WO2024257655A1 - 変性液状ジエン系重合体及びゴム用添加剤 - Google Patents

変性液状ジエン系重合体及びゴム用添加剤 Download PDF

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WO2024257655A1
WO2024257655A1 PCT/JP2024/020400 JP2024020400W WO2024257655A1 WO 2024257655 A1 WO2024257655 A1 WO 2024257655A1 JP 2024020400 W JP2024020400 W JP 2024020400W WO 2024257655 A1 WO2024257655 A1 WO 2024257655A1
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liquid diene
diene polymer
modified liquid
rubber
butadiene
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English (en)
French (fr)
Japanese (ja)
Inventor
友絵 ▲高▼▲崎▼
浩 神原
陽介 上原
敦 稲富
昭明 馬
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to CN202480039206.7A priority Critical patent/CN121311514A/zh
Priority to EP24823274.6A priority patent/EP4729550A1/en
Priority to JP2025527854A priority patent/JPWO2024257655A1/ja
Publication of WO2024257655A1 publication Critical patent/WO2024257655A1/ja
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    • 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
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/20—Incorporating sulfur atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/22—Incorporating nitrogen atoms into the molecule
    • 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

Definitions

  • the present invention relates to modified liquid diene polymers and rubber additives.
  • the objective of the present invention is therefore to provide a modified liquid diene polymer that, when added to a rubber composition, improves the dispersibility of other components and inhibits bleed-out.
  • the modified group represented by A modified liquid diene-based polymer in which the amount of structural units derived from butadiene is 20 to 100 mass % based on the total amount of the modified liquid diene-based polymer, and the amount of 1,2-bond units having a vinyl group based on the total amount of structural units derived from butadiene is 0 to 70 mol %.
  • a rubber additive comprising the modified liquid diene polymer according to any one of [1] to [6].
  • the rubber additive according to [7] further comprising at least one selected from the group consisting of a plasticizer, an antioxidant, a filler, and a colorant.
  • the present invention provides a modified liquid diene polymer that has the effect of improving the dispersibility of components in a rubber composition, such as plasticizers, antioxidants, fillers, colorants, etc., and also has the effect of suppressing bleed-out when added to a rubber composition.
  • FIG. 1 is a diagram showing images for evaluating dispersibility for Example 3 and Comparative Example 2.
  • the present invention relates to a modified liquid diene-based polymer containing a structural unit derived from butadiene, The weight average molecular weight is 4,000 to 150,000, Formula (I): [Wherein, R 1 represents an alkylene group having 1 to 10 carbon atoms or a phenylene group; R2 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms; * represents a bond.
  • the modified group represented by The amount of structural units derived from butadiene is 20 to 100 mass % based on the total amount of the modified liquid diene polymer, and the amount of 1,2-bond units having a vinyl group based on the total amount of structural units derived from butadiene is 0 to 70 mol %.
  • the modified liquid diene polymer of the present invention is a polymer that contains structural units derived from butadiene, is modified with a modifying group represented by formula (I), and is liquid at room temperature (25°C).
  • the amount of structural units derived from butadiene in the modified liquid diene polymer is 20 to 100% by mass relative to the total amount of the modified liquid diene polymer.
  • the amount of structural units derived from butadiene is preferably 30 to 100% by mass, more preferably 35 to 100% by mass, even more preferably 40 to 100% by mass, and even more preferably 50 to 100% by mass relative to the total amount of the modified liquid diene polymer.
  • the amount of structural units derived from butadiene can be calculated by 1 H-NMR or 13 C-NMR measurement, or from the amount of butadiene monomer in the monomer mixture used in producing the modified liquid diene-based polymer.
  • the structural unit derived from butadiene is not particularly limited as long as it is a structural unit derived from the monomer 1,3-butadiene.
  • Examples include 1,2-bond units, 1,4-bond units (cis-1,4-bond units and trans-1,4-bond units), and structural units in which a modifying group is bonded to these.
  • the 1,2-bond units, cis-1,4-bond units, and trans-1,4-bond units each have a vinyl group in the structural unit derived from butadiene.
  • examples of structural units in which a modifying group is bonded to these include structural units obtained by bonding a modifying group to a portion derived from the vinyl group in the 1,2-bond unit, and these structural units do not have a vinyl group.
  • the amount of 1,2-bond units having a vinyl group relative to the total amount of structural units derived from butadiene is 0 to 70 mol %.
  • the amount of 1,2-bond units having a vinyl group is 70 mol % or less, it is possible to prevent the viscosity of the modified liquid diene-based polymer from becoming too high, and to prevent a decrease in handleability.
  • the amount of 1,2-bond units having a vinyl group is preferably 5 to 70 mol %, more preferably 5 to 68 mol %.
  • 1,2-bond units having a vinyl group, 1,4-bond units, cis-1,4-bond units, and trans-1,4-bond units described below can be measured by 1 H-NMR and infrared absorption spectroscopy, respectively, and specifically can be measured by the method described in the Examples.
  • the structural unit derived from butadiene preferably includes a structural unit obtained by bonding a modifying group represented by formula (I) to a portion derived from a vinyl group in a 1,2-bond unit.
  • the amount of the structural unit is preferably 0.1 to 15 mol%, more preferably 1 to 10 mol%, and even more preferably 2 to 9 mol% based on the total amount of structural units derived from butadiene.
  • the amount of the structural unit can be calculated from the molecular weight of each monomer constituting the modified liquid diene polymer, the weight average molecular weight of the modified liquid diene polymer, the approximate value of the number of monomers constituting the modified liquid diene polymer, the approximate value of the number of each bond unit, and the average content of the modifying group determined as described above.
  • the amount of 1,4-bond units relative to the total amount of structural units derived from butadiene is preferably 30 to 100 mol%, more preferably 30 to 95 mol%, and even more preferably 32 to 95 mol%, based on the total amount of structural units derived from butadiene, from the viewpoints of handleability and manufacturability of the polymer having the modifying group represented by formula (I).
  • the amount of cis-1,4-bond units relative to the total amount of 1,4-bond units in the butadiene-derived structural units is preferably 20 to 60 mol %, more preferably 30 to 50 mol %.
  • the amount of trans-1,4-bond units relative to the total amount of 1,4-bond units in the structural units derived from butadiene is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and even more preferably 50 to 70 mol%.
  • the weight average molecular weight of the modified liquid diene polymer is 4,000 to 150,000. From the viewpoint of maintaining fluidity, the weight average molecular weight of the modified liquid diene polymer is preferably 4,000 to 140,000, more preferably 4,500 to 135,000, even more preferably 4,500 to 125,000, even more preferably 4,500 to 100,000, and particularly preferably 4,500 to 50,000. In the present invention, the weight average molecular weight of the liquid diene polymer is the weight average molecular weight in terms of polystyrene obtained by measurement using gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the weight average molecular weight of the liquid diene polymer When the weight average molecular weight of the liquid diene polymer is within the above range, it is in a liquid form at room temperature, making it easy to handle, excellent in processability during production, and good in economy.
  • the weight average molecular weight of the modified liquid diene polymer also affects the effect of suppressing bleed-out, and there is a tendency for bleed-out to be reduced when the weight average molecular weight is increased.
