WO2021054429A1 - Composition de caoutchouc, composition de caoutchouc pour pneumatique, et composition de caoutchouc pour semelle de chaussures - Google Patents

Composition de caoutchouc, composition de caoutchouc pour pneumatique, et composition de caoutchouc pour semelle de chaussures Download PDF

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WO2021054429A1
WO2021054429A1 PCT/JP2020/035409 JP2020035409W WO2021054429A1 WO 2021054429 A1 WO2021054429 A1 WO 2021054429A1 JP 2020035409 W JP2020035409 W JP 2020035409W WO 2021054429 A1 WO2021054429 A1 WO 2021054429A1
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conjugated diene
rubber composition
polymer
graft copolymer
based graft
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PCT/JP2020/035409
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English (en)
Japanese (ja)
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慶和 上野
神原　浩
敦 稲富
順矢 高井
昭明 馬
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株式会社クラレ
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Priority to JP2021546969A priority Critical patent/JP7285940B2/ja
Publication of WO2021054429A1 publication Critical patent/WO2021054429A1/fr

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    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • 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
    • 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
    • C08C19/25—Incorporating silicon 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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 containing a conjugated diene-based branched copolymer, a rubber composition for a tire, and a rubber composition for a sole.
  • Patent Document 1 describes a rubber composition containing a kumaron-inden resin having a softening point of 50 ° C. or lower, and it is possible to improve the grip performance and wear resistance of a tire obtained from the rubber composition in a well-balanced manner. Has been described.
  • Patent Document 2 describes a specific formulation of styrene-butadiene rubber having a specific bonded styrene amount and vinyl content, low molecular weight butadiene rubber having a specific cis-1,4-structure content and weight average molecular weight, and silica.
  • the rubber composition contained in the range is described, and it is described that the ice grip performance and the wet grip performance of the tire obtained from the rubber composition are improved.
  • the present invention has been made in view of the above circumstances, solves the above-mentioned problems, and has a wear resistance and ice grip performance of an article including a rubber composition such as a tire and a shoe sole or a crosslinked product of the composition.
  • a rubber composition, a rubber composition for a tire, and a rubber composition for a sole which can achieve both improvement.
  • a specific conjugated diene-based branched copolymer is contained in a rubber composition (for example, a rubber composition for a tire, a rubber composition for a sole), and the composition thereof.
  • a rubber composition for example, a rubber composition for a tire, a rubber composition for a sole
  • an article such as a tire or a sole made from a crosslinked product obtained from the composition can achieve both improvement in wear resistance and ice grip performance, and have completed the present invention. That is, the present invention relates to the following [1] to [12].
  • the conjugated diene-based branched copolymer (A) is attached to the main chain (a) of the polymer segment containing the conjugated diene unit via a branch point, which is different from the 1,4-bond content of the main chain.
  • the branch point of the conjugated diene-based graft copolymer (A1) is composed of one heteroatom selected from the group consisting of Si, Sn, Ge, Pb, P, B, and Al, according to [4].
  • the conjugated diene-based branched copolymer (A) is attached to the main chain (a) of the polymer segment containing the conjugated diene unit via a branch point, which is different from the 1,4-bond content of the main chain.
  • FIG. 1 shows a temperature dispersion curve standardized so that the maximum intensity is 1, and among the data shown by this temperature dispersion curve, only the data having an intensity of 0.5 or more is used to obtain a Gaussian function by the least squares method. It is a conceptual diagram which showed the approximate curve which is fitting, and the curve which consists of the difference between this temperature dispersion curve and the approximate curve.
  • the rubber composition of the present invention contains the following conjugated diene-based branched copolymer (A).
  • the rubber composition for a tire of the present invention contains the rubber composition.
  • the rubber composition for soles of the present invention contains the rubber composition.
  • the conjugated diene-based branched copolymer (A) used in the present invention is a polymer segment containing a conjugated diene unit having a different content (1,4-bonded content) of the conjugated diene unit bonded by a 1,4-bond. 1,4-Binding content mol% D 14 ( ⁇ 1) and 1,4-bonding content of the polymer segment ( ⁇ 1) containing the conjugated diene unit having the highest 1,4-bonding content.
  • the conjugated diene unit is a bonding form (1,4-bond, 1,2-bond).
  • this polymer is also referred to as a copolymer.
  • the branched copolymer is a copolymer having a plurality of polymer segments in which these segments are directly or indirectly bonded via a branch point, or these polymer segments are branched. It means a copolymer that is bonded without interposing points.
  • the direct bond via the branch point means that each polymer segment is directly bonded to the branch point
  • the indirect bond via the branch point means that at least one polymer segment is directly bonded to the branch point. It means that the polymer segment is attached to the branch point through the connecting chain.
  • branched copolymer for example, a star-type block copolymer in which at least one end of the polymer segment is bonded via a branch point, or directly or indirectly to a portion other than the terminal of the polymer segment to be the main chain.
  • Polymers, etc. may be mentioned.
  • the polymer segments ( ⁇ 1) and ( ⁇ 2) contain a conjugated diene unit.
  • the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and 1 , 3-Ocdiadiene, 1,3-Cyclohexadiene, 2-Methyl-1,3-octadiene, 1,3,7-Octatriene, Milsen, Farnesene, and Chloroprene.
  • conjugated diene 1,3-butadiene, isoprene, farnesene, and myrcene are preferable. Further, as the conjugated diene, it is preferable that at least one selected from the group consisting of butadiene and isoprene is contained.
  • the conjugated diene may be used alone or in combination of two or more.
  • the total content of the butadiene unit and the isoprene unit in the polymer segments ( ⁇ 1) and ( ⁇ 2) is preferably 50 to 100% by mass, preferably 60 to 100% by mass, based on all the monomer units constituting the polymer segment. It is more preferably to 100% by mass, and even more preferably 70 to 100% by mass.
  • the polymer segment ( ⁇ 1) or ( ⁇ 2) may consist of only at least one monomer unit selected from the group consisting of butadiene units and isoprene units.
  • the polymer segments ( ⁇ 1) and ( ⁇ 2) may contain other monomer units.
  • examples of other monomers include aromatic vinyl compounds.
  • examples of the aromatic vinyl compound include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-.
  • aromatic vinyl compounds styrene, ⁇ -methylstyrene, and 4-methylstyrene are preferable, and styrene and ⁇ -methylstyrene are more preferable.
  • the aromatic vinyl compound may be used alone or in combination of two or more.
  • the content of the monomer units other than the butadiene unit and the isoprene unit in the polymer segments ( ⁇ 1) and ( ⁇ 2) is preferably 40% by mass or less, more preferably 30% by mass or less, and 20 It is more preferably 0% by mass or less, and may be 0% by mass.
  • the content of the aromatic vinyl compound unit in the polymer segments ( ⁇ 1) and ( ⁇ 2) is preferably 40% by mass or less, more preferably 30% by mass or less, and 20% by mass or less. Is more preferable, and may be 0% by mass.
  • the polymer segment ( ⁇ 1) has a content of conjugated diene units bonded by 1,4-bonds (hereinafter, simply 1,4- It is also called the bond content), which is the highest polymer segment.
  • the "1,4-bond content” refers to 1,4-bonds (in the case of other than farnesene) in a total of 100 mol% of conjugated diene units contained in the conjugated diene-based branched copolymer (A).
  • 1,13-bond (for farnesen) (1,2-bond, 3,4-bond (for non-farnesen), and 3,13-bond (for farnesen)) conjugated diene units Means the total mol% of conjugated diene units other than).
  • the 1,4-bond content is the peak derived from the conjugated diene unit bonded by 1,4-bond (1,13-bond in the case of farnesene) using 1 H-NMR, 1,2-bond and 3 , 4-bonded (3,13-bonded in the case of farnesene), calculated from the area ratio with the peak derived from the conjugated diene unit.
  • the 1,4-bond content mol% D 14 ( ⁇ 1) of the polymer segment ( ⁇ 1) is preferably 40 to 95 mol%, more preferably 50 to 90 mol%.
  • the polymer segment ( ⁇ 2) has a content of conjugated diene units bonded by 1,4-bonds (hereinafter, simply 1,4- It is also called the bond content), which is the lowest polymer segment.
  • the 1,4-bond content mol% D 14 ( ⁇ 2) of the polymer segment ( ⁇ 2) is preferably 20 to 85 mol%, more preferably 30 to 85 mol%, still more preferably 40 to 80 mol%.
  • Difference between 1,4-bond content mol% D 14 ( ⁇ 1) of the polymer segment ( ⁇ 1) and 1,4-bond content mol% D 14 ( ⁇ 2) of the polymer segment ( ⁇ 2) ⁇ 14 D 14 ( ⁇ 1) ⁇ D 14 ( ⁇ 2) is 5 mol% or more, preferably 10 mol% or more, and more preferably 20 mol% or more.
  • the above ⁇ 14 is usually 70 mol% or less, preferably 60 mol% or less, and more preferably 50 mol% or less.
  • the way in which the polymer segment ( ⁇ 1) and the polymer segment ( ⁇ 2) are contained in the conjugated diene-based branched copolymer (A) is not particularly limited as long as the effects of the present invention are not impaired.
  • the conjugated diene-based branched copolymer (A) is a star-type block copolymer
  • one or more of the three or more polymer segments constituting the block copolymer is a polymer segment ( ⁇ 1).
  • one or more of them may be polymer segments ( ⁇ 2).
  • the conjugated diene-based branched copolymer (A) is a graft copolymer
  • the main chain of the graft copolymer is a polymer segment different from the polymer segments ( ⁇ 1) and ( ⁇ 2), and at least one polymer segment ( ⁇ 1) and at least one polymer as side chains. Aspects having a segment ( ⁇ 2); and the like.
  • the embodiment in which the conjugated diene-based branched copolymer (A) is a graft copolymer is preferable.
  • a conjugated diene-based graft copolymer (A1) having at least one side chain (b) of the polymer segment containing a unit is a preferable form.
  • the fact that the main chain (a) has a side chain (b) via a branch point means that the main chain (a) is connected to the branch point directly or through a connecting chain, and the side chain (b) is further connected to this branch point.
  • the term "bonded to the branch point directly” means that the branch point is directly bonded to the portion derived from the monomer unit constituting the main chain (a) or the side chain (b).
  • a branch point and a bond through a connecting chain means that one end of the connecting chain is bonded to a portion derived from a monomer unit constituting the main chain (a) or the side chain (b), and the other end of the connecting chain is bonded.
  • the branch point is directly connected to the end of.
  • the case represented by the following formula (III-1) is a case where the branch point is directly bonded to the main chain
  • the following formula (III-2) is the case where the main chain is connected to the branch point through the connecting chain.
  • Z 0 is a branch point and R 2a is a connecting chain.
  • R 2a is a divalent organic group, an alkylene group which may have a hetero atom is preferable.
  • the side chain (b) is directly connected to the branch point.
  • the branch point of the conjugated diene-based graft copolymer (A1) preferably consists of one heteroatom selected from the group consisting of Si, Sn, Ge, Pb, P, B, and Al, and preferably from one Si atom. Is more preferable.
  • the rubber composition for example, a rubber composition for a tire or a rubber composition for a sole
  • a filler silica or the like generally used as the filler is used.
  • the way in which the polymer segment ( ⁇ 1) and the polymer segment ( ⁇ 2) are contained in the conjugated diene-based graft copolymer (A1) is not particularly limited as long as the effects of the present invention are not impaired.
  • the main chain (a) of the conjugated diene-based graft copolymer (A1) is a polymer segment ( ⁇ 1)
  • the side chain (b) has at least one polymer segment ( ⁇ 2).
  • the main chain (a) of the conjugated diene-based graft copolymer (A1) is a polymer segment ( ⁇ 2) and has at least one or more polymer segments ( ⁇ 1) as a side chain (b);
  • the main chain (a) of the conjugated diene-based graft copolymer (A1) is a polymer segment different from the polymer segments ( ⁇ 1) and ( ⁇ 2), and at least one or more side chains (b) are formed.
