WO2018101366A1 - Composition de caoutchouc, et pneumatique - Google Patents

Composition de caoutchouc, et pneumatique Download PDF

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Publication number
WO2018101366A1
WO2018101366A1 PCT/JP2017/042918 JP2017042918W WO2018101366A1 WO 2018101366 A1 WO2018101366 A1 WO 2018101366A1 JP 2017042918 W JP2017042918 W JP 2017042918W WO 2018101366 A1 WO2018101366 A1 WO 2018101366A1
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WIPO (PCT)
Prior art keywords
mass
parts
range
resin
hydrocarbon resin
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PCT/JP2017/042918
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English (en)
Japanese (ja)
Inventor
淳 野澤
涼嗣 亀山
貞治 橋本
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日本ゼオン株式会社
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Priority to JP2018554216A priority Critical patent/JP6954305B2/ja
Publication of WO2018101366A1 publication Critical patent/WO2018101366A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/02—Copolymers of mineral oil hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a rubber composition having excellent processability and excellent balance between rolling resistance and wet grip performance.
  • a cross-linked product of a rubber composition in which silica is added to a rubber component as a filler constitutes a tire compared to a cross-linked product of a rubber composition in which carbon black is mixed. In this case, the rolling resistance is reduced. Therefore, a tire excellent in fuel efficiency can be obtained by constituting a tire using a crosslinked product of a rubber composition containing silica.
  • Patent Document 1 by preparing a rubber composition using an amine-modified conjugated diene polymer as a rubber component, a pneumatic tire with reduced heat generation and improved run-flat running durability can be provided.
  • Patent Document 2 by preparing a rubber composition using a hydrogenated conjugated diolefin-based polymer in which a polymer chain end is modified with an amide or an imide as a rubber component, the abrasion resistance, weather resistance, processability, etc. are improved. It is described that tires and the like that are excellent and generate little heat can be obtained.
  • the present invention has been made in view of the above problems, and has as its main object to provide a rubber composition that is excellent in workability and excellent in the balance between rolling resistance and wet grip performance.
  • the inventors have modified the hydrocarbon resin with a predetermined amount of an amine compound and have a weight within a predetermined range.
  • the present invention finds that a modified hydrocarbon resin having predetermined characteristics such as average molecular weight is involved in improving the workability of the rubber composition and improving the balance of both rolling resistance and wet grip performance. It has come to be completed.
  • 1 part by weight of the modified hydrocarbon resin is used for 100 parts by weight of the diene rubber comprising 30 parts by weight to 90 parts by weight of natural rubber and 10 parts by weight to 70 parts by weight of styrene-butadiene copolymer rubber.
  • a rubber composition comprising: 30 parts by mass and 20 parts by mass to 80 parts by mass of carbon black having a nitrogen adsorption specific surface area (N 2 SA) in the range of 70 m 2 / g to 150 m 2 / g,
  • the hydrocarbon resin is obtained by modifying a hydrocarbon resin with at least one of an amine compound, an amide compound or an imide compound, and has a weight average molecular weight (Mw) in the range of 1000 to 8000, and a softening point. Is provided within the range of 80 ° C to 150 ° C.
  • the hydrocarbon resin is a C5 petroleum resin or a C5 / C9 petroleum resin, and the C5 petroleum resin or the C5 / C9 petroleum resin is 20% by mass to 70% by mass of a 1,3-pentadiene monomer unit. 5 to 35% by mass of alicyclic monoolefin monomer unit having 4 to 6 carbon atoms, 1 to 50% by mass of acyclic monoolefin monomer unit having 4 to 8 carbon atoms, and alicyclic A hydrocarbon resin containing 0% by mass to 10% by mass of a diolefin monomer unit and 0% by mass to 50% by mass of an aromatic monoolefin monomer unit, and the modified hydrocarbon resin is the hydrocarbon resin 100
  • the mass part was obtained by modifying 0.01 parts by weight to 20 parts by weight of at least one compound selected from the group consisting of the amine compound, amide compound and imide compound, and the number average molecular weight (Mn) Is 500 Within the range of 4000, the Z average molecular weight
  • a pneumatic tire characterized by using the above rubber composition for a tread.
  • the present invention has an effect that it is possible to provide a rubber composition which is excellent in workability and has a good balance between rolling resistance and wet grip performance.
  • the present invention relates to a rubber composition and a pneumatic tire using it as a tread.
  • a rubber composition and a pneumatic tire of the present invention will be described in detail.
  • the rubber composition of the present invention is a modified hydrocarbon resin based on 100 parts by mass of diene rubber comprising 30 parts by mass to 90 parts by mass of natural rubber and 10 parts by mass to 70 parts by mass of styrene-butadiene copolymer rubber.
  • a rubber composition comprising 1 part by mass to 30 parts by mass and 20 parts by mass to 80 parts by mass of carbon black having a nitrogen adsorption specific surface area (N 2 SA) in the range of 70 m 2 / g to 150 m 2 / g.
  • N 2 SA nitrogen adsorption specific surface area
  • the modified hydrocarbon resin is obtained by modifying a hydrocarbon resin with at least one of an amine compound, an amide compound or an imide compound, and has a weight average molecular weight (Mw) in the range of 1000 to 8000, The softening point is in the range of 80 ° C to 150 ° C.
  • the rubber composition is, for example, at least one compound selected from the group consisting of an amine compound, an amide compound, and an imide compound (hereinafter sometimes referred to as an amine compound).
  • an amine compound an imide compound
  • the modified hydrocarbon resin by using the modified hydrocarbon resin, it is not clear why a rubber composition having excellent workability and a good balance of rolling resistance and wet grip performance can be obtained. Is inferred. That is, as the modified hydrocarbon resin, the dispersibility of the filler such as carbon black and silica by using the hydrocarbon resin modified with an amine compound having high affinity with the filler such as carbon black and silica in the rubber composition. Can be improved. Furthermore, the compatibility with diene rubber can be made excellent by setting the molecular weight and softening point of the modified hydrocarbon resin to predetermined values.
  • the modified hydrocarbon resin has excellent compatibility with the diene rubber and has excellent dispersion of fillers such as carbon black and silica, thereby increasing the reinforcing effect or diene.
  • the obtained rubber composition has a low loss coefficient tan ⁇ at 60 ° C. and a loss coefficient tan ⁇ at 0 ° C. Can be reasonably high.
  • a tire is manufactured using such a rubber composition, it is possible to form a tire having an excellent balance between rolling resistance and wet grip performance.
  • the rubber composition contains a predetermined amount of carbon black having a predetermined nitrogen adsorption specific surface area (N 2 SA), so that the rubber composition has an excellent balance of dispersibility in the rubber composition, and a balance between rolling resistance and wet grip performance. An excellent rubber composition can be obtained.
  • the rubber composition contains a predetermined amount of the modified hydrocarbon resin together with the carbon black, thereby suppressing a decrease in workability and improving the balance between rolling resistance and wet grip performance.
  • the rubber composition contains the modified hydrocarbon resin in a predetermined amount together with a predetermined carbon black with respect to the diene rubber, so that the processability is excellent and the rolling resistance and wet grip performance are improved. The balance is excellent.
  • the rubber composition of the present invention contains a diene rubber, a modified hydrocarbon resin and carbon black.
  • a diene rubber a modified hydrocarbon resin
  • carbon black a modified hydrocarbon resin
  • the modified hydrocarbon resin is a modified product of an amine compound of a hydrocarbon resin.
  • a hydrocarbon resin before being modified with an amine compound hereinafter sometimes referred to as a resin before modification
  • an amine compound and a modified hydrocarbon resin for modifying this hereinafter sometimes referred to as a modified resin.
  • hydrocarbon resin is a raw material resin before being modified with an amine compound.
  • any resin can be used as long as it can be modified with an amine compound to provide a rubber composition having excellent workability and a good balance between rolling resistance and wet grip performance. .
  • the hydrocarbon resin is preferably a C5 petroleum resin or a C5 / C9 petroleum resin. This is because the petroleum resin can stably provide a rubber composition having excellent processability and excellent balance between rolling resistance and wet grip performance.
  • the C5-based petroleum resin is one which refers to a hydrocarbon resin obtained by naphtha by polymerizing a monomer composition comprising at least one monomer included in the C 5 fraction obtained by thermal decomposition .