  • the weight average molecular weight of the modified liquid diene polymer may be adjusted to a desired range for various purposes required for the rubber composition.
  • the modified liquid diene polymer of the present invention can reduce bleed-out compared to an unmodified liquid diene polymer having a similar weight average molecular weight.
  • the number average molecular weight of the modified liquid diene polymer is preferably 200 to 150,000, more preferably 900 to 135,000, even more preferably 2,000 to 125,000, even more preferably 2,600 to 100,000, particularly preferably 2,600 to 50,000, and especially preferably 3,800 to 50,000, from the viewpoint of handleability such as threading.
  • the number average molecular weight of the liquid diene polymer can also be measured by gel permeation chromatography (GPC).
  • the molecular weight distribution (Mw/Mn) of the modified liquid diene polymer is preferably 1.0 to 20.0, more preferably 1.0 to 15.0, even more preferably 1.0 to 10.0, even more preferably 1.0 to 5.0, particularly preferably 1.0 to 2.0, particularly preferably 1.0 to 1.5, and most preferably 1.0 to 1.3. If Mw/Mn is within the above range, the viscosity of the resulting modified liquid diene polymer will vary less, which is more preferable.
  • the molecular weight distribution (Mw/Mn) refers to the ratio of the weight average molecular weight (Mw)/number average molecular weight (Mn) calculated in terms of standard polystyrene, determined by GPC measurement.
  • the modified liquid diene-based polymer has the formula (I): [Wherein, R 1 represents an alkylene group having 1 to 10 carbon atoms or a phenylene group; R2 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms; * represents a bond.
  • the modified liquid diene polymer has a modifying group represented by the formula (I).
  • the modifying group is hereinafter also referred to as a modifying group (I).
  • the modified liquid diene polymer may be modified with one type of modifying group represented by the formula (I), or may be modified with two or more types of modifying groups represented by the formula (I).
  • R 1 represents an alkylene group having 1 to 10 carbon atoms or a phenylene group.
  • alkylene groups having 1 to 10 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene.
  • the alkylene group may be linear or branched.
  • the alkylene group preferably has 1 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms.
  • the phenylene group is a divalent group having two bonds on the phenyl ring, and the two bonds may be in the ortho, meta, or para position.
  • the phenylene group may be a group in which at least one hydrogen atom bonded to a carbon atom on the phenyl ring is substituted with an alkyl group having 1 to 4 carbon atoms.
  • R 1 in formula (I) is preferably an alkylene group having 2 to 6 carbon atoms.
  • R2 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.
  • the alkyl group having 1 to 2 carbon atoms is a methyl group or an ethyl group.
  • R2 in formula (I) is preferably a hydrogen atom from the viewpoint of the interaction or reactivity between the additive such as a filler and the modified liquid diene-based polymer.
  • the * in formula (I) represents a bond.
  • the bond is preferably bonded to a structural unit derived from butadiene in the modified liquid diene polymer, more preferably to a portion derived from the vinyl group of the 1,4-bond unit or a portion derived from the vinyl group of the 1,2-bond unit, even more preferably to a portion derived from the vinyl group of the 1,2-bond unit, and even more preferably to a portion derived from the side chain vinyl group of the 1,2-bond unit. Therefore, the modifying group represented by formula (I) is preferably contained in the side chain of the diene polymer.
  • the structure of the modifying group represented by formula (I) can be analyzed, for example, by structural analysis of the resulting polymer using NMR analysis, or from the structure of the modifying compound used in synthesizing the polymer.
  • the average content of the modifying group represented by formula (I) per molecule of the modified liquid diene polymer is preferably 0.5 to 10, more preferably 0.5 to 7, even more preferably 0.5 to 5, still more preferably 1 to 5, and particularly preferably 1 to 4.5, from the viewpoints of suppressing bleed-out of the modified liquid diene polymer and the like, improving affinity with additives such as fillers, and improving dispersibility of the additives.
  • the average content of the modifying group represented by formula (I) can be determined by 1 H-NMR.
  • the amount of structural units derived from butadiene in the modified liquid diene polymer is 20 to 100% by mass based on the total amount of the modified liquid diene polymer.
  • the modified liquid diene polymer may be a homopolymer of butadiene, or a copolymer with other monomers that can be copolymerized with butadiene, such as conjugated diene monomers other than butadiene, aromatic vinyl compounds, etc.
  • the modified liquid diene polymer may have only structural units derived from butadiene, or may have structural units derived from conjugated diene monomers other than butadiene, structural units derived from aromatic vinyl compounds, etc. in addition to the structural units derived from butadiene.
  • Conjugated diene monomers other than butadiene include, for example, isoprene and ⁇ -farnesene, preferably at least one selected from the group consisting of isoprene and ⁇ -farnesene, and more preferably isoprene.
  • An example of an aromatic vinyl compound is styrene.
  • the amount of structural units derived from conjugated diene monomers other than butadiene, such as isoprene is preferably 0 to 80% by mass, more preferably 0 to 65% by mass, and even more preferably 0 to 50% by mass, based on the total amount of the modified liquid diene polymer.
  • the total amount of structural units derived from butadiene and structural units derived from conjugated diene monomers other than butadiene in the modified liquid diene polymer is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass, based on the total amount of the modified liquid diene polymer.
  • the modified liquid diene polymer is a copolymer of butadiene and another monomer that can be copolymerized with butadiene
  • the copolymer may be a random copolymer or a block copolymer.
  • the modified liquid diene polymer preferably does not have a hydroxyl group at its terminal. Whether or not the polymer has a hydroxyl group at its terminal can be confirmed by the neutralization titration method of the hydroxyl value according to JIS K 0070-1992, infrared absorption spectrum (IR), or 1H -NMR.
  • the modified liquid diene polymer as described above has the effect of improving the dispersibility of additives such as fillers and has the effect of suppressing bleed-out when added to a rubber composition, so it is possible to sufficiently disperse additives such as fillers while maintaining the stability of the rubber composition. Therefore, it can be suitably blended into any rubber composition containing a dispersion of fillers, etc. Therefore, the modified liquid diene polymer of the present invention is preferably used as a rubber additive.
  • the method for producing the modified liquid diene polymer is not particularly limited. For example, it is preferable to produce an unmodified liquid diene polymer by polymerizing butadiene and other monomers copolymerizable with butadiene, which are included as necessary, by, for example, a solution polymerization method, and then reacting the unmodified liquid polymer with a modifying compound to produce the modified liquid diene polymer.
  • a monomer containing butadiene is polymerized in a solvent using a Ziegler catalyst, a metallocene catalyst, or an anionically polymerizable active metal or active metal compound, if necessary in the presence of a polar compound.
  • Solvents include, for example, aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; and aromatic hydrocarbons such as benzene, toluene, and xylene.
  • aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane
  • alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane
  • aromatic hydrocarbons such as benzene, toluene, and xylene.
  • active metals capable of anion polymerization include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium; and lanthanoid rare earth metals such as lanthanum and neodymium.
