rubber.
  • the silane cross-linked rubber molded product of the present invention can be obtained by molding the silane cross-linkable rubber composition of the present invention and then bringing it into contact with water. Thereby, as described later, the silane coupling agent of the silane crosslinkable rubber contained in the silane crosslinkable rubber composition undergoes a crosslinking reaction to form a silane crosslinked rubber molded product.
  • the base rubber used in the present invention has a Mooney viscosity (ML (1 + 4) 125 ° C.) of 40 as a rubber component having a site where the silane coupling agent can be grafted and measured according to JIS K 6300-1: 2013. And ethylene- ⁇ olefin rubber which is 90 or less.
  • the base rubber may further contain a polypropylene resin.
  • the base rubber may further contain a rubber component other than the ethylene- ⁇ -olefin rubber and a resin component other than the polypropylene resin.
  • the rubber component other than the ethylene- ⁇ -olefin rubber is not particularly limited.
  • the resin component other than the polypropylene resin is not particularly limited, and examples thereof include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and an ethylene copolymer.
  • the base rubber contains these rubber component and resin component, the contents of these rubber component and resin component are not particularly limited, and are appropriately determined.
  • the content of each rubber component and each resin component is appropriately determined so that the total amount of the rubber component and the resin component is 100% by mass, and is preferably selected from the following range.
  • the ethylene- ⁇ olefin rubber used in the present invention is an ethylene- ⁇ olefin rubber having a Mooney viscosity (ML (1 + 4) 125 ° C.) measured in accordance with JIS K 6300-1: 2013 of more than 40 and 90 or less. If the Mooney viscosity is too small, the tensile strength may be insufficient. On the other hand, if the Mooney viscosity is too large, the moldability at a high linear velocity (high-speed moldability) may be inferior.
  • Mooney viscosity ML (1 + 4) 125 ° C.
  • the Mooney viscosity of the ethylene- ⁇ -olefin rubber is preferably 50 to 90 (ML (1 + 4) 125 ° C.), more preferably 50 to 80 (ML (1 + 4) 125 ° C.) in terms of tensile strength and moldability. 60 to 70 (ML (1 + 4) 125 ° C.) is more preferable. Mooney viscosity is measured based on a measurement method defined in JIS K 6300-1: 2013. The test is performed as follows. As a test piece to be used, a set of two test samples having a diameter of about 50 mm and a thickness of about 6 mm is prepared by a roll-through method described in JIS K 6300-1 5.3.1.
  • a disk-shaped metal L-shaped rotor is mounted in a cylindrical hollow portion (cavity) composed of two dies, and the rubber test piece obtained therein is filled. Thereafter, the rotor is rotated under constant conditions of a preheating time of 1 minute, a rotor rotation time of 4 minutes, and a test temperature of 125 ° C., and the torque applied to the rotor by the rubber resistance at this time is measured in Mooney units as the Mooney viscosity of the rubber.
  • the ethylene- ⁇ -olefin rubber is a rubber made of an ethylene- ⁇ -olefin copolymer, preferably a rubber made of a binary copolymer of ethylene and ⁇ -olefin, or an ethylene- ⁇ -olefin and diene. Examples thereof include rubber made of a terpolymer.
  • the diene of the terpolymer may be a conjugated diene or a non-conjugated diene, and is preferably a non-conjugated diene.
  • examples of the terpolymer include a terpolymer of ethylene, an ⁇ -olefin, and a conjugated diene, and a terpolymer of ethylene, an ⁇ -olefin, and a nonconjugated diene.
  • Preferred are binary copolymers of ethylene and ⁇ -olefin and terpolymers of ethylene, ⁇ -olefin and non-conjugated diene.
  • Examples of the conjugated diene include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like, and butadiene is preferable.
  • Non-conjugated dienes include, for example, dicyclopentadiene (DCPD), ethylidene norbornene (ENB), 1,4-hexadiene, and ethylidene norbornene is preferred.
  • DCPD dicyclopentadiene
  • ENB ethylidene norbornene
  • ethylidene norbornene is preferred.
  • Each component of a conjugated diene and a nonconjugated diene is used individually by 1 type, or can use 2 or more types together.
  • the ⁇ -olefin is preferably an ⁇ -olefin having 3 to 12 carbon atoms.
  • the ⁇ -olefin is not particularly limited, and examples thereof include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and 1-dodecene.
  • Examples of the rubber made of a binary copolymer of ethylene and ⁇ -olefin include ethylene-propylene rubber, ethylene-butene rubber, and ethylene-octene rubber.
  • Examples of the rubber composed of a terpolymer of ethylene, ⁇ -olefin and diene include ethylene-propylene-diene rubber and ethylene-butene-diene rubber.
  • ethylene-propylene rubber, ethylene-butene rubber, ethylene-propylene-diene rubber and ethylene-butene-diene rubber are preferable, ethylene-propylene rubber and ethylene-propylene-diene rubber are more preferable, ethylene-propylene rubber or ethylene-propylene-ethylidene.
  • Norbornene rubber is particularly preferred.
  • the ethylene- ⁇ -olefin rubber has an ethylene component content (referred to as ethylene content) in the copolymer of preferably 55 to 80% by mass, more preferably 60 to 75% by mass, and further preferably 62 to 70% by mass.
  • ethylene content is in the range of 55 to 80% by mass, both tensile strength and compression set can be achieved.
  • the ethylene content is a value measured according to the method described in ASTM D3900.
  • the ethylene- ⁇ olefin rubber has a diene component content (referred to as diene content) in the copolymer of preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 4% by mass.
  • diene content a diene component content in the copolymer of preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 4% by mass.
  • diene content can be measured by, for example, infrared absorption spectroscopy (FT-IR), proton NMR ( 1 H-NMR) method or the like.
  • the content of the ethylene- ⁇ -olefin rubber is 61 to 100 parts by mass in 100 parts by mass of the base rubber.
  • the content of the ethylene- ⁇ -olefin rubber is 61 parts by mass or more, the above excellent characteristics can be imparted to the molded body.
  • the lower limit of the ethylene- ⁇ -olefin rubber content is preferably 70 parts by mass, more preferably 75 parts by mass, and even more preferably 80 parts by mass.
  • the base rubber contains a polypropylene resin
  • the ethylene- ⁇ -olefin rubber content is preferably 70 to 99 parts by mass, more preferably 75 to 95 parts by mass, and more preferably 80 to 80 parts by mass in terms of moldability and compression set. 90 parts by mass is more preferable.
  • One type of ethylene- ⁇ -olefin rubber may be used alone, or two or more types may be used in combination.
  • Polypropylene resin A polypropylene resin (PP) will not be specifically limited if it is resin which consists of a polymer which contains a propylene component as a structural component.
  • Polypropylene resins include propylene homopolymer (h-PP), random polypropylene (r-PP) which is a copolymer with (preferably a small amount) ethylene and / or 1-butene, ethylene rubber, etc.
  • the melt flow rate (MFR, 230 ° C., 21.18N) of the polypropylene resin is not particularly limited, but is preferably 0.5 to 50 g / 10 minutes, particularly preferably 10 to 30 g / 10 minutes.
  • MFR 190 ° C., 21.18 N
  • MFR is a value measured under condition D of 190 ° C. and 21.18 N based on “Method A (manual cut-off method)” defined in JIS K 7210.
  • the base rubber contains a polypropylene resin
  • the content of the polypropylene resin is not particularly limited, but is preferably 1 to 30 parts by mass in 100 parts by mass of the base rubber, and 5 to 25 parts by mass. Is more preferably 10 to 20 parts by mass.
