WO2020226135A1 - Composition de caoutchouc, caoutchouc vulcanisé, et article moulé - Google Patents

Composition de caoutchouc, caoutchouc vulcanisé, et article moulé Download PDF

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WO2020226135A1
WO2020226135A1 PCT/JP2020/018416 JP2020018416W WO2020226135A1 WO 2020226135 A1 WO2020226135 A1 WO 2020226135A1 JP 2020018416 W JP2020018416 W JP 2020018416W WO 2020226135 A1 WO2020226135 A1 WO 2020226135A1
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Prior art keywords
rubber
mass
parts
chloroprene
acrylic
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PCT/JP2020/018416
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English (en)
Japanese (ja)
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貴史 砂田
ディネシュ クマール コトニース
アニル ケイ ボウミック
スリーナシュ ピー アール
Original Assignee
デンカ株式会社
インディアン インスティチュート オブ テクノロジー パトナ
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Priority to JP2021518384A priority Critical patent/JP7450891B2/ja
Publication of WO2020226135A1 publication Critical patent/WO2020226135A1/fr

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    • 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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention relates to a rubber composition using chloroprene rubber, a vulcanized rubber obtained by vulcanizing the rubber composition, and a molded product using the vulcanized rubber.
  • the rubber composition containing chloroprene rubber is used as a material for rubber products because it can obtain vulcanized rubber having excellent physical properties such as mechanical strength, weather resistance, and flame retardancy. Many of these rubber products are used outdoors, and in particular, rubber products used outdoors in cold regions are required to have cold resistance.
  • Patent Document 1 describes a cold-resistant rubber composition containing butadiene rubber, natural rubber, and chloroprene rubber as a rubber composition suitable for an air spring for a vehicle used in a cold region.
  • an object of the present invention is to provide a rubber composition capable of obtaining a vulcanized rubber having excellent cold resistance and tensile strength.
  • the present inventor has vulcanized a rubber composition containing a specific amount of chloroprene rubber, silicone rubber and acrylic rubber, which has sufficient cold resistance and tensile strength. They have found that rubber can be produced, and have completed the present invention.
  • one aspect of the present invention includes a total of 100 parts by mass of chloroprene rubber and silicone rubber and 1 to 30 parts by mass of acrylic rubber, and the mass ratio of chloroprene rubber to silicone rubber (chloroprene rubber: silicone rubber) is high.
  • a rubber composition of 60:40 to 95: 5 is provided.
  • Silicone rubber may contain a vinyl group.
  • Acrylic rubber may contain a carboxy group and / or an epoxy group. That is, the acrylic rubber may contain at least one functional group selected from a carboxy group and an epoxy group.
  • Another aspect of the present invention is to provide a vulcanized rubber obtained by vulcanizing the rubber composition and a molded product using the vulcanized rubber.
  • the molded product may be an automobile part.
  • a rubber composition capable of obtaining a vulcanized rubber having excellent cold resistance and tensile strength.
  • a vulcanized rubber and a molded product having excellent cold resistance and tensile strength.
  • the numerical range indicated by using "-" indicates the range including the numerical values before and after "-" as the minimum value and the maximum value, respectively. “A or more” in the numerical range means A and a range exceeding A. “A or less” in the numerical range means A and a range less than A.
  • the upper limit value or the lower limit value of the numerical range of one step can be arbitrarily combined with the upper limit value or the lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • the materials exemplified in the present specification may be used alone or in combination of two or more.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
  • the "alkyl group” may be linear, branched or cyclic.
  • the rubber composition according to one embodiment of the present invention includes chloroprene rubber, silicone rubber and acrylic rubber.
  • Chloroprene rubber The chloroprene rubber (also referred to as "chloroprene-based rubber") contained in the rubber composition of the present embodiment can impart excellent tensile strength to the vulcanized rubber obtained by vulcanizing the rubber composition.
  • Chloroprene rubber is a chloroprene polymer having a structural unit derived from chloroprene (2-chloro-1,3-butadiene).