  • alkali metals and alkaline earth metals are preferred, and alkali metals are more preferred.
  • an organic alkali metal compound is preferred.
  • the organic alkali metal compound include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium; polyfunctional organic lithium compounds such as dilithiomethane, dilithionaphthalene, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene, and the like.
  • organic lithium compounds are preferred, and organic monolithium compounds are more preferred.
  • the amount of organic alkali metal compound used can be set appropriately depending on the desired melt viscosity, molecular weight, etc. of the modified liquid diene polymer, but it is usually used in an amount of 0.01 to 3 parts by mass per 100 parts by mass of total monomers.
  • organic alkali metal compounds can also be reacted with secondary amines such as dibutylamine, dihexylamine, and dibenzylamine to be used as organic alkali metal amides.
  • secondary amines such as dibutylamine, dihexylamine, and dibenzylamine
  • polar compounds are usually used to adjust the microstructure (e.g., vinyl content) of the unmodified liquid diene polymer without deactivating the reaction.
  • polar compounds include ether compounds such as dibutyl ether, tetrahydrofuran, and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides, and phosphine compounds.
  • Polar compounds are usually used in an amount of 0.01 to 1,000 moles per mole of the organic alkali metal compound.
  • the temperature for solution polymerization is usually in the range of -80 to 150°C, preferably in the range of 0 to 100°C, and more preferably in the range of 10 to 90°C.
  • the polymerization method may be either batch or continuous.
  • the polymerization reaction can be stopped by adding a polymerization terminator.
  • polymerization terminators include alcohols such as methanol and isopropanol.
  • the resulting polymerization reaction liquid can be poured into a poor solvent such as methanol to precipitate the unmodified liquid diene polymer, or the polymerization reaction liquid can be washed with water, separated, and then dried to isolate the unmodified liquid diene polymer.
  • the unmodified liquid diene polymer thus obtained may be modified by reacting it as it is (without hydrogenation) with a compound that provides the functional group represented by formula (I), or it may be modified by reacting it with a compound that provides the functional group represented by formula (I) after hydrogenating at least a portion of the unsaturated bonds contained in the unmodified liquid diene polymer thus obtained.
  • the unmodified liquid diene polymer is not modified with a functional group such as a hydroxyl group.
  • a functional group such as a hydroxyl group.
  • the stability of the resulting modified liquid diene polymer tends to be superior.
  • the interaction (e.g., reactivity) of the functional group represented by formula (I) contained in the modified liquid diene polymer with a filler (e.g., silica) tends to be superior.
  • the unmodified liquid diene-based polymer may be, for example, a compound represented by the formula (II): [ R1 and R2 in formula (II) are the same as R1 and R2 in formula (I), respectively]
  • a modified liquid diene polymer modified with a modifying group represented by the above formula (I) can be produced by reacting the unmodified liquid diene polymer with one type of compound (II) or two or more types of compound (II).
  • the mercapto group (-SH) of compound (II) undergoes a radical addition reaction with the carbon-carbon unsaturated bond contained in the unmodified liquid diene polymer, thereby introducing the functional group represented by the above formula (I) into the polymer.
  • this radical addition reaction it is presumed that the radical addition reaction occurs preferentially with the carbon-carbon unsaturated bond in the side chain contained in the butadiene unit having a 1,2-bond in the unmodified liquid diene polymer.
  • R1 and R2 in the above formula (II) are the same as the definitions and specific examples of R1 and R2 in the above formula (I).
  • Specific compounds represented by the above formula (II) include 2-aminoethanethiol, 2-methylaminoethanethiol, 2-ethylaminoethanethiol, 2-dimethylaminoethanethiol, 2-diethylaminoethanethiol, p-aminothiophenol, p-methylaminothiophenol, and p-dimethylaminothiophenol.
  • the method of adding the compound represented by formula (II) to the unmodified liquid diene polymer is not particularly limited, and for example, a method can be adopted in which the compound represented by formula (II) and, if necessary, a radical catalyst are added to the unmodified liquid diene polymer, and the mixture is heated in the presence or absence of an organic solvent.
  • a radical catalyst there is no particular limit to the radical generator used, and commercially available organic peroxides, azo compounds, hydrogen peroxide, etc. can be used.
  • organic peroxides include, for example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, and 2,2-bis(t-butylperoxy).
  • the above azo compounds include, for example, 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis(2-(2-imidazolin-2-yl)propane), 2,2' -Azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), 2,2'-azobis(2-hydroxymethylpropiononitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl 2,2'-azobis(2-methylpropionate), 2-cyano-2-propylazoformamide, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, etc.
  • the organic solvents used in the above method generally include hydrocarbon solvents and halogenated hydrocarbon solvents.
  • hydrocarbon solvents such as n-butane, n-hexane, n-heptane, cyclohexane, benzene, toluene, and xylene are preferred.
  • an anti-aging agent may be added to suppress side reactions.
  • Preferred antioxidants for use in this case include, for example, 2,6-di-t-butyl-4-methylphenol (BHT), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol) (AO-40), 3,9-bis[1,1-dimethyl-2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (AO-80), 2,4-bis[(octylthio)methyl]-6-methylphenol (Irganox 1520L), 2,4-bis[(dodecylthio)methyl]-6-methylphenol (Irganox 1726), 2-[1-(2-hydroxy-3,5-di-t-pentylpheny
  • the amount of antioxidant added is preferably 0 to 10 parts by mass, and more preferably 0 to 5 parts by mass, per 100 parts by mass of unmodified liquid diene polymer.
  • the position at which the functional group is introduced may be the end of the polymer chain or a side chain of the polymer chain, but from the viewpoint of easily introducing multiple functional groups, a side chain of the polymer chain is preferable.
  • the functional group may be contained alone or in combination with two or more types.
  • the modified liquid diene polymer may be modified with one type of modifying compound, or may be modified with two or more types of modifying compounds.
  • the mixing ratio of the unmodified liquid diene polymer and the modified compound may be appropriately set so that the average number of functional groups per molecule of the modified liquid diene polymer is the desired value, but it is preferable to mix the unmodified liquid diene polymer and the modified compound (e.g., compound (II)) so that the mass ratio (unmodified liquid diene polymer/modified compound) is 0.3 to 50.
  • the modified compound e.g., compound (II)
  • a method for producing a modified liquid diene polymer having specific properties it is effective to carry out a radical addition reaction of a modified compound (e.g., compound (II)) at an appropriate reaction temperature for a sufficient reaction time.
  • a modified compound e.g., compound (II)
  • the temperature in the reaction of adding a modified compound to an unmodified liquid diene polymer is preferably 10 to 200°C, more preferably 50°C to 180°C.
  • the reaction time is preferably 1 to 200 hours, more preferably 1 to 100 hours, and even more preferably 1 to 50 hours.
  • the modified liquid diene polymer is used in a rubber additive.
  • the present invention also provides a rubber additive containing the modified liquid diene polymer.
  • the rubber additive may contain only the modified liquid diene polymer, or may contain the modified liquid diene polymer and other additives.
  • the other additives are not particularly limited, but may be, for example, plasticizers, antioxidants, fillers, colorants, etc.
