WO2025192584A1 - Polymère hydrocarboné insaturé contenant du soufre, additif pour caoutchouc, composition de caoutchouc et pneu - Google Patents

Polymère hydrocarboné insaturé contenant du soufre, additif pour caoutchouc, composition de caoutchouc et pneu

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Publication number
WO2025192584A1
WO2025192584A1 PCT/JP2025/009071 JP2025009071W WO2025192584A1 WO 2025192584 A1 WO2025192584 A1 WO 2025192584A1 JP 2025009071 W JP2025009071 W JP 2025009071W WO 2025192584 A1 WO2025192584 A1 WO 2025192584A1
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WO
WIPO (PCT)
Prior art keywords
sulfur
unsaturated hydrocarbon
rubber
hydrocarbon polymer
containing unsaturated
Prior art date
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Pending
Application number
PCT/JP2025/009071
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English (en)
Japanese (ja)
Inventor
祥吾 石坂
雄介 松尾
陽一 秋山
圭介 知野
誠 芦浦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Materials Corp
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Eneos Materials Corp
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Publication date
Application filed by Eneos Materials Corp filed Critical Eneos Materials Corp
Publication of WO2025192584A1 publication Critical patent/WO2025192584A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/02—Copolymers of mineral oil hydrocarbons

Definitions

  • the present invention relates to a sulfur-containing unsaturated hydrocarbon polymer.
  • the present invention also relates to a rubber additive containing the sulfur-containing unsaturated hydrocarbon polymer.
  • the present invention further relates to a rubber composition containing the rubber additive.
  • the present invention also relates to a tire manufactured using the rubber composition.
  • vulcanized rubber which is rubber components to which vulcanizing agents such as sulfur have been added.
  • vulcanized rubber which is rubber components to which vulcanizing agents such as sulfur have been added.
  • insoluble sulfur when used as a vulcanizing agent, blooming, a phenomenon in which insoluble sulfur migrates to the rubber surface and precipitates during the vulcanization process, can be suppressed.
  • this agent has low affinity with rubber and poor dispersibility.
  • Patent Document 1 a vulcanizing agent composition containing insoluble sulfur and dicyclopentadiene resin
  • Patent Document 2 The inventors then discovered that a specific sulfur-containing unsaturated hydrocarbon polymer could be used to improve tire performance (particularly wet grip and fuel economy) (see Patent Document 2), but further improvements were needed.
  • tire performance In addition to wear resistance, wet grip, and fuel economy, tire performance also requires a variety of other features, such as fracture resistance and resistance to deterioration. Therefore, there is a demand for the development of tires that combine all of these performance features.
  • a sulfur-containing unsaturated hydrocarbon polymer obtained by reacting sulfur with an unsaturated bond of a polymer of an unsaturated hydrocarbon having a norbornene skeleton,
  • a rubber additive comprising the sulfur-containing unsaturated hydrocarbon polymer according to any one of [1] to [5].
  • the rubber additive according to [6] which is a tire durability improver.
  • a rubber composition comprising the rubber additive according to [6] or [7] and a rubber component.
  • the rubber composition according to [8] which is for use in tires.
  • the present invention provides a rubber composition for producing tires that are excellent in abrasion resistance, fracture resistance (breaking strength, breaking elongation, cut-chip resistance), wet grip performance, fuel economy, a balance between wet grip performance and fuel economy, and degradation resistance (rubber bonding strength, heat aging resistance). Furthermore, the present invention makes it possible to produce tires that are excellent in the various tire performance characteristics described above.
  • FD-MS spectrum charts of the petroleum resins used in Preparation Examples 13 to 17. 1 is a chart of the FD-MS spectrum of the sulfur-containing unsaturated hydrocarbon polymer Q produced in Preparation Example 17. 1 is a chart of the FD-MS spectrum of the sulfur-containing unsaturated hydrocarbon polymer N produced in Preparation Example 14.
  • the sulfur-containing unsaturated hydrocarbon polymer of the present invention is a reaction product obtained by reacting sulfur with unsaturated bonds of an unsaturated hydrocarbon polymer having a norbornene skeleton, and the proportion of unsaturated bonds added in the form of trisulfide (-S 3 -) relative to the total number of unsaturated bonds in the norbornene skeleton ("trisulfide addition proportion") is 30 mol % or more.