  • the polymer segment ( ⁇ 1) may be included as a side chain
  • the polymer segment ( ⁇ 2) may be included as a side chain.
  • aspect (i) is preferable.
  • a branched portion including a form is a preferred embodiment. Among these, a branched structure including a form in which the branch point is connected to the branch point through a connecting chain as shown in the formula (III-4) is desirable.
  • the wavy line portion is the main chain (a)
  • Z 1 is the branch point (typically one heteroatom)
  • P is the side chain (b)
  • R 2b is the side chain.
  • V is a functional group (c) that may be contained in the conjugated diene-based graft copolymer (A1).
  • N represents the valence of Z 1
  • m and n are integers that independently satisfy the following equation (1).
  • Z 1 in the conjugated diene-based graft copolymer of the present invention the main chain 1 for it if there is one or more side chains with respect to this, Z 1 (m side chain is not bound is 0 ) Can be included, but even in that case, Z 1 is defined as a branch point.
  • the linking chain that can be contained in the conjugated diene-based graft copolymer (A1), for example, R 3 in the formulas (III-3) and (III-4), has an aryl group having 6 to 12 carbon atoms and a carbon number of carbon atoms. Indicates an alkyl group of 1 to 12 or a hydrogen atom. Among these, an alkyl group having 1 to 6 carbon atoms is preferable, and an n-butyl group, a sec-butyl group, an n-propyl group, an isopropyl group, an ethyl group, and a methyl group are more preferable.
  • R 3 may be one kind selected from the above group alone, or may contain two or more kinds.
  • R 3 may be a single group of one type or a plurality of groups of two or more types.
  • alkylene group having 1 to 12 carbon atoms having a hetero atom capable of becoming R 2b an alkylene group having 1 to 12 carbon atoms having S is preferable, and SR 2b' (R 2b'is an alkylene group having 1 to 12 carbon atoms. Shown) is more preferable.
  • the functional group (c) at least one group selected from the group consisting of an alkoxy group and a hydroxyl group is preferable.
  • the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and the like.
  • a methoxy group is used from the viewpoint of compatibility with a filler (C) (for example, silica) that can be contained in a rubber composition (for example, a rubber composition for a tire or a rubber composition for a sole).
  • a filler (C) for example, silica
  • a rubber composition for example, a rubber composition for a tire or a rubber composition for a sole.
  • Ethoxy group, and hydroxyl group are preferable.
  • the functional group (c) may be a single group of one type or a plurality of groups of two or more types.
  • the conjugated diene-based graft copolymer (A1) when the side chain (b) is directly bonded to one branch point, the heteroatom which is the branch point contained in the graft copolymer is focused on.
  • the valence of the heteroatom is N
  • the average number of side chains (b) directly bonded to one branch point is B
  • the conjugated diene-based graft copolymer (A1) may have at least one functional group (c) selected from the group consisting of an alkoxy group and a hydroxyl group bonded to the branch point.
  • the side chain (b) of the conjugated diene-based graft copolymer (A1) is directly bonded to one branch point, and the average number of the functional groups (c) bonded to one branch point is C, the above. It is preferable that the relationship of the following formula (2') is satisfied between the valence N of the branch point (typically a heteroatom) and the average number B of the side chain (b). N-1 ⁇ B + C, B> 0, C> 0 (2')
  • the average number X of the functional groups (c) bonded to the branch point per molecule of the conjugated diene-based graft copolymer (A1) is 10 or less. It is preferably 5 or less, and more preferably 5 or less. Further, the above X may be 0.
  • the average number X of the functional groups (c) bonded to the branch point per molecule of the conjugated diene-based graft copolymer (A1) is the functional group equivalent (g / eq) of the conjugated diene-based graft copolymer (A1). It is calculated from the following formula (3) using the number average molecular weight (Mn) converted to standard polystyrene.
  • the functional group equivalent of the conjugated diene-based graft copolymer (A1) means the mass of the conjugated diene bonded to each functional group and other monomers other than the conjugated diene contained as necessary. To do.
  • the functional group equivalent is calculated from the area ratio of the peak derived from the functional group and the peak derived from the polymer main chain using 1 H-NMR.
  • the peak derived from the functional group refers to the peak derived from the alkoxy group and the hydroxyl group.
  • X is 0.01 or more and 9.9 or less. It is preferably in the range of 0.02 or more and 9 or less.
  • the conjugated diene-based graft copolymer (A1) is an average number X of functional groups (c) directly bonded to the above-mentioned branch point per molecule of the conjugated diene-based graft copolymer (A1) and the conjugated diene-based graft copolymer. It is preferable that the average number Y of bifurcation points per molecule satisfies the relationship of the following formula (4).
  • the conjugated diene-based graft copolymer has an affinity with a filler (for example, silica) that can be contained in a rubber composition (for example, a rubber composition for tires and a rubber composition for soles).
  • a filler for example, silica
  • a rubber composition for example, a rubber composition for tires and a rubber composition for soles.
  • the properties tend to be inferior, and when the above (X / Y) is 1 or more, the stability of the conjugated diene-based graft copolymer (A1) tends to decrease.
  • (X / Y) (average number of functional groups (c) per branch point contained in the conjugated diene-based graft copolymer) is, for example, a conjugated diene-based system when Z is Si. Obtained from the results of measuring 29 Si-NMR of the graft copolymer. Specifically, the integral value obtained by multiplying the integrated value of Si having one functional group (c) bonded and Si having two functional groups (c) bonded by the number of functional groups is added up and integrated. Calculated by comparing with a simple sum of values. When Z is a heteroatom other than Si, the average number of the heteroatoms per molecule of the conjugated diene-based graft copolymer can be obtained in the same manner.
  • the above (X / Y) is 0.01 or more and 0.99.
  • the range is preferably as follows, more preferably 0.01 or more and 0.9 or less, and particularly preferably 0.01 or more and 0.5 or less.
  • the average number Y of branch points per molecule of the inductively coupled diene-based graft copolymer (A1) is when the branch points are specific heteroatoms (Si, Sn, Ge, Pb, P, B, or Al).
  • the average number of side chains (b) and the average number of functional groups (c) bonded to the branch point are the steps (A1) for producing the conjugated diene-based graft copolymer (A1) by the production method described later. At least selected from the molar ratio of the charged amount of the active terminal polymer (I) and the functional group-modified conjugated diene polymer (F) in -1) and the group consisting of an alkoxy group and a hydroxyl group in the step (A-2).
  • the amount and reaction time of the reagent used to inactivate at least a part of one remaining functional group (unreacted functional group V), and the type of polar compound used as needed It can be adjusted to a desired range depending on the amount of addition.
  • the average number of side chains (b) bonded to the branch point per molecule of the conjugated diene-based graft copolymer (A1) is W
  • the conjugated diene-based graft copolymer weight is W
  • (W / Y) satisfies the relationship of the following formula (6).
  • the above (W / Y) is more preferably 0.6 or more (0.6 ⁇ (W / Y)), and further preferably 0.8 or more (0.8 ⁇ (W / Y)).
  • the average number W of side chains (b) bonded to the above-mentioned branch point per molecule of the conjugated diene-based graft copolymer (A1) is the conjugated diene-based graft in the step (A-1) of the production method described later.
  • the amount of the active terminal polymer (I) to be the side chain (b) of the copolymer (A1) per active terminal (number of moles) and the amount of the functional group-modified conjugated diene polymer (F) charged (number of moles). ) Is calculated from the following equation (7).
  • (Average number W of side chains (b) bonded to the above branch point per molecule of conjugated diene-based graft copolymer (A1)) (active terminal of active terminal polymer (I) such that side chain (b)) Amount of charge per unit (number of moles)) / (Amount of charge of functional group-modified conjugated diene polymer (F) (number of moles)) (7) If the above (W / Y) is less than 0.5, the fluidity of the conjugated diene-based graft copolymer (A1) is lowered, and the balance between processability and mechanical properties tends to be poor.
  • the degree of branching of the conjugated diene-based graft copolymer (A1) is obtained by plotting the radius of gyration (R) of the conjugated diene-based graft copolymer (A1) on both logarithmic basis with respect to the weight average molecular weight (Mw) by the absolute method.
  • the random coil chain of a normal linear polymer shows a value of about 0.6 to 0.8 for both ⁇ s and ⁇ ⁇ , and if it is less than 0.6, the existence of a branched chain is suggested.
  • the value of ⁇ s or ⁇ ⁇ of the conjugated diene-based graft copolymer (A1) is preferably less than 0.6, more preferably 0.55 or less, and further preferably 0.50 or less. preferable.
  • the log-log plot of the weight average molecular weight (Mw) and the radius of gyration (R) or the intrinsic viscosity ( ⁇ ) by the absolute method of the conjugated diene-based graft copolymer (A1) is obtained by, for example, the SEC-MALS-VISCO method.
  • the SEC-MALS-VISCO method is a type of liquid chromatography (SEC) that separates polymer chains according to the difference in molecular size (hydrodynamic volume), and is a differential refractometer (RI) and a polygonal light scattering detector.
  • the radius of gyration and intrinsic viscosity of each molecular weight of the polymer solution size-sorted by SEC can be calculated.
  • the value of ⁇ s or ⁇ ⁇ of the conjugated diene-based graft copolymer (A1) is in the above range, the fluidity of the conjugated diene-based graft copolymer (A1) is improved, and the processability and mechanical properties are improved. It tends to be excellent in both.
  • the average number W of side chains (b) bonded to the branch point per molecule of the conjugated diene-based graft copolymer (A1) is preferably 1 or more, and more preferably 2 or more.
  • the rubber composition containing the conjugated diene-based graft copolymer (A1) for example, a rubber composition for a tire, a rubber composition for a sole
  • the workability will be improved and the mechanical properties of the rubber composition or the crosslinked product obtained from the composition will be improved.
  • the conjugated diene-based graft copolymer (A1) is at least one monomer unit selected from the group consisting of butadiene and isoprene in an amount of 50% by mass or more among all the monomer units constituting the polymer. Is a preferred embodiment.
  • the total content of the butadiene unit and the isoprene unit is more preferably 60 to 100% by mass, more preferably 70 to 100% by mass, based on all the monomer units of the conjugated diene-based graft copolymer (A1). Is even more preferable.
  • the content of the monomer unit other than the butadiene unit and the isoprene unit in the conjugated diene-based graft copolymer (A1) is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass or less. More preferably, it is by mass or less.
  • the aromatic vinyl compound unit is not more than the above range, the processability of the rubber composition (for example, the rubber composition for tires and the rubber composition for soles) tends to be improved.
  • the mass ratio of the main chain to the side chain in the conjugated diene-based graft copolymer (A1) is preferably in the range of 10/90 to 90/10, more preferably in the range of 15/85 to 80/20, and 20/80.
  • the range of ⁇ 70/30 is more preferable.
  • the processability of the rubber composition containing the conjugated diene-based graft copolymer (A1) is improved. Tend to do.
  • the conjugated diene-based graft copolymer (A1) has a main chain (a) as described above.
  • the main chain (a) refers to the entire portion derived from all the monomer units constituting the main chain.
  • the conjugated diene-based graft copolymer (A1) is produced by the production method described later, the unmodified conjugated diene which is a precursor of the functional group-modified conjugated diene-based polymer (F) used in the production is produced. Refers to the entire portion derived from the system polymer (F').
  • the main chain (a) is a unit other than a vinyl monomer unit derived from a vinyl monomer such as a conjugated diene or an aromatic vinyl compound (for example, Si derived from a residue of a coupling agent) in the polymer segment. It is preferable not to include a unit having an atom or an N atom).
