WO2020145089A1 - Composition de caoutchouc et produit en caoutchouc - Google Patents

Composition de caoutchouc et produit en caoutchouc Download PDF

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WO2020145089A1
WO2020145089A1 PCT/JP2019/050027 JP2019050027W WO2020145089A1 WO 2020145089 A1 WO2020145089 A1 WO 2020145089A1 JP 2019050027 W JP2019050027 W JP 2019050027W WO 2020145089 A1 WO2020145089 A1 WO 2020145089A1
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group
rubber composition
composition according
unsaturated bond
rubber
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PCT/JP2019/050027
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English (en)
Japanese (ja)
Inventor
貴夫 国実
小島　正章
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住友ベークライト株式会社
大塚化学株式会社
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Priority claimed from JP2019129000A external-priority patent/JP7312628B2/ja
Application filed by 住友ベークライト株式会社, 大塚化学株式会社 filed Critical 住友ベークライト株式会社
Priority to CN201980088299.1A priority Critical patent/CN113272152A/zh
Publication of WO2020145089A1 publication Critical patent/WO2020145089A1/fr

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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • the present invention relates to a rubber composition and a rubber product.
  • Patent Document 1 discloses a rubber composition using a phenol resin having a specific structure from the viewpoint of obtaining a rubber vulcanizate for tires having a high elastic modulus and high strength.
  • the present inventor as a result of intensive studies from the viewpoint of achieving both high elastic modulus and good hysteresis loss, found that it is effective to combine a specific phenol resin and a specific tetrazine compound, Has been completed.
  • the present invention is A phenolic resin having an unsaturated bond, A tetrazine compound represented by the general formula (1) or a salt thereof, [In the formula (1), X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents. ] There is provided a rubber composition having:
  • the present invention also provides a rubber product using the above rubber composition.
  • the present invention also provides a tire using the above rubber composition.
  • the present invention also includes a step (X) of mixing a raw material component containing a rubber component, a phenol resin having an unsaturated bond, and a tetrazine compound represented by the general formula (1) or a salt thereof, A step (Y) of mixing the mixed raw material components and a vulcanizing agent, Including In the step (X), A step (X-1) of simultaneously mixing the rubber component, the tetrazine compound represented by the general formula (1) or a salt thereof, and the phenol resin having an unsaturated bond, or the rubber component and the salt. A step (X-2) of mixing a mixture obtained by mixing a phenol resin having a saturated bond with a tetrazine compound represented by the general formula (1) or a salt thereof.
  • a method for producing a rubber composition which is any one of the above.
  • X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents. ]
  • 1 is a 1 H-NMR chart of Phenolic Resin 1.
  • 2 is a 1 H-NMR chart of Phenolic Resin 2.
  • 3 is a 1 H-NMR chart of Phenolic Resin 3.
  • 3 is a 1 H-NMR chart of Phenolic Resin 4.
  • the rubber composition of the present embodiment includes at least a phenol resin (A) having an unsaturated bond (hereinafter, also referred to as “phenol resin (A)”) and a tetrazine compound represented by the general formula (1), or The salt (henceforth the “tetrazine compound (B)" is also described.) is included.
  • phenol resin (A) having an unsaturated bond
  • tetrazine compound represented by the general formula (1) or The salt (henceforth the "tetrazine compound (B)" is also described.) is included.
  • the phenol resin (A) has an unsaturated bond.
  • the phenolic resin (A) having an unsaturated bond means that, for example, a substituent having an unsaturated bond is bound to an aromatic ring, or a compound having an unsaturated bond instead of a hydrogen atom of a hydroxyl group is bound to the aromatic ring. , Those having an unsaturated bond in the substituent derived from the raw material aldehyde, and the like.