  • trisulfide addition proportion is 30 mol % or more.
  • the presence of a specific proportion of trisulfides in the sulfur-containing unsaturated hydrocarbon polymer can improve reactivity with rubber.
  • the trisulfide addition ratio in the sulfur-containing unsaturated hydrocarbon polymer is preferably 35 mol% or more, more preferably 40 mol% or more, even more preferably 45 mol% or more, and even more preferably 50 mol% or more, and may be 95 mol% or less, 93 mol% or less, or 91 mol% or less. If the trisulfide addition ratio in the sulfur-containing unsaturated hydrocarbon polymer is 30 mol% or more, the reactivity of the sulfur-containing unsaturated hydrocarbon polymer with rubber is improved, making it possible to provide a rubber composition for producing tires with excellent performance in a variety of ways.
  • the trisulfide addition ratio in the sulfur-containing unsaturated hydrocarbon polymer can be calculated by confirming the progress of the reaction between the unsaturated bond in the norbornene skeleton and sulfur by 1 H-NMR measurement, analyzing the reaction product by field desorption mass spectrometry (FD-MS measurement), and quantifying the molecular peak where an increase in the mass of the trisulfide is observed.
  • the weight average molecular weight (Mw) of the sulfur-containing unsaturated hydrocarbon polymer is preferably 500 or more, more preferably 600 or more, even more preferably 700 or more, and still more preferably 800 or more, and is preferably 1500 or less, more preferably 1450 or less, even more preferably 1400 or less, and still more preferably 1350 or less.
  • the weight average molecular weight (Mw) can be measured by a conventionally known method of GPC (gel permeation chromatography) analysis.
  • compounds having at least an unsaturated bond in the norbornene skeleton as an unsaturated bond for reacting with sulfur can be used as raw materials for the unsaturated hydrocarbon polymer.
  • the unsaturated bond in the norbornene skeleton in the polymer has a distorted structure, which provides good reactivity with sulfur.
  • a petroleum resin obtained by (co)polymerizing a fraction containing an alicyclic unsaturated compound (hereinafter referred to as "alicyclic unsaturated compound petroleum resin") is used as the unsaturated hydrocarbon polymer.
  • Alicyclic unsaturated compound petroleum resins are obtained, for example, by dimerizing cyclopentadienes contained in a C5 fraction to produce dicyclopentadienes, which are then separated from other C5 fractions by distillation and polymerized by a Diels-Alder reaction under heating.
  • Cyclopentadiene includes not only cyclopentadiene but also those partially substituted with alkyl groups (e.g., methylcyclopentadiene).
  • Dicyclopentadienes include not only dicyclopentadiene (DCPD) but also those partially substituted with alkyl groups (e.g., methyldicyclopentadiene).
  • the C5 fraction is generally the remainder of the boiling range fraction obtained by thermal cracking of petroleum, after removing useful compounds such as ethylene, propylene, and butadiene, and is a fraction having a boiling range of about 20 to 110°C.
  • the alicyclic unsaturated compound-based petroleum resin may contain, as fractions, C5 fractions and C9 fractions other than cyclopentadienes.
  • C5 fractions other than cyclopentadienes include, for example, olefin hydrocarbons such as 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene, and diolefin hydrocarbons such as 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, and 3-methyl-1,2-butadiene.
  • olefin hydrocarbons such as 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene
  • diolefin hydrocarbons such as 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, and 3-methyl-1,2-butadiene.
  • the C9 fraction is generally a fraction having a boiling point range of about 100° C. to 280° C., among the fractions obtained by thermal cracking of petroleum.
  • Examples of the C9 fraction include styrene homologues such as ⁇ -methylstyrene, ⁇ -methylstyrene, and ⁇ -methylstyrene, and indene homologues such as indene and coumarone.
  • the alicyclic unsaturated compound-based petroleum resin of the present invention is produced by the Diels-Alder reaction, and the reaction may be carried out by adding 0.01 to 5% by weight of a Friedel-Crafts catalyst to the raw materials.
  • Typical Friedel-Crafts catalysts include, for example, aluminum trichloride, aluminum tribromide, boron trifluoride, or their phenol complexes or butanol complexes. Among these, aluminum trichloride, boron trifluoride phenol complexes, and boron trifluoride butanol complexes are preferred.