  • a unit other than the vinyl monomer unit is contained in the main chain skeleton, the main chain skeleton is cleaved under conditions where the bond between the hetero atom and carbon, which is a branching point described later, is broken, or by shearing or heat. Therefore, the physical properties tend to deteriorate.
  • the end of the polymer segment serving as the main chain may have a group other than the monomer unit.
  • the main chain (a) contains a conjugated diene unit as a monomer unit constituting the polymer.
  • Specific examples of the monomer that is the monomer unit constituting the main chain (a), description of preferred embodiments, and description of specific examples and preferred embodiments of the monomer unit contained in the main chain (a) are described. The same applies to the description of the polymer segments ( ⁇ 1) and ( ⁇ 2) contained in the conjugated diene-based branched copolymer (A).
  • the weight average molecular weight (Mw) of the main chain (a) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and 3,000 or more and 100. More preferably, it is 000 or less.
  • the Mw of the main chain (a) is, for example, a functional group-modified conjugated diene which is a component of the main chain described later when the conjugated diene-based graft copolymer (A1) is produced by the production method described later.
  • Mw is a standard polystyrene-equivalent weight average molecular weight obtained from gel permeation chromatography (GPC) measurements.
  • the 1,4-bond content of the main chain (a) depends on whether the main chain (a) is a polymer segment ( ⁇ 1), a polymer segment ( ⁇ 2), or a polymer segment other than these. The appropriate value may be set accordingly.
  • the 1,4-bonding content of the main chain (a) can be designed according to the purpose. For example, when the 1,4-bonding content is 50 mol% or more, the main chain (a) described later will be described.
  • the glass transition temperature (Tg) becomes low, the fluidity of the conjugated diene-based graft copolymer (A1) obtained, the tires, shoe soles, etc. obtained from the rubber composition containing the conjugated diene-based graft copolymer (A1), etc.
  • the wear resistance of the article tends to be excellent. Further, when it is 50 mol% or more, the reactivity of the obtained conjugated diene-based graft copolymer (A1) with respect to solid rubber tends to be excellent.
  • the 1,4-bond content of the main chain (a) is, for example, a component of the main chain (a) when the conjugated diene-based graft copolymer (A1) is produced by the production method described later.
  • a desired value can be obtained by controlling the type of solvent used in producing the unmodified conjugated diene polymer (F'), the polar compound used as necessary, the polymerization temperature, and the like.
  • the glass transition temperature (Tg) of the main chain (a) is butadiene unit, isoprene unit and butadiene unit, 1,4-bond content of conjugated diene unit other than isoprene unit, type of conjugated diene unit, single amount other than conjugated diene.
  • Tg is in the above range, for example, it is possible to suppress an increase in viscosity and facilitate handling.
  • Tg is the peak top value of DDSC determined by differential scanning calorimetry (DSC) measurement.
  • the side chain (b) contains a conjugated diene unit as a monomer unit constituting the polymer. Specific examples of the monomer that is the monomer unit constituting the side chain (b), description of preferred embodiments, etc., and specific examples of the monomer unit contained in the side chain (b) and description of preferred embodiments are described. The same applies to the description of the polymer segments ( ⁇ 1) and ( ⁇ 2) contained in the conjugated diene-based branched copolymer (A).
  • the side chain (b) is a homopolymer segment in which the polymer segment is composed of only one conjugated diene unit, or a copolymer containing one conjugated diene unit and another monomer unit different from this conjugated diene. It may be any of the segments. Further, the polymer constituting the side chain (b) may be one kind alone or two or more kinds.
  • the ratio of the conjugated diene units that can form the side chain (b) is not particularly limited and can be designed according to the purpose, but it is preferably 50% by mass or more, and 60% by mass or more. Is more preferable, and is particularly preferably 70% by mass or more, and may be 100% by mass.
  • the ratio of the conjugated diene unit is 50% by mass or more, the processability of the obtained conjugated diene-based graft copolymer (A1) tends to be improved.
  • the ratio of the aromatic vinyl compound unit that can form the side chain (b) is not particularly limited and can be designed according to the purpose, but it is preferably 50% by mass or more, and 60% by mass or more. It is more preferable, and it is particularly preferable that it is 70% by mass or more, and it may be 100% by mass.
  • the ratio of the aromatic vinyl compound unit is 50% by mass or more, the mechanical properties of the obtained conjugated diene-based graft copolymer (A1) tend to be improved.
  • the side chain (b) is a unit other than a vinyl monomer unit derived from a vinyl monomer such as a conjugated diene or an aromatic vinyl compound (for example, Si derived from a residue of a coupling agent) in the polymer segment. It is preferable not to include a unit having an atom or an N atom).
  • a unit other than the vinyl monomer is contained in the polymer segment of the side chain (b)
  • the bond between the hetero atom and carbon, which is a branching point described later is broken, or by shearing or heat. Since the polymer segment skeleton of the side chain (b) is cleaved, the physical properties tend to deteriorate.
  • the end of the polymer segment serving as a side chain may have a group other than the monomer unit.
  • the weight average molecular weight (Mw) of the side chain (b) is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 80,000 or less, and 3,000 or more and 50 or less. More preferably, it is 000 or less.
  • the Mw of the side chain (b) is, for example, an active terminal polymer which is a component of the side chain described later when the conjugated diene-based graft copolymer (A1) is produced by the production method described later. I) Mw.
  • the Mw of the side chain (b) is within the above range, the process passability during manufacturing tends to be excellent and the economic efficiency tends to be good.
  • the 1,4-bond content of the side chain (b) depends on whether the side chain (b) is a polymer segment ( ⁇ 1), a polymer segment ( ⁇ 2), or a polymer segment other than these. The appropriate value may be set accordingly.
  • the 1,4-bond content of the side chain (b) is, for example, the active terminal weight which is a component of the side chain described later when the conjugated diene-based graft copolymer (A1) is produced by the production method described later. It is calculated from the 1 H-NMR spectrum of the coalescence (I) in the same manner as in the case of the polymer segment contained in the conjugated diene-based branched copolymer (A).
  • the 1,4-bonding content of the side chain (b) can be designed according to the purpose. For example, when the 1,4-bonding content is 50 mol% or more, the side chain (b) described later The glass transition temperature (Tg) becomes low, the fluidity of the conjugated diene-based graft copolymer (A1) obtained, the tires, shoe soles, etc. obtained from the rubber composition containing the conjugated diene-based graft copolymer (A1), etc. The wear resistance of the article tends to be excellent. Further, when it is 50 mol% or more, the reactivity of the obtained conjugated diene-based graft copolymer (A1) with respect to solid rubber tends to be excellent.
  • the 1,4-bond content of the side chain (b) is, for example, a component of the side chain (b) when the conjugated diene-based graft copolymer (A1) is produced by the production method described later.
  • the desired value can be obtained by controlling the type of solvent used in producing the active terminal polymer (I), the polar compound used as necessary, the polymerization temperature, and the like.
  • the glass transition temperature (Tg) of the side chain (b) can vary depending on the 1,4-bonding content of the conjugated diene unit, the type of the conjugated diene unit, the content of units derived from a monomer other than the conjugated diene, and the like. , ⁇ 150 to 50 ° C. is preferable, ⁇ 130 to 50 ° C. is more preferable, and ⁇ 130 to 30 ° C. is further preferable.
  • Tg is in the above range, for example, it is possible to suppress an increase in viscosity and facilitate handling.
  • the amount of catalyst residue derived from the polymerization catalyst used in the production of the conjugated diene-based graft copolymer (A1) is preferably in the range of 0 to 200 ppm in terms of metal.
  • the metal that serves as a reference for the amount of catalyst residue is It becomes an alkali metal such as lithium.
  • the amount of the catalyst residue is in the above range, the tack does not decrease during processing and the like, and the heat resistance of the rubber composition of the present invention or the crosslinked product obtained from the composition is improved.
  • the amount of catalyst residue derived from the polymerization catalyst used in the production of the conjugated diene-based graft copolymer (A1) is more preferably 0 to 150 ppm, still more preferably 0 to 100 ppm in terms of metal.
  • the amount of catalyst residue can be measured by using, for example, an inductively coupled plasma mass spectrometer (ICP-MS) or a polarized Zeeman atomic absorption spectrophotometer.
  • a method of setting the amount of the catalyst residue of the conjugated diene-based graft copolymer (A1) to such a specific amount a method of purifying the conjugated diene-based graft copolymer (A1) and sufficiently removing the catalyst residue, etc. Can be mentioned.
  • a method for purification washing with water or warm water, an organic solvent typified by methanol, acetone, or supercritical fluid carbon dioxide is preferable. From an economical point of view, the number of washings is preferably 1 to 20 times, more preferably 1 to 10 times.
  • the cleaning temperature is preferably 20 to 100 ° C, more preferably 40 to 90 ° C.
  • the amount of polymerization catalyst required can be reduced by removing impurities that inhibit polymerization by distillation or an adsorbent before the polymerization reaction to increase the purity of the monomer and then performing polymerization.
  • the amount of catalyst residue can be reduced.
  • the conjugated diene-based graft copolymer (A1) preferably has a halogen content of 1000 ppm or less.
  • the reference halogen is It becomes chlorine.
  • the halogen content is in the above range, transparency, heat resistance, and weather resistance tend to be good.
  • the halogen content of the conjugated diene-based graft copolymer (A1) is more preferably 0 ppm or more and 1000 ppm or less, further preferably 0 ppm or more and 500 ppm or less, and particularly preferably 0 ppm or more and 100 ppm or less.
  • the halogen content can be measured by using, for example, combustion ion chromatography.
  • a functional group-modified conjugated diene which is a raw material for producing the conjugated diene-based graft copolymer (A1) is used.
  • the system polymer (F) include a method using an alkoxysilane-modified conjugated diene-based polymer in which a halide is not produced as a by-product.
  • the main chain (a2) composed of a polymer containing a conjugated diene unit is composed of a polymer containing a conjugated diene unit different from the 1,4-bond content of the main chain.
  • a conjugated diene-based graft copolymer (A2) bonded to the side chain (b2) and the monomer unit serving as a branched portion contained in the main chain (a2) is another preferable form.
  • the side chain density of the side chain (b2) of the conjugated diene-based graft copolymer (A2) is preferably 2.0 mol% or more. Further, it is preferable that the monomer unit serving as the branched portion does not contain a hetero atom. It is preferable that the connecting portion bonded to the side chain (b2) contained in the monomer unit serving as the branched portion is not an aromatic group derived from an aromatic vinyl compound.
  • the main chain (a2) of the conjugated diene-based graft copolymer (A2) contains a monomer unit serving as a branched portion.
  • the main chain (a2) is bound to the side chain (b2).
  • the branching portion is bonded to the side chain (b2) by forming a side chain with one of the atoms (typically carbon atoms) constituting the monomer unit serving as the branching portion in the main chain. It means that the atoms are bonded.
  • the method of binding the branched portion and the side chain (b2) will be described in detail below as an example of a method for producing the conjugated diene-based graft copolymer (A2).
  • the polymer serving as the main chain (a2) will be described in detail.
  • the conjugated diene-based graft copolymer (A2) it is preferable that the monomer unit serving as a branched portion does not contain a hetero atom.
  • the conjugated diene-based graft copolymer (A2) contains a hetero atom at a branch point such as the branch portion, shear stability and thermal stability tend to deteriorate.
  • a polymer which is a component of a main chain synthesized in advance is modified with a compound containing a silicon atom to obtain a functional group-modified polymer, and the functional group is obtained. It is synthesized by a method of reacting a modified polymer with an active terminal of a polymer obtained by polymerizing a monomer as a constituent unit of a side chain. Heteroatoms such as silicon atoms derived from this functional group-modified polymer are included in the branch point connecting the main chain and the side chain. Further, the graft polymer described in Japanese Patent No.
  • the branched portion contained in the main chain (a2) does not contain a hetero atom and is directly bonded to the side chain (b2).