  • One type of polypropylene resin may be used alone, or two or more types may be used in combination.
  • the inorganic filler used in the present invention can be used without particular limitation as long as it has a site that can be chemically bonded to the reaction site of the silane coupling agent by hydrogen bonding or covalent bonding.
  • Examples of the site that can be chemically bonded to the reaction site of the silane coupling agent in this inorganic filler include OH groups (hydroxy groups, water molecules containing water or water of crystal water, OH groups such as carboxy groups), amino groups, and SH groups. It is done.
  • examples of such inorganic fillers include metal hydrates such as compounds having hydrated water, hydroxyl groups or crystal water.
  • the metal hydrate include metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and further calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, and aluminum nitride.
  • inorganic acid salts or inorganic oxides such as hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite and the like having hydrated water and the like can be mentioned.
  • examples of the inorganic filler include boron nitride, silica (crystalline silica, amorphous silica, etc.), carbon black, clay, zinc oxide, tin oxide, titanium oxide, molybdenum oxide, three Antimony oxide, silicone compound, quartz, talc, zinc borate, white carbon, zinc borate, hydroxy hydroxystannate, zinc stannate.
  • the inorganic filler is preferably at least one selected from the group consisting of metal hydrate, talc, clay, silica, and carbon black.
  • An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
  • the average primary particle size of the inorganic filler is preferably 0.001 to 10 ⁇ m, more preferably 0.005 to 5 ⁇ m, further preferably 0.01 to 2 ⁇ m, and particularly preferably 0.015 to 1 ⁇ m.
  • the average primary particle size is determined by an optical particle size analyzer such as a laser diffraction / scattering particle size distribution measuring device after being dispersed with alcohol or water.
  • a surface-treated inorganic filler surface-treated with a silane coupling agent or the like can be used as the inorganic filler.
  • the silane coupling agent surface treatment inorganic filler include Kisuma 5L and Kisuma 5P (both trade names, magnesium hydroxide, manufactured by Kyowa Chemical Co., Ltd.) and the like.
  • the surface treatment amount of the inorganic filler with the silane coupling agent is not particularly limited, but is, for example, 2% by mass or less.
  • the silane coupling agent used in the present invention is a chemical bond between a grafting reaction site (group or atom) that can be grafted to the base rubber in the presence of radicals generated by the decomposition of an organic peroxide and an inorganic filler. It is sufficient to have at least a reactive site (including a site generated by hydrolysis, such as a silyl ester group) that can be reacted with a reactive site and capable of silanol condensation.
  • a hydrolyzable silane coupling agent having a hydrolyzable group at the terminal is preferable.
  • the silane coupling agent has an amino group, a glycidyl group or an ethylenically unsaturated group-containing group and a hydrolyzable group-containing group at the terminal, and more preferably ethylene at the terminal. It is a silane coupling agent having a group containing a polymerizable unsaturated group and a group containing a hydrolyzable group.
  • the group containing an ethylenically unsaturated group is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth) acryloyloxy group, a (meth) acryloyloxyalkylene group, and a p-styryl group. Moreover, you may use together these silane coupling agents and the silane coupling agent which has another terminal group.
  • silane coupling agent for example, a compound represented by the following general formula (1) can be used.
  • R a11 is a group containing an ethylenically unsaturated group
  • R b11 is an aliphatic hydrocarbon group, a hydrogen atom, or Y 13 .
  • Y 11 , Y 12 and Y 13 are hydrolyzable organic groups. Y 11 , Y 12 and Y 13 may be the same as or different from each other.
  • R a11 of the silane coupling agent represented by the general formula (1) is preferably a group containing an ethylenically unsaturated group, and the group containing an ethylenically unsaturated group is as described above, preferably vinyl. It is a group.
  • R b11 is an aliphatic hydrocarbon group, a hydrogen atom, or Y 13 described later, and the aliphatic hydrocarbon group is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms excluding the aliphatic unsaturated hydrocarbon group. Is mentioned. R b11 is preferably Y 13 described later.
  • Y 11 , Y 12 and Y 13 are hydrolyzable organic groups such as an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an acyloxy group having 1 to 4 carbon atoms. And an alkoxy group is preferred.
  • Specific examples of the hydrolyzable organic group include methoxy, ethoxy, butoxy, acyloxy and the like. Among these, methoxy or ethoxy is more preferable, and methoxy is particularly preferable from the viewpoint of the reactivity of the silane coupling agent.
  • the silane coupling agent is preferably a silane coupling agent having a high hydrolysis rate, more preferably R b11 is Y 13 and Y 11 , Y 12 and Y 13 are the same as each other.
  • a hydrolyzable silane coupling agent in which at least one of Y 11 , Y 12 and Y 13 is a methoxy group more preferably R b11 is Y 13 and Y 11 , Y 12 and Y 13 are Silane coupling agents that are the same as each other.
  • Particularly preferred are hydrolyzable silane coupling agents, all of which are methoxy groups.
  • silane coupling agent examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxysilane, allyltrimethoxysilane.
  • vinyl silanes such as ethoxysilane and vinyltriacetoxysilane
  • (meth) acryloxysilanes such as methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, and methacryloxypropylmethyldimethoxysilane.
  • Those having a glycidyl group at the end include 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
  • silane coupling agents a silane coupling agent having a vinyl group and an alkoxy group at the terminal is more preferable, and vinyltrimethoxysilane and vinyltriethoxysilane are particularly preferable.
  • the silane coupling agent may be used alone or in combination of two or more. Further, it may be used as it is or diluted with a solvent or the like.
  • Organic peroxide generates radicals by at least thermal decomposition and performs grafting reaction by radical reaction (including hydrogen radical abstraction reaction from rubber) between the grafting reaction site of the silane coupling agent and the base rubber as a catalyst. Work to raise.
  • the organic peroxide is not particularly limited as long as it generates radicals.
  • a compound represented by ( ⁇ O) —OO (C ⁇ O) R 6 is preferred.
  • R 1 to R 6 each independently represents an alkyl group, an aryl group, or an acyl group. Among R 1 to R 6 of each compound, those in which all are alkyl groups or those in which any one is an alkyl group and the remaining is an acyl group are preferable.
  • organic peroxides examples include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, , 5-Dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3 , 3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxide Oxybenzoate, tert-butyl peroxyisopropyl carbonate, dia Chill peroxide, lauroyl peroxide,
  • dicumyl peroxide 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2 are preferable in terms of odor, colorability, and scorch stability.
  • 5-Di- (tert-butylperoxy) hexyne-3 is preferred.
  • the decomposition temperature of the organic peroxide is preferably from 130 to 195 ° C., particularly preferably from 150 to 185 ° C.
  • the decomposition temperature of an organic peroxide means that when a single composition organic peroxide is heated, the decomposition temperature of the organic peroxide is halved to two or more kinds of compounds at a certain temperature or temperature range within one minute. It means the temperature at which a decomposition reaction takes place (half-life temperature for 1 minute). Specifically, it refers to the temperature at which heat absorption or heat generation starts when heated from room temperature in a nitrogen gas atmosphere at a rate of temperature increase of 5 ° C./min by thermal analysis such as DSC method.
  • the silanol condensation catalyst functions to cause a condensation reaction of the silane coupling agent grafted on the base rubber in the presence of moisture. Based on the action of the silanol condensation catalyst, the rubbers are cross-linked through a silane coupling agent. As a result, it has excellent tensile strength and small compression set without using vulcanization equipment, and can be molded at high temperature and high speed if necessary, and silane-crosslinked rubber molding in a shorter time than conventional methods for producing crosslinked EP rubber. The body is obtained.