  • the monomer contained in the C 5 fraction for example, 1,3-pentadiene, isoprene, cyclopentadiene can be mentioned conjugated diene monomer having a carbon number of 4-5 such as, among others in the present invention
  • the monomer composition preferably contains 1,3-pentadiene as the C 5 fraction, that is, the hydrocarbon resin preferably contains 1,3-pentadiene monomer units.
  • monomer, monomer naphtha may be included as C 5 fraction or C 9 fraction upon pyrolysis contained in C 9 fraction described later and monomers contained in the C 5 fraction If it is.
  • the monomer contained in the C 5 fraction, naphtha is not limited to monomer was obtained as C 5 fraction by thermal decomposition, it was obtained by other synthetic methods such as It may be a monomer.
  • the C5 / C9 petroleum resin, a monomer contained at least one and naphtha monomer include naphtha C 5 fraction obtained by thermal decomposition to C 9 fractions obtained by pyrolysis A hydrocarbon resin obtained by polymerizing a monomer containing at least one of the above.
  • Examples of the monomer contained in the C 9 fraction include aromatic monoolefins having 8 to 10 carbon atoms such as styrene, ⁇ -methylstyrene, vinyltoluene, indene and coumarone.
  • the C5 petroleum resin or C5 / C9 petroleum resin includes a 1,3-pentadiene monomer unit, an alicyclic monoolefin monomer unit having 4 to 6 carbon atoms, and A hydrocarbon resin containing at least an acyclic monoolefin monomer unit having 4 to 8 carbon atoms and, if necessary, an alicyclic diolefin monomer unit and an aromatic monoolefin monomer unit.
  • 1,3-pentadiene monomer unit 20% by mass to 70% by mass, C 4-6 alicyclic monoolefin monomer unit 5% by mass to 35% by mass, carbon number 4 1 to 50% by mass of acyclic monoolefin monomer units of 8 to 8%, 0 to 10% by mass of alicyclic diolefin monomer units, and 0 to 10% by mass of aromatic monoolefin monomer units
  • the C5 petroleum resin or the C5 / C9 petroleum resin is the above-described hydrocarbon resin, that is, by using the hydrocarbon resin having the predetermined monomer unit and ratio as the pre-modification resin, the modification This is because the hydrocarbon resin can provide a rubber composition having excellent processability and excellent balance between rolling resistance and wet grip performance.
  • the content of the 1,3-pentadiene monomer unit in the resin before modification may be in the range of 20% by mass to 70% by mass, and may be in the range of 25% by mass to 67% by mass. In particular, it is preferably in the range of 30% by mass to 65% by mass, and particularly preferably in the range of 33% by mass to 63% by mass. This is because when the content is within the above range, the modified hydrocarbon resin can provide a rubber composition having excellent workability and excellent balance between rolling resistance and wet grip performance.
  • the cis / trans isomer ratio in 1,3-pentadiene is not particularly limited and may be any ratio.
  • the alicyclic monoolefin having 4 to 6 carbon atoms is a hydrocarbon compound having 4 to 6 carbon atoms having one ethylenically unsaturated bond and a non-aromatic ring structure in its molecular structure.
  • Specific examples of the alicyclic monoolefin having 4 to 6 carbon atoms include cyclobutene, cyclopentene, cyclohexene, methylcyclobutene, and methylcyclopentene.
  • the content of the alicyclic monoolefin monomer unit having 4 to 6 carbon atoms in the resin before modification can be in the range of 5% by mass to 35% by mass, and is 8% by mass to 33% by mass. It is preferably within the range, and more preferably within the range of 10% by mass to 32% by mass, and particularly preferably within the range of 13% by mass to 30% by mass. This is because when the content is within the above range, the modified hydrocarbon resin can provide a rubber composition having excellent workability and excellent balance between rolling resistance and wet grip performance.
  • the ratio of each of the corresponding compounds may be any ratio, and is not particularly limited, but preferably contains at least cyclopentene, and has 4 to 6 carbon atoms.
  • the proportion of cyclopentene in the alicyclic monoolefin is more preferably 50% by mass or more.
  • An acyclic monoolefin having 4 to 8 carbon atoms is a chain hydrocarbon compound having 4 to 8 carbon atoms having one ethylenically unsaturated bond in its molecular structure and no ring structure.
  • Specific examples of the acyclic monoolefin having 4 to 8 carbon atoms include butenes such as 1-butene, 2-butene and isobutylene (2-methylpropene); 1-pentene, 2-pentene, 2-methyl-1 -Pentenes such as butene, 3-methyl-1-butene, 2-methyl-2-butene; hexenes such as 1-hexene, 2-hexene, 2-methyl-1-pentene; 1-heptene, 2-heptene Heptenes such as 2-methyl-1-hexene; 1-octene, 2-octene, 2-methyl-1-heptene, diisobutylene (2,4,4-trimethyl-1-pentene and 2,4,4- Octenes such as tri
  • the content of the acyclic monoolefin monomer unit having 4 to 8 carbon atoms in the pre-modification resin can be in the range of 1% by mass to 50% by mass, and 5% by mass to 45% by mass. It is preferably within the range, more preferably within the range of 10% by mass to 42% by mass, and particularly preferably within the range of 15% by mass to 40% by mass. This is because when the content is within the above range, the modified hydrocarbon resin can provide a rubber composition having excellent workability and excellent balance between rolling resistance and wet grip performance.
  • the ratio of each of the corresponding compounds may be any ratio, and is not particularly limited.
  • at least 2-methyl-2-butene Preferably, at least one selected from the group consisting of isobutylene and diisobutylene is included, and the total amount of 2-methyl-2-butene, isobutylene and diisobutylene occupies in the acyclic monoolefin having 4 to 8 carbon atoms
  • the ratio is more preferably 50% by mass or more.
  • the pre-modification resin may contain an alicyclic diolefin as a raw material.
  • An alicyclic diolefin is a hydrocarbon compound having two or more ethylenically unsaturated bonds and a non-aromatic ring structure in its molecular structure.
  • Specific examples of the alicyclic diolefin include multimers of cyclopentadiene such as cyclopentadiene and dicyclopentadiene, and multimers of methylcyclopentadiene and methylcyclopentadiene.
  • the content of the alicyclic diolefin monomer unit in the resin before modification may be in the range of 0% by mass to 10% by mass, and may be in the range of 0% by mass to 7% by mass. In particular, it is preferably in the range of 0% by mass to 5% by mass, and particularly preferably in the range of 0% by mass to 3% by mass. This is because when the content is within the above range, the modified hydrocarbon resin can provide a rubber composition having excellent workability and excellent balance between rolling resistance and wet grip performance.
  • the resin before modification may contain an aromatic monoolefin in its raw material.
  • An aromatic monoolefin is an aromatic compound having one ethylenically unsaturated bond in its molecular structure. Specific examples of the aromatic monoolefin, styrene, alpha-methyl styrene, vinyl toluene, indene, aromatic monoolefin having 8 to 10 carbon atoms contained in the C 9 fraction, such as coumarone.
  • the content of the aromatic monoolefin monomer unit in the resin before modification can be in the range of 0% by mass to 50% by mass, and preferably in the range of 0% by mass to 45% by mass. In particular, it is preferably in the range of 0% by mass to 43% by mass, and particularly preferably in the range of 0% by mass to 40% by mass.
  • the ratio of each compound (including isomers) corresponding to the aromatic monoolefin monomer unit may be any ratio, and is not particularly limited, but the aromatic monoolefin having 8 to 10 carbon atoms is selected.
  • the proportion of the total amount of the aromatic monoolefin having 8 to 10 carbon atoms is preferably 30% by mass or more, more preferably 40% by mass or more, and especially 50% by mass It is preferable that it is above, and it is particularly preferable that it is 60% by mass. This is because when the content is within the above range, the modified hydrocarbon resin can provide a rubber composition having excellent workability and excellent balance between rolling resistance and wet grip performance.
  • Resin before modification is 1,3-pentadiene monomer unit, alicyclic monoolefin monomer unit having 4 to 6 carbon atoms, acyclic monoolefin monomer unit having 4 to 8 carbon atoms, alicyclic
  • diolefin monomer units and aromatic monoolefin monomer units it is possible to obtain a modified hydrocarbon resin that provides a rubber composition that is excellent in processability and has a good balance of rolling resistance and wet grip performance. As long as it is possible, other monomer units may be included.