  • the conjugated diene-based graft copolymer (A2) is heteroatom at a portion (connection point) where the main chain and the side chain are bonded, as in the polymer described in the above-mentioned conventional literature. Does not contain atoms.
  • the linking portion to be bonded to the side chain (b2) contained in the monomer unit to be the branching portion contained in the main chain (a2) is derived from the aromatic vinyl compound. It is preferable that it is not an aromatic group.
  • the connecting portion is not an aromatic group derived from an aromatic vinyl compound
  • the monomer unit itself which is the branched portion contained in the main chain, is a monomer unit derived from a monomer other than the aromatic vinyl compound (for example, conjugated diene), or the branched portion contained in the main chain Even if the monomer unit itself is a monomer unit derived from an aromatic vinyl compound, it means that the side chain (b2) is not bonded to the aromatic group of the aromatic vinyl compound. To do.
  • a specific example will be described.
  • the aromatic vinyl compound is, for example, 4-methylstyrene having a substituent having a high anionic activity (high reactivity with an organic lithium compound) in the aromatic group
  • the portion of the methyl group derived from 4-methylstyrene The reactivity is high, and the side chain (b2) is bound to this methyl group portion.
  • an aromatic vinyl compound having no substituent having high anionic activity in the aromatic group for example, styrene
  • the monomer unit (-) derived from styrene which is the skeleton of the main chain (a2).
  • side chain (b2) contained in the partial, side chain (b2) is bonded to a portion of the CH 2 adjacent to CH 2 in which the benzene ring is attached.
  • the side chain (b2) is not bonded to the benzene ring derived from styrene, and the connecting portion in the branched portion contained in the main chain (a2) is an aromatic group derived from an aromatic vinyl compound. There will be no.
  • the connecting portion bonded to the side chain (b2) contained in the monomer unit serving as the branched portion contained in the main chain (a2) is aromatic. It is preferably not an aromatic group derived from a vinyl compound.
  • the connecting portion is the aromatic group, shear stability and thermal stability tend to deteriorate.
  • the graft polymer described in Journal of Polymer Science: Part A: Polymer Chemistry, 2007, 45, 3513, or Japanese Patent No. 5508066 is a macromonomer (a weight obtained by polymerizing a monomer that is a constituent unit of a side chain).
  • a single amount that is a constituent unit of the main chain with a macromonomer obtained by directly reacting an aromatic vinyl compound having a polymerizable functional group other than CH 2 C-bonded to an aromatic group at the active end of the coalescence. It is synthesized by a method of polymerizing with a body. Derived from this macromonomer, the connecting portion that binds to the side chain (b2) contained in the branched portion in the main chain (a2) becomes an aromatic group.
  • conjugated diene-based graft copolymer (A2) for example, as is clear from an example of the method for producing the conjugated diene-based graft copolymer (A2) described in detail below, branching in the main chain (a2). It is preferable that the connecting portion to be bonded to the side chain (b2) contained in the portion is not an aromatic group.
  • the average number of side chains (b2) per molecule of the conjugated diene-based graft copolymer (A2) is preferably 2 or more, more preferably 5 or more, further preferably 10 or more, and 15 or more. The above is particularly preferable.
  • the average number of side chains (b2) per molecule of the conjugated diene-based graft copolymer (A2) is, for example, the step (A2) when the conjugated diene-based graft copolymer (A2) is produced by the production method described later. It is calculated from the charging ratio of the organic alkali metal compound used for the lithium formation reaction in A'-1) and the conjugated diene-based polymer that is the constituent unit of the main chain.
  • the side chain density of the side chain (b2) is preferably 1.6 mol% or more, more preferably 2.0 mol% or more. 3.0 mol% or more is further preferable, 4.5 mol% or more is further preferable, and 6.0 mol% or more is particularly preferable.
  • the side chain density of the conjugated diene-based graft copolymer (A2) is within the above range, the product containing the dungling chain obtained from the product containing the conjugated diene-based graft copolymer (A2) of the present invention can be used.
  • the peak intensity of tan ⁇ derived from the relaxation of the dungling chain tends to be excellent.
  • the side chain density of the side chain (b2) is the average number of side chains (b2) per molecule of the conjugated diene-based graft copolymer (A2) and the number average molecular weight of the main chain (a2) in terms of standard polystyrene. It is calculated from the following formula (2) using (Mn).
  • (Side chain density) (Average number of side chains (b2) per molecule of conjugated diene-based graft copolymer (A2)) / [(Number average molecular weight of main chain (a2) Mn) / (Molecular weight of styrene unit) ] ⁇ 100 (2)
  • the Mn of the main chain (a2) becomes a component of the main chain in advance when the conjugated diene-based graft copolymer (A2) is produced by the method for producing the conjugated diene-based graft copolymer (A2) described later. It is Mn of the synthesized conjugated diene polymer (M) in terms of standard polystyrene.
  • the way in which the polymer segment ( ⁇ 1) and the polymer segment ( ⁇ 2) are contained in the conjugated diene-based graft copolymer (A2) is not particularly limited as long as the effects of the present invention are not impaired.
  • the main chain (a2) of the conjugated diene-based graft copolymer (A2) is a polymer segment ( ⁇ 1), and has at least one or more polymer segments ( ⁇ 2) as a side chain (b2).
  • the main chain (a2) of the conjugated diene-based graft copolymer (A2) is a polymer segment ( ⁇ 2) and has at least one or more polymer segments ( ⁇ 1) as a side chain (b2);
  • the main chain (a2) of the conjugated diene-based graft copolymer (A2) is a polymer segment different from the polymer segments ( ⁇ 1) and ( ⁇ 2), and at least one or more side chains (b2) are formed.
  • the polymer segment ( ⁇ 1) may be included as a side chain
  • the polymer segment ( ⁇ 2) may be included as a side chain.
  • aspect (i) is preferable.
  • the conjugated diene-based graft copolymer (A2) of the present invention is at least one selected from the group consisting of 1,3-butadiene and isoprene in an amount of 40% by mass or more among all the monomer units constituting the polymer.
  • One embodiment is preferably a monomer unit.
  • the total content of 1,3-butadiene units and isoprene units is more preferably 50 to 100% by mass, more preferably 60 to 100% by mass, based on all the monomer units of the conjugated diene-based graft copolymer (A2). It is more preferably%.
  • the content of monomer units other than 1,3-butadiene units and isoprene units in the conjugated diene-based graft copolymer (A2) of the present invention is preferably 60% by mass or less, preferably 50% by mass. The following is more preferable, and 40% by mass or less is further preferable.
  • the aromatic vinyl compound unit is not more than the above range, the processability of the rubber composition (for example, the rubber composition for tires and the rubber composition for soles) tends to be improved.
  • the conjugated diene-based graft copolymer (A2) has a main chain (a2) composed of a polymer containing a conjugated diene unit.
  • the main chain contained in the conjugated diene-based graft copolymer (A2) refers to the entire portion derived from all the monomer units including the conjugated diene unit constituting the main chain.
  • it refers to the entire portion derived from the conjugated diene-based polymer (M) synthesized in advance.
  • the pre-synthesized conjugated diene-based polymer (M) contains 1,3-butadiene units having a vinyl bond.
  • the main chain (a2) contains a conjugated diene unit as a monomer unit constituting the polymer.
  • Specific examples of the monomer that is the monomer unit constituting the main chain (a2), description of preferred embodiments, and description of specific examples and preferred embodiments of the monomer unit contained in the main chain (a2) are described. The same applies to the description of the polymer segments ( ⁇ 1) and ( ⁇ 2) contained in the conjugated diene-based branched copolymer (A).
  • the weight average molecular weight (Mw) of the main chain (a2) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and 3,000 or more and 100. More preferably, it is 000 or less.
  • the Mw of the main chain (a2) is the Mw of the conjugated diene-based polymer (M) synthesized in advance when produced by the method for producing the conjugated diene-based graft copolymer (A2) described later.
  • Mw of the main chain (a2) is within the above range, when the conjugated diene-based graft copolymer (A2) is produced by the production method described later, the process passability at the time of production is excellent and the economy is economical. It tends to be good.
  • the 1,4-bond content of the main chain (a2) depends on whether the main chain (a2) is a polymer segment ( ⁇ 1), a polymer segment ( ⁇ 2), or a polymer segment other than these. The appropriate value may be set accordingly.
  • the 1,4-bonding content of the main chain (a2) can be designed according to the purpose. For example, when the 1,4-binding content is 50 mol% or more, the main chain (a2) described later will be described.
  • the glass transition temperature (Tg) becomes low, the fluidity of the conjugated diene-based graft copolymer (A2) obtained, the tires, shoe soles, etc. obtained from the rubber composition containing the conjugated diene-based graft copolymer (A2), etc.
  • the wear resistance of the article tends to be excellent. Further, when it is 50 mol% or more, the reactivity of the obtained conjugated diene-based graft copolymer (A2) with respect to solid rubber tends to be excellent.
  • the 1,4-bond content of the main chain (a2) is, for example, a component of the main chain (a2) when the conjugated diene-based graft copolymer (A2) is produced by the production method described later.
  • a desired value can be obtained by controlling the type of solvent used in producing the pre-synthesized polymer (M), the polar compound used as necessary, the polymerization temperature, and the like.
  • the glass transition temperature (Tg) of the main chain (a2) is 1,4-bond content of butadiene unit, isoprene unit and butadiene unit, conjugated diene unit other than isoprene unit, type of conjugated diene unit, and single amount other than conjugated diene. Although it may vary depending on the content of the unit derived from the body, ⁇ 150 to 50 ° C. is preferable, ⁇ 130 to 50 ° C. is more preferable, and ⁇ 130 to 30 ° C. is further preferable. When Tg is in the above range, for example, it is possible to suppress an increase in viscosity and facilitate handling. In the present invention, Tg is the peak top value of DDSC determined by differential scanning calorimetry (DSC) measurement.
  • DSC differential scanning calorimetry
  • the side chain (b2) contains a conjugated diene unit as a monomer unit constituting the polymer. Specific examples of the monomer that is the monomer unit constituting the side chain (b2), description of preferred embodiments, etc., and specific examples of the monomer unit contained in the side chain (b2) and description of preferred embodiments are described. The same applies to the description of the polymer segments ( ⁇ 1) and ( ⁇ 2) contained in the conjugated diene-based branched copolymer (A).
  • the side chain (b2) is a homopolymer segment in which the polymer segment is composed of only one conjugated diene unit, or a copolymer containing one conjugated diene unit and another monomer unit different from this conjugated diene. It may be any of the segments. Further, the polymer constituting the side chain (b2) may be one kind alone or two or more kinds.
  • the ratio of conjugated diene units that can form the side chain (b2) is not particularly limited and can be designed according to the purpose, but it is preferably 50% by mass or more, and 60% by mass or more. Is more preferable, and is particularly preferably 70% by mass or more, and may be 100% by mass.
  • the ratio of the conjugated diene unit is 50% by mass or more, the processability of the obtained conjugated diene-based graft copolymer (A2) tends to be improved.
  • the ratio of the aromatic vinyl compound unit that can form the side chain (b2) is not particularly limited and can be designed according to the purpose, but it is preferably 50% by mass or more, and 60% by mass or more. It is more preferable, and it is particularly preferable that it is 70% by mass or more, and it may be 100% by mass.
  • the ratio of the aromatic vinyl compound unit is 50% by mass or more, the mechanical properties of the obtained conjugated diene-based graft copolymer (A2) tend to be improved.
  • the number average molecular weight (Mn) of the side chain (b2) is preferably 500 or more, more preferably 1,000 or more, further preferably 2,000 or more, and particularly preferably 3,000 or more.
  • the Mn is preferably 1,100,000 or less, more preferably 50,000 or less, further preferably 20,000 or less, and particularly preferably 15,000 or less.