  • the chloroprene polymer may be a homopolymer of chloroprene (polychloroprene), a copolymer of chloroprene and another monomer (copolymer of chloroprene), or a mixture of these polymers.
  • Examples of the monomer capable of forming a copolymer with chloroprene include 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene, ethylene, styrene, and acrylonitrile. , Butadiene, acrylic acid and its esters, and methacrylic acid and its esters.
  • the monomer capable of forming a copolymer with these chloroprenes one type may be used alone, or two or more types may be used in combination.
  • the content of structural units derived from chloroprene in chloroprene rubber is 40% by mass or more, based on the total amount of all structural units constituting chloroprene rubber, from the viewpoint of obtaining vultured rubber having excellent cold resistance and tensile strength. It may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more.
  • the chloroprene rubber may contain a structure derived from the molecular weight modifier used in the polymerization step.
  • the chloroprene rubber may be classified into, for example, a mercaptan-modified type, a xanthate-modified type, and a sulfur-modified type, depending on the type of the molecular weight modifier used.
  • the mercaptan-modified type chloroprene rubber can be obtained by using alkyl mercaptans such as n-dodecyl mercaptan, tert-dodecyl octyl mercaptan, and octyl mercaptan as a molecular weight modifier.
  • a xanthate-modified type of chloroprene rubber can be obtained by using an alkylxanthate compound as a molecular weight modifier.
  • the sulfur-modified type chloroprene rubber may be a polymer obtained by polymerizing a monomer mixture containing chloroprene in the presence of sulfur, plasticized with thiuram disulfide, and adjusted to a predetermined Mooney viscosity. ..
  • any type of chloroprene rubber can be used.
  • One type of chloroprene rubber may be used alone, or two or more types may be used in combination.
  • the manufacturing method of chloroprene rubber is not particularly limited.
  • the chloroprene rubber can be produced by a method including a polymerization step of polymerizing a monomer mixture containing chloroprene.
  • the chloroprene rubber can be obtained, for example, by copolymerizing the monomer mixture containing chloroprene by an emulsion polymerization method in the presence of an emulsifier, a polymerization initiator, a molecular weight modifier and the like.
  • silicone rubber contained in the rubber composition of the present embodiment can impart excellent cold resistance to the vulcanized rubber obtained by vulcanizing the rubber composition.
  • Silicone rubber can be obtained by a method of forming a silicone resin into a rubber shape.
  • the silicone resin may be a component that can be cured by a curing reaction such as peroxide crosslinking, condensation reaction crosslinking, addition reaction crosslinking, or ultraviolet crosslinking.
  • One type of silicone rubber may be used alone, or two or more types may be used in combination.
  • the silicone rubber may be a polysiloxane having a structural unit represented by the following formula (1).
  • R 1 and R 2 independently represent an alkyl group having 1 to 5 carbon atoms and an alkenyl group or an aryl group having 2 to 5 carbon atoms, respectively.
  • R 1 and R 2 may be the same or different.
  • the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group and a propyl group
  • examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group and a propenyl group as an aryl group.
  • a phenyl group can be mentioned.
  • R 1 and R 2 are preferably to exhibit at least one selected from each independently a methyl group and vinyl group, R 1 and R 2 It is more preferable that at least one exhibits a vinyl group.
  • the silicone rubber preferably contains a vinyl group-containing silicone rubber (hereinafter, also referred to as "vinyl group-containing silicone rubber”) from the viewpoint of obtaining a vulcanized rubber having excellent cold resistance and tensile strength.
  • the rubber composition of the present embodiment contains acrylic rubber in addition to chloroprene rubber and silicone rubber. As will be described later, the acrylic rubber can function as a compatibilizer for compromising the chloroprene rubber and the silicone rubber. It is considered that the vinyl group-containing silicone rubber has higher reactivity with the acrylic rubber than the vinyl group-free silicone rubber (that is, “vinyl group-free silicone rubber”).