  • Other monomers used for constituting such other monomer units may be compounds having addition polymerizability that can be addition copolymerized with 1,3-pentadiene or the like other than the aforementioned monomers.
  • the other monomers include carbon numbers other than 1,3-pentadiene such as 1,3-butadiene, 1,2-butadiene, isoprene, 1,3-hexadiene, and 1,4-pentadiene.
  • An unsaturated monoolefin having 7 or more carbon atoms such as cycloheptene; an acyclic monoolefin having 4 to 8 carbon atoms such as ethylene, propylene and nonene.
  • the content of the other monomer units in the resin before modification in the resin before modification is not particularly limited as long as the modified hydrocarbon resin having the predetermined characteristics can be obtained. Usually, it is in the range of 0% by mass to 30% by mass, preferably in the range of 0% by mass to 25% by mass, and more preferably in the range of 0% by mass to 20% by mass. This is because the modified hydrocarbon resin can provide a rubber composition having excellent workability and excellent balance between rolling resistance and wet grip performance.
  • the method for producing the pre-modification resin is not particularly limited as long as the polymerizable component (monomer mixture A) having a monomer capable of constituting the above-described monomer unit is suitably subjected to addition polymerization.
  • the resin before modification can be obtained by addition polymerization using a Friedel-Crafts type cationic polymerization catalyst.
  • the following aluminum halide (A), halogenated hydrocarbon (B1) in which a halogen atom is bonded to a tertiary carbon atom, and a carbon-carbon bond are used.
  • a halogenated hydrocarbon (B) selected from the group consisting of halogenated hydrocarbons (B2) in which a halogen atom is bonded to a carbon atom adjacent to the saturated bond a polymerization catalyst is used,
  • polymerize can be mentioned.
  • the addition amount of each monomer contained in the monomer mixture A can be the same as the content of each monomer unit in the hydrocarbon resin. Therefore, as the pre-modification resin, 1,3-pentadiene monomer unit 20 mass% to 70 mass%, alicyclic monoolefin monomer unit 4 to 6 carbon atoms 5 mass% to 35 mass%, carbon number 4 1 to 50% by mass of acyclic monoolefin monomer units of 8 to 8%, 0 to 10% by mass of alicyclic diolefin monomer units, and 0 to 10% by mass of aromatic monoolefin monomer units In the case of producing a hydrocarbon resin containing 50% by mass, the above production method is more specifically, 5% by mass of 1,3-pentadiene 20% by mass to 70% by mass and C 4-6 alicyclic monoolefin.
  • % To 35% by mass, 1 to 50% by mass of acyclic monoolefin having 4 to 8 carbon atoms, 0 to 10% by mass of alicyclic diolefin, and 0 to 50% by mass of aromatic monoolefin A polymerization step of polymerizing the monomer mixture A containing How to you can be cited.
  • aluminum halide (A) examples include aluminum chloride (AlCl 3 ) and aluminum bromide (AlBr 3 ). Of these, aluminum chloride is preferably used from the viewpoint of versatility.
  • the amount of aluminum halide (A) used is not particularly limited, but is preferably in the range of 0.05 to 10 parts by mass, more preferably 100 parts by mass of the polymerizable component (monomer mixture A). It is within the range of 0.1 to 5 parts by mass.
  • the activity of the polymerization catalyst becomes extremely good.
  • halogenated hydrocarbon (B1) in which a halogen atom is bonded to a tertiary carbon atom include t-butyl chloride, t-butyl bromide, 2-chloro-2-methylbutane, and triphenylmethyl chloride. .
  • t-butyl chloride is particularly preferably used because it has an excellent balance between activity and ease of handling.
  • Examples of the unsaturated bond in the halogenated hydrocarbon (B2) in which a halogen atom is bonded to a carbon atom adjacent to the carbon-carbon unsaturated bond include a carbon-carbon double bond and a carbon-carbon triple bond, and an aromatic ring It also includes a carbon-carbon conjugated double bond in Specific examples of such compounds include benzyl chloride, benzyl bromide, (1-chloroethyl) benzene, allyl chloride, 3-chloro-1-propyne, 3-chloro-1-butene, 3-chloro-1-butyne, Examples include cinnamon chloride. Among these, benzyl chloride is preferably used because it is excellent in balance between activity and ease of handling.
  • halogenated hydrocarbon (B) may be used by 1 type, or may be used in combination of 2 or more types.
  • the amount of the halogenated hydrocarbon (B) used is preferably in the range of 0.05 to 50, more preferably in the range of 0.1 to 10, in terms of the molar ratio to the aluminum halide (A).
  • the order of adding each component of the monomer mixture and the polymerization catalyst to the polymerization reactor is not particularly limited, and may be added in any order, but the polymerization reaction is well controlled, From the viewpoint of more accurately controlling the weight average molecular weight and the like, after adding the monomer mixture and a part of the components of the polymerization catalyst to the polymerization reactor and starting the polymerization reaction, the remainder of the polymerization catalyst is subjected to the polymerization reaction It is preferable to add to the vessel.
  • the pre-modification resin it is preferable to first mix the aluminum halide (A) and the alicyclic monoolefin. This is because by subjecting the aluminum halide (A) and the alicyclic monoolefin to contact treatment, gel formation can be prevented, and a pre-modified resin in which the weight average molecular weight and the like are accurately controlled can be obtained.
  • the amount of the alicyclic monoolefin mixed with the aluminum halide (A) is preferably at least 5 times (mass ratio) the amount of the aluminum halide (A). If the amount of the alicyclic monoolefin is too small, the effect of preventing gel formation may be insufficient.
  • the mass ratio of alicyclic monoolefin to aluminum halide (A) is preferably 5: 1 to 120: 1, more preferably 10: 1 to 100: 1, and even more preferably 15: 1 to 80: 1. . If the alicyclic monoolefin is used in an excessive amount from this ratio, the catalytic activity is lowered and the polymerization may not proceed sufficiently.
  • the charging order is not particularly limited, and the aluminum halide (A) may be charged into the alicyclic monoolefin, and conversely, An alicyclic monoolefin may be introduced into the aluminum halide (A). Since mixing usually involves exotherm, an appropriate diluent can also be used. As the diluent, a solvent described later can be used.
  • a mixture M of an aluminum halide (A) and an alicyclic monoolefin as described above a mixture a containing at least 1,3-pentadiene and an acyclic monoolefin is mixed with the mixture M. It is preferable to do.
  • the mixture a may contain an alicyclic diolefin.
  • the preparation method of the mixture a is not particularly limited, and each of the pure compounds may be mixed to obtain the target mixture a.
  • a mixture containing the target monomer derived from a fraction of a naphtha decomposition product May be used to obtain the desired mixture a.
  • the C5 fraction after extraction of isoprene and cyclopentadiene (including its multimer) can be preferably used.
  • the type of the solvent is not particularly limited as long as it does not inhibit the polymerization reaction, but saturated aliphatic hydrocarbons or aromatic hydrocarbons are preferable.
  • saturated aliphatic hydrocarbon used as the solvent include n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, n-heptane, 2-methylhexane, 3-methylhexane, and 3-ethylpentane.
  • Examples include 5-10 chain saturated aliphatic hydrocarbons; cyclic saturated aliphatic hydrocarbons having 5 to 10 carbon atoms such as cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like.
  • aromatic hydrocarbon used as the solvent include aromatic hydrocarbons having 6 to 10 carbon atoms such as benzene, toluene and xylene.
  • a solvent may be used individually by 1 type and may be used as a 2 or more types of mixed solvent.
  • the amount of the solvent used is not particularly limited, but is preferably in the range of 10 parts by weight to 1,000 parts by weight with respect to 100 parts by weight of the polymerizable component (monomer mixture A), and 50 parts by weight to More preferably, it is in the range of 500 parts by weight.
  • a mixture of an addition polymerizable component and a non-addition polymerizable component such as a mixture of cyclopentane and cyclopentene derived from the C5 fraction is added to the polymerization reaction system, and the addition polymerizable component is a single amount. It can be used as a component of the body mixture, and the non-addition polymerizable component can be used as a solvent.