  • the Mn of the side chain (b2) is, for example, the step (A) described later when the conjugated diene graft copolymer (A2) is produced by the method for producing the conjugated diene graft copolymer (A2) described later.
  • the 1,4-bond content of the side chain (b2) depends on whether the side chain (b2) is a polymer segment ( ⁇ 1), a polymer segment ( ⁇ 2), or a polymer segment other than these. The appropriate value may be set accordingly.
  • the 1,4-bond content of the side chain (b2) is, for example, the 1,4-bond content of the side chain (b2) when the conjugated diene-based graft copolymer (A2) is produced by the production method described later. is a 1,4-bond content of 1 conjugated diene was calculated by H-NMR spectrum graft copolymer (A2), 1,4-bond content of the main chain (a2) described above, and the main chain, side chain It can be calculated from the charge ratio of the monomer units constituting.
  • the 1,4-bonding content of the side chain (b2) can be designed according to the purpose. For example, when the 1,4-bonding content is 50 mol% or more, the side chain (b2) described later The glass transition temperature (Tg) becomes low, the fluidity of the conjugated diene-based graft copolymer (A2) obtained, the tires, shoe soles, etc. obtained from the rubber composition containing the conjugated diene-based graft copolymer (A2), etc. The wear resistance of the article tends to be excellent. Further, when it is 50 mol% or more, the reactivity of the obtained conjugated diene-based graft copolymer (A2) with respect to solid rubber tends to be excellent.
  • the 1,4-bond content of the side chain (b2) is a component of, for example, the side chain (b2) described above when the conjugated diene-based graft copolymer (A2) is produced by the production method described later.
  • the desired value can be obtained by controlling the type of solvent used in producing the active terminal polymer (I) to be used, the polar compound used as necessary, the polymerization temperature, and the like.
  • the glass transition temperature (Tg) of the side chain (b2) can vary depending on the 1,4-bonding content of the conjugated diene unit, the type of the conjugated diene unit, the content of units derived from a monomer other than the conjugated diene, and the like. , ⁇ 150 to 50 ° C. is preferable, ⁇ 130 to 50 ° C. is more preferable, and ⁇ 130 to 30 ° C. is further preferable.
  • Tg is in the above range, for example, it is possible to suppress an increase in viscosity and facilitate handling.
  • the mass ratio of the main chain to the side chain in the conjugated diene-based graft copolymer (A2) of the present invention is preferably in the range of 1/99 to 90/10, more preferably in the range of 3/97 to 80/20, 5 The range of / 95 to 70/30 is more preferable.
  • the mass ratio of the main chain to the side chain is in the above range, the processability of the polymer composition containing the conjugated diene-based graft copolymer (A2) tends to be improved.
  • the conjugated diene-based graft copolymer (A2) of the present invention has a catalyst residue amount derived from the polymerization catalyst used for its production in the range of 0 to 200 ppm in terms of metal. It is preferably 0 to 150 ppm, more preferably 0 to 100 ppm.
  • the amount of catalyst residue can be measured by using, for example, an inductively coupled plasma mass spectrometer (ICP-MS) or a polarized Zeeman atomic absorption spectrophotometer.
  • the method for measuring the amount of catalyst residue and the method for setting the amount of catalyst residue to such a specific amount are the same as in the case of the conjugated diene-based graft copolymer (A1).
  • conjugated diene-based branched copolymer (A) used in the present invention typically the conjugated diene-based graft copolymer (A1) or (A2), the conjugated diene-based branched copolymer (A) is added. Normalized so that the maximum intensity of the temperature dispersion curve of tan ⁇ obtained by dynamic viscoelasticity measurement of sulfide is 1, and fitting to the Gaussian function by the least squares method using only the data having an intensity of 0.5 or more.
  • the maximum intensity in the high temperature region is 0.22 or more than the temperature showing the maximum intensity in the standardized temperature dispersion curve.
  • the vulcanized product was standardized so that the maximum intensity of the temperature dispersion curve of tan ⁇ obtained by dynamic viscoelasticity measurement when vulcanized at 150 ° C. for 60 minutes using sulfur as a vulcanizing agent was 1. It is a vulcanized product in which the amount of sulfur is adjusted so that the value of tan ⁇ at 80 ° C. is 0.06.
  • an unvulcanized product of the conjugated diene-based branched copolymer (A) adjusted under the following compounding conditions is press-molded (thickness 2 mm, temperature: 150 ° C., pressure: 2 MPa, time: 60 minutes). ) Can be obtained. Then, a strip piece of 20 mm ⁇ 5 mm ⁇ 2 mm necessary for the dynamic viscoelasticity measurement described later is cut out.
  • -Mixing conditions 3.5 parts by mass of zinc flower, 2 parts by mass of steaic acid, N- (tert-butyl) -2-benzothiazolesulfenamide 1 with respect to 100 parts by mass of the conjugated diene-based branched copolymer (A). .
  • the peak intensity of tan ⁇ derived from the relaxation of the dungling chain is the maximum intensity in the normalized temperature dispersion curve in the curve consisting of the difference between the approximate curve obtained by the following fitting conditions and the normalized temperature dispersion curve. It is the maximum intensity in the temperature region higher than the temperature indicated by. -Fitting condition
  • the maximum strength of the temperature dispersion curve of tan ⁇ obtained by the above dynamic viscoelasticity measurement was standardized to be 1.
  • the Gaussian function was fitted by the least squares method using only the data whose intensity was 0.5 or more with respect to the maximum intensity.
  • Y is the intensity value of the normalized temperature dispersion curve of tan ⁇
  • X is the temperature
  • w and u are variables.
  • the temperature at which the maximum intensity value was shown was used as the initial value of u.
  • the temperature dispersion curve ((1), (2)) standardized so that the maximum intensity of tan ⁇ is 1 in FIG. 1; among the data shown by this temperature dispersion curve, the intensity is 0.5 or more.
  • Approximate curve ((1'), (2')) fitted to the Gaussian function by the least squares method using only data; curve consisting of the difference between this temperature dispersion curve and the approximate curve ((1 "), ( A conceptual diagram of 2 ")) is shown.
  • a solid line ((1) to (1 ")) the maximum intensity of the curve consisting of the difference is 0.22 in a temperature region higher than the temperature indicating the maximum intensity in the standardized temperature dispersion curve.
  • a dotted line ((2) to (2 ") the maximum intensity of the curve consisting of the difference in a temperature region higher than the temperature indicating the maximum intensity in the normalized temperature dispersion curve is 0. It is a case of less than .22.
  • the peak intensity of tan ⁇ derived from the relaxation of the dangling chain obtained by the dynamic viscoelasticity measurement of the vulcanized product is defined.
  • This sulfide can be obtained from a structure containing the conjugated diene-based graft copolymer of the present invention to a structure having poor fluidity (for example, a three-dimensional network structure portion contained in a crosslinked polymer, or a crystal contained in a crystalline polymer).
  • the structural part, the phase-separated structural part derived from the polymer block that does not flow at room temperature contained in the block copolymer), and one of them is bonded to the structure, but the other is not bonded to the structure.
  • a polymer chain that is, a dungling chain
  • tan ⁇ which is an index of relaxation of the dungling chain when the product is used.
  • A conjugated diene-based branched copolymer
  • A1 or (A2) even if the dynamic viscoelasticity is measured in the unvulcanized state, the dynamic viscoelasticity can be measured.
  • tan ⁇ is greatly increased by the flow of the main chain, so that it is difficult to appropriately evaluate and compare the peak intensity of tan ⁇ derived from the relaxation of the dungling chain.
  • the movement of the main chain is restricted by vulcanization. Dynamic viscoelasticity measurement is carried out at. Further, in order to more appropriately isolate and evaluate the increase in tan ⁇ due to the flow of the main chain and the tan ⁇ derived from the relaxation of the dangling chain, the degree of vulcanization must be the same. According to the study by the present inventors, as described above, the amount of sulfur is adjusted so that the strength of tan ⁇ at 80 ° C.
  • the vulcanization of the conjugated diene-based branched copolymer (A) under the above-mentioned conditions is carried out from the one containing the conjugated diene-based branched copolymer (A) to the above-mentioned conjugated diene-based branched copolymer.
  • a product containing a dungling chain derived from the coalescence (A) is prepared. When this product is used, it is a condition for measuring the peak intensity of tan ⁇ , which is an index of relaxation of the dangling chain. Therefore, this measurement condition does not limit the method of using the product containing the conjugated diene-based branched copolymer (A).
  • the substance containing the conjugated diene-based branched copolymer (A) is, for example, a substance containing a three-dimensional network structure crosslinked with peroxide or UV crosslinked, or by mixing with another resin having a high molecular weight.
  • an uncrosslinked composition that limits the movement of polymer segments that can be the main chain contained in the system-branched copolymer (A) typically, the conjugated diene-based graft copolymer (A1) or (A2)).
  • the rubber composition containing the conjugated diene-based branched copolymer (A) satisfying the condition regarding the strength of the temperature dispersion curve of tan ⁇ derived from the relaxation of the dungling chain is a rubber composition.
  • the above-mentioned crosslinked product (whether or not the crosslinking method is sulfur) or the uncrosslinked rubber composition can exhibit excellent vibration damping performance.
  • the conjugated diene-based branched copolymer (A) preferably has T1 in the range of -100 to 60 ° C., where T1 is the temperature at which the maximum intensity of the temperature dispersion curve of tan ⁇ is 1. Yes, ⁇ 95 to 50 ° C. is more preferable, and ⁇ 90 to 40 ° C. is even more preferable.
  • T1 is in the above range, the low temperature characteristics of the conjugated diene-based branched copolymer (A) tend to be excellent.
  • the conjugated diene-based branched copolymer (A) has the following formula (A), where T2 is the temperature indicating the maximum intensity in a temperature region higher than T1 in the curve consisting of the difference between the approximate curve and the standardized temperature dispersion curve. 1); 0 ⁇ T2-T1 ⁇ 80 (1) It is a preferable aspect to satisfy the relationship of. T2-T1 is preferably 1 ° C. or higher, more preferably 3 ° C. or higher, and particularly preferably 5 ° C. or higher. Further, it is preferably 70 ° C. or lower, more preferably 60 ° C. or lower, and particularly preferably 50 ° C. or lower. When T2-T1 is in the above range, the peak intensity of tan ⁇ derived from the relaxation of the dangling chain, which will be described later, tends to be excellent.
  • the melt viscosity of the conjugated diene-based branched copolymer (A) measured at 38 ° C. is preferably 0.1 to 2,000 Pa ⁇ s, more preferably 0.1 to 1500 Pa ⁇ s, and 0.1 to 1000 Pa ⁇ s. s is more preferable.
  • the melt viscosity of the conjugated diene-based branched copolymer (A) is within the above range, the process passability during production tends to be excellent and the economic efficiency tends to be good.
  • the melt viscosity of the conjugated diene-based branched copolymer (A) is a value measured by a Brookfield type viscometer at 38 ° C.
  • the weight average molecular weight (Mw) of the conjugated diene-based branched copolymer (A) is preferably 5,000 or more and 200,000 or less, more preferably 30,000 or more and 200,000 or less, and 100, More preferably, it is 000 or more and 200,000 or less.
  • Mw The weight average molecular weight of the conjugated diene-based branched copolymer (A) is within the above range, the process passability during production tends to be excellent and the economic efficiency tends to be good. Further, the processability of the rubber composition containing the conjugated diene-based branched copolymer (A) (for example, a rubber composition for a tire and a rubber composition for a sole) tends to be improved.
  • two or more kinds of conjugated diene-based branched copolymers (A) having different Mw may be used in combination. Further, two or more kinds of conjugated diene-based branched copolymers (A) may be used in combination.
  • the weight average molecular weight (Mw) of the conjugated diene-based branched copolymer (A) is 5,000 or more and 100,000 or less, and more preferably 10,000 or more and 100,000 or less. It is more preferably 30,000 or more and 100,000 or less, and even more preferably 50,000 or more and 100,000 or less.