  • the rubber additive contains only a modified liquid diene polymer, or contains a modified liquid diene polymer and further contains at least one selected from the group consisting of a plasticizer, an antioxidant, a filler, and a colorant.
  • the amount of modified liquid diene polymer contained in the rubber additive is not particularly limited, but may be, for example, 50-100 mass%, 70-100 mass%, 80-100 mass%, 90-100 mass%, etc., based on the total amount of the rubber additive.
  • the amount of modified liquid diene polymer may be 50-99 mass%, 70-97 mass%, 80-95 mass%, etc., based on the total amount of the rubber additive.
  • a rubber additive is an additive that is added to a rubber component when used.
  • An example of a rubber component is solid rubber. Therefore, the rubber additive of the present invention is preferably a solid rubber additive. Furthermore, from the viewpoint of obtaining an effect of improving the dispersibility of fillers and the like, the rubber additive is preferably used together with a filler.
  • the filler may be, for example, inorganic fillers such as carbon black, silica, clay, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium oxide, glass fiber, fibrous filler, glass balloons, etc.; organic fillers such as resin particles, wood powder, and cork powder.
  • inorganic fillers such as carbon black, silica, clay, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium oxide, glass fiber, fibrous filler, glass balloons, etc.
  • organic fillers such as resin particles, wood powder, and cork powder.
  • the filler content per 100 parts by mass of solid rubber is preferably 0.5 to 200 parts by mass, more preferably 20 to 180 parts by mass, even more preferably 25 to 150 parts by mass, and even more preferably 30 to 150 parts by mass. If the filler content is within the above range, processability, rolling resistance performance, mechanical strength, and abrasion resistance are improved.
  • carbon black examples include furnace black, channel black, thermal black, acetylene black, and ketjen black.
  • furnace black is preferred from the viewpoint of improving the crosslinking rate and mechanical strength.
  • carbon blacks may be used alone or in combination of two or more types.
  • the average particle size of carbon black is preferably 5 to 100 nm, more preferably 5 to 80 nm, even more preferably 5 to 70 nm, and even more preferably 5 to 25 nm, from the viewpoint of improving dispersibility, mechanical strength, hardness, etc.
  • the average particle size of carbon black can be determined by measuring the particle diameter using a transmission electron microscope and calculating the average value.
  • furnace black products include, for example, "Diablack” manufactured by Mitsubishi Chemical Corporation and “Seat” manufactured by Tokai Carbon Co., Ltd.
  • acetylene black products include, for example, “Denka Black” manufactured by Denki Kagaku Kogyo Co., Ltd.
  • ketjen black products include, for example, "ECP600JD” manufactured by Lion Corporation.
  • carbon black may be subjected to an acid treatment using nitric acid, sulfuric acid, hydrochloric acid or a mixture of these acids, or a surface oxidation treatment using a heat treatment in the presence of air.
  • the carbon black may be subjected to a heat treatment at 2,000 to 3,000° C. in the presence of a graphitization catalyst.
  • boron As the graphitization catalyst, boron, boron oxides (e.g., B 2 O 2 , B 2 O 3 , B 4 O 3 , B 4 O 5 , etc.), boron oxoacids (e.g., orthoboric acid, metaboric acid, tetraboric acid, etc.) and salts thereof, boron carbides (e.g., B 4 C, B 6 C, etc.), boron nitride (BN), and other boron compounds are preferably used.
  • boron carbides e.g., B 4 C, B 6 C, etc.
  • BN boron nitride
  • Carbon black can also be used after adjusting the particle size by grinding or other methods.
  • High-speed rotary grinders hammer mills, pin mills, cage mills), various ball mills (rolling mills, vibrating mills, planetary mills), stirring mills (bead mills, attritors, flow-tube mills, annular mills), etc. can be used to grind carbon black.
  • silica examples include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and aluminum silicate.
  • wet silica is preferred from the viewpoint of further improving processability, mechanical strength, and abrasion resistance.
  • These silicas may be used alone or in combination of two or more types.
  • the average particle size of silica is preferably 0.5 to 200 nm, more preferably 5 to 150 nm, even more preferably 10 to 100 nm, and even more preferably 10 to 50 nm.
  • the average particle size of silica can be determined by measuring the diameter of the particles using a transmission electron microscope and calculating the average value.
  • the average particle size of the aluminum hydroxide is preferably 5 to 20 nm, more preferably 5 to 15 nm, and even more preferably 5 to 10 nm.
  • Resin microbeads are preferably added as a foaming agent.
  • the average particle size of the resin microbeads is preferably 10 to 100 ⁇ m, and even more preferably 15 to 90 ⁇ m.
  • a rubber composition According to the present invention, a rubber composition can be obtained which contains at least the modified liquid diene-based polymer of the present invention and a rubber component (preferably a solid rubber).
  • Solid rubber (A) refers to rubber that can be handled in a solid state at 20°C.
  • the Mooney viscosity ML(1+4) of solid rubber (A) at 100°C is usually 20 to 200.
  • solid rubber (A) include natural rubber, styrene butadiene rubber (hereinafter also referred to as "SBR"), butadiene rubber, isoprene rubber, butyl rubber, halogenated butyl rubber, ethylene propylene diene rubber, butadiene acrylonitrile copolymer rubber, chloroprene rubber, acrylic rubber, fluororubber, and urethane rubber.
  • SBR styrene butadiene rubber
  • SBR styrene butadiene rubber
  • isoprene rubber butyl rubber
  • halogenated butyl rubber ethylene propylene diene rubber
  • butadiene acrylonitrile copolymer rubber chloroprene rubber
  • acrylic rubber fluor
  • the number average molecular weight (Mn) of the solid rubber (A) is preferably 80,000 or more, and more preferably within the range of 100,000 to 3,000,000, from the viewpoint of fully exhibiting the properties of the resulting rubber composition and crosslinked product.
  • the number average molecular weight in this specification is the number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
  • natural rubber examples include TSR (Technically Specified Rubber) such as SMR (TSR produced in Malaysia), SIR (TSR produced in Indonesia), and STR (TSR produced in Thailand), as well as natural rubber commonly used in the tire industry, such as RSS (Ribbed Smoked Sheet), high-purity natural rubber, epoxidized natural rubber, hydroxylated natural rubber, hydrogenated natural rubber, and modified natural rubber such as grafted natural rubber.
  • TSR Technically Specified Rubber
  • SMR Technically Specified Rubber
  • SIR SIR
  • STR TSR produced in Thailand
  • RSS Rabbed Smoked Sheet
  • high-purity natural rubber high-purity natural rubber
  • epoxidized natural rubber epoxidized natural rubber
  • hydroxylated natural rubber hydroxylated natural rubber
  • hydrogenated natural rubber and modified natural rubber
  • modified natural rubber such as grafted natural rubber.
  • SMR20, STR20, and RSS#3 are preferred in terms of less variation in quality and ease of availability.
  • the SBR a typical SBR used for tires can be used.
  • the styrene content is preferably 0.1 to 70 mass%, more preferably 5 to 50 mass%, and even more preferably 15 to 35 mass%.