  • the polymerization temperature for carrying out the polymerization reaction is not particularly limited, but is preferably in the range of ⁇ 20 ° C. to 100 ° C., and preferably in the range of 0 ° C. to 75 ° C. If the polymerization temperature is too low, the polymerization activity may be lowered and productivity may be inferior. If the polymerization temperature is too high, controllability such as the weight average molecular weight of the resin before modification may be inferior.
  • the pressure for performing the polymerization reaction may be atmospheric pressure or increased pressure.
  • the polymerization reaction time can be appropriately selected, but is usually selected within the range of 10 minutes to 12 hours, preferably 30 minutes to 6 hours.
  • the polymerization reaction can be stopped by adding a polymerization terminator such as methanol, an aqueous sodium hydroxide solution or an aqueous ammonia solution to the polymerization reaction system when a desired polymerization conversion rate is obtained.
  • a polymerization terminator such as methanol, an aqueous sodium hydroxide solution or an aqueous ammonia solution
  • the method for producing the pre-modified resin has at least the polymerization step, but may have other steps as necessary.
  • the other steps include, for example, a catalyst residue that is generated when a polymerization terminator is added in the polymerization step after the polymerization step to inactivate the polymerization catalyst, and the catalyst residue insoluble in the solvent is removed by filtration or the like.
  • the polymerization reaction is stopped by the removal step and the polymerization step, the unreacted monomer and solvent are removed, and the low molecular weight oligomer component is removed by steam distillation or the like, followed by cooling to obtain a solid unmodified resin. It can have a recovery process.
  • Amine-based compound The amine-based compound is at least one compound selected from the group consisting of an amine compound, an amide compound, and an imide compound.
  • the amine compound is a compound having an amine structure in which 0 to 2 hydrogen atoms and one or more hydrocarbon groups are covalently bonded to nitrogen.
  • the amine compound has an amine structure, and the modified hydrocarbon resin only needs to provide a rubber composition having excellent workability and excellent balance of rolling resistance and wet grip performance.
  • those having a hydrocarbon group bonded to the nitrogen atom within the range of 1 to 3, that is, primary amine, secondary amine and tertiary amine can be used.
  • the hydrocarbon group an aliphatic hydrocarbon group and an aromatic hydrocarbon group can be used.
  • the aromatic hydrocarbon group refers to a group in which the site directly bonded to the nitrogen atom is an aromatic ring, and even if it has an aromatic ring such as a benzyl group, the site bonded directly to the nitrogen atom Those in which is not an aromatic ring are included in the aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group may include any structure of a chain aliphatic group and a cyclic aliphatic group, or may include an unsaturated group. Furthermore, the cyclic aliphatic group and the aromatic hydrocarbon group may be a carbocyclic group containing only carbon as an atom constituting the cyclic structure, but may be a heterocyclic group containing an atom other than carbon.
  • aliphatic hydrocarbon group and the aromatic hydrocarbon group a substituted product in which a hydrogen atom contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group is substituted with a substituent can also be used.
  • a substituent at least one of a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic hydrocarbon group is bonded via an atom other than carbon such as an amine structure or a nitrogen atom such as —OCH 3 , an oxygen atom, or a sulfur atom.
  • the amine compound if the modified hydrocarbon resin is capable of providing a rubber composition having excellent workability and a good balance between rolling resistance and wet grip performance, an amine in the molecule can be used.
  • the amine compound has two or more amine structures
  • the two or more amine structures may be the same structure or different structures.
  • an amine compound includes two amine structures, a primary amine structure and a secondary amine structure, includes two secondary amine structures, and one secondary amine structure is the other secondary amine structure.
  • the hydrocarbon groups bonded to nitrogen may have different structures.
  • the molecular weight of the amine compound is not particularly limited as long as it can be stably bonded to the resin before modification, and can be, for example, in the range of 50 to 500, particularly in the range of 100 to 300. Preferably there is.
  • Examples of the primary amine include amines in which aliphatic hydrocarbon groups having a total of 6 to 20 carbon atoms in the compound are bonded as hydrocarbon groups such as 1-hexylamine, 1-heptylamine, 1-octylamine, and the like.
  • Examples of the hydrocarbon group include amines to which heteroaromatic groups contained in an aromatic hydrocarbon group are bonded, and among them, amines to which a total of 8 to 12 carbon atoms in the compound are bonded. Can be preferably used.
  • Examples of the secondary amine include 1,6-bis (ethylamino) hexane, 1,2-bis (tert-butylamino) ethane, N′-benzyl-N, N-dimethylethylenediamine, and N-benzyl-N. , N′-dimethylethylenediamine and other hydrocarbon groups in which a total of 6 to 20 carbon atoms of aliphatic hydrocarbon groups are bonded, and heteroaromatic groups contained in aromatic hydrocarbon groups are bonded as hydrocarbon groups Among them, amines to which aliphatic hydrocarbon groups having 8 to 12 carbon atoms in total in the compound are bonded can be preferably used.
  • tertiary amine examples include fatty acids having 6 to 20 carbon atoms in total in the compound as hydrocarbon groups such as N′-benzyl-N, N-dimethylethylenediamine and N-benzyl-N, N′-dimethylethylenediamine.
  • examples include amines to which aromatic hydrocarbon groups are bonded, and amines to which heteroaromatic groups contained in aromatic hydrocarbon groups are bonded as hydrocarbon groups.
  • fatty acids having 8 to 12 carbon atoms in total in the compound An amine or the like to which an aromatic hydrocarbon group is bonded can be preferably used.
  • the amine compound when it has a secondary amine structure and a tertiary amine structure such as N′-benzyl-N, N-dimethylethylenediamine, the amine compound corresponds to both the secondary amine and the tertiary amine. It is.
  • N′-benzyl-N, N-dimethylethylenediamine has (1) benzyl group (carbon number 7) and (2) ethylene group (—C 2 H 5 ) as hydrocarbon groups constituting the secondary amine structure.
  • one hydrogen atom has an aliphatic hydrocarbon group (—C 2 H 4 —N— (CH 3 ) 2 : carbon number 4) substituted with an amine structure, and has at least 7 carbon atoms. Having a hydrocarbon group.
  • N′-benzyl-N, N-dimethylethylenediamine has (1) two methyl groups (1 carbon number) and (2) ethylene group (—C 2 H) as hydrocarbon groups constituting the tertiary amine structure.
  • diamine examples include 1,6-bis (ethylamino) hexane, 1,2-bis (tert-butylamino) ethane, 1,4-di (aminomethyl) cyclohexane, 4-amino-1-diethylaminopentane, N -Amine having a total of 6 to 20 carbon atoms bonded as a hydrocarbon group, such as benzyl-N, N'-dimethylethylenediamine, in the compound, or a complex contained in an aromatic hydrocarbon group as a hydrocarbon group
  • examples include amines to which aromatics are bonded, and among these, amines to which aliphatic hydrocarbon groups having 8 to 12 carbon atoms in total in the compound are bonded can be preferably used.
  • Examples of the triamine include amines and carbons bonded with aliphatic hydrocarbon groups having a total of 6 to 20 carbon atoms in the compound as hydrocarbon groups such as bis (4-aminobutyl) amine and bis (6-aminohexyl) amine.
  • Examples of the hydrogen group include amines to which a heteroaromatic group contained in an aromatic hydrocarbon group is bonded. Among them, amines to which a total of 8 to 12 carbon atoms of an aliphatic hydrocarbon group in the compound are bonded. It can be preferably used.
  • the amine compound may contain only one type or may contain two or more types.
  • the amide compound may be a compound having one or more amide bonds in the molecule, and for example, a compound represented by the following formula (1) can be used.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group.
  • the hydrocarbon group in R 1 to R 3 can be the same as that described in the section “(1) Amine compound”.
  • R 1 to R 3 may be the same functional group or different functional groups.
  • the hydrocarbon group in R 1 to R 3 can provide a rubber composition in which the modified hydrocarbon resin is excellent in workability and has a good balance of rolling resistance and wet grip performance. It suffices that a part of the hydrogen atoms of the aliphatic hydrocarbon group and aromatic hydrocarbon group contained as the hydrocarbon group is substituted with an amide structure or an amine structure. That is, the amide compound is not limited to a monoamide having only one amide structure in the molecule, but has two or more amide structures covalently bonded via R 1 to R 3 as the hydrocarbon group. For example, diamide, triamide and the like can be used. The amide compound may have an amide structure and an amine structure bonded via R 1 to R 3 as the hydrocarbon group.