  • the Mw of the conjugated diene-based branched copolymer (A) is within the above range, the process passability during production tends to be excellent and the economic efficiency tends to be good.
  • the weight average molecular weight (Mw) of the conjugated diene-based branched copolymer (A) is more than 100,000 and 1,000,000 or less, and more than 100,000 and 500,000 or less. Preferably, it is more preferably more than 100,000 and 300,000 or less, further preferably more than 100,000 and 200,000 or less.
  • the rubber composition of the present invention or the crosslinked product obtained from the composition tends to have excellent wear resistance.
  • two or more kinds of conjugated diene-based branched copolymers (A) having different Mw may be used in combination. Further, two or more kinds of conjugated diene-based branched copolymers (A) may be used in combination.
  • the molecular weight distribution (Mw / Mn) of the conjugated diene-based branched copolymer (A) is preferably 1.0 to 20.0, more preferably 1.0 to 10.0, and even more preferably 1.0 to 5.0. , 1.0 to 2.0 are particularly preferable.
  • Mw / Mn is within the above range, the viscosity variation of the conjugated diene-based branched copolymer (A) is small, and the tire, sole, etc. at the time of producing the rubber composition of the present invention or obtained from the rubber composition, etc. This is more preferable because the change in viscosity during the production of the article is small.
  • the molecular weight distribution means the ratio Mw / Mn of Mw and Mn calculated from the standard polystyrene-equivalent Mw and the number average molecular weight (Mn) values obtained by GPC measurement.
  • the method for producing the conjugated diene-based branched copolymer (A) is not particularly limited.
  • the conjugated diene-based branched copolymer (A) is a graft copolymer, for example, a polymerizable functional group is added to the active terminal of a polymer obtained by polymerizing a monomer that is a constituent unit of a side chain.
  • Examples thereof include a method of modifying with a functional group and reacting the functional group-modified polymer with the active end of the polymer obtained by polymerizing a monomer serving as a constituent unit of a side chain.
  • the weight average molecular weight and vinyl content (1,4-bond content) of the main chain and side chains of the conjugated diene-based graft copolymer, the number of side chains, etc. can be freely controlled. Since a desired functional group can be easily introduced, a method of reacting the functional group-modified polymer which is a constituent element of the main chain with the active terminal of the polymer obtained by polymerizing a monomer which is a constituent unit of the side chain is preferable. ..
  • Method for producing conjugated diene-based graft copolymer (A1) (coupling method)>
  • the method for producing the conjugated diene-based graft copolymer (A1) is as follows (A-).
  • a production method including 1) and step (B) is a preferable form.
  • P (In formula (I), P represents a polymer segment containing a conjugated diene unit, and X represents an active end of anionic polymerization.)
  • V represents an alkoxy group or a hydroxyl group
  • Z is Si, Sn, Ge, Pb, P, B, or Al
  • R 1 is an aryl group having 6 to 12 carbon atoms and a carbon number of carbons. It represents an alkyl group of 1 to 12 or a hydrogen atom
  • N represents the valence of Z
  • n is an integer satisfying the following formula (8); 1 ⁇ n ⁇ N-1 (8)
  • V may be the same or different, and when Nn is 2 or more, R 1 may be the same or different, and when a plurality of branched chains are contained in the main chain.
  • Z may be the same or different.
  • the branched chain of the functional group-modified conjugated diene-based polymer (F) means a portion other than the main chain of the functional group-modified conjugated diene-based polymer (F), and this main chain constitutes the main chain. Refers to the entire moiety derived from all monomeric units, including the conjugated diene unit. For example, when the functional group-modified conjugated diene-based polymer (F) is produced from the unmodified conjugated diene-based polymer (F') which is a precursor by the method described later, the unmodified conjugated diene-based polymer (F') is used. Refers to the entire part derived from F').
  • the active terminal polymer (I) can be produced by using a known polymerization method. For example, by anionic polymerization of a monomer containing a conjugated diene in the presence of a polar compound, if necessary, using an anionically polymerizable active metal or an active metal compound as an initiator in a solvent inert to the polymerization terminal. , The active terminal polymer (I) can be obtained.
  • P contained in the active terminal polymer (I) is a polymer segment containing a conjugated diene unit.
  • the P of this active terminal polymer becomes the side chain (b) of the graft copolymer obtained in the present invention.
  • an organic alkali metal compound is preferable, and an organic lithium compound is more preferable.
  • the organic lithium compound include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and pentyllithium.
  • the solvent examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene. , Aromatic hydrocarbons such as toluene and xylene.
  • a polar compound may be added during the above anionic polymerization.
  • Polar compounds are usually used in anionic polymerization to adjust the microstructure of conjugated diene units (1,4-bond content, vinyl content, etc.) without inactivating the reaction.
  • the polar compound 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 polar compound is usually used in an amount of 0.01 to 1000 mol per 1 mol of the organic alkali metal compound.
  • the temperature of the anionic 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 mode may be either a batch type or a continuous type.
  • the active terminal polymer (I) finally becomes the side chain (b) of the conjugated diene-based graft copolymer (A1).
  • the description of the weight average molecular weight (Mw) of P of the active terminal polymer (I), the 1,4-bond content, the preferred embodiment of Tg, and the like is described in the side chain (b) of the conjugated diene-based graft copolymer (A1). ) Is the same.
  • the functional group-modified conjugated diene-based polymer (F) can be obtained, for example, by modifying the unmodified conjugated diene-based polymer (F') with a functional group in the modification step described later.
  • the method for producing the unmodified conjugated diene polymer (F') is not particularly limited, but for example, an emulsion polymerization method and a solution polymerization method are preferable, and a solution polymerization method is more preferable from the viewpoint of the molecular weight distribution of the obtained polymer. ..
  • the portion of the functional group-modified conjugated diene-based polymer (F) other than the functional group-modified portion becomes the main chain (a) of the conjugated diene-based graft copolymer (A1).
  • conjugated diene which is a monomer unit constituting the unmodified conjugated diene polymer (F'), and monomers other than conjugated diene (aromatic vinyl).
  • the description of specific examples, preferred examples, suitable contents, etc. of the compound) is the same as that for the main chain (a) of the conjugated diene-based graft copolymer (A1). Further, the description of the weight average molecular weight (Mw), 1,4-bond content, preferred embodiment of Tg of the unmodified conjugated diene polymer (F') is described in the main chain of the conjugated diene graft copolymer (A1). It is the same as the explanation regarding (a).
  • emulsification polymerization method which is an example of the method for producing an unmodified conjugated diene polymer (F')
  • a known or known method can be applied.
  • a monomer containing a predetermined amount of conjugated diene is emulsified and dispersed in a dispersion medium in the presence of an emulsifier, and emulsion polymerization is carried out with a radical polymerization initiator.
  • Examples of the emulsifier include long-chain fatty acid salts having 10 or more carbon atoms and rosin salts.
  • Examples of the long-chain fatty acid salt include potassium salts or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, and stearic acid.
  • the dispersion medium may contain a water-soluble organic solvent such as methanol or ethanol as long as the stability during polymerization is not impaired.
  • radical polymerization initiator examples include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, hydrogen peroxide and the like.
  • a chain transfer agent may be used to adjust the molecular weight of the obtained unmodified conjugated diene polymer (F').
  • the chain transfer agent include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpenes, turpinolene, ⁇ -terpinene, ⁇ -methylstyrene dimer and the like.
  • the temperature of emulsion polymerization can be appropriately set depending on the type of radical polymerization initiator used, but is usually in the range of 0 to 100 ° C, preferably in the range of 0 to 60 ° C.
  • the polymerization mode may be either continuous polymerization or batch polymerization.
  • the polymerization reaction can be stopped by adding a polymerization inhibitor.
  • the polymerization terminator include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite.
  • an anti-aging agent may be added if necessary.
  • unreacted monomers are removed from the obtained latex as needed, and then salts such as sodium chloride, calcium chloride and potassium chloride are used as coagulants, and nitric acid, sulfuric acid and the like are used as necessary.
  • the unmodified conjugated diene polymer (F') is coagulated while adjusting the pH of the coagulation system to a predetermined value by adding an acid, and then the polymer is recovered by separating the dispersion medium. Then, the unmodified conjugated diene polymer (F') is obtained by washing with water, dehydrating, and then drying.
  • latex and an emulsified dispersion may be mixed in advance and recovered as an oil-expanded unmodified conjugated diene polymer (F').
  • a known or known method can be applied.
  • a Ziegler-based catalyst, a metallocene-based catalyst, or an anionically polymerizable active metal or active metal compound is used as an initiator, and if necessary, in the presence of a polar compound, a single amount containing a conjugated diene. Polymerize the body.
  • the solvent examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, Examples include aromatic hydrocarbons such as toluene and xylene.
  • an anionic polymerizable active metal or an active metal compound is preferable, and an anionic polymerizable active metal compound is more preferable.
  • anionic polymerizable active metals examples 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. .. Among these, alkali metals and alkaline earth metals are preferable, and alkali metals are more preferable.
  • an organic alkali metal compound is preferable.
  • the organic alkali metal compound include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stillbenlithium; , 1,4-Dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene and other polyfunctional organic lithium compounds; sodium naphthalene, potassium naphthalene and the like.
  • an organic lithium compound is preferable, and an organic monolithium compound is more preferable.
  • the amount of the initiator used can be appropriately set according to the melt viscosity, molecular weight, etc. of the unmodified conjugated diene polymer (F') and the functionally modified conjugated diene polymer (F), but the total amount including the conjugated diene is included. It is usually used in an amount of 0.01 to 3 parts by mass with respect to 100 parts by mass of the polymer.
  • the organic alkali metal compound can also be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine or dibenzylamine. ..
  • Polar compounds are usually used in anionic polymerization to adjust the microstructure (1,4-bond content, vinyl content, etc.) of conjugated diene units without inactivating the reaction.
  • the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran, ethylene glycol diethyl ether and 2,2-di (2-tetrahydrofuryl) propane; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphines. Examples include compounds.
  • the polar compound is usually used in an amount of 0.01 to 1000 mol per 1 mol of the organic alkali metal compound.
  • the temperature of 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 mode may be either a batch type or a continuous type.
  • the polymerization reaction of the above solution polymerization can be stopped by adding a polymerization terminator.
  • the polymerization terminator include alcohols such as methanol and isopropanol.
  • the obtained polymerization reaction solution is poured into a poor solvent such as methanol to precipitate an unmodified conjugated diene polymer (F'), or the polymerization reaction solution is washed with water, separated, and dried.
  • a modified conjugated diene polymer (F') can be isolated.
  • the functional group-modified conjugated diene-based polymer (F) having a moiety containing a functional group represented by the above formula (II) as a branched chain.
  • the method for producing the above is not particularly limited, but from the viewpoint of introducing a functional group having a preferable structure, for example, a mercapto group (-SH) is added to the carbon-carbon unsaturated bond contained in the unmodified conjugated diene-based polymer (F').
  • a method of introducing a functional group derived from an alkoxysilane compound by subjecting a compound having () to a radical addition reaction, a carbon-carbon unsaturated bond contained in an unmodified conjugated diene polymer (F') with a platinum compound-containing catalyst in addition, a method of introducing a functional group derived from an alkoxysilane compound by hydrosilylation in the presence of a co-catalyst used as needed can be mentioned.
  • these production methods from the viewpoint of availability of modification reagents and catalysts and production cost, a method of radical addition reaction of a compound having a mercapto group (-SH) is preferable, and the obtained functional group-modified conjugated diene system weight is preferable.
  • a method of introducing a functional group derived from an alkoxysilane compound by hydrosilylation is preferable.