  • the compatibility between the chloroprene rubber and the silicone rubber in the rubber composition becomes better, and the cold resistance and tensile strength of the vulcanized rubber obtained by vulcanizing the rubber composition become higher. It is thought that it will improve.
  • the silicone rubber contains a vinyl group-containing silicone rubber
  • the content of the vinyl group-containing silicone rubber is 1 part by mass or more, 10 parts by mass or more, 30 parts by mass or more, and 50 parts by mass or more based on 100 parts by mass of the silicone rubber. , 70 parts by mass or more, 90 parts by mass or more, or 95 parts by mass or more.
  • the content of the vinyl group-containing silicone rubber may be 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more based on a total of 100 parts by mass of the chloroprene rubber and the silicone rubber. It may be 40 parts by mass or less, 35 parts by mass or less, or 30 parts by mass or less.
  • vinyl group-containing silicone rubber examples include silicone rubber containing a vinyl group at the end, silicone rubber containing a vinyl group in the side chain, and silicone rubber containing a vinyl group in the end and side chains.
  • the acrylic rubber (also referred to as "acrylic rubber") contained in the rubber composition of the present embodiment can function as a compatibilizer for compromising the chloroprene rubber and the silicone rubber. Since chloroprene rubber and silicone rubber have different polarities, it is difficult to make them compatible with each other well. However, the present inventor has found that the chloroprene rubber and the silicone rubber are uniformly mixed by blending the acrylic rubber. That is, in the rubber composition of the present embodiment, acrylic rubber can contribute to the improvement of compatibility, and by improving the compatibility of the rubber composition, a vulcanized rubber having excellent cold resistance and tensile strength can be obtained. Can be done.
  • Acrylic rubber is a (meth) acrylate polymer having a structural unit derived from a (meth) acrylic acid alkyl ester.
  • Acrylic rubber can be obtained by polymerizing a monomer mixture containing a (meth) acrylic acid alkyl ester.
  • the acrylic rubber may be, for example, a copolymer obtained by using (meth) acrylic acid alkyl ester as a main component of a monomer mixture and copolymerizing it with a crosslinked monomer described later.
  • the content of the structural unit derived from the (meth) acrylic acid alkyl ester in the acrylic rubber is 40% by mass or more, 45% by mass or more, or 50% by mass or more based on the total amount of all the structural units constituting the acrylic rubber. It may be 99% by mass or less, 95% by mass or less, or 90% by mass or less.
  • the (meth) acrylic acid alkyl ester is a concept including both a methacrylic acid alkyl ester and an acrylic acid alkyl ester. The same applies to other similar expressions such as (meth) acrylate.
  • the (meth) acrylic acid alkyl ester may contain, for example, a compound represented by the following formula (2).
  • CH 2 CR 3- COOR 4 (2)
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkyl group having 1 to 20 carbon atoms.
  • R 3 is preferably a hydrogen atom.
  • R 4 is an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, still be an alkyl group having 2-5 carbon atoms It is preferably an alkyl group having 2 to 4 carbon atoms, and particularly preferably.
  • Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and n-pentyl ().
  • One type of (meth) acrylic acid alkyl ester may be used alone, or two or more types may be used in combination.
  • the (meth) acrylic acid alkyl ester preferably contains an acrylic acid alkyl ester from the viewpoint of obtaining a vulcanized rubber having excellent cold resistance and tensile strength.
  • Acrylic rubber may further have a structural unit derived from a crosslinked monomer capable of forming a copolymer with a (meth) acrylic acid alkyl ester.
  • the cross-linking seat monomer is a monomer having a functional group forming a cross-linking seat (also referred to as a cross-linking point).
  • a cross-linking seat monomer containing a carboxy group and / or an epoxy group as a functional group that is, a cross-linking seat monomer containing at least one functional group selected from a carboxy group and an epoxy group
  • the crosslinked seat monomer contained is more preferable.