  • silanol condensation catalyst used in the present invention examples include organotin compounds, metal soaps, platinum compounds and the like.
  • Common silanol condensation catalysts include, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, zinc stearate, lead stearate, barium stearate, calcium stearate, sodium stearate, naphthenic acid Lead, lead sulfate, zinc sulfate, organic platinum compounds and the like are used.
  • organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctiate, and dibutyltin diacetate are particularly preferable.
  • the silanol condensation catalyst is used by mixing with rubber as desired.
  • rubber also referred to as carrier rubber
  • carrier rubber is not particularly limited, and each rubber component or each resin component described as the base rubber can be used.
  • the silane cross-linked rubber molded product and the silane cross-linkable rubber composition may contain various additives generally used in the rubber product as long as the effects of the present invention are not impaired.
  • additives include crosslinking aids, antioxidants, lubricants, metal deactivators, colorants, and fillers (including flame retardant (auxiliary) agents) other than the above inorganic fillers. It is done.
  • silane crosslinkable rubber composition and the method for producing the silane crosslinkable rubber molded product of the present invention will be specifically described.
  • Each of the “method for producing a silane-crosslinked rubber molded product” and the “method for producing a silane-crosslinkable rubber composition” of the present invention performs at least the following step (1). Therefore, the “method for producing a silane-crosslinked rubber molded product” of the present invention and the “method for producing a silane-crosslinkable rubber composition” of the present invention will be described together below. May be referred to as a manufacturing method.)
  • Step (1) With respect to 100 parts by weight of the base rubber, 0.3 to 400 parts by weight of an inorganic filler, 1 to 15 parts by weight of a silane coupling agent, 0.01 to 0.6 parts by weight of an organic peroxide, Step of melting and mixing 0.0001 to 0.5 parts by mass of silanol condensation catalyst to obtain a silane crosslinkable rubber composition as a molten mixture
  • Step (2) Silane crosslinkable rubber composition obtained in step (1) Step of molding a product to obtain a molded body
  • Step (3) Step of obtaining a silane-crosslinked rubber molded body by contacting the molded body obtained in step (2) with water
  • Step (1) melts and mixes all of the base rubber in step (a), it has steps (a) and (c), and melts and mixes part of the base rubber in the following step (a) When doing, it has a process (a), a process (b), and a process (c).
  • the “base rubber” is a base rubber for forming a silane cross-linked rubber molded article or a silane cross-linkable rubber composition. Therefore, in the production method of the present invention, it is only necessary that the silane crosslinkable rubber composition obtained in step (1) contains 100 parts by mass of the base rubber.
  • the silane crosslinkable rubber composition obtained in step (1) contains 100 parts by mass of the base rubber.
  • the step (a) “a mode in which the total amount (100 parts by mass) of the base rubber is blended” and “a mode in which a part of the base rubber is blended” are included.
  • the remainder of the base rubber may be mixed as a carrier rubber in the step (b).
  • “part of the base rubber” is a rubber used in the step (a) of the base rubber, and a part of the base rubber itself (having the same composition as the base rubber) constitutes the base rubber.
  • the “remaining part of the base rubber” is the remaining rubber excluding a part of the base rubber used in the step (a), specifically, the remaining part of the base rubber itself (the same composition as the base rubber). The remainder of the components constituting the base rubber and the remaining components constituting the base rubber.
  • the content of 100 parts by weight of the base rubber in the step (1) is the total amount of each component mixed in the step (a) and the step (b).
  • the base rubber is preferably compounded in the step (a) in an amount of preferably 80 to 99 parts by mass, more preferably 94 to 98 parts by mass. In b), preferably 1 to 20 parts by mass, more preferably 2 to 6 parts by mass are blended.
  • step (1) the content of the ethylene- ⁇ -olefin rubber and the polypropylene resin in the base rubber is as described above.
  • the content of the organic peroxide is 0.01 to 0.6 parts by weight, preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the base rubber.
  • the grafting reaction does not proceed at the time of melt mixing, and the silane coupling agents are condensed to obtain sufficient tensile strength and small compression set. May not be possible.
  • the amount exceeds 0.6 parts by mass many of the base rubbers are directly cross-linked by side reactions to form bumps, resulting in poor appearance.
  • the grafting reaction can be carried out in an appropriate range, and the moldability is not generated without causing gelled defects. Can be obtained.
  • the content of the inorganic filler is 0.3 to 400 parts by mass, preferably 1 to 200 parts by mass, and more preferably 3 to 100 parts by mass with respect to 100 parts by mass of the base rubber.
  • the silane coupling agent is likely to volatilize, and the grafting reaction and crosslinking reaction of the silane coupling agent may not proceed.
  • a small compression set or high tensile strength may not be obtained when a silane-crosslinked rubber molded body is obtained.
  • the amount exceeds 400 parts by mass the interaction between the rubbers becomes small, and the original properties of the rubber are impaired. For this reason, a small compression set and high tensile strength cannot be obtained, and the maximum linear drawing speed may be slowed because the burden on the motor or the like of the extruder is increased.
  • the content of the silane coupling agent is 1 to 15 parts by weight, preferably 3 to 15 parts by weight, more preferably more than 4 parts by weight and 15 parts by weight or less with respect to 100 parts by weight of the base rubber. More preferably, it is more than 4 parts by mass and 10 parts by mass or less.
  • the content of the silane coupling agent is less than 1 part by mass, the crosslinking reaction does not proceed sufficiently, and a small compression set may not be obtained.
  • it exceeds 15 parts by mass the silane coupling agent cannot be completely adsorbed on the surface of the inorganic filler, and the silane coupling agent volatilizes during kneading, which is not economical.
  • suck condenses, and there exists a possibility that an external appearance may deteriorate by producing a spot and burning in a molded object.
  • silane coupling agent When the content of the silane coupling agent is 3 to 15 parts by mass, particularly more than 4 parts by mass and 15 parts by mass or less, both the crosslinking reaction between the base rubbers and the condensation reaction between the silane coupling agents are performed. A silane-crosslinked rubber molded article having a beautiful appearance can be produced.
  • the reaction by the decomposition of the organic peroxide causes the cross-linking of the base rubbers when the content of the silane coupling agent exceeds 4 parts by mass.
  • the grafting reaction between the silane coupling agent and the base rubber and the condensation reaction between the silane coupling agents, which are faster than the reaction rate, are dominant. Therefore, the cross-linking reaction between the rubbers which causes rough appearance and bumps is less likely to occur.
  • the cross-linking reaction between the base rubbers can be effectively suppressed according to the content of the silane coupling agent.
  • molding becomes favorable.
  • the said defect by the crosslinking reaction of base rubbers decreases, even if it restarts after stopping an extruder, it becomes difficult to generate
  • the cross-linking reaction between the base rubbers can be suppressed, and a silane cross-linked rubber molded article having a good appearance can be produced.
  • the condensation reaction between silane coupling agents also has a high reaction rate. However, since many silane coupling agents are fixed by being bonded or adsorbed to the inorganic filler, the condensation reaction between the silane coupling agents bonded or adsorbed to the inorganic filler hardly occurs.
  • the condensation reaction between the free silane coupling agents may occur without binding or adsorbing to the inorganic filler, but in the present invention, most of the silane coupling agent is bonded or adsorbed to the inorganic filler, It does not lead to the generation of gel-like spots. As described above, it is considered that a silane-crosslinked rubber molded article having a clean appearance can be produced by using a specific amount of the silane coupling agent.
  • the content of the silanol condensation catalyst is 0.0001 to 0.5 parts by mass, preferably 0.001 to 0.3 parts by mass with respect to 100 parts by mass of the base rubber.