  • the phenolic resin (A) Since the phenolic resin (A) has an unsaturated bond, it becomes possible to cause an addition reaction with the tetrazine compound (B) described later. Since the skeleton of the phenol resin (A) is rigid, it is possible to realize a high elastic modulus of the vulcanized product, while the tetrazine compound (B) has a three-dimensional structure of the vulcanized product of the phenol resin (A). It is presumed that by interposing between the two, the properties of the rubber are retained and an appropriate viscoelasticity is secured, so that a good hysteresis loss property is obtained.
  • the phenol resin (A) preferably has at least one structural unit represented by the following general formula (2).
  • R 1 represents a substituent having an unsaturated bond.
  • the hysteresis loss in the frequency region that affects the rolling resistance of the tire generally correlates with tan ⁇ of dynamic viscoelasticity at 60° C., and the dynamic viscosity at 60° C. It can be evaluated using the elastic tan ⁇ . The lower the tan ⁇ at 60° C., the lower the hysteresis loss that affects the rolling resistance of the tire, and the better the fuel economy performance.
  • the unsaturated bond contained in R 1 is preferably a carbon-carbon unsaturated bond (carbon-carbon double bond, and carbon-carbon triple bond). Further, R 1 is more preferably a hydrocarbon group having a linear or branched unsaturated bond having 2 to 25 carbon atoms, and any one of the hydrogen atoms bonded to the carbon atom is an atom other than the hydrogen atom. It may be substituted. These may be used alone or in combination of two or more.
  • the phenol resin (A) preferably has at least one structural unit represented by the following general formula (3).
  • R 2 represents a substituent having an unsaturated bond.
  • R 3 represents hydrogen, an alkyl group, an aryl group, a hydroxyl group, an ether group, an amino group, a carboxyl group, an ester group, an aldehyde group, a sulfide group, a thiol group, or a methylol group.
  • the unsaturated bond contained in R 2 is preferably a carbon-carbon unsaturated bond (carbon-carbon double bond, and carbon-carbon triple bond).
  • R 2 is more preferably a hydrocarbon group having a linear or branched unsaturated bond having 2 to 25 carbon atoms, and any hydrogen atom bonded to the carbon atom is an atom other than a hydrogen atom. It may be substituted. These may be used alone or in combination of two or more.
  • the alkyl group in R 3 is preferably a linear or branched hydrocarbon group having 1 to 25 carbon atoms, and any hydrogen atom bonded to a carbon atom is substituted with an atom other than a hydrogen atom. May be.
  • the phenol resin (A) is a condensate of phenols and aldehydes, and as a method for obtaining a phenol resin having an unsaturated bond, for example, a phenol having an unsaturated bond or an aldehyde having an unsaturated bond is used. Or by reacting a phenol resin having no unsaturated bond with a compound having an unsaturated bond to introduce an unsaturated bond. These methods may be used alone or in combination.
  • phenols having an unsaturated bond include those having an unsaturated bond in the side chain.
  • vinylphenol, allylphenol, eugenol, curcumin, coumaric acid, hydroxycinnamic acid and its derivatives, cardanol and its unpurified cashew nut shell liquid, Urushiol and its unpurified lacquer, thithiol, lachol, etc. Can be mentioned.
  • Preferred are vinylphenol, allylphenol, cardanol and cashew nut shell liquid, and particularly preferred are cardanol and cashew nut shell liquid. These may be used alone or in combination, and may be used in combination with phenols containing no unsaturated bond.
  • the phenols containing no unsaturated bond are not particularly limited, and examples thereof include phenol, cresol, xylenol, dihydroxybenzene, naphthol, ethylphenol, propylphenol, butylphenol, pentylphenol, hexylphenol, octylphenol, nonylphenol.
  • Saturated alkylphenols such as bis(hydroxyphenyl)methane, bis(hydroxyphenyl)ethane, bis(hydroxyphenyl)propane, bis(hydroxyphenyl)butane, bis(hydroxyphenyl)cyclohexane, bis(hydroxyphenyl)sulfone, bis( Examples thereof include bisphenols such as hydroxyphenyl)propylbenzene and bis(hydroxyphenyl)ketone.