  • the vinyl content is preferably 0.1 to 60 mass%, and more preferably 0.1 to 55 mass%.
  • the "vinyl content" in the SBR means the proportion of 1,2-bonds contained in the butadiene structural unit, and can be determined by 1 H-NMR measurement.
  • the weight average molecular weight (Mw) of SBR is preferably 100,000 to 2,500,000, more preferably 150,000 to 2,000,000, and even more preferably 200,000 to 1,500,000. Within the above range, both processability and mechanical strength can be achieved. Note that the weight average molecular weight in this specification is the polystyrene-equivalent weight average molecular weight determined by gel permeation chromatography (GPC) measurement.
  • the glass transition temperature of SBR determined by differential thermal analysis is preferably -95 to 0°C, and more preferably -95 to -5°C. By setting the glass transition temperature within the above range, the viscosity of the SBR can be set within a range that is easy to handle.
  • SBR is obtained by copolymerizing styrene and butadiene.
  • the manufacturing method of SBR there are no particular limitations on the manufacturing method of SBR, and any of the emulsion polymerization method, solution polymerization method, gas phase polymerization method, and bulk polymerization method can be used, but among these manufacturing methods, the emulsion polymerization method and solution polymerization method are preferred.
  • Emulsion-polymerized styrene butadiene rubber (hereinafter also referred to as E-SBR) can be produced by a known or similar normal emulsion polymerization method. For example, it can be obtained by emulsifying and dispersing a given amount of styrene and butadiene monomers in the presence of an emulsifier, and then emulsion-polymerizing them with a radical polymerization initiator.
  • Solution-polymerized styrene-butadiene rubber (hereinafter also referred to as S-SBR) can be produced by a conventional solution polymerization method. For example, it can be obtained by polymerizing styrene and butadiene using an active metal capable of anionically polymerizing in a solvent, optionally in the presence of a polar compound.
  • Solvents include, for example, aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; and aromatic hydrocarbons such as benzene and toluene. These solvents are usually preferably used in a range in which the monomer concentration is 1 to 50% by mass.
  • active metals capable of anion polymerization include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium; and lanthanoid rare earth metals such as lanthanum and neodymium.
  • alkali metals and alkaline earth metals are preferred, and alkali metals are more preferred.
  • organic alkali metal compounds are more preferably used.
  • the organic alkali metal compounds include, for example, organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium; polyfunctional organic lithium compounds such as dilithiomethane, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene, and the like.
  • organic lithium compounds are preferred, and organic monolithium compounds are more preferred.
  • the amount of the organic alkali metal compound used is determined appropriately according to the molecular weight of the required S-SBR.
  • the organic alkali metal compounds can also be used as organic alkali metal amides by reacting them with secondary amines such as dibutylamine, dihexylamine, and dibenzylamine.
  • the polar compound there are no particular limitations on the polar compound, so long as it is one that is normally used in anionic polymerization to adjust the microstructure of the butadiene moiety and the distribution of styrene in the copolymer chain without inactivating the reaction.
  • examples include ether compounds such as dibutyl ether, tetrahydrofuran, and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides, and phosphine compounds.
  • the temperature of the polymerization reaction is usually in the range of -80 to 150°C, preferably 0 to 100°C, and more preferably 30 to 90°C.
  • the polymerization method may be either batchwise or continuous. In order to improve the random copolymerization of styrene and butadiene, it is preferable to continuously or intermittently supply styrene and butadiene to the reaction liquid so that the composition ratio of styrene and butadiene in the polymerization system is within a specific range.
  • the polymerization reaction can be stopped by adding an alcohol such as methanol or isopropanol as a polymerization terminator. After the polymerization reaction has been stopped, the solvent can be separated from the polymerization solution by direct drying or steam stripping, and the desired S-SBR can be recovered. Note that the polymerization solution can also be mixed with an extender oil before removing the solvent, and the resulting product can be recovered as oil-extended rubber.
  • an alcohol such as methanol or isopropanol
  • the solvent can be separated from the polymerization solution by direct drying or steam stripping, and the desired S-SBR can be recovered. Note that the polymerization solution can also be mixed with an extender oil before removing the solvent, and the resulting product can be recovered as oil-extended rubber.
  • modified SBR in which functional groups have been introduced may be used as long as the effects of the present invention are not impaired.
  • functional groups include amino groups, alkoxysilyl groups, hydroxyl groups, epoxy groups, and carboxyl groups.
  • a method for producing modified SBR includes, for example, a method of adding a coupling agent such as tin tetrachloride, tetrachlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, or 2,4-tolylenediisocyanate that can react with the polymerization active terminals, or a polymerization terminal modifier such as 4,4'-bis(diethylamino)benzophenone or N-vinylpyrrolidone, or other modifiers described in JP 2011-132298 A, before adding a polymerization terminator.
  • the position of the polymer where the functional group is introduced may be the polymerization terminal or a side chain of the polymer chain.
  • butadiene rubber for example, commercially available butadiene rubber polymerized using Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel; lanthanoid rare earth metal catalysts such as triethylaluminum-organic acid neodymium-Lewis acid; or organic alkali metal compounds as with S-SBR can be used.
  • Butadiene rubber polymerized using Ziegler catalysts has a high cis content and is therefore preferred.
  • butadiene rubber with an ultra-high cis content obtained using a lanthanoid rare earth metal catalyst may be used.
  • the vinyl content of the butadiene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
  • the glass transition temperature varies depending on the vinyl content, but is preferably -40°C or less, and more preferably -50°C or less.
  • the weight average molecular weight (Mw) of the butadiene rubber is preferably 90,000 to 2,000,000, and more preferably 150,000 to 1,500,000. When Mw is within the above range, the processability and mechanical strength are good.
  • the butadiene rubber may have a branched structure or polar functional groups by using a polyfunctional modifier, such as tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in the molecule, or an alkoxysilane containing an amino group.
  • a polyfunctional modifier such as tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in the molecule, or an alkoxysilane containing an amino group.
  • isoprene rubber for example, commercially available isoprene rubber polymerized using Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel; lanthanoid rare earth metal catalysts such as triethylaluminum-organic acid neodymium-Lewis acid; or organic alkali metal compounds as with S-SBR can be used.
  • Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel
  • lanthanoid rare earth metal catalysts such as triethylaluminum-organic acid neodymium-Lewis acid
  • the vinyl content of the isoprene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
  • the glass transition temperature varies depending on the vinyl content, but is preferably -20°C or less, and more preferably -30°C or less.
  • the weight average molecular weight (Mw) of isoprene rubber is preferably 90,000 to 2,000,000, and more preferably 150,000 to 1,500,000. When Mw is within the above range, the processability and mechanical strength are good.
  • the isoprene rubber may have a branched structure or polar functional groups by using a polyfunctional modifier, such as tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in the molecule, or an alkoxysilane containing an amino group.
  • a polyfunctional modifier such as tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in the molecule, or an alkoxysilane containing an amino group.
  • the content of the modified liquid diene polymer (B) relative to 100 parts by mass of the solid rubber (A) is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 45 parts by mass, even more preferably 0.5 to 40 parts by mass, particularly preferably 1 to 40 parts by mass, particularly more preferably 2 to 40 parts by mass, extremely preferably 3 to 35 parts by mass, and extremely more preferably 5 to 30 parts by mass.