  • the content of the silanol condensation catalyst is 0.0001 to 0.5 parts by mass, the crosslinking reaction by the condensation reaction of the silane coupling agent tends to proceed almost uniformly, and the appearance, tensile strength and compression permanentness of the silane crosslinked rubber molded product Distortion is excellent and productivity is improved. That is, if the content of the silanol condensation catalyst is too small, sufficient tensile strength or small compression set may not be obtained. On the other hand, if the amount is too large, the crosslinking reaction due to the condensation reaction of the silane coupling agent becomes uneven, and the appearance and productivity may be inferior.
  • step (a) all or a part of the base rubber, the inorganic filler, the silane coupling agent, and the organic peroxide are charged into the mixer at the above contents, and the decomposition temperature of the organic peroxide
  • a silane master batch is prepared by melting and kneading while heating to the above temperature.
  • the temperature at which the above components are melt-mixed is equal to or higher than the decomposition temperature of the organic peroxide, preferably the decomposition temperature of the organic peroxide + (1 to 80) ° C.
  • the temperature of the melt mixing is preferably 80 to 250 ° C, more preferably 100 to 240 ° C.
  • This mixing temperature is preferably set after the base rubber is melted. When the mixing temperature is within the above range, the above components are melted, the organic peroxide is decomposed, and the necessary grafting reaction proceeds sufficiently in step (a). Other conditions can be set as appropriate.
  • the mixing time may be a time during which the grafting reaction of the silane coupling agent to the polyolefin resin sufficiently proceeds at the melting temperature, and is preferably 5 minutes to 1 hour, for example.
  • the mixing method is not particularly limited as long as it is a method usually used for rubber, plastic and the like.
  • the mixing device is appropriately selected according to, for example, the content of the inorganic filler.
  • a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, various kneaders, or the like is used as the kneading apparatus.
  • a closed mixer such as a Banbury mixer or various kneaders is preferable in terms of rubber dispersibility and stability of the crosslinking reaction.
  • the inorganic filler is mixed in excess of 100 parts by mass with respect to 100 parts by mass of the base rubber, it is preferable to melt and mix with a continuous kneader, a pressure kneader, or a Banbury mixer.
  • each of the above components can be melt-mixed at a time, but preferably, the silane coupling agent is not mixed with the silane masterbatch alone, but is mixed in a premixed state with an inorganic filler. Can also be done.
  • the premixed silane coupling agent is present so as to surround the surface of the inorganic filler, and part or all of the silane coupling agent is adsorbed or bonded to the inorganic filler. Thereby, volatilization of the silane coupling agent can be reduced during subsequent melt mixing. Moreover, it is possible to prevent the silane coupling agent that is not adsorbed or bonded to the inorganic filler from condensing and becoming difficult to melt and mix.
  • the method of mixing the inorganic filler, the silane coupling agent and the organic peroxide is not particularly limited, and the organic peroxide may be mixed with the inorganic filler or the like, or the inorganic filler and the silane coupling agent. May be mixed in any of the mixing stages.
  • the organic peroxide may be mixed with the inorganic filler after being mixed with the silane coupling agent, or may be separately mixed with the inorganic filler separately from the silane coupling agent. In the present invention, it is better to mix the organic peroxide and the silane coupling agent substantially together.
  • only the silane coupling agent may be mixed with the inorganic filler, and then the organic peroxide may be mixed.
  • an inorganic filler previously mixed with a silane coupling agent can be used.
  • the organic peroxide may be mixed with other components or may be a simple substance.
  • a rubber component or a resin component may be present as long as the temperature below the decomposition temperature is maintained.
  • Examples of the mixing method of the inorganic filler, the silane coupling agent, and the organic peroxide include mixing methods such as wet processing and dry processing. Specifically, a wet process in which a silane coupling agent is added in a state where an inorganic filler is dispersed in a solvent such as alcohol or water, a dry process in which both are added by heating or non-heating, and both are mentioned.
  • dry processing is preferred in which a silane coupling agent is added to an inorganic filler, preferably a dried inorganic filler, with heating or non-heating and mixed. This premixing is preferably performed with a mixer-type kneader such as a Banbury mixer or a kneader.
  • the premixing may be performed using a mixer such as a Henschel mixer, or may be performed manually.
  • a mixer such as a Henschel mixer
  • the silane coupling agent and the inorganic filler have a strong bond, so that the volatilization of the silane coupling agent can be effectively suppressed, but the grafting reaction to the base rubber may be difficult to proceed. is there.
  • the binding force between the inorganic filler and the silane coupling agent becomes relatively weak, so that the grafting reaction efficiently proceeds and the silanol condensation reaction easily proceeds.
  • the mixture obtained and the whole or a part of the base rubber are then melt-kneaded while being heated above the decomposition temperature of the organic peroxide.
  • step (a) it is preferable to knead the above-mentioned components without substantially mixing the silanol condensation catalyst.
  • the condensation reaction of a silane coupling agent can be suppressed, it is easy to melt and mix, and a desired shape can be obtained during extrusion molding.
  • substantially not mixed does not exclude the unavoidably existing silanol condensation catalyst, and is present to such an extent that the above-mentioned problem due to silanol condensation of the silane coupling agent does not occur. Means good.
  • the silanol condensation catalyst may be present as long as it is 0.01 part by mass or less with respect to 100 parts by mass of the base rubber.
  • the above additives may be mixed in any step or in the components, but are preferably mixed in carrier rubber.
  • an antioxidant is added in a large amount (for example, 1 part by mass or more) to the silane master batch, crosslinking inhibition occurs due to a radical scavenging effect and the like, and as a result, the grafting reaction may not proceed sufficiently.
  • the step (a) is performed to prepare a silane master batch (also referred to as silane MB).
  • this silane MB is preferably used together with a silanol condensation catalyst or a catalyst master batch described later in the production of the molten mixture (silane crosslinkable rubber composition) prepared in step (1).
  • Silane MB contains a silane crosslinkable rubber (silane graft rubber) in which a silane coupling agent is grafted onto a base rubber to such an extent that it can be molded by the step (2) described later.
  • the mixing ratio of the rubber as the carrier rubber and the silanol condensation catalyst is not particularly limited, but is preferably set so as to satisfy the above content in the step (1).
  • the mixing may be a method capable of uniformly mixing, and includes mixing (melting mixing) performed under melting of rubber.
  • the melt mixing can be performed in the same manner as the melt mixing in the step (a).
  • the mixing temperature can be 80 to 250 ° C., more preferably 100 to 240 ° C. Other conditions such as the mixing time can be set as appropriate.
  • step (b) other rubber components or resin components can be used as the carrier rubber instead of or in addition to the remainder of the base rubber. That is, in the step (b), the remainder of the base rubber when a part of the base rubber is melt-mixed in the step (a), or a rubber component or a resin component other than the base rubber used in the step (a), and silanol
  • the catalyst MB may be prepared by melt mixing with a condensation catalyst.
  • the carrier rubber is another rubber component or resin component, the content of the other rubber component or resin component can be promoted quickly in the step (a), and in addition, it is less likely to cause blistering during molding. Is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, and even more preferably 4 to 20 parts by weight with respect to 100 parts by weight of the base rubber.
  • an inorganic filler may be used in the step (b).
  • content of an inorganic filler is not specifically limited, 350 mass parts or less are preferable with respect to 100 mass parts of carrier rubber.
  • the silanol condensation catalyst is difficult to disperse and the crosslinking reaction is difficult to proceed.
  • the catalyst MB prepared in this way is a mixture of a silanol condensation catalyst, a carrier rubber, and an inorganic filler that is optionally added.