  • the acrylic rubber used in the present embodiment is preferably an acrylic rubber containing a carboxy group and / or an epoxy group (that is, an acrylic rubber containing at least one functional group selected from a carboxy group and an epoxy group), and a carboxy group.
  • Acrylic rubber containing the above is more preferable. That is, the acrylic rubber used in the present embodiment preferably has a crosslinked seat monomer derived from a crosslinked seat monomer containing at least one functional group selected from a carboxy group and an epoxy group, and has a crosslinked seat containing a carboxy group. It is more preferable to have a structural unit derived from the monomer. Such acrylic rubber has better performance as a compatibilizer.
  • the cross-linked monomer containing one carboxy group may be a cross-linked monomer containing one carboxy group, a cross-linked monomer containing two or more carboxy groups, or a mixture thereof.
  • Examples of the crosslinked monomer containing a carboxy group include an aliphatic unsaturated carboxylic acid, an aromatic unsaturated carboxylic acid, an aliphatic unsaturated carboxylic acid ester containing a carboxy group, and an aromatic unsaturated carboxylic acid containing a carboxy group. Saturated carboxylic acid ester can be mentioned.
  • Examples of the aliphatic unsaturated carboxylic acid include an aliphatic unsaturated carboxylic acid containing one carboxy group such as acrylic acid, methacrylic acid, crotonic acid, and 2-pentenoic acid; and maleic acid, fumaric acid, and itaconic acid.
  • An aliphatic unsaturated carboxylic acid containing two carboxy groups can be mentioned.
  • Examples of the aliphatic unsaturated carboxylic acid ester containing a carboxy group include monoalkyl esters of divalent aliphatic unsaturated carboxylic acids such as maleic acid monoalkyl ester and fumaric acid monoalkyl ester; maleic acid monocyclohexyl and fumaric acid. Examples thereof include monocycloalkyl esters of divalent aliphatic unsaturated carboxylic acids such as monocyclohexyl acid.
  • Examples of the aromatic unsaturated carboxylic acid include cinnamic acid.
  • the crosslinked seat monomer containing an epoxy group may be a crosslinked seated monomer containing one epoxy group, a crosslinked seated monomer containing two or more epoxy groups, or a mixture thereof.
  • the crosslinked monomer containing an epoxy group include (meth) acrylates containing an epoxy group such as glycidyl acrylate and glycidyl methacrylate; an epoxy group such as allyl glycidyl ether and methallyl glycidyl ether and an ethylenically unsaturated double bond.
  • examples include ethers containing.
  • crosslinked seat monomer capable of forming a copolymer with the (meth) acrylic acid alkyl ester
  • one type may be used alone, or two or more types may be used in combination.
  • the acrylic rubber may further have a structural unit derived from another monomer copolymerizable with the (meth) acrylic acid alkyl ester as long as the object of the present invention is not impaired.
  • examples of such other monomers include ethylenically unsaturated compounds, and examples of the ethylenically unsaturated compounds include (meth) acrylates other than (meth) acrylic acid alkyl esters (for example, (meth) acrylic).
  • Acid alkoxy ester alkyl vinyl ketone, vinyl ether, allyl ether, vinyl aromatic compound, vinyl nitrile, maleic acid dialkyl ester, fumaric acid dialkyl ester, itaconic acid dialkyl ester, citraconic acid dialkyl ester, mesaconic acid dialkyl ester, 2-pentene Examples thereof include a diacid dialkyl ester and an acetylenedicarboxylic acid dialkyl ester.
  • Specific compounds include, for example, ethylene, methoxyethyl acrylate, vinyl acetate, methyl vinyl ketone, vinyl ethyl ether, allyl methyl ether, styrene, ⁇ -methylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, acrylonitrile, and methacrylate.