  • the content of the modified liquid diene polymer (B) is within the above range, the dispersion state of other components in the rubber composition, particularly the filler (C), becomes ideal, and the rigidity of the obtained composition and crosslinked product is improved.
  • the grip performance (wet grip performance and/or ice grip performance) is improved, thereby improving the steering stability.
  • the rolling resistance performance is also good.
  • the content of the modified liquid diene-based polymer (B) per 100 parts by mass of the solid rubber (A) is preferably 5 to 25 parts by mass, more preferably 5 to 20 parts by mass, and even more preferably 10 to 20 parts by mass.
  • the content of the solid rubber (A) is preferably 20 to 90 mass %, more preferably 25 to 85 mass %, and even more preferably 30 to 80 mass %, based on the total amount of the rubber composition.
  • the content of the solid rubber (A) is within the above range, the rubber composition has a good balance between gripping properties and abrasion resistance.
  • the rubber composition includes a filler.
  • the filler (C) include the fillers described above, such as carbon black and/or silica.
  • the filler (C) contains carbon black and/or silica, and it is more preferable that the filler contains silica.
  • the content of the filler (C) relative to 100 parts by mass of the solid rubber (A) is preferably 0.5 to 200 parts by mass, more preferably 20 to 180 parts by mass, even more preferably 25 to 150 parts by mass, and even more preferably 30 to 150 parts by mass.
  • the content of the filler (C) is within the above range, the processability, rolling resistance performance, mechanical strength, and abrasion resistance are improved.
  • the content of the filler (C) is preferably 33 to 140 parts by mass, more preferably 35 to 130 parts by mass, even more preferably 40 to 120 parts by mass, even more preferably 50 to 110 parts by mass, and extremely preferably 60 to 100 parts by mass.
  • the amount of filler other than silica and carbon black in filler (C) is not particularly limited, but may be, for example, 0 to 120 parts by mass, preferably 0 to 90 parts by mass, more preferably 0 to 80 parts by mass, and even more preferably 0 to 70 parts by mass, per 100 parts by mass of solid rubber (A).
  • the total mass of the solid rubber (A), modified liquid diene-based polymer (B), and filler (C) contained in the rubber composition according to a preferred embodiment of the present invention is preferably 10 to 100 mass%, more preferably 15 to 100 mass%, based on the total amount of the rubber composition.
  • the rubber composition according to a preferred embodiment of the present invention may further contain a crosslinking agent (D) to crosslink the rubber.
  • a crosslinking agent (D) include sulfur, sulfur compounds, oxygen, organic peroxides, phenolic resins, amino resins, quinones and quinone dioxime derivatives, halogen compounds, aldehyde compounds, alcohol compounds, epoxy compounds, metal halides and organometallic halides, and silane compounds.
  • the sulfur compounds include morpholine disulfide and alkylphenol disulfides.
  • organic peroxides examples include cyclohexanone peroxide, methyl acetoacetate peroxide, t-butyl peroxyisobutyrate, t-butyl peroxybenzoate, benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, di-t-butyl peroxide, and 1,3-bis(t-butylperoxyisopropyl)benzene.
  • crosslinking agents (D) may be used alone or in combination of two or more.
  • the rubber composition may further contain a vulcanization accelerator (E).
  • a vulcanization accelerator (E) examples include guanidine compounds, sulfenamide compounds, thiazole compounds, thiuram compounds, thiourea compounds, dithiocarbamic acid compounds, aldehyde-amine compounds, aldehyde-ammonia compounds, imidazoline compounds, and xanthate compounds. These vulcanization accelerators (E) may be used alone or in combination of two or more.
  • the vulcanization accelerator (E) is preferably contained in an amount of 0.1 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the solid rubber (A).
  • the rubber composition may further contain a vulcanization aid (F).
  • a vulcanization aid examples include fatty acids such as stearic acid, metal oxides such as zinc oxide, and fatty acid metal salts such as zinc stearate. These vulcanization aids (F) may be used alone or in combination of two or more types.
  • the amount of the vulcanization aid (F) is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the solid rubber (A).
  • the rubber composition contains silica as the filler (C)
  • the rubber composition further contains a silane coupling agent.
  • silane coupling agents include sulfide compounds, mercapto compounds, vinyl compounds, amino compounds, glycidoxy compounds, nitro compounds, and chloro compounds.
  • Sulfide compounds include, for example, bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-trimethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, and 3-trimethoxysilylpropyl-N,N-dimethylsilyl.
  • thiocarbamoyl tetrasulfide 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazole tetrasulfide, 3-triethoxysilylpropyl benzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, and 3-octanoylthio-1-propyltriethoxysilane.
  • Examples of mercapto compounds include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane.
  • vinyl compounds examples include vinyltriethoxysilane and vinyltrimethoxysilane.
  • amino compounds include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane.
  • glycidoxy compounds include gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, and gamma-glycidoxypropylmethyldimethoxysilane.
  • nitro compounds include 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane.
  • chloro-based compounds examples include 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, and 2-chloroethyltriethoxysilane.
  • Other compounds include, for example, octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, and hexadecyltrimethoxysilane.
  • silane coupling agents may be used alone or in combination of two or more.
  • silane coupling agents bis(3-triethoxysilylpropyl) disulfide, bis(3-triethoxysilylpropyl) tetrasulfide, and 3-mercaptopropyltrimethoxysilane are preferred from the viewpoints of the large additive effect and cost.
  • the amount of the silane coupling agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass, per 100 parts by mass of silica. If the content of the silane coupling agent is within the above range, dispersibility, coupling effect, reinforcement, and abrasion resistance are improved.
  • the rubber composition according to a preferred embodiment of the present invention contains at least one resin.
  • the resin may be a synthetic resin or a natural resin. These resins may be used alone or in combination of two or more types.
  • Synthetic resins include petroleum-based resins, and oligomers obtained by polymerizing raw materials consisting of C5 fractions, C9 fractions, refined components of C5 fractions, refined components of C9 fractions, or mixtures of these fractions or refined components can be used. Oligomers obtained in this manner that have been modified by hydrogenation or the like can also be used.
  • C5 fractions include cyclopentadiene, dicyclopentadiene, isoprene, 1,3-pentadiene, 2-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, and cyclopentene.
  • C9 fractions include styrene, allylbenzene, ⁇ -methylstyrene, vinyltoluene, ⁇ -methylstyrene, and indene.
  • alkylphenol resins and xylene resins can also be used.
  • a rosin-based resin or a terpene-based resin can be used as the natural resin.
  • the rosin-based resin is a resin obtained from pine trees, and the main component is a mixture of abietic acid and its isomers. It also includes those modified by esterification, polymerization, hydrogenation, etc. Examples of unmodified rosin-based resins include tall rosin, gum rosin, and wood rosin. It also includes polymerized rosin, disproportionated rosin, hydrogenated rosin, maleic acid-modified rosin, fumaric acid-modified rosin, and those modified by esterification, hydrogenation, etc.