  • the polymerization temperature is preferably 0 to 100°C, and particularly preferably 0 to 80°C.
  • the catalyst amount and polymerization time are preferably in the range of 0.1 to 2.0 parts by mass of catalyst per 100 parts by mass of feedstock oil, and 0.1 to 10 hours.
  • the reaction pressure is preferably atmospheric pressure to 1 MPa.
  • the alicyclic unsaturated petroleum resin of the present invention may partially polymerize compounds having various functional groups.
  • functional groups include alcohol compounds and phenol compounds having hydroxyl groups.
  • alcohol compounds include alcohol compounds having unsaturated bonds such as allyl alcohol and 2-butene-1,4-diol.
  • phenol compounds that can be used include alkylphenols such as phenol, cresol, xylenol, p-t-butylphenol, p-octylphenol, and p-nonylphenol. These compounds having hydroxyl groups may be used alone or in combination of two or more.
  • the polymerization method can be selected from thermal polymerization, which involves heating at approximately 150°C to 300°C for 1 to 10 hours, primarily the Diels-Alder reaction mentioned above, or the Friedel-Crafts reaction mentioned above.
  • These resins mentioned above preferably have a softening point of 200°C or less (measurement method: ASTM E28-58-T), and more preferably 45 to 160°C.
  • the above-mentioned alicyclic unsaturated compound-based petroleum resin can also be partially hydrogenated.
  • the hydrogenation conditions are arbitrary, but the alicyclic unsaturated compound-based petroleum resin is mixed with one or more solvents selected from saturated hydrocarbons, saturated cyclic hydrocarbons, and aromatic hydrocarbons, each having a boiling point at atmospheric pressure of substantially 140 to 280°C, and the reaction is carried out using a general hydrogenation catalyst containing nickel, molybdenum, cobalt, palladium, platinum, etc., at a reaction temperature of 150 to 320°C, a reaction pressure of 30 to 300 kg/ cm2 , and a reaction time of 1 to 10 hours.
  • Neoresin EP-140 softening point: 140°C
  • Quintone 1105 softening point: 107°C
  • Quintone 1325 softening point: 125°C
  • the sulfur-containing unsaturated hydrocarbon polymer can be obtained by reacting the above-mentioned unsaturated hydrocarbon polymer with sulfur through an appropriate heating reaction.
  • a solvent or additive to facilitate the reaction can be appropriately used.
  • the solvent include conventionally known organic solvents, aromatic oils, and petroleum resins.
  • a petroleum resin it is preferably a saturated hydrocarbon petroleum resin obtained by hydrogenating the above-mentioned unsaturated hydrocarbon petroleum resin, and saturated DCPD/C9 resin is more preferred.
  • Conventionally known antioxidants, basic compounds, and the like may also be used as additives.
  • Examples of the basic compound include alkylamines such as hexylamine, heptylamine, octylamine, triethylamine, diisopropylethylamine, and 2-ethylhexylamine; aromatic amines such as aniline, alkylated diphenylamine, and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine; guanidines such as urea, alkylated urea, thiourea, alkylated thiourea, 1,3-diphenylguanidine, and 1,3-di-o-tolylguanidine; pyridines; nitrogen-containing heterocyclic compounds such as hexamethylenetetramine; and sulfenamides such as N,N-biscyclohexylbenzothiazole-2-sulfenamide, N-cyclohexylbenzothiazole-2-sulfen
  • the amount of sulfur added to the unsaturated hydrocarbon polymer is not particularly limited, but is preferably 0.1 equivalents or more, more preferably 0.3 equivalents or more, even more preferably 0.5 equivalents or more, even more preferably 1.0 equivalents or more, and preferably 5.0 equivalents or less, more preferably 4.0 equivalents or less, even more preferably 3.0 equivalents or less, and even more preferably 2.0 equivalents or less, per unsaturated bond (double bond) of the unsaturated hydrocarbon.
  • the unsaturated bonds in the polymer of unsaturated hydrocarbon may remain after the reaction with sulfur or may be completely consumed, and it is preferable that only the unsaturated bonds in the norbornene skeleton of the polymer of unsaturated hydrocarbon react with sulfur.