  • the catalyst MB is used as a master batch set together with the silane MB in the production of the silane crosslinkable rubber composition prepared in the step (1).
  • the step (c) is performed in which the silane MB and the silanol condensation catalyst or the catalyst MB are mixed to obtain a molten mixture.
  • the mixing method may be any mixing method as long as a uniform molten mixture can be obtained as described above.
  • Mixing is basically the same as the melt mixing in step (a). Mixing is carried out at a temperature at which the base rubber and other resin components melt.
  • the mixing temperature is appropriately selected according to the melting temperature of the base rubber or carrier rubber.
  • the mixing temperature is, for example, preferably 100 to 250 ° C., more preferably 120 to 220 ° C. Other conditions such as mixing (kneading) time can be set as appropriate.
  • step (c) in order to avoid the silanol condensation reaction, it is preferable that the silane MB and the silanol condensation catalyst are not mixed and kept at a high temperature for a long time.
  • This step (c) may be any step as long as the silane MB and the silanol condensation catalyst are mixed to obtain a molten mixture, and the silanol condensation catalyst and the catalyst MB containing the carrier rubber and the silane MB are melt mixed. Is preferred.
  • step (1) that is, the method for producing the silane crosslinkable rubber composition of the present invention is performed, and the silane crosslinkable rubber composition of the present invention is obtained as a molten mixture.
  • This silane crosslinkable rubber composition contains 61 to 100% by mass of an ethylene- ⁇ olefin rubber having a Mooney viscosity (ML (1 + 4) 125 ° C.) measured in accordance with JIS K 6300-1: 2013 of more than 40 and 90 or less.
  • the silane crosslinkable rubber contained in the silane crosslinkable rubber composition is a silane crosslinkable rubber in which a silane coupling agent is grafted onto a base rubber.
  • the reaction site of the silane coupling agent may be bonded or adsorbed to the inorganic filler, but is not silanol condensed as described later.
  • the silane crosslinkable rubber is a crosslinkable rubber in which a silane coupling agent bonded or adsorbed to an inorganic filler is grafted to the base rubber, and a crosslink in which a silane coupling agent not bonded to or adsorbed to the inorganic filler is grafted to the base rubber.
  • the silane crosslinkable rubber may have a silane coupling agent to which an inorganic filler is bonded or adsorbed and a silane coupling agent to which an inorganic filler is not bonded or adsorbed.
  • the silane coupling agent and the unreacted rubber component may be included.
  • the silane cross-linkable rubber is a base rubber containing 61 to 100% by mass of an ethylene- ⁇ olefin rubber having a Mooney viscosity (ML (1 + 4) 125 ° C.) measured in accordance with JIS K 6300-1: 2013 of more than 40 and 90 or less.
  • a rubber obtained by grafting reaction of 1 to 15 parts by mass of a silane coupling agent with 70 to 100% by mass in 100 parts by mass is preferable.
  • the reaction rate of the silane coupling agent when the silane coupling agent is grafted to the base rubber (also referred to as grafting rate) is not particularly limited as long as the effect of the present invention is not impaired. In the present invention, it is difficult to uniquely determine the grafting rate.
  • the grafting rate according to the measurement method described in the examples described later is 70 to 100% by mass (the silane grafting amount is 0.7 to 15 mass parts), preferably 75 to 100 mass% (silane graft amount is 0.75 to 15 mass parts), more preferably 80 to 100 mass% (silane graft amount is 0.8 to 15 mass parts). More preferably, it is part by mass).
  • the grafting ratio is 70 to 100% by mass, the base rubber is sufficiently cross-linked, which is suitable for imparting the above-described excellent characteristics.
  • the grafting rate can be set within a predetermined range depending on the type or content of the organic peroxide, the type of silane coupling agent, the use of a closed mixer, and the like.
  • steps (a) to (c) can be performed simultaneously or sequentially.
  • step (2) and step (3) are performed.
  • the step (2) of molding the obtained molten mixture to obtain a molded body is performed.
  • This process (2) should just be able to shape
  • the molding method include extrusion molding using an extruder, injection molding using an injection molding machine, press molding using a press molding machine, and molding using other molding machines. Extrusion is preferred when the product of the invention is a wire or fiber optic cable.
  • the molding speed (extrusion speed) of the silane crosslinkable rubber composition of the present invention is not particularly limited, and is usually 1 to less than 1 to 20 m / min, preferably 1 Can be set to ⁇ 10m / min.
  • the molding speed in order to further improve productivity, can be set at a linear speed of 20 to 100 m / min.
  • extrusion molding can also be performed at high temperature.
  • the molding temperature is set to a high temperature
  • extrusion molding can be performed at a high extrusion speed as described above even when rubber having a high Mooney viscosity is used.
  • the production method of the present invention can realize an excellent appearance.
  • the molding temperature is set to a high temperature, it can be set to, for example, 150 ° C. or higher, and preferably 180 to 250 ° C.
  • a process (2) can be performed simultaneously with a process (c) or continuously. That is, as one embodiment of the melt mixing in the step (c), a melt molding material such as silane MB, silanol condensation catalyst or catalyst MB is melt-mixed at the time of melt molding, for example, at the time of extrusion molding, or just before that.
  • a melt molding material such as silane MB, silanol condensation catalyst or catalyst MB is melt-mixed at the time of melt molding, for example, at the time of extrusion molding, or just before that.
  • pellets such as dry blends may be mixed together at room temperature or high temperature and introduced into a molding machine (melt mixing), or mixed and then melt mixed, pelletized again, and then introduced into the molding machine. Also good.
  • a series of steps in which a molding material of silane MB and silanol condensation catalyst or catalyst MB is melt-kneaded in a coating apparatus, and then extrusion coated on the outer peripheral surface of a conductor or the like and molded into a desired shape. Can be adopted.
  • a molded body of the silane crosslinkable rubber composition is obtained.
  • this molded product is partially crosslinked, but is in a partially crosslinked state that retains the moldability that can be molded in the step (2). Therefore, the silane crosslinked rubber molded product of the present invention is formed into a molded product that has been crosslinked or finally crosslinked by performing the step (3).
  • a step of bringing the molded product obtained in the step (2) into contact with water is performed.
  • the reaction sites of the silane coupling agent are condensed to cause a crosslinking reaction.
  • the reaction site is hydrolyzed to become silanol, and the hydroxyl group of silanol is condensed with the silanol condensation catalyst present in the molded body, thereby causing a crosslinking reaction.
  • a silane-crosslinked rubber molded product in which the silane coupling agent is crosslinked by silanol condensation can be obtained.
  • the process itself in this step (3) can be performed by a normal method.
  • Condensation between silane coupling agents proceeds only by leaving at room temperature. Therefore, in the step (3), it is not necessary to positively contact the molded body with water.
  • the molded body can be positively brought into contact with moisture.
  • a method of positively contacting water such as immersion in warm water, charging into a wet heat tank, exposure to high-temperature steam, and the like. In this case, pressure may be applied to allow moisture to penetrate inside.
  • Such a technique is effective in the case of an electric wire having a large coating thickness or a molded body having a large volume.
  • this silane cross-linked rubber molded article contains a cross-linked rubber obtained by cross-linking a silane cross-linkable rubber through a silane coupling agent.
  • this silane crosslinked rubber molding contains a silane crosslinked rubber and an inorganic filler.
  • the inorganic filler may be bonded to the silane coupling agent of the silane crosslinked rubber.
  • the silane crosslinked rubber is obtained by bonding or adsorbing a plurality of crosslinked rubbers to the inorganic filler by the silane coupling agent, thereby bonding (crosslinking) the crosslinked rubber via the inorganic filler and the silane coupling agent, and the above-mentioned crosslinking property.