  • the terpene-based resin is an oligomer obtained by polymerizing a raw material containing a terpene-based monomer. It also includes oligomers modified by hydrogenation, etc. of this oligomer.
  • the terpene monomer include ⁇ -pinene, ⁇ -pinene, dipentene, limonene, myrcene, alloocimene, ocimene, ⁇ -phellandrein, ⁇ -terpinene, ⁇ -terpinene, terpinolene, 1,8-cineole, 1,4-cineole, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol, sabinene, paramentadienes, carenes, etc., which have a monoterpene, sesquiterpene, diterpene, etc., skeleton.
  • coumarone monomers such as benzofuran (C 8 H 6 O), vinyl aromatic compounds, phenol monomers, etc., which are copolymerizable with the terpene monomer, may be included, and the resulting oligomers may also be modified by hydrogenation or the like.
  • the amount of resin in the rubber composition is preferably 0 to 400 parts by mass, more preferably 0 to 200 parts by mass, and even more preferably 0 to 150 parts by mass, per 100 parts by mass of solid rubber.
  • the rubber composition contains a resin, it is possible to impart adhesion to the rubber composition, improve processability, and improve the slipperiness of the rubber.
  • the rubber composition may contain silicone oil, aromatic oil, TDAE (Treated Distilled Aromatic Extracts), MES (Mild Extracted Solvates), RAE (Residual Aromatic Extracts), process oils such as paraffin oil and naphthene oil, and resin components such as coumarone-indene resins as softeners as necessary for the purpose of improving processability, fluidity, etc., within the scope of not impairing the effects of the present invention.
  • the rubber composition contains the above process oil as a softener, the content is preferably less than 50 parts by mass per 100 parts by mass of the solid rubber (A).
  • the rubber composition may contain additives such as antiaging agents, waxes, antioxidants, lubricants, light stabilizers, scorch inhibitors, processing aids, colorants such as pigments and dyes, flame retardants, antistatic agents, matting agents, antiblocking agents, UV absorbers, release agents, foaming agents, antibacterial agents, antifungal agents, and fragrances, as necessary, to improve weather resistance, heat resistance, oxidation resistance, and the like, within a range that does not impair the effects of the present invention.
  • antioxidants include hindered phenol compounds, phosphorus compounds, lactone compounds, and hydroxyl compounds.
  • antiaging agents include amine-ketone compounds, imidazole compounds, amine compounds, phenol compounds, sulfur compounds, and phosphorus compounds. These additives may be used alone or in combination of two or more.
  • the method for producing the rubber composition is not particularly limited as long as the above-mentioned components can be mixed uniformly.
  • Examples of the apparatus used for producing the rubber composition include tangential or intermeshing internal mixers such as kneader-ruder, Brabender, Banbury mixer, and internal mixer, single screw extruder, twin screw extruder, mixing roll, and roller.
  • the rubber composition can usually be produced at a temperature range of 70 to 270°C.
  • a crosslinked product can be obtained by crosslinking the above rubber composition.
  • the crosslinking conditions of the rubber composition can be appropriately set depending on the application, etc. For example, when sulfur or a sulfur compound is used as a crosslinking agent and the rubber composition is placed in a mold and heated to crosslink (vulcanize), the crosslinking temperature is usually 120 to 200°C and the pressure condition is usually 0.5 to 2.0 MPa, and crosslinking (vulcanization) can be performed.
  • the rubber composition and the crosslinked product of the rubber composition can also be used as at least a part of a tire.
  • the tire obtained in this manner has excellent rolling resistance and good abrasion resistance because the dispersion state of other components such as the filler (C) is ideal (for example, the Payne effect is sufficiently reduced).
  • a tire obtained from the rubber composition as described above also has excellent grip properties (wet grip properties and/or ice grip properties). Furthermore, bleeding out of the modified liquid diene polymer is suppressed, and the tire has excellent stability.
  • tire parts in which the above rubber composition and the cross-linked product of the rubber composition can be used include treads (cap treads, under treads), sidewalls, rubber reinforcing layers for run-flat tires (liners, etc.), rim cushions, bead fillers, bead insulation, bead apexes, clinch apexes, belts, belt cushions, breakers, breaker cushions, chafers, chafer pads, strip apexes, etc.
  • tires for which the rubber composition and the crosslinked product of the rubber composition can be used include pneumatic tires and non-pneumatic tires, among which pneumatic tires are preferred.
  • the tire can be suitably used as a summer tire or a winter tire (such as a studless tire, a snow tire, or a studded tire).
  • the tire can be used as a passenger car tire, a large passenger car tire, a large SUV tire, a heavy-duty tire for trucks and buses, a light truck tire, a two-wheeled vehicle tire, a run-flat tire, a racing tire (high-performance tire), or the like.
  • the rubber composition and the cross-linked product of the rubber composition can be used for purposes other than tires, such as packing, sheet members, hoses, belts, rubber-coated fabrics, footwear, and adhesives.
  • the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the modified liquid diene polymer were determined in terms of standard polystyrene by gel permeation chromatography (GPC) using the following measuring device and conditions: ⁇ Apparatus: Tosoh Corporation's GPC device "HLC-8320GPC” Separation column: Tosoh Corporation "TSKgel Super HZ4000 x 2" Eluent: Tetrahydrofuran Eluent flow rate: 0.35 mL/min Sample concentration: 5 mg/10 mL Column temperature: 40°C
  • the composition ratio was calculated using formula (i) from the detected absorption peak absorbance (A V ) derived from 1,2-bonds, absorption peak absorbance (A C ) derived from cis-1,4-bonds, absorption peak absorbance (A T ) derived from trans-1,4-bonds, and Morero's absorption coefficient.
  • the peak integral values of the peak derived from the 1,2-bond and the peaks derived from the 1,2-bond and the 1,4-bond were determined in the 1 H-NMR spectrum obtained in Measurement 1.
  • the abundance ratios (X, Y, Z) (molar ratio) of the peak derived from the 1,2-bond, the peak derived from the 1,4-bond, and the peak derived from 2-aminoethanethiol were calculated from the ratio of the peak integral values obtained in Measurement 1.
  • the ratio (mol%) of 1,2-bond units having vinyl groups to the total amount of structural units derived from butadiene in the modified liquid diene polymer was calculated.
  • melt viscosity of the unmodified liquid diene polymer at 38° C. was measured by a Brookfield viscometer (manufactured by BROOKFIELD ENGINEERING LABS. INC.).
  • the weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw/Mn), ratio of cis-1,4-bond units and ratio of trans-1,4-bond units in 1,4-bond units, and melt viscosity of the unmodified liquid diene polymers 1 to 4 obtained as described above were measured according to the methods described above. The results are shown in Table 1.
  • the amount of structural units derived from butadiene in unmodified polymers 1 to 3 was 100% by mass relative to the total amount of the polymer.
  • unmodified polymer 4 the amount of structural units derived from butadiene and structural units derived from isoprene was 90% by mass and 10% by mass, respectively, relative to the total amount of the polymer.