  • the conditions for the heating reaction can be set appropriately depending on the type of unsaturated hydrocarbon polymer and the ratio of sulfur to it, but can be carried out, for example, at 80 to 230°C, preferably 100 to 200°C. In this case, it is more preferable to use heating conditions of 110 to 160°C, highly efficient stirring conditions to more efficiently react the unsaturated hydrocarbon polymer with sulfur, and to set a reaction time of approximately 0.1 to 2 hours.
  • Highly efficient stirring conditions for example, are preferably achieved by stirring at an intensity that provides a power of preferably 10 J/s or more, more preferably 15 J/s or more, per 1 kg of reaction product.
  • Sulfur added to unsaturated bonds in unsaturated hydrocarbon polymers is relatively highly reactive, and if it is subjected to a re-reaction, the more desirable form of sulfur addition will be lost.
  • additives heating conditions, stirring conditions, and reaction time, it is possible to promote the sulfur addition reaction while suppressing re-reaction compared to conventional methods, and to maintain more of the more desirable form of sulfur addition.
  • the resulting reaction product may be purified before use, or may be blended directly into a rubber composition.
  • the rubber additive of the present invention contains the above-mentioned sulfur-containing unsaturated hydrocarbon polymer.
  • the sulfur-containing unsaturated hydrocarbon polymer is as described above.
  • a tire can be produced that has excellent abrasion resistance, fracture resistance (breaking strength, breaking elongation, cut/chip resistance), wet grip performance, fuel economy, a balance between wet grip performance and fuel economy, and deterioration resistance (rubber bonding ability, heat aging resistance). Therefore, the above-mentioned sulfur-containing unsaturated hydrocarbon polymer can be used as a rubber additive (particularly, a tire durability improver).
  • the rubber additive of the present invention when blended into a rubber composition for tires, can improve the cut and chip resistance of the tire.
  • Cut and chip refers to the phenomenon in which chunks larger than normal wear debris fall off from the tread and sidewalls of a tire while the tire is running.
  • the rubber composition of the present invention contains the above-mentioned rubber additive and a rubber component.
  • the rubber additive is as described above.
  • the amount of the rubber additive mixed is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, per 100 parts by mass of the rubber component.
  • the rubber component is not particularly limited, but preferably contains a diene rubber.
  • the sulfur-containing unsaturated hydrocarbon polymer has a higher reactivity with diene rubber and is more likely to react with rubber molecular chains than unsaturated petroleum resin (which does not contain sulfur), which is a general unsaturated hydrocarbon polymer. Therefore, by using a diene rubber, it is possible to improve the wet grip performance and fuel economy of the tire in a balanced manner.
  • non-diene rubber may also be blended as the rubber component.
  • the content of diene rubber in the rubber component is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass.
  • Diene-based rubbers include natural rubber (NR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), nitrile rubber (NBR), chloroprene rubber (CR), ethylene-propylene-diene terpolymer rubber (EPDM), butyl rubber (IIR), etc., as well as modified diene-based rubbers of these.
  • Modified diene-based rubbers include diene-based rubbers modified by methods such as main chain modification, single-end modification, both-end modification, and hydrogenation.
  • modified functional groups of modified synthetic diene-based rubbers include various functional groups such as epoxy groups, amino groups, alkoxysilyl groups, and hydroxyl groups, and one or more of these functional groups may be contained in the modified synthetic diene-based rubber.
  • diene rubber there are no particular restrictions on the manufacturing method of diene rubber, and examples include emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, and cationic polymerization. There are also no particular restrictions on the glass transition temperature.
  • Natural rubber includes natural rubber latex, technically graded rubber (TSR), smoked sheet rubber (RSS), gutta percha, eucommia-derived natural rubber, guayule-derived natural rubber, Russian dandelion-derived natural rubber, and plant-based fermented rubber. Furthermore, modified natural rubbers such as epoxidized natural rubber, methacrylic acid-modified natural rubber, styrene-modified natural rubber, sulfonic acid-modified natural rubber, and zinc sulfonate-modified natural rubber are also included in the natural rubber category.
  • non-diene rubbers A wide range of known non-diene rubbers can be used. Specific examples include olefin rubbers such as ethylene-propylene rubber (EPM), chlorosulfonated polyethylene rubber (CSM), acrylic rubber (ACM), urethane rubber (U), silicone rubber (VMQ, PVMQ, FVMQ), fluororubber (FKM), and polysulfide rubber (T).