  • the acrylic rubber used in the present embodiment preferably contains a copolymer of an acrylic acid alkyl ester and a cross-linked monomer containing a carboxy group and / or an epoxy group, and is cross-linked containing an acrylic acid alkyl ester and a carboxy group. It is more preferable to contain a copolymer with the seat monomer. That is, the acrylic rubber contains a copolymer having a structural unit derived from an acrylic acid alkyl ester and a structural unit derived from a crosslinked monomer containing at least one functional group selected from a carboxy group and an epoxy group.
  • a copolymer having a structural unit derived from an acrylic acid alkyl ester and a structural unit derived from a crosslinked monomer containing a carboxy group is preferable to contain a copolymer having a structural unit derived from an acrylic acid alkyl ester and a structural unit derived from a crosslinked monomer containing a carboxy group.
  • Acrylic rubber is obtained by copolymerizing, for example, a monomer mixture containing a (meth) acrylic acid alkyl ester and a crosslinked monomer by a known method such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization. be able to.
  • a method for producing acrylic rubber can be appropriately selected by those skilled in the art.
  • the rubber composition of this embodiment contains chloroprene rubber as a main component.
  • the content of chloroprene rubber in the rubber composition of the present embodiment may be 40% by mass or more, 45% by mass or more, or 50% by mass or more, based on the total amount of the rubber composition, 90% by mass or less, 85. It may be 0% by mass or less or 80% by mass or less.
  • the mass ratio of chloroprene rubber to silicone rubber (chloroprene rubber: silicone rubber) is 60:40 to 95: 5.
  • the mass ratio of the chloroprene rubber to the silicone rubber is 60:40 or more, the tensile strength of the vulcanized rubber obtained by vulcanizing the rubber composition can be improved.
  • the mass ratio of chloroprene rubber to silicone rubber is preferably 65:35 to 95: 5, more preferably 65:35 to 90:10, still more preferably 70:30 to 90:10, and even more preferably 70:30. It is ⁇ 85:15, particularly preferably 70: 30-80: 20.
  • the rubber composition of the present embodiment contains 1 to 30 parts by mass of acrylic rubber with respect to a total of 100 parts by mass of chloroprene rubber and silicone rubber.
  • the content of the acrylic rubber is within this range, the compatibility between the chloroprene rubber and the silicone rubber can be improved, and a vulcanized rubber having excellent tensile strength and cold resistance can be obtained.
  • the lower limit of the content of acrylic rubber is preferably 3 parts by mass, more preferably 5 parts by mass, still more preferably 7 parts by mass, and particularly preferably 9 parts by mass.
  • the upper limit of the content of the acrylic rubber is preferably 25 parts by mass, more preferably 20 parts by mass, still more preferably 15 parts by mass, and particularly preferably 12 parts by mass.
  • raw materials other than chloroprene rubber, silicone rubber and acrylic rubber are not particularly limited and may be appropriately selected depending on the purpose and application.
  • raw materials that can be contained in the rubber composition include known additives such as vulcanizing agents, vulcanization accelerators, lubricants or processing aids, fillers, and plasticizers.
  • the sulfide agent examples include sulfur; beryllium, magnesium, zinc, calcium, barium, germanium, titanium, tin, zirconium, antimony, vanadium, bismuth, molybdenum, tungsten, tellurium, selenium, iron, nickel, cobalt, osmium and the like.
  • One type of vulcanizing agent may be used alone, or two or more types may be used in combination. Among these vulcanizing agents, from the viewpoint of high vulcanization effect, it is preferable to use at least one selected from magnesium oxide and zinc oxide, and it is more preferable to use magnesium oxide and zinc oxide in combination.
  • the content of the vulcanizing agent in the rubber composition can be, for example, 0.1 to 20 parts by mass in total with respect to 100 parts by mass in total of the chloroprene rubber and the silicone rubber, and is 1 part by mass or more and 3 parts by mass. It may be 5 parts by mass or more or 5 parts by mass or more, and may be 15 parts by mass or less or 10 parts by mass or less.
  • the vulcanization accelerator examples include a thiourea-based vulcanization accelerator, a guanidine-based vulcanization accelerator, a thiuram-based vulcanization accelerator, and a thiazole-based vulcanization accelerator.