  • the reaction site of the silane coupling agent of the rubber hydrolyzes and undergoes silanol condensation reaction with each other, thereby containing at least a crosslinked rubber crosslinked via the silane coupling agent.
  • the bond (crosslinking) via the inorganic filler and the silane coupling agent and the crosslinking via the silane coupling agent may be mixed. Further, it may contain a silane coupling agent, an unreacted rubber component and / or a silane crosslinkable rubber which is not crosslinked.
  • the reason for grafting in the production method of the present invention is not yet clear, but is considered as follows. That is, when the base rubber is heated and kneaded at a temperature higher than the decomposition temperature of the organic peroxide together with the inorganic filler and the silane coupling agent in the presence of the organic peroxide, the organic peroxide is decomposed to generate radicals. On the other hand, grafting of the silane coupling agent occurs. In addition, due to the heating in the above melt mixing, a chemical bond forming reaction is caused in part by a covalent bond between a silane coupling agent and a group such as a hydroxyl group on the surface of the inorganic filler.
  • the final cross-linking reaction may be performed in step (3), and if a specific amount of the silane coupling agent is blended with the base rubber as described above, extrusion processability (moldability) at the time of molding is impaired. It becomes possible to mix
  • a base rubber containing ethylene- ⁇ olefin rubber having a high Mooney viscosity at the above content is mixed, molded and crosslinked by the silane crosslinking method. Therefore, a silane-crosslinked rubber molded article having excellent compression set, high tensile strength, and excellent appearance can be produced. Furthermore, the method for producing a silane-crosslinked rubber molded body of the present invention is such that the base rubber is molded and cross-linked by the silane cross-linking method described above, so that no EP rubber vulcanization facility is required for performing the cross-linking reaction. Productivity can be increased with respect to rubber vulcanization.
  • the method for producing a silane-crosslinked rubber molded body of the present invention can suppress rubber crosslinking during molding, and if necessary, the molding temperature can be set to a high temperature as described above, and the linear velocity can be set to a higher value. You can also
  • the mechanism of action of the above process of the present invention is not yet clear, but is estimated as follows. That is, by using an inorganic filler and a silane coupling agent before and / or during kneading with the base rubber, the silane coupling agent is bonded to a group capable of chemically bonding with the inorganic filler at the reaction site. , Retained. Alternatively, it is physically and chemically adsorbed and held in the hole or surface of the inorganic filler without being bonded to the inorganic filler.
  • a silane coupling agent that binds to the inorganic filler with a strong bond (the reason is, for example, the formation of a chemical bond with a group capable of chemically reacting on the surface of the inorganic filler) and a weak bond.
  • Bonding silane coupling agents (for example, interactions due to hydrogen bonds, interactions between ions, partial charges or dipoles, and effects due to adsorption can be considered) can be formed.
  • the silane coupling agent is hardly volatilized from the rubber composition (rubber kneaded material) as will be described later, and the other terminal.
  • the base rubber is bonded to the site capable of grafting reaction.
  • a silane crosslinkable rubber having a different bond to the inorganic filler and having a silane coupling agent grafted to the base rubber is formed.
  • the diene components in the base rubber are also crosslinked by radicals generated by the decomposition of the organic peroxide.
  • the silane coupling agent, the organic peroxide, and the inorganic filler are mixed, it is considered that the grafting reaction of the silane coupling agent proceeds preferentially.
  • the silane coupling agent having a strong bond with the inorganic filler among the silane coupling agents is retained in the bond with the inorganic filler, and the grafting reaction site is a site where the grafting reaction of the base rubber is possible Grafting reaction with (radical site of rubber generated by abstraction of hydrogen radical by radical generated by decomposition of organic peroxide).
  • a plurality of silane coupling agents are bonded to the surface of one inorganic filler particle through a strong bond, a plurality of rubbers are bonded through the inorganic filler particle.
  • the crosslinked network via the inorganic filler is expanded. That is, a silane crosslinkable rubber formed by grafting reaction of the silane coupling agent bonded to the inorganic filler onto the base rubber is formed.
  • silane coupling agent having a strong bond with an inorganic filler In the case of a silane coupling agent having a strong bond with an inorganic filler, the condensation reaction in the presence of water by this silanol condensation catalyst is unlikely to occur, and the bond with the inorganic filler is retained.
  • the reason why the silanol condensation reaction hardly occurs is considered to be that the binding energy between the inorganic filler and the silane coupling agent is very high and the condensation reaction does not occur even under the silanol condensation catalyst.
  • the base rubber and the inorganic filler are bonded, and the rubber is crosslinked through the silane coupling agent.
  • the adhesion between the base rubber and the inorganic filler is strengthened, and a molded article excellent in mechanical strength, tensile strength and compression set can be obtained.
  • silane coupling agents can be bonded to the surface of one inorganic filler particle, and high mechanical strength can be obtained.
  • the silane coupling agent bonded with a strong bond to the inorganic filler contributes to improvement of mechanical properties and tensile strength.
  • the silane coupling agent having a weak bond with the inorganic filler is detached from the surface of the inorganic filler, and the grafting reaction site of the silane coupling agent is a site where the grafting reaction of the base rubber is possible. And the grafting reaction takes place. That is, a silane crosslinkable rubber is formed by grafting reaction of the silane coupling agent released from the inorganic filler onto the base rubber. The silane coupling agent in the graft portion thus produced is then mixed with a silanol condensation catalyst and brought into contact with moisture to cause a condensation reaction (crosslinking reaction).
  • the tensile strength of the silane cross-linked rubber molded product obtained by this cross-linking reaction is increased, and it becomes possible to obtain a silane cross-linked rubber molded product having a small compression set in addition to heat resistance.
  • the silane coupling agent bonded with a weak bond to the inorganic filler contributes to improvement of the degree of crosslinking, that is, improvement of heat resistance and suppression of compression set.
  • the crosslinking reaction by condensation using a silanol condensation catalyst in the presence of water in the step (3) is performed after forming the molded body.
  • operativity in the process until a molded object formation is excellent.
  • the condensation reaction using the silanol condensation catalyst does not proceed in an extruder having almost no moisture, extrusion at a high temperature is possible in the step (2). Therefore, molding at high temperature and high speed is also possible.
  • the appearance is excellent because the condensation of the silane coupling agents is suppressed as described above.
  • the silane coupling agent of 3 to 15 parts by mass, particularly more than 4 parts by mass and 15 parts by mass or less is mixed with the inorganic filler, as described above, the process (1), particularly the process ( The cross-linking reaction between rubbers during melt kneading in a) can be effectively suppressed.
  • the silane coupling agent is bonded to the inorganic filler, and is not easily evaporated during the melt kneading in the step (1), particularly the step (a), and the reaction between the free silane coupling agents is also effective. Can be suppressed. Therefore, even if the extruder is stopped and then restarted, poor appearance hardly occurs, and a silane-crosslinked rubber molded article having a good appearance can be produced.
  • restarting after stopping it cannot be uniquely described depending on the composition of the base rubber, processing conditions, etc., but for example, it can be restarted at 190 ° C. for an interval of 30 minutes, preferably 90 minutes. Say.
  • the silane-crosslinked rubber molded article of the present invention has at least the following characteristics (measurement method is the same as in the examples) and is excellent in appearance. That is, the compression set of the silane crosslinked rubber molded body is preferably 40% or less, more preferably 30% or less, and further preferably 20% or less. Although a minimum is not specifically limited, For example, it is 10%.