  • proportion (a) is the proportion (mol %) of each bond unit relative to the total amount of structural units derived from butadiene in the modified liquid diene polymer
  • proportion (b) is the proportion (mol %) of each bond unit relative to the total amount of 1,4-bond units in the modified liquid diene polymer.
  • Solution-polymerized styrene-butadiene rubber HPR355 (manufactured by ENEOS Materials Corporation, alkoxysilyl groups introduced at the ends, styrene content 28% by mass, vinyl content 56% by mass)
  • STR20 Natural rubber produced in Thailand Butadiene rubber: BR01 (manufactured by ENEOS Materials Corporation, Mw: 550,000, cis content 95% by mass)
  • Silica-silane coupling agent > Silica: ULTRASIL7000GR (manufactured by Evonik Japan, wet silica, average particle size 14 nm) Silane coupling agent: Si-75 (manufactured by Evonik Japan)
  • Zinc oxide ZnO (manufactured by Sakai Chemical Industry Co., Ltd.) Stearic acid: Lunac S-20 (Kao Corporation) Wax: Suntite S (Seiko Chemical Co., Ltd.) Antioxidant: Norak 6C (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)
  • Vulcanizing agent Insoluble sulfur Myucron OT-20 (manufactured by Shikoku Chemical Industry Co., Ltd.)
  • Vulcanization accelerator 1 Noccela CZ (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)
  • Vulcanization accelerator 2 Noccelaer D (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)
  • Examples 1 to 17 and Comparative Examples 1 to 9 Production of Rubber Compositions
  • the solid rubber, polymer, filler, plasticizer, silane coupling agent, zinc oxide, stearic acid, wax, and antioxidant were each charged into an internal Banbury mixer and kneaded for 6 to 8 minutes so that the starting temperature was 60° C. and the resin temperature was 145 to 160° C., and then the mixture was taken out of the mixer and cooled to room temperature. Next, this mixture was again charged into the internal Banbury mixer and kneaded for 4 to 6 minutes so that the starting temperature was 90° C.
  • the obtained rubber composition was press molded (150-170°C, 30-50 minutes) to prepare a vulcanized rubber sheet (thickness 2 mm), and the physical properties were evaluated based on the following methods.
  • the measurement methods for each evaluation are as follows. The obtained evaluation results are shown in Tables 3, 4, and 5.
  • ⁇ Rubber hardness> A test piece of 40 mm length x 5 mm width was cut out from the vulcanized rubber sheet obtained by press-molding the rubber composition prepared in each of the Examples and Comparative Examples, and the hardness was measured by a type A hardness tester with reference to JIS K6253.
  • the rubber hardness is shown in Tables 3, 4, and 5 as a relative value when the values of Comparative Example 1 for Examples 1 and 2, Comparative Example 2 for Examples 3 and 4, Comparative Example 3 for Examples 5 to 7, Comparative Example 4 for Examples 8 and 9, Comparative Example 5 for Examples 10 to 12, Comparative Example 6 for Examples 13 and 14, Comparative Example 7 for Example 15, Comparative Example 8 for Example 16, and Comparative Example 9 for Example 17 are set to 100.
  • the rubber compositions to which the polymer of the present invention was added exhibited higher rubber hardness than rubber compositions containing diene polymers of comparable molecular weights and comparable amounts of fillers.
  • the higher rubber hardness is understood to be due to the polymer of the present invention improving the dispersibility of other components contained in the rubber composition, such as fillers.
  • the results in Figure 1 also show that the dispersibility of other components is improved in the rubber composition to which the polymer of the present invention was added.
  • the polymer of the present invention not only had the above-mentioned effect of improving dispersibility, but also had the effect of suppressing bleed-out.

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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)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2024/020400 2023-06-16 2024-06-04 変性液状ジエン系重合体及びゴム用添加剤 Ceased WO2024257655A1 (ja)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54123144A (en) * 1978-03-17 1979-09-25 Nippon Zeon Co Ltd Water-based coating composition
JPS5924763A (ja) * 1982-08-02 1984-02-08 Nippon Soda Co Ltd 電着塗料組成物およびその電着塗装方法
JP2000344949A (ja) 1999-03-31 2000-12-12 Nippon Mitsubishi Oil Corp 自動車タイヤトレッド用ゴム組成物
JP2005220224A (ja) * 2004-02-05 2005-08-18 Fuji Photo Film Co Ltd 重合体、及び該重合体からなる酸化防止剤
JP2011132298A (ja) 2009-12-22 2011-07-07 Sumitomo Rubber Ind Ltd 変性共重合体、それを用いたゴム組成物および空気入りタイヤ
JP2013249359A (ja) 2012-05-31 2013-12-12 Bridgestone Corp ゴム組成物及びタイヤ
JP2017137412A (ja) * 2016-02-03 2017-08-10 東ソー株式会社 アミノ化石油樹脂及びその製造方法
JP2019500471A (ja) * 2015-12-29 2019-01-10 株式会社ブリヂストン ポリオレフィングラフト化ポリジエンポリマー、並びにその製造及び使用方法
WO2019172185A1 (ja) 2018-03-07 2019-09-12 株式会社クラレ 変性液状ジエン系重合体およびゴム組成物
JP2020125456A (ja) * 2019-02-01 2020-08-20 ハンコック タイヤ アンド テクノロジー カンパニー リミテッドＨａｎｋｏｏｋ Ｔｉｒｅ ＆ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．， Ｌｔｄ． 無溶媒反応型接着組成物及びこれを用いたタイヤの製造方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54123144A (en) * 1978-03-17 1979-09-25 Nippon Zeon Co Ltd Water-based coating composition
JPS5924763A (ja) * 1982-08-02 1984-02-08 Nippon Soda Co Ltd 電着塗料組成物およびその電着塗装方法
JP2000344949A (ja) 1999-03-31 2000-12-12 Nippon Mitsubishi Oil Corp 自動車タイヤトレッド用ゴム組成物
JP2005220224A (ja) * 2004-02-05 2005-08-18 Fuji Photo Film Co Ltd 重合体、及び該重合体からなる酸化防止剤
JP2011132298A (ja) 2009-12-22 2011-07-07 Sumitomo Rubber Ind Ltd 変性共重合体、それを用いたゴム組成物および空気入りタイヤ
JP2013249359A (ja) 2012-05-31 2013-12-12 Bridgestone Corp ゴム組成物及びタイヤ
JP2019500471A (ja) * 2015-12-29 2019-01-10 株式会社ブリヂストン ポリオレフィングラフト化ポリジエンポリマー、並びにその製造及び使用方法
JP2017137412A (ja) * 2016-02-03 2017-08-10 東ソー株式会社 アミノ化石油樹脂及びその製造方法
WO2019172185A1 (ja) 2018-03-07 2019-09-12 株式会社クラレ 変性液状ジエン系重合体およびゴム組成物
JP2020125456A (ja) * 2019-02-01 2020-08-20 ハンコック タイヤ アンド テクノロジー カンパニー リミテッドＨａｎｋｏｏｋ Ｔｉｒｅ ＆ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．， Ｌｔｄ． 無溶媒反応型接着組成物及びこれを用いたタイヤの製造方法

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TW202509096A (zh) 2025-03-01

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