  • One type of vulcanization accelerator may be used alone, or two or more types may be used in combination.
  • it is preferable to use a thiourea-based vulcanization accelerator it is preferable to use a thiourea-based vulcanization accelerator, and it is more preferable to use a cyclic thiourea-based vulcanization accelerator such as ethylene thiourea.
  • the content of the vulcanization accelerator in the rubber composition can be, for example, 0.1 to 5 parts by mass in total with respect to 100 parts by mass in total of the chloroprene rubber and the silicone rubber, and 0.2 parts by mass. It may be more than or equal to 0.3 parts by mass or more, and may be 3 parts by mass or less or 1 part by mass or less.
  • Lubricants or processing aids can be added to improve the processability and surface slipperiness of the rubber composition.
  • a lubricant or a processing aid By adding a lubricant or a processing aid, the rubber composition tends to be easily peeled off from the roll, the molding die, the screw of the extruder, etc. when the rubber composition is kneaded or vulcanized. ..
  • the lubricant or processing aid include fatty acids such as stearic acid, paraffin-based processing aids such as polyethylene, and fatty acid amides.
  • the lubricant and the processing aid one type may be used alone, or two or more types may be used in combination. Among these, it is preferable to use fatty acids such as stearic acid.
  • the content of the lubricant and the processing aid in the rubber composition can be, for example, 0.1 to 5 parts by mass in total with respect to 100 parts by mass in total of the chloroprene rubber and the silicone rubber, and 0.2 mass by mass. It may be 3 parts or more or 0.3 parts by mass or more, and may be 3 parts by mass or less or 1 part by mass or less.
  • Fillers can be added to adjust the hardness of the rubber and improve the mechanical strength. Fillers include, for example, carbon black, silica, talc, and calcium carbonate. One type of filler may be used alone, or two or more types may be used in combination.
  • the content of the filler in the rubber composition can be, for example, 10 to 100 parts by mass in total with respect to 100 parts by mass in total of the chloroprene rubber and the silicone rubber, and is 20 parts by mass or more and 25 parts by mass or more. , Or 30 parts by mass or more, 80 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less.
  • the plasticizer can be added to improve the processability of the rubber composition.
  • the plasticizer include vegetable oils such as rapeseed oil, flaxseed oil, castor oil and palm oil, phthalate plasticizers, aromatic dicarboxylic acid dialkyl esters such as DUP (diundecyl phthalate), DOS (dioctyl sebacate) and DOA ( Dialkyl SL of aliphatic dicarboxylic acid such as dioctyl adipate), ester plasticizer, ether ester plasticizer, thioether plasticizer, aroma oil, naphthenic oil, lubricating oil, process oil, paraffin, liquid paraffin, vaseline, Examples thereof include petroleum-based plasticizers such as petroleum asphalt.
  • plasticizer may be used alone, or two or more types may be used in combination.
  • plasticizers it is preferable to use an aliphatic dicarboxylic acid dialkyl ester, and more preferably DOS, from the viewpoint of obtaining a vulcanized rubber having better cold resistance.
  • the content of the plasticizer in the rubber composition can be, for example, 1 to 50 parts by mass in total with respect to 100 parts by mass in total of the chloroprene rubber and the silicone rubber, and 5 parts by mass or more and 10 parts by mass or more. Alternatively, it may be 15 parts by mass or more, 40 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less.
  • the content of the aliphatic dicarboxylic acid dialkyl ester is 1 part by mass or more and 3 parts by mass or more in total with respect to 100 parts by mass in total of the chloroprene rubber and the silicone rubber. It may be 5 parts by mass or more, 7 parts by mass or more, or 10 parts by mass or more, and may be 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 25 parts by mass or less, or 20 parts by mass or less.