  • EPM ethylene-propylene rubber
  • CSM chlorosulfonated polyethylene rubber
  • ACM acrylic rubber
  • U urethane rubber
  • U silicone rubber
  • VMQ silicone rubber
  • PVMQ PVMQ
  • FVMQ fluororubber
  • T polysulfide rubber
  • the rubber composition of the present invention can also contain elastomers, provided that their functionality is not impaired.
  • elastomers include thermoplastic elastomers selected from the group consisting of polystyrene-based elastomeric polymers such as styrene-isoprene-styrene triblock copolymer (SIS), styrene-butadiene-styrene triblock copolymer (SBS), and their hydrogenated products (SEBS, SEPS, SEEPS), polyolefin-based elastomers, polyvinyl chloride-based elastomers, polyurethane-based elastomers, polyester-based elastomers, and polyamide-based elastomers.
  • polystyrene-based elastomeric polymers such as styrene-isoprene-styrene triblock copolymer (SIS), styrene-butadiene-styrene
  • the rubber composition of the present invention may contain other processing aids such as a silane coupling agent, a vulcanizing agent, a vulcanization accelerator, a vulcanization accelerator aid, an antioxidant, a softener, an antioxidant, a filler, and a plasticizer, within a range that does not impair the functions of the rubber composition.
  • processing aids such as a silane coupling agent, a vulcanizing agent, a vulcanization accelerator, a vulcanization accelerator aid, an antioxidant, a softener, an antioxidant, a filler, and a plasticizer
  • silane coupling agent When silica is added, it is preferable to add a silane coupling agent.
  • silane coupling agents can be used, such as bis[3-(triethoxysilyl)propyl]tetrasulfide, bis[3-(triethoxysilyl)propyl]disulfide, 3-octanoylthio-1-propyltriethoxysilane, and their homocondensates or cocondensates with 3-mercaptopropyltriethoxysilane.
  • Commercially available bis[3-(triethoxysilyl)propyl]tetrasulfide can be used, such as Si-69 manufactured by Evonik.
  • silane coupling agent added is preferably 1 to 20% by mass, and more preferably 2 to 10% by mass, of the silica amount.
  • vulcanizing agents include sulfur-based vulcanizing agents such as powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, and alkylphenol disulfide, as well as zinc oxide, magnesium oxide, litharge, p-quinone dioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene, methylene dianiline, phenolic resin, brominated alkylphenol resin, and chlorinated alkylphenol resin.
  • the amount of vulcanizing agent added is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
  • vulcanization accelerators include thiuram-based accelerators such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and tetramethylthiuram monosulfide (TMTM); aldehyde/ammonia-based accelerators such as hexamethylenetetramine; guanidine-based accelerators such as diphenylguanidine (DPG); thiazole-based accelerators such as 2-mercaptobenzothiazole (MBT) and dibenzothiazyl disulfide (DM); sulfenamide-based accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide (CBS) and N-t-butyl-2-benzothiazylsulfenamide (BBS); and dithiocarbamate-based accelerators such as zinc dimethyldithiocarbamate (ZnPDC).
  • TMTD tetra
  • vulcanization accelerators examples include fatty acids such as acetyl acid, propionic acid, butanoic acid, stearic acid, acrylic acid, and maleic acid; zinc fatty acids such as zinc acetylate, zinc propionate, zinc butanoate, zinc stearate, zinc acrylate, and zinc maleate; and zinc oxide.
  • the amount of vulcanization accelerator added is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
  • antioxidants include aliphatic and aromatic hindered amine and hindered phenol compounds.
  • the amount of antioxidant blended is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
  • the softener may be any conventionally known softener, and includes, but is not limited to, petroleum-based softeners such as aroma oil, paraffin oil, and naphthenic oil, and plant-based softeners such as palm oil, castor oil, cottonseed oil, and soybean oil. When used, one or more of these may be selected and used as appropriate.
  • a softener is contained, from the standpoint of ease of handling, it is preferable to contain, among the softeners mentioned above, those that are liquid at room temperature such as 25°C, for example, petroleum-based softeners such as aroma oil, paraffin oil, and naphthenic oil, with aroma oil being particularly preferred.
  • the aromatic oil used is T-DAE (Treated-Distillate Aromatic Extracts: a petroleum-derived rubber softener obtained as an extract fraction from vacuum-extracted crude diesel. To reduce highly carcinogenic polycyclic aromatic compounds, the solvent extraction is repeated twice.)