  • a phenol resin containing an unsaturated bond is obtained by another method, only phenols containing no unsaturated bond may be used.
  • Phenols containing no unsaturated bond are preferably phenol, cresol, xylenol, dihydroxybenzene, naphthol, butylphenol, octylphenol, bis(hydroxyphenyl)methane and bis(hydroxyphenyl)propane. These may be used alone or in combination.
  • aldehydes having an unsaturated bond examples include acrolein, allyl aldehyde, crotonaldehyde and the like. These may be used alone or in combination, or may be used in combination with aldehydes containing no unsaturated bond.
  • the aldehydes containing no unsaturated bond are not particularly limited, but include formaldehyde, paraformaldehyde, trioxane, tetraoxymethylene, polyoxymethylene, hexamethylenetetramine, acetaldehyde, paraaldehyde, propionaldehyde, butyraldehyde, caproaldehyde, Examples include octyl aldehyde, chloral, furfural, glyoxal, benzaldehyde, phenylacetaldehyde, o-tolualdehyde and hydroxybenzaldehyde.
  • paraxylylene dichloride paraxylylene dimethyl ether, or furfuryl alcohol, which reacts with phenols similarly to aldehydes, may be used.
  • a phenol resin containing an unsaturated bond is obtained by another method, only aldehydes containing no unsaturated bond may be used.
  • the aldehydes containing no unsaturated bond are preferably formaldehyde, paraformaldehyde, hexamethylenetetramine, benzaldehyde, hydroxybenzaldehyde, furfural, furfuryl alcohol, paraxylylene dichloride, paraxylylene dimethyl ether, and particularly preferably formaldehyde, Paraformaldehyde and hexamethylenetetramine. These may be used alone or in combination.
  • the conditions for reacting the phenols and the aldehydes to obtain the phenolic resin (A) having an unsaturated bond are not particularly limited, but the phenols and the aldehydes are heated at 50° C. to 200° C. Are listed.
  • the molar ratio of phenols to aldehydes is not particularly limited, but for example, the amount of aldehydes may be 0.1 mol to 4.0 mols per mol of phenols, It can be preferably 0.2 mol to 2.0 mol, particularly preferably 0.3 mol to 1.0 mol.
  • the catalyst is reacted in the presence of an organic acid, phosphoric acid, organic phosphonic acid, a transition metal salt or a basic catalyst.
  • organic acid include acetic acid, oxalic acid, formic acid, lactic acid and malic acid.
  • organic phosphonic acid include aminopolyphosphonic acids such as ethylenediaminetetrakismethylenephosphonic acid, ethylenediaminebismethylenephosphonic acid, aminotrismethylenephosphonic acid, ⁇ -aminoethylphosphonic acid N,N-diacetic acid and aminomethylphosphonic acid N,N.
  • transition metal catalyst for example, inorganic salts or organic acid salts of transition metals such as titanium, iron, zinc, nickel, cobalt, copper, chromium, manganese, etc. can be used.
  • the basic catalyst include sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, methylethylamine, triethylamine, and other amines, calcium, magnesium, barium, and the like.
  • Alkaline earth metal oxides and hydroxides, alkaline substances such as sodium carbonate, hexamethylenetetramine and the like can be used.
  • the apparatus for producing the phenolic resin (A) having an unsaturated bond is not particularly limited.
  • the reaction is carried out in a vessel such as a reaction vessel equipped with a heater, a cooler and a stirrer, or continuously with a continuous mixer or the like. It does not matter if the reaction is performed.
  • a compound having an unsaturated bond for example, when a phenol resin having an unsaturated bond is reacted with a compound having an unsaturated bond to obtain a phenol resin (A) having an unsaturated bond,
  • phenol resin (A) having an unsaturated bond examples thereof include epoxy compounds, chlorides, isocyanate compounds and drying oils.