  • the molecular weight of the amide compound is not particularly limited as long as it can be stably bonded to the resin before modification, and can be, for example, in the range of 50 to 500, particularly in the range of 100 to 300. Preferably there is.
  • an amide compound described in JP-A-2000-53706 can be used, and more specifically, N, N-dimethylformamide, acetamide, N, N-diethylacetamide , Aminoacetamide, N, N-dimethyl-N ′, N′-dimethylaminoacetamide, N, N-dimethylaminoacetamide, N, N-ethylaminoacetamide, N, N-dimethyl-N′-ethylaminoacetamide, acrylamide N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, nicotinamide, isonicotinamide, picolinic acid amide, N, N-dimethylisonicotinamide, succinic acid amide, phthalic acid amide, N, N, N ′ , N′-tetramethylphthalamide, oxamide and N N, N ′, N′-tetramethyloxamide,
  • the amide compound may include only one type or may include two or more types.
  • Imide compound As said imide compound, what is necessary is just a compound which has one or more imide bonds in a molecule
  • the cyclic imide compound represented by following formula (2) or (3) can be used.
  • R 4 , R 5 and R 6 and R 7 , R 8 and R 9 in formulas (2) and (3) are each independently a hydrogen atom or a hydrocarbon group.
  • the hydrocarbon group for R 4 to R 9 can be the same as that described in the section “(1) Amine compound”.
  • R 4 to R 9 may be the same functional group as each other or different functional groups.
  • the hydrocarbon groups in R 4 to R 9 are those that can give a rubber composition in which the modified hydrocarbon resin has excellent workability and a good balance between rolling resistance and wet grip performance. It suffices that a part of the hydrogen atoms of the aliphatic hydrocarbon group and aromatic hydrocarbon group contained as the hydrocarbon group is substituted with an imide structure, an amide structure or an amine structure. That is, the imide compound is not limited to a monoimide having only one imide structure in the molecule, and has two or more imide structures bonded via R 7 to R 9 as the hydrocarbon group. Diimide, triimide and the like can also be used. The imide compound may have an amide structure and at least one of an amide structure and an amine structure bonded via R 7 to R 9 as the hydrocarbon group.
  • the molecular weight of the imide compound is not particularly limited as long as it can stably bind to the resin before modification, and can be, for example, in the range of 50 to 500, and in particular, in the range of 100 to 300. Preferably there is.
  • an imide compound described in JP-A-2000-53706 can be used, and more specifically, succinimide, N-methyl succinimide, maleimide, N-methyl.
  • succinimide, phthalimide, N-methylphthalimide, bismaleimide and the like can be mentioned, and among them, N-alkylmaleimide compounds such as N-methylmaleimide can be preferably used.
  • the imide compound may contain only one type or may contain two or more types.
  • the amine compound is at least one compound selected from the group consisting of an amine compound, an amide compound, and an imide compound. Accordingly, the amine compound may include only an amine compound, only an amide compound, or only an imide compound, and may include two types of compounds, an amine compound and an amide compound, an amine compound, It may contain three kinds of compounds, an amide compound and an imide compound. In the present invention, the amine compound preferably includes an amide compound.
  • the modified hydrocarbon resin is obtained by modifying the hydrocarbon resin with an amine compound.
  • “obtained by modification” means that the amine compound is bonded to the hydrocarbon resin by a covalent bond.
  • the product obtained by modifying 100 parts by mass of a hydrocarbon resin with 0.01 to 20 parts by mass of an amine compound is derived from an amine compound that is bonded to 100 parts by mass of the hydrocarbon resin. This means that the mass of the site to be within the range of 0.01 to 20 parts by mass.
  • the content of the amine compound that is, the content of the site derived from the amine compound bonded to 100 parts by mass of the hydrocarbon resin as the pre-modified resin is in the range of 0.01 to 20 parts by mass. It is preferably in the range of 0.1 to 10 parts by weight, more preferably in the range of 0.1 to 8 parts by weight, It is preferably in the range of 5 to 5 parts by mass. This is because when the content is within the above range, the modified hydrocarbon resin can provide a rubber composition having excellent workability and excellent balance between rolling resistance and wet grip performance.
  • any method can be used as long as the amine compound can be covalently bonded to the pre-modification resin.
  • an amine modification method a known method can be appropriately used. Specifically, as the above-mentioned amine modification method, by mixing a resin before modification, an amine compound and a peroxide initiator, free peroxide is generated in the resin before modification by the peroxide initiator. Can be used, such as a method of reacting an amine compound with an amine compound, a method of mixing an amine compound with a pre-denaturing resin having an active terminal, and the like.
  • the amount of the amine compound added to the pre-modified resin may be any amount that can bind a desired amount of the amine compound.
  • the amine compound in the modified hydrocarbon resin may be the same amount or more.
  • reaction conditions in the amine modification method using free radicals described above are not particularly limited as long as a desired amount of amine compound can be bound to the resin before modification, and the kind of resin before modification and the kind of amine compound.
  • the reaction temperature may be 0 ° C. to 200 ° C. and the reaction time may be 5 minutes to 20 hours.
  • the amine modification method can also be performed in an organic solvent, for example.
  • an organic solvent may be the same as the solvent that can be used for the polymerization reaction of the pre-modification resin described in the section “1. Hydrocarbon resin”.
  • the amine modification method may be, for example, a method in which amine modification is performed in a solvent used in polymerization of a resin before modification.
  • the peroxide initiator is not particularly limited as long as it can bind a desired amount of an amine compound to the resin before modification.
  • an inorganic peroxide such as sodium persulfate, diisopropylbenzene hydroperoxide, etc.
  • Known peroxide initiators such as organic peroxides can be used.
  • inorganic peroxide, organic peroxide, etc. for example, those described in JP-A-2004-285230 can be used.
  • the amount of the peroxide initiator used is not particularly limited as long as a desired amount of the amine compound can be bound to the pre-modification resin, and is appropriately set according to the addition amount of the amine compound. .
  • the amine modification method may be a method of bonding an amine compound to the resin before modification via a known silane coupling agent, if necessary.
  • denaturation it can be made to be the same as that of the above-mentioned amine modification method.
  • silane coupling agent for example, a bifunctional silane coupling agent having a vinyl group and a reactive functional group capable of binding to a nitrogen atom contained in an amine compound can be used.
  • the functional group for reaction include a hydroxyl group, a carboxy group, a ketone group, an epoxy group, a halogen group, and a sulfonic acid group. Among them, a hydroxyl group, a carboxyl group, and the like are preferable.
  • the bifunctional silane coupling agent which has such a vinyl group and the functional group for reaction it can select suitably from a well-known silane coupling agent.
  • the amount of the silane coupling agent used as a spacer between the amine compound and the resin before modification, including those not bonded to the amine compound, is usually included as part of the resin before modification. It is what
  • Examples of the method for bonding the pre-modified resin bonded with the silane coupling agent and the amine compound include, for example, a method in which the pre-modified resin bonded with the silane coupling agent and the amine compound are mixed and heat-treated. Can do.
  • the heat treatment may be performed within a temperature range of 50 ° C. to 300 ° C. for 5 minutes to 20 hours.
  • a diluent an antigelling agent, a reaction accelerator and the like may be present as necessary.
  • a diluent may be the same as the solvent that can be used for the polymerization reaction of the pre-modification resin described in the section “1. Hydrocarbon resin”.
  • the heat treatment may be performed, for example, in a solvent used in the polymerization of the resin before modification.
  • amine modification method a method in which an amine compound is bonded to a resin before modification by reacting a nitrogen atom of the amine compound with an acidic group such as a carboxyl group or an acid anhydride group contained in the resin before modification. It may be.
  • an acidic group introduced into the resin before modification by using a polymerizable component (monomer mixture A) containing a monomer having an acidic group may be used.
  • the acidic group introduced by doing so may be used.
  • the acid modification method may include a method in which an acid anhydride group is introduced as an acidic group, and the resin before modification and the unsaturated dicarboxylic acid anhydride are mixed and heat-treated.