  • Other examples include A/O (Asphalt/Oil) mix and NC-RAE (Residual Aromatic Extracts).
  • the amount of softener blended is preferably 10 to 200 parts by mass, and more preferably 20 to 100 parts by mass, per 100 parts by mass of the rubber component.
  • Fillers include silica and barium sulfate, with silica being preferred.
  • the amount of filler mixed is preferably 10 to 200 parts by mass, and more preferably 20 to 100 parts by mass, per 100 parts by mass of the rubber component.
  • colorants include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochlorides, and sulfates, as well as azo pigments and copper phthalocyanine pigments.
  • the blending amount of the colorant is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
  • processing aids can be kneaded using a known rubber mixer, such as a roll, Banbury mixer, or kneader, and then vulcanized under any conditions to be used as a rubber composition.
  • a known rubber mixer such as a roll, Banbury mixer, or kneader
  • the amounts of these other processing aids added can be conventional amounts, as long as they do not conflict with the objectives of the present invention.
  • the method for producing the rubber composition comprises a step of kneading a rubber component with the rubber additive containing the sulfur-containing unsaturated hydrocarbon polymer.
  • the method for producing the rubber composition may preferably further include a step of kneading the vulcanizing agent. More preferably, it may further include a step of kneading the vulcanizing agent and the vulcanization accelerator.
  • the method for producing the rubber composition may involve appropriately blending and kneading the other processing aids mentioned above, as long as the functionality of the rubber composition is not impaired.
  • a conventional kneading device can be used to produce the rubber composition, and the kneading temperature, time, compounding order, etc. can be selected as appropriate.
  • a tire can be manufactured by a conventionally known method and common technical knowledge widely known to those skilled in the art.
  • the rubber composition can be extruded, molded using a tire building machine, and then heated and pressurized using a vulcanizer to form crosslinks, thereby manufacturing a tire.
  • the tire can be improved in terms of abrasion resistance, fracture resistance (breaking strength, breaking elongation, cut-chip resistance), wet grip performance, fuel economy, the balance between wet grip performance and fuel economy, and deterioration resistance (rubber bonding property, heat aging resistance).
  • the tires there are no particular limitations on the uses of the tires, and examples include passenger car tires, heavy-duty tires, motorcycle tires, and studless tires. Among these, the tire is particularly suitable for use in passenger car tires.
  • the tire can be applied to any part of the tire, and there are no particular restrictions on the part to which it is applied, and it can be selected appropriately depending on the purpose, such as the tire tread, carcass, sidewall, inner liner, undertread, or belt.
  • the rubber composition of the present invention can also be used to produce rubber products other than tires, such as automotive rubber parts (exterior and interior parts, weather strips, boots, mounts, seals, sealers, and gaskets), hoses, belts, sheets, vibration-isolating rubber, rollers, linings, rubber-coated fabrics, sealing materials, gloves, fenders, medical rubber (syringe gaskets, tubes, and catheters), gaskets (for home appliances and construction), asphalt modifiers, grips, toys, shoes, sandals, keypads, gears, and PET bottle cap liners.
  • the reaction product obtained below was dissolved in tetrahydrofuran to a concentration of 10 g / L to prepare a measurement sample.
  • the sample was measured using a Tosoh HLC-8320GPC (column used: TSKgel SuperHZ column series) as a measuring device, and the weight average molecular weight (Mw) was calculated using a calibration curve prepared in advance using an Agilent polystyrene kit (EasiVial PS-M and PS-L).
  • the amount of free sulfur (unreacted sulfur) in the reaction product was quantified by preparing a calibration curve in advance using sulfur (Fujifilm Wako Pure Chemical Industries, Ltd., powder, chemical grade).
  • trisulfide addition proportion The proportion of sulfur added in the form of trisulfides relative to the total amount of unsaturated bonds in the norbornene skeleton in a sulfur-containing unsaturated hydrocarbon polymer (hereinafter referred to as the "trisulfide addition proportion") can be calculated by measuring the target sample using a conventionally known FD-MS (field desorption-mass spectrometry, apparatus: JEOL JMS-T200GCx plus, counter electrode voltage: -10 kV, measurement mass range: m/z 35 to 1600), analyzing the molecular weight of the target sample, and quantifying the molecular peak where an increase in the mass of the trisulfide is observed.