  • the epoxy compound having an unsaturated bond for example, vinyl glycidyl ether, allyl glycidyl ether, etc.
  • the chloride having an unsaturated bond for example, vinyl chloride, allyl chloride, etc.
  • the isocyanate compound having an unsaturated bond for example, methacryloyl Isocyanate, methacryloyloxyethyl isocyanate, isocyanatoethyl methacrylate, isocyanatoethyl acrylate, and the like
  • the drying oil include flaxseed oil, tung oil, mustard oil, perilla oil, walnut oil, citrus oil, safflower oil, sunflower oil and the like. To be These may be used alone or in combination.
  • a resin further modified with oil can be used as the phenol resin (A) having an unsaturated bond.
  • oil used for modification include rosin oil and tall oil.
  • the ratio of peaks derived from unsaturated bonds is such that peaks derived from hydrogen bonded to carbon atoms (0.2 to 7).
  • 0.5 ppm or more preferably 20% or less, more preferably 0.7% or more and 15% or less, and further preferably 1% or more and 10% or less. Is more preferable.
  • the number average molecular weight of the phenol resin (A) is preferably 400 to 3000, more preferably 800 to 2000, and even more preferably 1000 to 1800. As a result, a resin having good handleability can be stably obtained.
  • the number average molecular weight of the phenol resin (A) is preferably 400 to 3000, more preferably 800 to 2000, and even more preferably 1000 to 1800.
  • compatibility with other compounding agents can be improved and good handleability can be maintained.
  • the number average molecular weight of the phenol resin (A) to be equal to or less than the above upper limit, it is possible to prevent the viscosity from becoming too high, and it is easy to obtain good solubility in a solvent.
  • the above-mentioned number average molecular weight is calculated by using GPC (gel permeation chromatography) under a predetermined condition and measuring with a differential refractometer as a detector, and then converting with standard polystyrene. ..
  • the content of the phenol resin (A) is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and further preferably 1 to 10% by mass, based on the entire rubber composition.
  • the content of the phenol resin (A) is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and further preferably 1 to 10% by mass, based on the entire rubber composition.
  • Tetrazine compound (B) The tetrazine compound (B) is represented by general formula (1). This allows the rubber product using the rubber composition to have an appropriate hysteresis loss.
  • X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents. ]
  • alkyl group examples include linear, branched or cyclic alkyl groups, and specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and s-butyl. , T-butyl, 1-ethylpropyl, n-pentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, etc.
  • Cyclic alkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like can be mentioned.
  • a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and n-pentyl group is more preferable, and a methyl or ethyl group is preferable. Is more preferable.
  • alkylthio group examples include a linear, branched or cyclic alkylthio group, and examples thereof include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio, t-butylthio, 1-ethylpropylthio, n-pentylthio, neopentylthio, n-hexylthio, isohexylthio, 3-methylpentylthio, etc.
  • a methylthio, ethylthio, isopropylthio, or isobutylthio group is preferable, and a methylthio group or an ethylthio group is more preferable.
  • aralkyl group examples include benzyl, phenethyl, trityl, 1-naphthylmethyl, 2-(1-naphthyl)ethyl, 2-(2-naphthyl)ethyl groups and the like. Of these, a benzyl group or a phenethyl group is preferable, and a benzyl group is more preferable.
  • aryl group examples include phenyl, biphenyl, naphthyl, dihydroindenyl, and 9H-fluorenyl group. Of these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • arylthio group examples include phenylthio, biphenylthio, and naphthylthio groups.
  • heterocyclic group examples include 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 3-pyridazyl, 4-pyridazyl, 4-(1 , 2,3-Triazyl), 5-(1,2,3-triazyl), 2-(1,3,5-triazyl), 3-(1,2,4-triazyl), 5-(1,2) , 4-triazyl), 6-(1,2,4-triazyl), 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl, 3-quinoxalyl, 5-quinoxalyl, 6-quinoxyl
  • X 1 and X 2 are preferably heterocyclic groups, and more preferably the heterocyclic groups are pyridyl group, furanyl group, 2-pyridyl group and 3-pyridyl group.