  • the silane cross-linked rubber molded article has a tensile strength of preferably 8 MPa or more, more preferably 10 MPa or more, and further preferably 12 MPa or more. Although an upper limit is not specifically limited, For example, it is 25 MPa. A method for measuring the tensile strength will be described later.
  • the silane cross-linkable rubber composition of the present invention can produce a silane cross-linked rubber molded article having the above-mentioned excellent characteristics. Moreover, the rubber cross-linking step is unnecessary, and the productivity is excellent. Furthermore, it is excellent in high-temperature moldability and high-speed moldability, and exhibits high productivity.
  • the high temperature moldability and the high speed moldability are as described above, and are specifically described in the examples.
  • the silane cross-linked rubber molded product of the present invention may be a product containing a silane cross-linked rubber molded product or a product consisting only of a silane cross-linked rubber molded product.
  • the product containing the silane cross-linked rubber molded product include a product comprising a silane cross-linked rubber molded product and other members such as a support, a support frame and the like.
  • the term “product” is used to include a semi-finished product, a part, and a member.
  • silane-crosslinked rubber molded article of the present invention various industrial cables (including electric wires) coating materials, rubber molding materials (for example, automotive glass run channels, weather strips, rubber hoses, wiper blade rubbers, gaskets, anti-vibration rubbers), etc. Is mentioned.
  • the silane-crosslinked rubber molded article of the present invention is preferably a product that requires at least one of excellent compression set and high tensile strength.
  • a product is not particularly limited.
  • a product that requires a compression set of 40% or less at 70 ° C. a product that requires a tensile strength of 8 MPa or more, or a product that requires the compression set and the tensile strength.
  • sheath materials preferably, sheath materials (jacket materials) and insulating materials among various industrial cable coating materials, and further rubber molding materials (weather strips, gaskets, etc.) Is mentioned.
  • the production method of the present invention can be applied to the production of components that require a small compression set, products that require high tensile strength, product components such as rubber materials, or members thereof.
  • the production method of the present invention can produce a silane-crosslinked rubber molded article having excellent characteristics as described above without requiring a vulcanization facility and with good productivity. Therefore, the production method of the present invention can be particularly preferably applied to products that require at least one of a small compression set and a high tensile strength.
  • the production method of the present invention can be suitably applied to the production of electric wires and optical cables, among these products, and can form these covering materials (insulators and sheaths).
  • the product of the present invention is an extrusion-molded product such as an electric wire or cable
  • the molding material is extruded on the outer periphery of the conductor or the like while being melt-kneaded in the extruder (extrusion coating apparatus), etc.
  • Can be manufactured step (c) and step (2)).
  • Such a product uses a general-purpose extrusion coating apparatus without using a special machine such as an electron beam cross-linking machine or a rubber vulcanizing equipment, and a silane cross-linkable rubber composition in which a large amount of an inorganic filler is added.
  • insulating layer (the coating layer comprising the silane crosslinkable rubber composition of the present invention or the silane crosslinkable rubber molded product) formed around the conductor is not particularly limited, but is generally about 0.15 to 5 mm. It is.
  • Table 1 shows the Mooney viscosity (ML (1 + 4) 125 ° C.), ethylene content and diene content (measured by infrared absorption spectroscopy) of the ethylene- ⁇ -olefin rubber.
  • ⁇ Rubber component> (Ethylene- ⁇ olefin rubber, EP rubber) "EP24” (trade name, manufactured by JSR, ethylene-propylene-ethylidene norbornene rubber) “NODEL 3745P” (NORDEL (registered trademark), manufactured by Dow Chemical Company, ethylene-propylene-ethylidene norbornene rubber) "EPT 3092PM” (Mitsui EPT (registered trademark), manufactured by Mitsui Chemicals, ethylene-propylene-ethylidene norbornene rubber) "Nodel 4785HM” (NORDEL (registered trademark), manufactured by Dow Chemical Company, ethylene-propylene-ethylidene norbornene rubber) "EP103AF” (trade name, manufactured by JSR, ethylene-propylene-ethylidene norbornene rubber) "Vistalon 878P” (Vistalon (registered trademark), manufactured by Exxon Mobil, ethylene-
  • ⁇ Silane coupling agent > "KBM1003" (trade name, manufactured by Shin-Etsu Silicone, vinyltrimethoxysilane)
  • Organic peroxide > “Perhexa 25B” (trade name, manufactured by NOF Corporation, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, half-life temperature of 179.8 ° C. for 1 minute)
  • Silanol condensation catalyst> “ADK STAB OT-1” trade name, manufactured by ADEKA, dioctyltin dilaurate
  • Examples 1 to 9 and Comparative Examples 1 to 6 In Examples 1 to 9 and Comparative Examples 1 to 6, a part of the EP rubber was used in the step (a), and the remaining part (5 parts by mass) of the EP rubber was used as the carrier rubber for the catalyst MB in the step (b). An inorganic filler, a silane coupling agent, and an organic peroxide were mixed at a mass ratio shown in Table 1 at room temperature (25 ° C.). The obtained mixture and base rubber containing a part of EP rubber are melt-mixed for 5 minutes at a temperature (185 ° C.) above the decomposition temperature of the organic peroxide using a 2 L Banbury mixer (manufactured by Nippon Roll Co., Ltd.).
  • the material was discharged at a material discharge temperature of 130 ° C. and pelletized to obtain silane MB (step (a)).
  • the obtained silane MB contains a silane crosslinkable EP rubber obtained by grafting a silane coupling agent to an EP rubber.
  • the silane MB obtained in step (a) and the catalyst MB obtained in step (b) have an electric wire coating extruder (L / D (ratio of effective screw length L to diameter D) of 25 and a screw diameter of 25 mm ⁇ ). ), And dry blended at 25 ° C. for about 1 minute to obtain a dry blend.
  • L / D ratio of effective screw length L to diameter D
  • the obtained dry blended product is put into the above-mentioned extrusion molding machine for covering electric wires, and the outer diameter of a 0.8 mm ⁇ conductor (an annealed copper wire) is finished to an outer diameter of 1.2 mm ⁇ under the following extrusion temperature conditions.
  • the wire precursor was manufactured by extrusion coating at a speed of 10 m / min.
  • Extrusion temperature conditions are divided into 3 zones C1, C2, and C3, with the temperature control in the cylinder part of the wire coating extruder from the feeder side to the die side, C1 zone is 150 ° C, C2 zone is 170 ° C, C3 zone Was set to 190 ° C, and the die temperature (molding temperature) was set to 200 ° C.
  • a silane crosslinkable rubber composition was prepared by melt-mixing the dry blend in an electric wire coating extruder prior to extrusion. This silane crosslinkable rubber composition contains the silane crosslinkable EP rubber, the inorganic filler and the silanol condensation catalyst having the contents shown in Table 1.
  • the electric wire precursor thus obtained was left in a 25 ° C., 50% RH environment for 24 hours to be brought into contact with water to produce an electric wire.
  • This electric wire had a silane cross-linked rubber molded article containing a silane cross-linked EP rubber obtained by cross-linking EP rubber with a silane coupling agent and an inorganic filler having a content shown in Table 1.
  • a molten strand having a diameter of about 35 mm was obtained in the same manner as in the production of the electric wire except that a dry blend was extruded without using a conductor.
  • the obtained molten strand was cut into a length of about 15 mm, and was pressed into a cylindrical mold having a size of 29.0 mm ⁇ and a thickness of 12.5 mm while being in a molten state, and press preformed. Thereafter, using a press molding machine, the cylindrical mold was preheated at 150 ° C. for 10 minutes, and then the press-preformed strand was placed in the preheated cylindrical mold, and press molded at 150 ° C.