  • FD-MS field desorption-mass spectrometry, apparatus: JEOL JMS-T200GCx plus, counter electrode voltage: -10 kV, measurement mass range: m/z 35 to 1600
  • the precipitation-filtration process was repeated three times for each experiment, and the solids were collected for the entire reaction solution.
  • the resulting solids were dried under reduced pressure at 0.1 kPa and 50°C for approximately 8 hours, yielding 41.4 g of a brown powdery solid.
  • GPC analysis of the resulting solids revealed a Mw of 4,030, and the calibration curve indicated a free sulfur content of 0.2% by mass.
  • the trisulfide addition ratio was calculated to be 18 mol%.
  • Tables 1 and 2 show the raw material compositions and trisulfide addition ratios in each preparation example. Tables 1 and 2 also show the amount of free sulfur in the reaction product and the average amount of sulfur introduced.
  • the amount of free sulfur in the reaction product refers to the amount of unreacted sulfur after sulfur is consumed in the target reaction (adding sulfur to the unsaturated bonds in the norbornene skeleton) and other side reactions (bonding such as resin-sulfur-resin to increase molecular weight).
  • Example 1 The following components were kneaded using a 250 mL kneader (Labo Plastomill manufactured by Toyo Seiki Seisaku-sho, Ltd.) to obtain a rubber composition. Details of the kneading operation performed are as follows (i) to (ii).
  • Kneading 1 A rubber (conjugated diene polymer) was charged into an internal pressure kneader heated to 100°C, and then silica, carbon black, aroma oil, stearic acid, an antioxidant, zinc oxide, a silane coupling agent, and a sulfur-containing unsaturated hydrocarbon polymer A were further charged therein, followed by kneading at 60 rpm for 3 minutes and 30 seconds and then discharging.
  • Mixing 2 After the mixture was released and the temperature was sufficiently reduced, a vulcanization accelerator and sulfur were added to the above-mentioned mixture in an internal pressure kneader heated to 70°C, and the mixture was mixed to obtain a rubber composition.
  • Rubber (the conjugated diene polymer synthesized above) 100 parts by mass Silica (manufactured by Tosoh Corporation, product name: Nipsil AQ) 70 parts by mass Silane coupling agent (manufactured by Degussa, product name: Si75) 5.6 parts by mass of carbon black (manufactured by Tokai Carbon Co., Ltd., product name: Seest KH) 5.6 parts by mass of aromatic oil (manufactured by ENEOS Corporation, trade name: T-DAE) 10 parts by mass of sulfur-containing unsaturated hydrocarbon polymer A 10 parts by mass of stearic acid (manufactured by New Japan Chemical Co., Ltd., trade name: Stearic Acid 300) 2 parts by mass of antioxidant (manufactured by Ouchi Shinko Chemical Co., Ltd., product name: Nocrac 6C) 1 part by mass of zinc oxide (manufactured by Toho Zinc Co., Ltd., trade name: Ginrei R) 3 parts by mass
  • Example 2 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer B was used instead of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Example 3 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer C was used instead of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Example 4 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer D was used instead of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Example 5 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer E was used instead of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Example 6 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer F was used instead of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Example 7 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer G was used instead of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Example 8 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer H was used instead of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Example 9 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer I was used instead of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Example 10 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer J was used instead of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Example 11 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer K was used in place of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Example 12 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer M was used instead of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Example 13 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer N was used instead of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Example 14 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer O was used instead of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Example 15 A rubber composition was obtained in the same manner as in Example 1, except that the sulfur-containing unsaturated hydrocarbon polymer P was used instead of the sulfur-containing unsaturated hydrocarbon polymer A.
  • Examples 1 to 11 are reported as the reciprocal of the relative value when the value in Comparative Example 1 is set to 100, and Examples 12 to 15 are reported as the reciprocal of the relative value when the value in Comparative Example 2 is set to 100.
  • the larger the value the better the wear resistance.
  • the values for Examples 1 to 11 are reported as relative values with the value for Comparative Example 1 taken as 100, and the values for Examples 12 to 15 are reported as relative values with the value for Comparative Example 2 taken as 100.