  • the salt of the tetrazine compound represented by the formula (1) is not particularly limited, but examples thereof include inorganic acid salts such as hydrochlorides, sulfates and nitrates; organic acid salts such as acetates and methanesulfonates; Alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts and calcium salts; quaternary ammonium salts such as dimethylammonium and triethylammonium.
  • inorganic acid salts such as hydrochlorides, sulfates and nitrates
  • organic acid salts such as acetates and methanesulfonates
  • Alkali metal salts such as sodium salts and potassium salts
  • alkaline earth metal salts such as magnesium salts and calcium salts
  • quaternary ammonium salts such as dimethylammonium and triethylammonium.
  • tetrazine compounds (B) include, for example, the following. 1,2,4,5-tetrazine, 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, 3,6-bis(3-pyridyl)-1,2,4,5- Tetrazine, 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine, 3,6-diphenyl-1,2,4,5-tetrazine, 3,6-dibenzyl-1,2,4 ,5-tetrazine, 3,6-bis(2-furanyl)-1,2,4,5-tetrazine, 3-methyl-6-(3-pyridyl)-1,2,4,5-tetrazine, 3, 6-bis(3,5-dimethyl-1-pyrazolyl)-1,2,4,5-tetrazine, 3,6-bis(2-thienyl)-1,2,4,5-tetrazine, 3-methyl- 6-(2-pyridyl)-1,2,4,5-tetraz
  • the rubber composition of the present embodiment may further contain the following components.
  • Rubber component (C) As the rubber component (C), natural rubber (NR), ethylene-propylene copolymer rubber (EPM), acrylic rubber (ACM), chlorinated polyethylene (CM), epichlorohydrin rubber (CO, ECO), chlorosulfonated polyethylene (CSM), isoprene rubber (IR), butyl rubber (IIR), nitrile rubber (NBR), and diene rubber.
  • NR natural rubber
  • EPM ethylene-propylene copolymer rubber
  • ACM acrylic rubber
  • CM chlorinated polyethylene
  • CO epichlorohydrin rubber
  • CO chlorosulfonated polyethylene
  • IR isoprene rubber
  • IIR butyl rubber
  • NBR nitrile rubber
  • the above-mentioned diene rubber may be any rubber containing a diene monomer as at least a part of the monomers constituting the rubber.
  • natural rubber NR
  • SBR styrene-butadiene copolymer rubber
  • BR polybutadiene rubber
  • IR polyisoprene rubber
  • NBR acrylonitrile-butadiene copolymer rubber
  • IIR butyl rubber
  • EPDM ethylene-propylene-diene terpolymer rubber
  • EBR ethylene-butadiene copolymer rubber
  • PBR Propylene-butadiene copolymer rubber
  • PBR Propylene-butadiene copolymer rubber
  • the rubber composition of the present embodiment contains 0.1 to 30 parts by mass of the phenol resin (A) and 0.01 to 10 parts by mass of the tetrazine compound (B) with respect to 100 parts by mass of the rubber component (C). It is more preferable that the phenol resin (A) is contained in an amount of 0.5 to 20 parts by mass, the tetrazine compound (B) is contained in an amount of 0.02 to 8 parts by mass, and the phenol resin (A) is contained in an amount of 1 to 10 parts by mass. It is more preferable to include (B) in an amount of 0.05 to 5 parts by mass.
  • the filler (D) is not particularly limited, but examples thereof include inorganic fillers such as carbon black, silica, calcium carbonate, magnesium carbonate, alumina, magnesium oxide, aluminum hydroxide, magnesium hydroxide, talc, clay, and mica, and An organic filler is mentioned. These may be used alone or in combination of two or more. Among them, inorganic fillers are preferable, and carbon black and silica are more preferable, from the viewpoint of increasing the elastic modulus.