  • a functional group derived from an alkoxysilane compound is introduced by radically adding a compound having a mercapto group (-SH) to a carbon-carbon unsaturated bond contained in the unmodified conjugated diene-based polymer (F').
  • a method of radical addition reaction of the silane compound (IV) represented by the following formula (IV) to the carbon-carbon unsaturated bond contained in the unmodified conjugated diene-based polymer (F') is preferable.
  • R 4 represents a divalent alkylene group having 1 to 6 carbon atoms
  • R 5 and R 6 are independently aryl groups having 6 to 12 carbon atoms and alkyl having 1 to 12 carbon atoms, respectively.
  • n is an integer of 1 to 3
  • R 5 may be the same or different
  • R 6 may be the same. It may be different.
  • silane compound (IV) examples include mercaptomethylenemethyldiethoxysilane, mercaptomethylenetriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethoxydimethylsilane, and 2-.
  • the mercapto group (-SH) of the silane compound (IV) is derived from the silane compound (IV) by radical addition reaction to the carbon-carbon unsaturated bond contained in the unmodified conjugated diene polymer (F').
  • a functional group-modified conjugated diene-based polymer (F) having a functional group to be treated, specifically, a partial structure represented by the following formula (V) as a functional group can be obtained.
  • the method for adding the silane compound (IV) to the unmodified conjugated diene polymer (F') is not particularly limited, and for example, the silane compound (IV) is added to the unmodified conjugated diene polymer (F'). Further, if necessary, a method of adding a radical generator and heating in the presence or absence of an organic solvent can be adopted.
  • the radical generator to be used is not particularly limited, and commercially available organic peroxides, azo compounds, hydrogen peroxide and the like can be used.
  • organic peroxide examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, and 1,1-bis (t-butylperoxy).
  • azo compound examples include 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), and 2,2'-azobis (2-methylbutyronitrile). , 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis (2- (2-imidazoline) -2-yl) propane), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), 2,2'-azobis (2-hydroxymethylpropion) Nitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl 2,2'-azobis (2-methylpropionate), 2-cyano-2-propylazoformamide, 2-phenylazo-4- Examples thereof include methoxy-2,4-dimethylvaleronitrile.
  • the radical generator may be used alone or in combination of two or more.
  • Examples of the organic solvent used in the above method generally include a hydrocarbon solvent and a halogenated hydrocarbon solvent.
  • hydrocarbon solvents such as n-butane, n-hexane, n-heptane, cyclohexane, benzene, toluene, and xylene are preferable.
  • the organic solvent may be used alone or in combination of two or more.
  • an anti-aging agent may be added from the viewpoint of suppressing side reactions.
  • Preferred anti-aging agents used at this time include, for example, 2,6-dit-butyl-4-methylphenol (BHT), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4.
  • the amount of the antiaging agent added is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass with respect to 100 parts by mass of the unmodified conjugated diene polymer (F').
  • the temperature in the reaction of adding the silane compound (IV) to the unmodified conjugated diene polymer (F') 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, still more preferably 1 to 50 hours.
  • R 7 and R 8 independently represent an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms, where n is an integer of 1 to 3 and n is. If it is 2 or more, R 7 may be the same or different, and if 3-n is 2 or more, R 8 may be the same or different.
  • silane compound (VI) examples include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, and dimethylethoxysilane. These silane compounds may be used alone or in combination of two or more.
  • a functional group-modified conjugated diene polymer (F) having a partial structure represented by the following formula (VII) as a functional group can be obtained.
  • the platinum compound-containing catalyst used in the hydrosilylation reaction is not particularly limited, and is, for example, platinum chloride, an alcohol solution of platinum chloride, platinum-1,3-divinyl-1,1,3,3-tetramethyl. Toluene or xylene solution of disiloxane complex, tetraxtriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobis acetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadien platinum, etc., platinum-carbon, platinum-alumina, platinum- Examples thereof include a carrying catalyst such as silica.
  • a zero-valent platinum complex is preferable, and a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is more preferable.
  • the amount of the platinum compound-containing catalyst used is not particularly limited, but from the viewpoint of reactivity, productivity, etc., the amount of platinum atoms contained in 1 mol of the silane compound (VI) is 1 ⁇ 10 -7.
  • the amount to be ⁇ 1 ⁇ 10 ⁇ 2 mol is preferable, and the amount to be 1 ⁇ 10 -7 to 1 ⁇ 10 -3 mol is more preferable.
  • the co-catalyst in the above reaction it is preferable to use one or more selected from ammonium salts of inorganic acids, acid amide compounds and carboxylic acids.
  • ammonium salt of the inorganic acid examples include ammonium chloride, ammonium sulfate, ammonium amidosulfate, ammonium nitrate, monoammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium diaphosphate, ammonium carbonate, and ammonium hydrogencarbonate. , Ammonium sulfide, ammonium borate, ammonium borofluoride and the like. Among these, ammonium salts of inorganic acids having a pKa of 2 or more are preferable, and ammonium carbonate and ammonium hydrogen carbonate are more preferable.
  • Examples of the acid amide compound include formamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, acrylamide, malonamide, succinamide, maleamide, fumalamide, benzamide, phthalamide, palmitate amide and stearate amide. Can be mentioned.
  • carboxylic acid examples include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, pentanoic acid, caproic acid, heptanic acid, octanoic acid, lactic acid, and glycolic acid.
  • formic acid, acetic acid and lactic acid are preferable, and acetic acid is more preferable.
  • the amount of the co-catalyst used is not particularly limited, but 1 ⁇ 10 -5 to 5 ⁇ 10 -1 mol per 1 mol of the silane compound (VI) is used from the viewpoint of reactivity, selectivity, cost and the like. Preferably, 1 ⁇ 10 -4 to 5 ⁇ 10 -1 mol is more preferable.
  • a solvent can also be used.
  • the solvent examples include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ethyl acetate, butyl acetate and the like.
  • Ester-based solvents; aprotonic polar solvents such as N, N-dimethylformamide; chlorinated hydrocarbon-based solvents such as dichloromethane and chloroform. These solvents may be used alone or in admixture of two or more.
  • the reaction temperature in the hydrosilylation reaction is not particularly limited, and can usually be carried out at a temperature of 0 ° C. or higher, and if necessary, under heating conditions, but 0 to 200 ° C. is preferable. In order to obtain an appropriate reaction rate, the reaction is preferably carried out under heating, and from such a viewpoint, the reaction temperature is more preferably 40 to 110 ° C, further preferably 40 to 90 ° C.
  • the reaction time is also not particularly limited, and is usually about 1 to 60 hours, but 1 to 30 hours is preferable, and 1 to 20 hours is more preferable.
  • the functional group-modified conjugated diene polymer (F) one functional group having a partial structure represented by the above formula (V) or the above formula (VII) may be contained alone, or two or more thereof are contained. You may. Therefore, the functional group-modified conjugated diene-based polymer (F) may be a diene-based polymer modified with one compound selected from the group consisting of the above-mentioned silane compound (IV) and silane compound (VI). Alternatively, it may be a diene-based polymer modified with two or more kinds of compounds.
  • Z in the above formula (II) is preferably Si or Sn, and is preferably Si. More preferred.
  • An alkoxy group is preferable as V in the above formula (II) from the viewpoints of transparency, thermal stability, weather resistance, and reactivity in the coupling step described later of the obtained conjugated diene-based graft copolymer (A1). , An alkoxy group having 1 to 5 carbon atoms is more preferable, and a methoxy group and an ethoxy group are particularly preferable.
  • n in the above formula (II) is an integer satisfying the above formula (1), it is the side that binds to the reactivity in the coupling step described later and the branch point of the obtained conjugated diene-based graft copolymer (A1). From the viewpoint of controlling the number of chains, 2 or more is preferable, 3 or more is more preferable, and it is particularly preferable that the valence is the same as Z.
  • the average number of portions represented by the above formula (II) per molecule of the functional group-modified conjugated diene polymer (F) is preferably 1 to 50, more preferably 2 to 30, and further 3 to 20. preferable.
  • the average number of functional groups V in the above formula (II) per molecule of the functional group-modified conjugated diene polymer (F) is preferably 2 to 150, more preferably 4 to 90, and 6 to 60. More preferred.
  • the average number of functional groups V in the above formula (II) per molecule of the functional group-modified conjugated diene polymer (F) is the functional group of the functional group V contained in the functional group-modified conjugated diene polymer (F). It is calculated from the following formula (9) using the equivalent amount (g / eq) and the number average molecular weight (Mn) converted to standard polystyrene.
  • the functional group equivalent of the functional group V contained in the functional group-modified conjugated diene polymer (F) is other than the conjugated diene bonded to one functional group V and the conjugated diene contained as necessary. It means the mass of the monomer.
  • the functional group equivalent is calculated from the area ratio of the peak derived from the functional group V to the peak derived from the polymer main chain using 1 H-NMR.
  • the peak derived from the functional group V refers to the peak derived from the alkoxy group and the hydroxyl group.
  • the mixing ratio of the unmodified conjugated diene polymer (F') and the above-mentioned silane compound (IV) or silane compound (VI) is, for example, the formula (II) per molecule of the functionally modified conjugated diene polymer (F).
  • the average number of functional groups V contained in) may be appropriately set to a desired value.
  • the unmodified conjugated diene polymer (F') and the above-mentioned silane compound (IV) or silane compound (VI) may be set.
  • To (unmodified conjugated diene polymer (F') / silane compound (IV) or silane compound (VI)) may be mixed so as to be 0.3 to 100.
  • the preferred range of Mw and 1,4-bond content of the functional group-modified conjugated diene-based polymer (F) is the same as that of the unmodified conjugated diene-based polymer (F').
  • the melt viscosity of the functional group-modified conjugated diene polymer (F) measured at 38 ° C. is preferably 0.1 to 2,000 Pa ⁇ s, more preferably 0.1 to 1500 Pa ⁇ s, and 0.1 to 1000 Pa ⁇ s. -S is more preferable.
  • the melt viscosity of the functional group-modified conjugated diene polymer (F) is within the above range, the process passability during production tends to be excellent and the economic efficiency tends to be good.
  • the active terminal polymer (I) is reacted with the functional group-modified conjugated diene polymer (F) to cause the functional group V in the portion represented by the above formula (II) and the above.
  • the substitution reaction of the active terminal polymer (I) occurs, and a conjugated diene-based graft copolymer (A1) in which the active terminal polymer (I) as a side chain is bonded to the heteroatom Z which is a branch point is formed. (Hereinafter, this reaction is referred to as a coupling reaction).
  • the functional group V (at least one remaining functional group selected from the group consisting of an alkoxy group and a hydroxyl group) unreacted in the coupling reaction and the inactivation step described later is a conjugated diene-based graft copolymer (A1). ), The functional group V remains as it is or is hydrolyzed to be selected from the group consisting of an alkoxy group and a hydroxyl group bonded to the branch point of the conjugated diene graft copolymer (A1). At least one functional group (c) is formed.
  • a conjugated diene-based graft copolymer is produced by the reaction of two kinds of polymers as described above, a polymer having a silyl chloride group as a reactive functional group, which is often used in the past, is used as one of the raw materials.
  • Halides are produced as by-products. Due to this halide, the transparency, heat resistance, and weather resistance of the obtained conjugated diene-based graft copolymer tend to decrease. Further, chlorosilanes used for synthesizing a polymer having a silyl chloride group as a reactive functional group are very reactive and highly harmful, and therefore have a problem in handleability.
  • the molar ratio of (amount of active terminal polymer (I) charged) / (amount of functional group-modified conjugated diene polymer (F) charged) is the above-mentioned branching per molecule of conjugated diene graft copolymer (A1).
  • the average number W of the side chains (b) directly bonded to the points may be appropriately set to a desired value, but is preferably 2 to 200, more preferably 3 to 100, for example. It is more preferably 5 to 50.