  • the vulcanized rubber according to the embodiment of the present invention is a vulcanized rubber of the above rubber composition, and can be obtained by vulcanizing the above rubber composition. Therefore, the vulcanized rubber of the present embodiment is excellent in cold resistance and tensile strength.
  • the vulcanization temperature can be appropriately adjusted depending on the composition of the rubber composition, the type of vulcanizing agent, etc., and is usually 140 ° C. to 200 ° C., preferably 150 ° C. to 190 ° C.
  • the vulcanization time can also be appropriately adjusted depending on the composition of the rubber composition, the type of vulcanizing agent, the vulcanization method, and the like.
  • the vulcanization method known methods such as press vulcanization, injection vulcanization, direct kettle vulcanization, indirect kettle vulcanization, direct steam continuous vulcanization, normal pressure continuous vulcanization, and continuous vulcanization press can be used. ..
  • the rubber composition may be molded into a desired shape and then vulcanized, or may be vulcanized during molding of the rubber composition, or the rubber composition may be molded after being vulcanized. May be good.
  • the molded product according to the embodiment of the present invention is a molded product made of the vulcanized rubber (for example, a molded product containing the vulcanized rubber), and can be obtained by using the vulcanized rubber.
  • the molded product of the present embodiment can be obtained, for example, by a method of molding the rubber composition into a desired shape before or after vulcanization, and a method of vulcanizing during molding of the rubber composition.
  • the molding method is not particularly limited, and known methods such as press molding, injection molding, and extrusion molding can be used.
  • the molded product of this embodiment has excellent cold resistance and tensile strength, it is suitably used as a rubber product that is used outdoors in cold regions and requires strength. Specifically, it is suitable for cold weather rubber, wipers, hoses and other automobile parts, rubber bearings used for railways or bridges, outdoor packing, and the like.
  • MCR Modular compact rheometer
  • Test Example 1 The results of Test Example 1 are shown in Table 1 below.
  • Stearic acid Brand name Lunac S-70V, manufactured by Kao Corporation (vulcanizing agent)
  • Magnesium oxide Brand name Kyowamag (registered trademark) 150, manufactured by Kyowa Chemical Industry Co., Ltd.
  • Zinc oxide 2 types manufactured by Sakai Chemical Industry Co., Ltd. (vulcanization accelerator) Accelerator 22-S: Product name, ethylene thiourea, manufactured by Kawaguchi Chemical Industry Co., Ltd.
  • Comparative Example 1 in which the mass ratio of chloroprene rubber and silicone rubber was 99: 1, the tensile strength was good, but the cold resistance was slightly inferior.
  • Comparative Example 2 in which the mass ratio of the chloroprene rubber and the silicone rubber was 55:45, the cold resistance was good, but the tensile strength was inferior.
  • Comparative Example 3 containing no acrylic rubber had a slightly poor cold resistance
  • Comparative Example 4 containing 35 parts by mass of acrylic rubber with respect to a total of 100 parts by mass of chloroprene rubber and silicone rubber had a slightly poor tensile strength. It was.
  • the mass ratio of chloroprene rubber to silicone rubber is 60:40 to 95: 5
  • the content of acrylic rubber is 1 to 30 parts by mass with respect to a total of 100 parts by mass of chloroprene rubber and silicone rubber.
  • both tensile strength and cold resistance were good. From these results, it was confirmed that vulcanized rubber having both tensile strength and cold resistance can be obtained by setting the content of various rubbers within the range of the present invention.
  • Example 2 a vinyl group-containing silicone rubber is blended, in Example 9, a vinyl group-free silicone rubber is blended, and in Example 10, a vinyl group-containing silicone rubber and a vinyl group-free silicone rubber have a mass of 1: 1. Formulated in ratio. The highest tensile strength was in Example 2, and the next highest was in Example 10. In addition, Examples 2 and 10 showed higher cold resistance than Example 9. From these results, it was confirmed that the tensile strength and cold resistance were further improved by using the vinyl group-containing silicone rubber.