  • Rubber bonding ability Test pieces of appropriate size were cut from the vulcanized rubber sheet obtained above. Next, using the test pieces, a solvent extraction test was performed in accordance with JIS K6229B, and the rubber bondability was evaluated from the amount of extraction. For Examples 1 to 11, the values are reported as the reciprocal of the relative value when the value for Comparative Example 1 is set to 100, and for Examples 12 to 15, the values are reported as the reciprocal of the relative value when the value for Comparative Example 2 is set to 100. A larger value indicates a smaller amount of extraction and higher rubber bondability.
  • Heat aging resistance was evaluated based on the rate of change in breaking strength and breaking elongation before and after heat aging.
  • Examples 1 to 11 are reported as relative values when the value in Comparative Example 1 is set to 100
  • Examples 12 to 15 are reported as relative values when the value in Comparative Example 2 is set to 100. The smaller the value, the smaller the rate of change in breaking strength and breaking elongation, indicating better heat aging resistance.
  • Examples 1 to 11 by adding a sulfur-containing unsaturated hydrocarbon polymer having a trisulfide addition ratio of 30 mol % or more, the tires were superior in abrasion resistance, fracture resistance (breaking strength, breaking elongation, cut/chip resistance), wet grip performance, fuel economy, the balance between wet grip performance and fuel economy, and deterioration resistance (rubber bonding ability, heat aging resistance) compared to Comparative Example 1, in which a sulfur-containing unsaturated hydrocarbon polymer having a trisulfide addition ratio of 18 mol % was added.
  • Examples 12 to 15 by adding a sulfur-containing unsaturated hydrocarbon polymer having a trisulfide addition ratio of 30 mol% or more, the tires were superior in abrasion resistance, fracture resistance (breaking strength, breaking elongation, cut/chip resistance), wet grip performance, fuel economy, the balance between wet grip performance and fuel economy, and deterioration resistance (rubber bonding ability, heat aging resistance) compared to Comparative Example 2, in which a sulfur-containing unsaturated hydrocarbon polymer having a trisulfide addition ratio of 23 mol% was added.

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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)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Tires In General (AREA)

Abstract

La présente invention a pour but de proposer un polymère hydrocarboné insaturé contenant du soufre avec lequel il est possible, par incorporation par mélange dans une composition de caoutchouc pour un pneu, d'améliorer, pour le pneu, la résistance à l'usure, la résistance à la fracture (force de rupture, allongement à la rupture, résistance aux ébréchures), la propriété d'adhérence sur sol mouillé, l'économie de carburant, l'équilibre entre la propriété d'adhérence sur sol mouillé et l'économie de carburant, et la résistance à la détérioration (propriété de liaison au caoutchouc et résistance au vieillissement thermique). À cet effet, l'invention porte sur un polymère hydrocarboné insaturé contenant du soufre qui est obtenu par réaction du soufre avec les liaisons insaturées d'un polymère d'un hydrocarbure insaturé ayant un squelette de norbornène, le taux ajouté sous la forme d'un trisulfure (-S3-) par rapport à la quantité totale de liaisons insaturées dans le squelette de norbornène étant de 30% en moles ou plus.
PCT/JP2025/009071 2024-03-15 2025-03-11 Polymère hydrocarboné insaturé contenant du soufre, additif pour caoutchouc, composition de caoutchouc et pneu Pending WO2025192584A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63301244A (ja) * 1987-06-02 1988-12-08 Bridgestone Corp ゴム組成物
JP2021031568A (ja) * 2019-08-22 2021-03-01 Ｅｎｅｏｓ株式会社 含硫黄不飽和炭化水素重合体およびその製造方法、ゴム用添加剤、ゴム組成物、ならびにタイヤ
WO2023032664A1 (fr) * 2021-08-30 2023-03-09 Ｅｎｅｏｓ株式会社 Composition de caoutchouc ainsi que procédé de fabrication de celle-ci, et pneumatique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63301244A (ja) * 1987-06-02 1988-12-08 Bridgestone Corp ゴム組成物
JP2021031568A (ja) * 2019-08-22 2021-03-01 Ｅｎｅｏｓ株式会社 含硫黄不飽和炭化水素重合体およびその製造方法、ゴム用添加剤、ゴム組成物、ならびにタイヤ
WO2023032664A1 (fr) * 2021-08-30 2023-03-09 Ｅｎｅｏｓ株式会社 Composition de caoutchouc ainsi que procédé de fabrication de celle-ci, et pneumatique

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