  • This cylindrical rubber molded article was a silane-crosslinked rubber molded article containing a silane-crosslinked EP rubber obtained by crosslinking EP rubber with a silane coupling agent and an inorganic filler having a content shown in Table 1.
  • extrusion molding was carried out by setting the C1 to C3 zones of the extruder to 90 ° C. and the die temperature to 100 ° C.
  • the obtained electric wire precursor was cross-linked by passing through a 20 m long chemical cross-linking tube set in a steam environment having a temperature of 200 ° C. and a pressure of 10 MPa to produce an electric wire.
  • a molten strand having a diameter of 35 mm was obtained in the same manner as in the production of the electric wire except that pellets were extruded without using a conductor.
  • the molten strand was cut into a length of 15 mm and pressed into a cylindrical mold having a size of 29.0 mm ⁇ and a thickness of 12.5 mm, and press preforming was performed. Thereafter, using a press molding machine, the mold was preheated at 170 ° C. for 10 minutes, and then the press-preformed strand was put into a preheated mold, and press molded at 170 ° C. for 60 minutes at a pressure of 4 MPa. This produced a 29.0 mm ⁇ , 12.5 mm thick cylindrical rubber molded product.
  • ⁇ Tensile strength> A tensile test was performed based on JIS C 3005. Tensile strength was measured at a distance between gauge points of 20 mm and a tensile speed of 200 mm / min using a tubular piece obtained by drawing a conductor from the obtained electric wire, and evaluated according to the following evaluation criteria. The case where the tensile strength is 12 MPa or more is “A”, the case where it is 10 MPa or more and less than 12 MPa is “B”, the case where it is 8 MPa or more but less than 10 MPa is “C”, the case where it is less than 8 MPa is “D”. " In the present invention, the tensile strength of the evaluation “C” is a pass level of the test of the present invention.
  • the compression set was measured using the cylindrical rubber molded product produced in each example. Using a compression device equipped with two compression plates and spacers (thickness is 75% of the thickness of the cylindrical rubber molded product), the cylindrical rubber molded product is compressed by 25% in the thickness direction. (Compression rate 25%), heated to 70 ° C. in this state and held for 22 hours. Thereafter, the compression was released at room temperature (23 ° C.), and after cooling for 30 minutes (final temperature was 23 ° C.), the thickness of the cylindrical rubber molded product was measured. The compression set was calculated from the thickness of the cylindrical rubber molded product before and after compression by the following formula and evaluated according to the following evaluation criteria.
  • CS [(t 0 -t 2 ) / (t 0 -t 1 )] ⁇ 100
  • t 1 Spacer thickness (mm) t 2 cylindrical rubber thickness after the molded product of the compression (removed from the compression device, the thickness after 30 minutes) (mm) “A” when the compression set is 20% or less, “B” when the compression set exceeds 20% and 30% or less, “C” when the compression set exceeds 30% and 40% or less, 40 The percentage exceeding% was designated as “D”.
  • evaluation "C" is a pass level of the test of the present invention.
  • Extrudability high temperature moldability and high speed moldability
  • the silane crosslinkable rubber composition each melt blended dry blend prepared in each of the above examples was evaluated, 1.
  • High temperature formability molding temperature
  • the high temperature formability was evaluated according to the following evaluation criteria by the set extrusion molding temperature (die temperature).
  • the evaluation criteria were “A” when the dry blend could be extruded under the extrusion temperature condition where the die temperature of the extruder was set to 200 ° C., and “B” when the extrusion could not be performed.
  • the evaluation “A” of the high temperature formability is a pass level of the test of the present invention.
  • the C1 to C3 zones were set to 90 ° C. and the die temperature was set to 100 ° C.
  • high-speed moldability was evaluated according to the following evaluation criteria at the maximum production speed (maximum linear velocity) at which extrusion molding is possible.
  • the maximum production speed at which extrusion molding is possible is the linear speed at which the extruded coating does not break during the extrusion (so-called resin breakage) and the motor load does not exceed the above limit value. Shall be.
  • the high-speed moldability has an evaluation “C” that is a pass level of the test of the present invention.
  • Comparative Example 1 using an EP rubber having a low Mooney viscosity (ML (1 + 4) 125 ° C.) had a low tensile strength.
  • Comparative Example 2 using EP rubber having a high Mooney viscosity (ML (1 + 4) 125 ° C.) the maximum linear velocity was slow.
  • Comparative Example 3 having a small content of inorganic filler had a low tensile strength and a large compression set.
  • Comparative Example 4 in which the content of the inorganic filler was excessive the tensile strength was low, the compression set was large, and the maximum linear velocity was also slow.
  • Comparative Example 5 having a low silane coupling agent content had a large compression set.
  • Comparative Example 6 with a high content of silane coupling agent had a poor appearance, and in the extrusion moldability test, extrusion at a wire speed of 45 m / min was possible, but the appearance of the obtained electric wire was poor.
  • Comparative Examples 7 and 8 which are rubber cross-linking methods that are not silane cross-linking methods, both could not be extruded at 200 ° C., and the maximum linear velocity was slow even if extrusion at 100 ° C. was possible.
  • the comparative example 7 also failed in the tensile strength.
  • the present invention can produce a silane-crosslinked rubber molded article and a silane-crosslinked rubber molded article having both small compression set, high tensile strength and excellent appearance. Further, the present invention can produce a silane cross-linked rubber molded article and a silane cross-linked rubber molded article having such excellent characteristics without requiring an EP rubber vulcanization facility, and can be molded at high temperature and high speed if necessary, and produced with high productivity. can do.

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Abstract

L'invention concerne une composition de caoutchouc réticulable au silane qui comprend : un caoutchouc réticulable au silane dans lequel un agent adhésif au silane est greffé sur un caoutchouc de base qui contient 61 à 100% en masse d'un caoutchouc éthylène-α-oléfine de consistance Mooney （ＭＬ（１＋４）１２５℃） supérieure à 40 et inférieure ou égale à 90 ; 0,3 à 400 parties en masse d'une charge inorganique pour 100 parties en masse dudit caoutchouc de base ; et 0,0001 à 0,5 partie en masse d'un catalyseur de condensation silanol. L'invention concerne également : un corps moulé en caoutchouc réticulé au silane constitué par mise en contact de la composition de caoutchouc réticulable au silane ainsi formée avec une eau ; un article moulé en caoutchouc réticulé au silane contenant ce corps moulé en caoutchouc réticulé au silane ; et un procédé de fabrication de la composition de caoutchouc réticulable au silane et du corps moulé en caoutchouc réticulé au silane.
PCT/JP2016/056386 2015-03-03 2016-03-02 Composition de caoutchouc réticulable au silane ainsi que corps moulé en caoutchouc réticulé au silane, procédé de fabrication de ceux-ci, et article moulé en caoutchouc réticulé au silane Ceased WO2016140251A1 (fr)

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JP2018193450A (ja) * 2017-05-16 2018-12-06 住友ゴム工業株式会社 タイヤ用ゴム組成物の製造方法
JP2018193451A (ja) * 2017-05-16 2018-12-06 住友ゴム工業株式会社 タイヤ用ゴム組成物の製造方法
JP2021152100A (ja) * 2020-03-24 2021-09-30 古河電気工業株式会社 水膨張性シラン架橋ゴム組成物、水膨張性シラン架橋ゴム成形体、及び止水材
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JP2021152100A (ja) * 2020-03-24 2021-09-30 古河電気工業株式会社 水膨張性シラン架橋ゴム組成物、水膨張性シラン架橋ゴム成形体、及び止水材
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