  • the content of the filler (D) is preferably 20 to 100 parts by mass, more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the rubber composition.
  • the content of the filler (D) is at least the above lower limit, the hardness of the rubber can be increased, and when it is at most the above upper limit, the fluidity is easily obtained.
  • the curing agent is used to vulcanize the phenolic resin (A).
  • the curing agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include hexamethylenetetramine, benzoxazine, resol-type phenol resin, and initial condensate of melamine/formaldehyde, and initial melamine/formaldehyde. Examples thereof include methyl etherified products of condensates such as hexamethoxymethylmelamine and pentamethoxymethylmelamine. These may be used alone or in combination of two or more.
  • the content of the curing agent is preferably 1 to 60 parts by mass and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the phenol resin (A).
  • the content of the curing agent is preferably 1 to 60 parts by mass and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the phenol resin (A).
  • the rubber composition of the present embodiment as other optional components, compounding agents commonly used in the rubber industry, for example, softening agents, antioxidants, vulcanization accelerators, vulcanization acceleration aids, coupling agents, etc. Can be appropriately selected and blended within a range that does not impair the object of the present invention.
  • the method for producing the rubber composition of the present embodiment includes the step (X) of mixing the raw material components including the rubber component (C), the phenol resin (A), and the tetrazine compound (B), A step (Y) of mixing a raw material component and a vulcanizing agent is included, and the step (X) simultaneously includes a rubber component (C), a tetrazine compound (B), and a phenol resin (A).
  • the mixing step (X-1) or the step (X-2) of mixing the mixture obtained by mixing the rubber component (C) and the phenol resin (A) with the tetrazine compound (B). Is a method.
  • the tetrazine compound (B) is added together with the phenol resin (A), or the tetrazine compound (B) is added after the phenol resin (A) to obtain a high elastic modulus and a good elasticity.
  • a rubber composition that is compatible with hysteresis loss can be effectively and stably obtained.
  • the phenol resin (A), the tetrazine compound (B) and other optional components are mixed and masticated, and then a vulcanizing agent such as sulfur is blended, and a Banbury mixer, a roll, an intensive mixer, or a twin-screw extruder.
  • a desired rubber composition can be obtained by performing main kneading such as kneading, heating, and extrusion using the above.
  • main kneading such as kneading, heating, and extrusion using the above.
  • the phenol resin (A) and the tetrazine compound (B) react efficiently during the production of the rubber composition, and the rubber elastic modulus can be stably improved.
  • the reaction temperature of the phenol resin (A) and the tetrazine compound (B) is preferably 80°C or higher and 250°C or lower, more preferably 90°C or higher and 200°C or lower, and further preferably 100°C or higher and 170°C or lower. .. Thereby, both can be made to react stably.
  • the reaction between the phenol resin (A) and the tetrazine compound (B) in the rubber composition of the present embodiment can be confirmed by analyzing the 13 C-NMR spectrum. That is, in the 13 C-NMR spectrum, a new saturated aliphatic carbon-derived peak (near 25 ppm), which was not found in the phenol resin (A), was found in the region (0 to 80 ppm) where the saturated aliphatic carbon-derived peak appeared. It can be confirmed by being observed.
  • the present inventor has assumed a thermal history of kneading rubber, and modified phenol obtained by mixing the phenol resin (A) and the tetrazine compound (B) at 120° C. for 3 minutes using a kneader.
  • the rubber product obtained by vulcanizing the rubber composition of the present embodiment is applied to applications such as semiconductor parts, aircraft parts, automobile parts, castings, industrial machine parts, electronic parts, electric parts, and mechanical parts.
  • the method for molding the rubber product is not particularly limited, and examples thereof include known methods such as an injection molding method, a compression molding method, an extrusion molding method, and a cast molding method.
  • the rubber product may have any form, and may be an intermediate molded product or a final molded product.
  • the rubber product is preferably applied to automobile parts, and more preferably a tire member, from the viewpoint of exhibiting the effects of achieving both high elastic modulus and hysteresis loss.