  • Examples of unsaturated carboxylic acids used for introducing carboxyl groups include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like, and ethylenically unsaturated carboxylic acids having 8 or less carbon atoms, and Examples include Diels-Alder adducts of conjugated dienes such as 3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid and ⁇ , ⁇ -unsaturated dicarboxylic acids having 8 or less carbon atoms.
  • Examples of unsaturated dicarboxylic acid anhydrides used for introducing acid anhydride groups include ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides having 8 or less carbon atoms, such as maleic anhydride, itaconic anhydride, citraconic anhydride, and 3 Diels-Alder adducts of conjugated dienes such as, 6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride and ⁇ , ⁇ -unsaturated dicarboxylic anhydrides having 8 or less carbon atoms. .
  • the blending amount of an acid modifier such as an unsaturated carboxylic acid introduced to acid-modify such a pre-modification resin, including those not bound to an amine compound is usually It is included as a part.
  • the reaction may be performed within a temperature range of 50 ° C. to 300 ° C. for 5 minutes to 20 hours.
  • the acid modification reaction may contain a diluent, an anti-gelling agent, a reaction accelerator and the like as necessary.
  • examples of the reaction for bonding an acidic group and an amine compound include a method in which a resin before modification or a resin before modification after acid modification and an amine compound are mixed and heat-treated.
  • a resin before modification or a resin before modification after acid modification and an amine compound are mixed and heat-treated.
  • the method of heat-processing it can be made to be the same as that of the heat processing method which couple
  • the amine modification method described above is applied to the resin A before modification in which a maleic anhydride is used as the unsaturated dicarboxylic anhydride and a carboxylic anhydride group as an acidic group is introduced.
  • denatured hydrocarbon resin B by making a system compound react is shown.
  • following formula (4) shows the example which uses the diamine compound containing two amine structures as an amine compound.
  • the following formulas (5) and (6) show examples in which an amide compound containing an amine structure and an amide structure is used as the amine compound, and the formula (5) shows an amide structure contained in the amine compound. Is reacted with an acidic group, and formula (6) shows an example in which a nitrogen atom of an amine structure contained in an amine compound reacts with an acidic group.
  • a secondary modification reaction in which an amine compound bonded to a modified hydrocarbon resin further reacts with a modified hydrocarbon resin after the primary modification reaction in which the amine compound is bonded to the pre-modified resin. It may be.
  • an amine structure or an amide structure contained in an amine compound bonded to the modified hydrocarbon resin may be further modified. And the like which react with an acidic group or the like contained in the like.
  • the secondary modification reaction may occur for the same modified hydrocarbon resin as the modified hydrocarbon resin bonded by the primary modification reaction, or may occur for a different modified hydrocarbon resin or a pre-modified resin, It may produce a crosslinked modified hydrocarbon resin.
  • the secondary modification reaction is such that the nitrogen atom of the amine structure contained in the amine compound bonded to the modified hydrocarbon resin reacts with an acidic group contained in the same modified hydrocarbon resin.
  • the formula (8) shows that the secondary modification reaction is carried out with respect to the same acidic group as that in which the nitrogen atom of the amide structure contained in the amine compound bonded to the modified hydrocarbon resin is reacted with the amine compound.
  • An example in which a cyclic imide structure is newly generated by reacting again is shown.
  • the weight average molecular weight (Mw) of the modified hydrocarbon resin is not particularly limited as long as it is within the range of 1,000 to 8,000, but among these, 1,200 to 6,000. Is preferably within the range of 1,400 to 4,500, and more preferably within the range of 1,400 to 4,500. This is because when the weight average molecular weight (Mw) is within the above-mentioned range, the modified hydrocarbon resin can be excellent in compatibility with the diene rubber. As a result, the modified hydrocarbon resin can easily reduce the loss coefficient tan ⁇ at 60 ° C. of the cross-linked product of the rubber composition, and can be excellent in rolling resistance. Further, when the weight average molecular weight (Mw) is within the above-mentioned range, the modified hydrocarbon resin can easily increase the loss coefficient tan ⁇ at 0 ° C. and has excellent rolling resistance. Because it can.
  • the number average molecular weight (Mn) of the modified hydrocarbon resin can be in the range of 500 to 4000, preferably in the range of 550 to 3000, particularly in the range of 600 to 2500. It is more preferable. This is because when the number average molecular weight (Mn) is within the above range, the modified hydrocarbon resin can be excellent in compatibility with the diene rubber. As a result, the modified hydrocarbon resin can easily reduce the loss coefficient tan ⁇ at 60 ° C. of the cross-linked product of the rubber composition, and can be excellent in rolling resistance.
  • the modified hydrocarbon resin may have a Z average molecular weight (Mz) in the range of 2,000 to 25,000, particularly preferably in the range of 3,000 to 20,000. , Preferably in the range of 4,000 to 1,5000. This is because when the Z average molecular weight (Mz) is within the above range, the modified hydrocarbon resin can be excellent in compatibility with the diene rubber. As a result, the modified hydrocarbon resin can easily reduce the loss coefficient tan ⁇ at 60 ° C. of the cross-linked product of the rubber composition, and can be excellent in rolling resistance.
  • Mz Z average molecular weight
  • the number average molecular weight (Mn), the weight average molecular weight (Mw), and the Z average molecular weight (Mz) of the modified hydrocarbon resin are determined as polystyrene-converted values measured by high performance liquid chromatography.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mz Z average molecular weight of the modified hydrocarbon resin
  • the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight of the modified hydrocarbon resin can be in the range of 1.0 to 4.0, and more preferably in the range of 1.2 to 3.5. It is preferably within the range, and more preferably within the range of 1.4 to 3.0. This is because when the ratio is within the above range, the modified hydrocarbon resin can be excellent in compatibility with the diene rubber. As a result, the modified hydrocarbon resin can easily reduce the loss coefficient tan ⁇ at 60 ° C. with respect to the crosslinked product of the rubber composition and can be excellent in wet grip performance. .
  • the ratio of the Z average molecular weight to the weight average molecular weight (Mz / Mw) of the modified hydrocarbon resin can be in the range of 1.0 to 4.5, and in particular, in the range of 1.0 to 4.0. It is preferably within the range, and more preferably within the range of 1.0 to 3.5. This is because when the ratio is within the above range, the modified hydrocarbon resin can be excellent in compatibility with the diene rubber. As a result, the modified hydrocarbon resin can easily reduce the loss coefficient tan ⁇ at 60 ° C. with respect to the crosslinked product of the rubber composition and can be excellent in wet grip performance. .
  • the softening point of the modified hydrocarbon resin is not particularly limited as long as it is in the range of 80 ° C. to 150 ° C. Among them, it is preferably in the range of 85 ° C. to 145 ° C., particularly 90 ° C. It is more preferable that the temperature be within a range of ⁇ 140 ° C. This is because when the softening point is within the above-described range, the modified hydrocarbon resin can have excellent compatibility with the diene rubber. As a result, the modified hydrocarbon resin can easily reduce the loss coefficient tan ⁇ at 60 ° C. of the cross-linked product of the rubber composition, and can be excellent in rolling resistance. In addition, since the softening point is within the above range, the modified hydrocarbon resin can easily increase the loss coefficient tan ⁇ at 0 ° C. and can have excellent wet grip performance. is there.
  • the softening point in the present invention is a value measured according to JIS K 6863 for a modified hydrocarbon resin, for example.
  • the blending amount of the modified hydrocarbon resin is not particularly limited as long as it is 1 to 30 parts by mass with respect to 100 parts by mass of the diene rubber, but among them, with respect to 100 parts by mass of the diene rubber. It is preferably in the range of 5 to 20 parts by mass. This is because, when the blending amount is within the above-described range, the rubber composition has excellent processability and excellent balance between rolling resistance and wet grip performance.
  • the blending amount of the modified hydrocarbon resin includes two or more kinds of modified hydrocarbon resins, such as those in which the modified hydrocarbon resin is a modified C5 petroleum resin and a modified C5 / C9 petroleum resin. When included, the total amount of all the modified hydrocarbon resins can be obtained.