  • Examples 1 to 10 containing an acrylic rubber containing a carboxy group and Example 11 containing an acrylic rubber containing an epoxy group were both excellent in tensile strength and cold resistance. Further, when comparing Example 2 and Example 11 having the same composition except for the type of acrylic rubber, Example 2 had better tensile strength and cold resistance. From these results, it was suggested that acrylic rubber containing a carboxy group and / or an epoxy group is preferable, and acrylic rubber containing a carboxy group is more preferable.
  • Test Example 2 Vulcanized rubber was prepared with the formulation shown in Table 2 below. The production procedure was the same as in Test Example 1 except that a filler and a plasticizer were further added after kneading the chloroprene rubber, the silicone rubber and the acrylic rubber. Then, the tensile strength and cold resistance were measured by the same procedure as in Test Example 1. The results of Test Example 2 are shown in Table 2 below.
  • filler and plasticizer in Table 2 are as follows.
  • the other raw materials in Table 2 are the same as those in Table 1.
  • Carbon black SRF carbon black, Asahi # 50, manufactured by Asahi Carbon Co., Ltd.
  • plasticizer Naphthenic oil: Diana process oil NP-24, manufactured by Idemitsu Kosan Co., Ltd.
  • DOS Dioctyl sebacate, Sansosizer DOS, manufactured by New Japan Chemical Co., Ltd.
  • Example 13 shown in Table 2 the DOS of Example 12 was changed to 15 parts by mass, and vulcanized rubber was produced in the same procedure as in Example 12 except for that. It was suggested that the vulcanized rubber obtained in Example 13 was superior in cold resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention fournit une composition de caoutchouc qui contient 100 parties en masse au total d'un caoutchouc de chloroprène et d'un caoutchouc silicone, et 1 à 30 parties en masse d'un caoutchouc acrylique, le rapport massique dudit caoutchouc de chloroprène et dudit caoutchouc silicone (caoutchouc de chloroprène : caoutchouc silicone) étant compris entre ６０：４０ et ９５：５.
PCT/JP2020/018416 2019-05-08 2020-05-01 Composition de caoutchouc, caoutchouc vulcanisé, et article moulé WO2020226135A1 (fr)

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JPH08311249A (ja) * 1995-05-23 1996-11-26 Denki Kagaku Kogyo Kk クロロプレン系重合体組成物及びその製造方法
CN102911465A (zh) * 2012-09-18 2013-02-06 铜陵市铜都特种线缆厂 一种高阻燃耐火电力电缆料及其制备方法
CN102911413A (zh) * 2012-10-15 2013-02-06 安徽华通电缆集团有限公司 一种氯丁橡胶绝缘控制电缆料及其制备方法
CN103589024A (zh) * 2013-10-29 2014-02-19 绿宝电缆（集团）有限公司 一种耐寒耐油改性多橡胶共混电缆料
JP2020015819A (ja) * 2018-07-25 2020-01-30 デンカ株式会社 ゴム組成物、加硫ゴム及びその成形品

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* Cited by examiner, † Cited by third party
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CN104262724A (zh) 2014-09-16 2015-01-07 青岛市高科专利技术转移平台有限公司 一种橡胶密封材料配方

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08311249A (ja) * 1995-05-23 1996-11-26 Denki Kagaku Kogyo Kk クロロプレン系重合体組成物及びその製造方法
CN102911465A (zh) * 2012-09-18 2013-02-06 铜陵市铜都特种线缆厂 一种高阻燃耐火电力电缆料及其制备方法
CN102911413A (zh) * 2012-10-15 2013-02-06 安徽华通电缆集团有限公司 一种氯丁橡胶绝缘控制电缆料及其制备方法
CN103589024A (zh) * 2013-10-29 2014-02-19 绿宝电缆（集团）有限公司 一种耐寒耐油改性多橡胶共混电缆料
JP2020015819A (ja) * 2018-07-25 2020-01-30 デンカ株式会社 ゴム組成物、加硫ゴム及びその成形品

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