  • a tire member from the viewpoint of exhibiting the effects of achieving both high elastic modulus and hysteresis loss.
  • it can be suitably used for at least one member of a tread portion, a sidewall portion, a carcass portion, a belt portion, a bead portion, a rim cushion portion, a run flat reinforcing liner portion, and other reinforcing rubber portions.
  • the rubber product of the present embodiment for example, when used in the tread of the tire, the rubber composition of the present embodiment is extruded into the shape of the tread portion of the tire in the unvulcanized stage, the usual on a tire molding machine.
  • An unvulcanized tire is molded by laminating the tires by a method. Then, the unvulcanized tire can be heated and pressed in a vulcanizer to obtain the tire.
  • the molding temperature is preferably about 100 to 220°C, more preferably about 120 to 200°C, and further preferably about 130 to 190°C. If the molding temperature exceeds 190°C, the rubber may deteriorate, and if it is less than 100°C, molding may not be possible.
  • FIG. 1 is a cross-sectional view that schematically shows the cross section of a tire.
  • a tire 100 includes a tread portion 11 that is in direct contact with a road surface during traveling, a shoulder portion 12 that serves as a shoulder portion of the tire 100 to protect the carcass 15, and a sidewall that serves as a side surface of the tire 100 and protects the carcass 15. It has a portion 13, a beat portion 14 for fixing the tire 100 to a rim portion provided on a wheel and for fixing both ends of the carcass 15, a carcass 15 forming a skeleton of the tire 100, and a belt portion 16.
  • An inner liner 18 is arranged inside the tire 100.
  • the belt portion 16 is arranged between the tread portion 11 and the carcass 16 and is used to reinforce the tread portion 11. Specifically, the belt portion 16 is arranged outside the crown portion of the carcass 15 and plays a role of increasing the rigidity of the tread portion 11. Further, the beat portion 14 of the tire 100 is provided with a beat core 17 for locking the end portion of the carcass 15 so as to be folded back, and for receiving the pull of the carcass 15 during traveling and fixing it to the rim portion.
  • the tire 100 is fixed to the rim portion of the wheel, and air is retained between the tire 100 and the wheel to form a pneumatic tire.
  • Tetrazine compound (B) -Tetrazine compound 1 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, manufactured by Otsuka Chemical Co., Ltd.
  • Rubber component (C) -Rubber component 1 diene rubber, Nipol 1723, oil-extended styrene-butadiene rubber, manufactured by Nippon Zeon Co., Ltd.
  • -Rubber component 2 diene rubber, natural rubber, RSS3, inorganic filler (D) manufactured by Tochi Co., Ltd.
  • ⁇ Silica Nipsil AQ, manufactured by Tosoh Silica Co., Ltd.
  • ⁇ Vulcanization accelerator DPG: 1,3-diphenylguanidine, manufactured by Tokyo Chemical Industry Co., Ltd.
  • Vulcanization accelerator (DM) di-2-benzothiazolyl disulfide, manufactured by Tokyo Chemical Industry Co., Ltd./Sulfur: manufactured by Tokyo Chemical Industry Co., Ltd.
  • Phenolic resin (A), tetrazine compound (B), rubber component (C), inorganic filler (D), vulcanization accelerator and other components other than sulfur were used in a 250 cc closed Banbury mixer. And kneaded at 120° C. for 5 minutes. After kneading, the mixture was discharged outside the mixer and cooled at room temperature. Subsequently, the kneaded product was put into the Banbury mixer again, and a vulcanization accelerator and sulfur were further added and kneaded for 5 minutes to obtain a rubber composition.
  • ⁇ Dynamic viscoelasticity 60°C tan ⁇
  • a test piece was cut out from a 2 mm thick vulcanized sheet to have a width of 10 mm and a length of 40 mm, and a dynamic viscoelasticity tester (ARES G2, manufactured by TA Instruments Co., Ltd.) had a span of 22 mm, a strain of 2%, and a frequency.