  • the method for producing the modified hydrocarbon resin a method having an amine modification step of modifying 100 parts by mass of the hydrocarbon resin, which is a resin before modification, with 0.01 to 20 parts by mass of the amine compound is used. It can.
  • the method of modifying with the amine compound, that is, the amine modifying method, and the like can be the same as the contents described in the above section “2. Amine compound”, and thus the description thereof is omitted here. .
  • the diene rubber is composed of natural rubber and styrene-butadiene copolymer rubber. That is, in the rubber composition, when the total blending amount of the natural rubber and the styrene-butadiene copolymer rubber is 100 parts by mass, the modified hydrocarbon resin is blended in an amount of 1 to 30 parts by mass, and the carbon black is 20 parts by mass. From 80 parts by weight is blended.
  • styrene-butadiene copolymer rubber emulsion polymerized styrene-butadiene copolymer rubber, solution polymerized styrene-butadiene copolymer rubber and the like can be used.
  • the natural rubber and styrene-butadiene copolymer rubber are not particularly limited in molecular weight or microstructure, and may be epoxidized even if they are end-modified with amine, amide, silyl, alkoxysilyl, carboxyl, hydroxyl groups, etc. May be.
  • the natural rubber and styrene-butadiene copolymer rubber may be hydrogenated, but are preferably not hydrogenated.
  • the amount of the natural rubber is not particularly limited as long as it is in the range of 30 to 90 parts by mass in 100 parts by mass of the diene rubber, but is in the range of 35 to 85 parts by mass. In particular, it is preferably in the range of 40 to 80 parts by mass.
  • the amount of the styrene-butadiene copolymer rubber is not particularly limited as long as it is in the range of 10 to 70 parts by mass in 100 parts by mass of the diene rubber, but 15 to 65 parts by mass. In particular, it is preferably in the range of 20 to 60 parts by mass. This is because, when the blending amount is within the above-described range, the rubber composition has excellent processability and excellent balance between rolling resistance and wet grip performance.
  • Carbon black The carbon black is blended in the rubber composition together with the diene rubber and the modified hydrocarbon resin.
  • the carbon black has a nitrogen adsorption specific surface area (N 2 SA) in the range of 70 m 2 / g to 150 m 2 / g.
  • the nitrogen adsorption specific surface area of the carbon black is not particularly limited as long as it is within the range of 70 m 2 / g to 150 m 2 / g, but is within the range of 80 m 2 / g to 130 m 2 / g. It is preferable. This is because, when the nitrogen adsorption specific surface area is within the above range, a rubber composition having excellent workability and a good balance between rolling resistance and wet grip performance can be provided.
  • the nitrogen adsorption specific surface area (N 2 SA) can be determined according to JIS K6217-2.
  • any carbon black having the predetermined nitrogen adsorption specific surface area may be used.
  • those generally used for rubber compositions described in JP-A-2016-30795 can be used.
  • furnace black, acetylene black, thermal black, channel black, graphite, and the like can be used as the carbon black.
  • the blending amount of the carbon black is not particularly limited as long as it is in the range of 20 to 80 parts by mass with respect to 100 parts by mass of the diene rubber.
  • the content is preferably in the range of 30 to 70 parts by mass, and particularly preferably in the range of 35 to 65 parts by mass. This is because, when the blending amount is within the above-described range, the rubber composition has excellent processability and excellent balance between rolling resistance and wet grip performance.
  • the rubber composition of the present invention contains a diene rubber, a modified hydrocarbon resin, and carbon black, but may contain other components as necessary.
  • silane coupling agents for example, silane coupling agents, cross-linking agents, cross-linking accelerators, cross-linking activators, anti-aging agents, activators, process oils, plasticizers, lubricants, tackifiers, etc. are necessary.
  • the amount can be mixed.
  • Such other components and their contents can be the same as those described in JP-A-2016-30795, for example.
  • the other components can include fillers other than carbon black having the predetermined nitrogen adsorption specific surface area.
  • the filler other than the predetermined carbon black those generally used in rubber compositions can be used, for example, silica, clay, diatomaceous earth, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxide.
  • Mica aluminum hydroxide, various metal powders, wood powder, glass powder, ceramic powder, etc., and inorganic hollow fillers such as glass balloons and silica balloons; made of polystyrene, polyvinylidene fluoride, polyvinylidene fluoride copolymer, etc.
  • An organic hollow filler etc. can be mentioned.
  • silica described in JP-A-2016-30795 can be used.
  • the filler should just contain at least 1 type, may contain only 1 type, and may mix and use 2 or more types.
  • the filler content other than the predetermined carbon black is not particularly limited as long as it can provide a rubber composition that is excellent in workability and has a good balance between rolling resistance and wet grip performance.
  • the said content is a ratio with respect to 100 mass parts of diene rubbers, for example, and is 120 mass parts or less normally.
  • the rubber composition may contain only the diene rubber as a rubber component, that is, only natural rubber and styrene-butadiene copolymer rubber, but the other component may be other than the diene rubber.
  • the rubber component may be included.
  • Examples of the other rubber components include natural rubber and styrene such as isoprene rubber (IR), butadiene rubber (BR), acrylonitrile-butadiene copolymer rubber (NBR), and ethylene-propylene-diene terpolymer (EPDM). -Diene rubbers other than butadiene copolymer rubbers.
  • natural rubber and styrene such as isoprene rubber (IR), butadiene rubber (BR), acrylonitrile-butadiene copolymer rubber (NBR), and ethylene-propylene-diene terpolymer (EPDM).
  • IR isoprene rubber
  • BR butadiene rubber
  • NBR acrylonitrile-butadiene copolymer rubber
  • EPDM ethylene-propylene-diene terpolymer
  • -Diene rubbers other than butadiene copolymer rubbers.
  • the other rubber component may be blended in any amount as long as it is excellent in processability and can provide a rubber composition with a good balance of rolling resistance and wet grip performance. It can be 10 parts by mass or less with respect to 100 parts by mass of the diene rubber, and is preferably 5 parts by mass or less.
  • the rubber composition of the present invention may be prepared by kneading each component according to a conventional method.
  • a component excluding a thermally unstable component such as a crosslinking agent or a crosslinking accelerator and a diene rubber are used.
  • a heat-unstable component such as a crosslinking agent or a crosslinking accelerator can be mixed with the kneaded product to obtain a desired composition.
  • the kneading temperature of the component excluding the thermally unstable component and the diene rubber is preferably in the range of 80 ° C. to 200 ° C., more preferably in the range of 120 ° C.
  • the kneaded product and the thermally unstable component are usually mixed after cooling to 100 ° C. or lower, preferably 80 ° C. or lower.
  • a known crosslinking method can be used.
  • a molding machine corresponding to a desired shape such as an extruder, an injection molding machine, a compressor
  • Examples of the method include forming by a roll or the like, performing a crosslinking reaction by heating, and fixing the shape as a crosslinked product.
  • the molding temperature is usually in the range of 10 ° C to 200 ° C, preferably in the range of 25 ° C to 120 ° C.
  • the crosslinking temperature is usually in the range of 100 ° C.
  • the crosslinking time is usually in the range of 1 minute to 24 hours, preferably 2 minutes to 12 hours. And particularly preferably within the range of 3 minutes to 6 hours.
  • the rubber cross-linked product even if the surface is cross-linked, it may not be sufficiently cross-linked to the inside. Good.
  • the heating method a general method used for crosslinking of the rubber composition such as press heating, steam heating, oven heating, hot air heating, etc. may be appropriately selected.
  • the rubber composition of the present invention has an excellent balance between rolling resistance and wet grip performance.
  • the rubber composition of the present invention is preferably used as a material for each part of the tire such as a tread (cap tread, base tread), carcass, sidewall, bead portion, etc. of the tire, taking advantage of such characteristics.
  • a tread cap tread, base tread
  • carcass sidewall
  • bead portion etc. of the tire
  • it can be suitably used for tire parts such as treads, carcass, sidewalls, and bead portions, and particularly excellent in low heat generation. Therefore, it can be particularly suitably used for a tread of a fuel-efficient tire, and particularly, it is preferably used for a base tread (under tread).
  • the pneumatic tire of the present invention is characterized by using the above rubber composition in a tread.
  • the tread is one that uses the above rubber composition, that is, one that is formed using the rubber composition, and usually contains a cross-linked product of the rubber composition.