  • the tan ⁇ at 60° C. at 10 Hz was evaluated. The smaller the value, the lower the hysteresis loss and the better.
  • the unit is dimensionless.
  • the number average molecular weight and unsaturated bond amount of the phenol resins 1 to 4 were measured by the following procedure.
  • the 1 H-NMR charts are shown in FIGS. 2 to 5, respectively.
  • -Number average molecular weight measured by GPC (gel permeation chromatography) using one TSKgel G1000HXL, two G2000HXL, and one G3000HXL manufactured by Tosoh, using a solvent tetrahydrofuran at a column temperature of 40°C and a flow rate of 1 ml/min. The number average molecular weight was calculated in terms of polystyrene.
  • -Amount of unsaturated bond a peak derived from an unsaturated bond (peak at 4.5 to 6.0 ppm) and a peak derived from hydrogen bonded to a carbon atom (0.2 to 7.5 ppm) in 1 H-NMR spectrum. Peak) was measured, and the ratio (%) of the peak derived from the unsaturated bond to the peak derived from the hydrogen bonded to the carbon atom was calculated excluding the peak derived from the heavy solvent.
  • the NMR measurement was carried out using JNM-AL300 manufactured by JEOL Ltd. with a heavy acetone solvent and an integration number of 64 times.

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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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de caoutchouc qui comprend : une résine phénolique ayant une liaison insaturée ; et un composé de tétrazine représenté par la formule générale (1) ou un sel de celui-ci. [Dans La formule (1), X1 et X2 peuvent être identiques ou différents et représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe alkylthio, un groupe aralkyle, un groupe aryle, un groupe arylthio, un groupe hétérocyclique ou un groupe amino ; et ces groupes peuvent avoir un ou plusieurs substituants, respectivement.]
PCT/JP2019/050027 2019-01-07 2019-12-20 Composition de caoutchouc et produit en caoutchouc WO2020145089A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021006084A1 (fr) * 2019-07-11 2021-01-14 住友ベークライト株式会社 Résine phénolique pour composition de caoutchouc, composition de caoutchouc et produit en caoutchouc
WO2021006085A1 (fr) * 2019-07-11 2021-01-14 住友ベークライト株式会社 Composition de résine phénolique, procédé de production de composition de résine phénolique et produit en caoutchouc

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007002070A (ja) * 2005-06-22 2007-01-11 Bridgestone Corp ゴム組成物およびそれを用いた空気入りタイヤ
JP2009035683A (ja) * 2007-08-03 2009-02-19 Yokohama Rubber Co Ltd:The タイヤ用ゴム組成物
WO2012133426A2 (fr) * 2011-03-28 2012-10-04 横浜ゴム株式会社 Pneu pour charges lourdes
JP2018150436A (ja) * 2017-03-10 2018-09-27 大塚化学株式会社 ゴム組成物及びタイヤ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007002070A (ja) * 2005-06-22 2007-01-11 Bridgestone Corp ゴム組成物およびそれを用いた空気入りタイヤ
JP2009035683A (ja) * 2007-08-03 2009-02-19 Yokohama Rubber Co Ltd:The タイヤ用ゴム組成物
WO2012133426A2 (fr) * 2011-03-28 2012-10-04 横浜ゴム株式会社 Pneu pour charges lourdes
JP2018150436A (ja) * 2017-03-10 2018-09-27 大塚化学株式会社 ゴム組成物及びタイヤ

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021006084A1 (fr) * 2019-07-11 2021-01-14 住友ベークライト株式会社 Résine phénolique pour composition de caoutchouc, composition de caoutchouc et produit en caoutchouc
WO2021006085A1 (fr) * 2019-07-11 2021-01-14 住友ベークライト株式会社 Composition de résine phénolique, procédé de production de composition de résine phénolique et produit en caoutchouc

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