  • the pneumatic tire only needs to have a tread formed using the rubber composition, and other parts may also be formed using the rubber composition.
  • the tread formed using the rubber composition may be a part of the tread or the entire tread, but preferably includes at least a base tread.
  • the present invention is not limited to the above embodiment.
  • the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
  • the gel permeation chromatography analysis uses “HLC-8320GPC” manufactured by Tosoh Corporation as a measuring device, and the column uses three connected “TSKgel SuperMultipore HZ” manufactured by Tosoh Corporation, with tetrahydrofuran as a solvent. , 40 ° C. and a flow rate of 1.0 mL / min.
  • Measurement item Dynamic storage elastic modulus E ' : Dynamic loss modulus E '' : Loss tangent tan ⁇ -Sample preparation method: punching from sheet-Specimen shape: length 50 mm x width 2 mm x thickness 2 mm ⁇ Number of specimens: 1 ⁇ Distance between clamps: 20mm
  • Table 1 summarizes the types and amounts of the components in the polymerization reactor during the polymerization reaction.
  • pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010, manufactured by BASF) as an antioxidant. 0.2 part was added, and then 2.0 parts of maleic anhydride was added and reacted at 230 ° C. for 1 hour. Then, 1.0 part of N-acetylethylenediamine was added as an amine compound at 200 ° C. The addition reaction was carried out for 1 hour. Thereafter, the molten resin was taken out from the distillation kettle and allowed to cool to room temperature to obtain a modified hydrocarbon resin of Production Example 1. About the obtained modified hydrocarbon resin of Production Example 1, the number average molecular weight, weight average molecular weight, Z average molecular weight, molecular weight distribution, and softening point were measured. These measurement results are summarized in Table 1 below.
  • amine compound (parts) / resin before modification (100 parts) in Table 1 were calculated using maleic anhydride used for acid modification as part of the raw material of the resin before modification.
  • the mixture was kneaded at 90 ° C. as a starting temperature, kneaded at 145 ° C. to 155 ° C. for 60 seconds or more (primary kneading), and then the kneaded product was discharged from the mixer.
  • the obtained kneaded product was cooled to room temperature and then kneaded again (secondary kneading) at 90 ° C. for 2 minutes in a Banbury mixer, and then the kneaded product was discharged from the mixer.
  • the temperature of the kneaded product at the end of kneading was 145 ° C.
  • the obtained kneaded product was mixed with 1.7 parts of sulfur and a vulcanization accelerator: N-cyclohexyl-2-benzothiazolylsulfenamide (CBS, trade name “Noxeller CZ- G ”(manufactured by Ouchi Shinsei Chemical Co., Ltd.) was added and kneaded (kneaded with a vulcanizing agent), and then the sheet-like rubber composition was taken out.
  • CBS N-cyclohexyl-2-benzothiazolylsulfenamide
  • the kneading conditions for primary kneading, secondary kneading and vulcanizing agent kneading were as shown below.
  • Example 2 and Comparative Examples 1 to 7 As shown in Table 2 below, a rubber composition was obtained in the same manner as in Example 1 except that the type and amount of resin such as modified hydrocarbon resin and the type and amount of carbon black were adjusted.
  • Comparative Example 5 carbon black having a nitrogen adsorption specific surface area (N 2 SA) of 65 m 2 / g (Cibot Black N330T manufactured by Cabot Japan Co., Ltd.) was used.
  • Comparative Example 6 carbon black (# 3400B manufactured by Mitsubishi Chemical Corporation) having a nitrogen adsorption specific surface area (N 2 SA) of 165 m 2 / g was used.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • N 2 SA nitrogen adsorption specific surface area

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Tires In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention a pour objet de fournir une composition de caoutchouc qui présente une excellente usinabilité, et un excellent équilibre entre résistance au roulement et performance d'adhérence sur sol mouillé. Plus précisément, l'invention concerne une composition de caoutchouc qui est constituée par mélange de 1 à 30 parties en masse d'une résine hydrocarbure modifiée, et de 20 à 80 parties en masse d'un noir de carbone de surface spécifique d'adsorption d'azote （Ｎ２ＳＡ）comprise à l'intérieur d'une plage de ７０ｍ２／ｇ à １５０ｍ２／ｇ, pour 100 parties en masse d'un caoutchouc diénique constitué de 30 à 90 parties en masse d'un caoutchouc naturel et de 10 à 70 parties en masse d'un caoutchouc de copolymère styrène-butadiène. Cette composition de caoutchouc est caractéristique en ce que ladite résine hydrocarbure modifiée est telle qu'une résine hydrocarbure est modifiée par au moins un composé parmi un composé amine, un composé amide ou un composé imide. La masse moléculaire moyenne en poids (Mw) de la composition de caoutchouc est comprise dans une plage de 1000 à 8000, et son point de ramollissement est compris dans une plage de 80 à 150°C.
PCT/JP2017/042918 2016-12-01 2017-11-29 Composition de caoutchouc, et pneumatique WO2018101366A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2019044660A1 (fr) * 2017-08-31 2019-03-07 日本ゼオン株式会社 Composition de copolymère à blocs multiples obtenue par traitement de modification, et film
WO2024038848A1 (fr) * 2022-08-16 2024-02-22 株式会社レゾナック Élastomère styrénique modifié par maléimide, et procédé de production d'élastomère styrénique modifié par maléimide

Families Citing this family (1)

* Cited by examiner, † Cited by third party
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JP2022184469A (ja) * 2021-06-01 2022-12-13 Ｅｎｅｏｓ株式会社 石油樹脂、ゴム用添加剤、未架橋ゴム組成物及び架橋ゴム

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JP2007217543A (ja) * 2006-02-16 2007-08-30 Bridgestone Corp ゴム組成物およびそれを用いた空気入りタイヤ
JP2008184505A (ja) * 2007-01-29 2008-08-14 Bridgestone Corp タイヤ用ゴム組成物及びそれを用いた空気入りタイヤ。
JP2009126987A (ja) * 2007-11-27 2009-06-11 Toyo Tire & Rubber Co Ltd タイヤトレッド用ゴム組成物
JP2010159316A (ja) * 2009-01-06 2010-07-22 Tosoh Corp ゴム組成物
JP2015203079A (ja) * 2014-04-15 2015-11-16 株式会社ブリヂストン ゴム組成物および空気入りタイヤ
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JPS5491541A (en) * 1977-12-28 1979-07-20 Setsuchiyakuzai Kenkiyuushiyo Chloroprene latex type adhesive
JP2005105209A (ja) * 2003-10-01 2005-04-21 Yokohama Rubber Co Ltd:The 高減衰エラストマー組成物
JP2007217543A (ja) * 2006-02-16 2007-08-30 Bridgestone Corp ゴム組成物およびそれを用いた空気入りタイヤ
JP2008184505A (ja) * 2007-01-29 2008-08-14 Bridgestone Corp タイヤ用ゴム組成物及びそれを用いた空気入りタイヤ。
JP2009126987A (ja) * 2007-11-27 2009-06-11 Toyo Tire & Rubber Co Ltd タイヤトレッド用ゴム組成物
JP2010159316A (ja) * 2009-01-06 2010-07-22 Tosoh Corp ゴム組成物
JP2015203079A (ja) * 2014-04-15 2015-11-16 株式会社ブリヂストン ゴム組成物および空気入りタイヤ
JP2016003274A (ja) * 2014-06-17 2016-01-12 横浜ゴム株式会社 ゴム組成物およびそれを用いた空気入りタイヤ

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019044660A1 (fr) * 2017-08-31 2019-03-07 日本ゼオン株式会社 Composition de copolymère à blocs multiples obtenue par traitement de modification, et film
JPWO2019044660A1 (ja) * 2017-08-31 2021-01-07 日本ゼオン株式会社 変性処理により得られるマルチブロック共重合体組成物およびフィルム
JP7198208B2 (ja) 2017-08-31 2022-12-28 日本ゼオン株式会社 変性処理により得られるマルチブロック共重合体組成物およびフィルム
WO2024038848A1 (fr) * 2022-08-16 2024-02-22 株式会社レゾナック Élastomère styrénique modifié par maléimide, et procédé de production d'élastomère styrénique modifié par maléimide

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