  • the molar ratio of (charged amount of active terminal polymer (I)) / (charged amount of functional group-modified conjugated diene polymer (F)) is smaller than 2, the number of side chains that can be introduced decreases, and is more than 200. If it is large, the coupling rate described later tends to decrease.
  • the coupling reaction is usually carried out in a temperature range of 0 to 100 ° C. for 0.5 to 50 hours.
  • the functional group-modified conjugated diene polymer (F) may be diluted and used, and the diluting solvent is not particularly limited as long as it is inactive with respect to the active terminal and does not adversely affect the reaction.
  • the diluting solvent is not particularly limited as long as it is inactive with respect to the active terminal and does not adversely affect the reaction.
  • hexane or cyclohexane Saturated aliphatic hydrocarbons such as heptane, octane, decane, toluene, benzene and xylene, or aromatic hydrocarbons.
  • a Lewis base may be added as an additive during the coupling reaction.
  • Lewis base examples include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; triethylamine, N, N, N', N'-tetramethylethylenediamine and N-methylmorpholine. And the like, amines and the like. These Lewis bases may be used alone or in combination of two or more.
  • the functional group-modified conjugated diene-based polymer (F) may be added to the reaction vessel in which the active terminal polymer (I) is synthesized, or conversely, the functional group-modified conjugated diene-based polymer weight may be added.
  • the active terminal polymer (I) may be added to the coalescence (F).
  • both the active terminal polymer (I) and the functional group-modified conjugated diene polymer (F) may be diluted with a solvent and used if necessary.
  • the active terminal polymer (I) may be used alone or in combination of two or more, and the functional group-modified conjugated diene polymer (F) may also be used alone. Also, two or more types may be used in combination.
  • the coupling rate in the coupling reaction is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more. If the coupling ratio is less than 50%, the mechanical properties of the obtained conjugated diene-based graft copolymer (A1) are deteriorated, which is not preferable.
  • the coupling rate is increased by increasing the amount of the functional group-modified conjugated diene polymer (F) added, increasing the amount of Lewis base added, increasing the reaction temperature, or increasing the reaction time. be able to.
  • the coupling reaction can be carried out until the coupling rate reaches a desired range. After that, the coupling reaction can be stopped by adding a polymerization terminator such as methanol or isopropanol.
  • the number of at least one functional group (c) selected from the group consisting of an alkoxy group and a hydroxyl group that can be directly bonded to the branch point is the active terminal polymer (I) in the coupling reaction and the functional group-modified conjugated diene system.
  • Step (A-2) In the method for producing the conjugated diene-based graft copolymer (A1), after the step (A-1), in order to adjust the number of functional groups (c) directly bonded to the branch point to a desired range, (A-2) At least a part of at least one remaining functional group (functional group V existing unreacted) selected from the group consisting of an alkoxy group and a hydroxyl group in the conjugated diene-based graft copolymer (A1). Step to inactivate (hereinafter referred to as inactivation step); Is a preferred embodiment.
  • inactivation step Step to inactivation step
  • the inactivation step (A-2) is preferably performed before the recovery step (B).
  • Examples of the reagent used for inactivating the alkoxy group and the hydroxyl group include methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, and the like.
  • Alkyl lithiums such as sec-butyl lithium and t-butyl lithium; alkyl sodiums such as methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium, sec-butyl sodium and t-butyl sodium; methyl Alkyl potassiums such as potassium, ethyl potassium, n-propyl potassium, isopropyl potassium, n-butyl potassium, sec-butyl potassium, t-butyl potassium; methylmagnesium bromide, ethylmagnesium bromide, t-butylmagnesium bromide, t-butyl Alkyl magnesium halides such as magnesium chloride and sec-butylmagnesium iodide; dialkyl copper lithium such as dimethyl copper lithium, diethyl copper lithium, methyl ethyl copper lithium, methyl n-propyl copper lithium, ethyl n-butyl copper lithium
  • Luis bases such as lithium diisopropylamide, lithium diisoethylamide, lithium dit-butylamide and the like; Among these, n-butyllithium, sec-butyllithium, methyllithium, methylmagnesium bromide, and dimethylcopper lithium are preferable because it is desirable that the steric hindrance is small in order for the inactivation reaction to proceed rapidly.
  • the molar ratio of the amount is preferably 0.5 or more, more preferably 1.0 or more, and further preferably 2.0 or more. Further, it is preferably 100 or less, more preferably 50 or less, and further preferably 20 or less.
  • the inactivation reaction of the above step (A-2) is usually carried out in a temperature range of 0 to 100 ° C. for 0.1 to 50 hours.
  • the inactivating reagent may be diluted and used, and the diluting solvent is not particularly limited as long as it is inactive with respect to the inactivating reagent and does not adversely affect the reaction.
  • the diluting solvent is not particularly limited as long as it is inactive with respect to the inactivating reagent and does not adversely affect the reaction.
  • Saturated aliphatic hydrocarbons such as decane, toluene, benzene and xylene or aromatic hydrocarbons can be mentioned.
  • a Lewis base may be added as an additive during the inactivation reaction, and examples of the Lewis base include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. Examples thereof include amines such as triethylamine, N, N, N', N'-tetramethylethylenediamine and N-methylmorpholin. These Lewis bases may be used alone or in combination of two or more.
  • the inactivation reaction can be carried out until the number of functional groups (c) that can be directly bonded to the branch point reaches a desired range.
  • the inactivating reagent can be inactivated by adding a polymerization terminator such as methanol or isopropanol.
  • Step (B) In the method for producing the conjugated diene-based graft copolymer (A1), (B) Step of recovering the obtained conjugated diene-based graft copolymer (A1); including.
  • the obtained conjugated diene-based graft copolymer (A1) of the present invention is recovered.
  • the method for recovering the conjugated diene-based graft copolymer (A1) is not particularly limited, but a solution containing the conjugated diene-based graft copolymer (A1) can be obtained in the step (A-1) or the step (A-2). If so, for example, pour the obtained solution into a poor solvent such as methanol to precipitate the conjugated diene-based graft copolymer (A1), or wash the polymerization reaction solution with water, separate it, and then dry it. Can be recovered by isolating the conjugated diene-based graft copolymer (A1).
  • Step (A'-1) The method for producing the polymer (M) containing the conjugated diene unit which is a component of the main chain in the above step (A'-1) is not particularly limited, but for example, an emulsion polymerization method and a solution polymerization method are preferable, and the obtained weight is preferable.
  • the solution polymerization method is more preferable from the viewpoint of the molecular weight distribution of the coalescence.
  • the polymer (M) containing a conjugated diene unit becomes the main chain (a2) of the conjugated diene-based graft copolymer (A2) of the present invention.
  • conjugated diene which is a monomer unit constituting the polymer (M) containing a conjugated diene unit, and a monomer other than the conjugated diene (aromatic vinyl compound).
  • suitable contents and the like are the same as those for the main chain (a2) of the conjugated diene-based graft copolymer (A2).
  • the description of the weight average molecular weight (Mw) of the polymer (M) containing the conjugated diene unit, the vinyl content, the preferred embodiment of Tg, etc. is the description of the main chain (a2) of the conjugated diene-based graft copolymer (A2). Is similar to.
  • emulsion polymerization method which is an example of a method for producing a polymer (M) containing a conjugated diene unit
  • a known or known method can be applied.
  • a monomer containing a predetermined amount of conjugated diene is emulsified and dispersed in a dispersion medium in the presence of an emulsifier, and emulsion polymerization is carried out with a radical polymerization initiator.
  • Examples of the emulsifier include long-chain fatty acid salts having 10 or more carbon atoms and rosin salts.
  • Examples of the long-chain fatty acid salt include potassium salts or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, and stearic acid.
  • the dispersion medium may contain a water-soluble organic solvent such as methanol or ethanol as long as the stability during polymerization is not impaired.
  • radical polymerization initiator examples include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, hydrogen peroxide and the like.
  • a chain transfer agent may be used to adjust the molecular weight of the obtained polymer (M) containing the conjugated diene unit.
  • the chain transfer agent include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpenes, turpinolene, ⁇ -terpinene, ⁇ -methylstyrene dimer and the like.
  • the temperature of emulsion polymerization can be appropriately set depending on the type of radical polymerization initiator used, but is usually in the range of 0 to 100 ° C, preferably in the range of 0 to 60 ° C.
  • the polymerization mode may be either continuous polymerization or batch polymerization.
  • the polymerization reaction can be stopped by adding a polymerization inhibitor.
  • the polymerization terminator include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite.
  • an anti-aging agent may be added if necessary.
  • unreacted monomers are removed from the obtained latex as needed, and then salts such as sodium chloride, calcium chloride and potassium chloride are used as coagulants, and nitric acid, sulfuric acid and the like are used as necessary.
  • the polymer (M) containing the conjugated diene unit is coagulated while adjusting the pH of the coagulation system to a predetermined value by adding an acid, and then the polymer is recovered by separating the dispersion medium. Then, the polymer (M) containing the conjugated diene unit is obtained by washing with water, dehydrating, and then drying.
  • the latex and the spreading oil prepared as an emulsified dispersion may be mixed in advance and recovered as a polymer (M) containing an oil-expanded conjugated diene unit.
  • a known or known method can be applied.
  • a Ziegler-based catalyst, a metallocene-based catalyst, or an anionically polymerizable active metal or active metal compound is used as an initiator, and if necessary, in the presence of a polar compound, a single amount containing a conjugated diene. Polymerize the body.
  • the solvent examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, Examples include aromatic hydrocarbons such as toluene and xylene.
  • an anionic polymerizable active metal or an active metal compound is preferable, and an anionic polymerizable active metal compound is more preferable.
  • anionic polymerizable active metals examples 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. .. Among these, alkali metals and alkaline earth metals are preferable, and alkali metals are more preferable.
  • an organic alkali metal compound is preferable.
  • the organic alkali metal compound include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stillbenlithium; , 1,4-Dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene and other polyfunctional organic lithium compounds; sodium naphthalene, potassium naphthalene and the like.
  • an organic lithium compound is preferable, and an organic monolithium compound is more preferable.
  • the amount of the initiator used can be appropriately set according to the melt viscosity, molecular weight, etc. of the polymer (M) containing the conjugated diene unit, but is usually 0. It is used in an amount of 01 to 3 parts by mass.
  • the organic alkali metal compound can also be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine or dibenzylamine. ..
  • Polar compounds are usually used in anionic polymerization to adjust the microstructure (vinyl content) of the conjugated diene site without inactivating the reaction.
  • the polar compound 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 polar compound is usually used in an amount of 0.01 to 1000 mol per 1 mol of the organic alkali metal compound.
  • the temperature of 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 mode may be either a batch type or a continuous type.
  • the polymerization reaction of the above solution polymerization can be stopped by adding a polymerization terminator.
  • the polymerization terminator include alcohols such as methanol and isopropanol.
  • the obtained polymerization reaction solution is poured into a poor solvent such as methanol to precipitate a polymer (M) containing a conjugated diene unit, or the polymerization reaction solution is washed with water, separated, and dried to obtain the above-mentioned conjugated diene.
  • the polymer (M) containing the unit can be isolated.
  • the polymerization reaction solution after the polymerization is stopped may be used as it is in the thiolation reaction as long as it does not affect the lithiolysis reaction. Further, if necessary, a part of the solvent may be removed, or a solvent may be added to dilute the polymerization reaction solution.
  • the anionic active site contained in the polymer (M) obtained as described above is lithiated by reacting with an organolithium compound in the presence of a polar compound.
  • organolithium compound used for the lithium formation of the polymer (M) in the above step (A'-1) examples include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium and hexyllithium.
  • Organolithium compounds such as phenyllithium and stillbenlithium; polyfunctionality such as dilithiomethane, dilithionaphthalene, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene and the like.
  • the side chain density is calculated by the following formula (2).
  • (Side chain density) (Average number of side chains (b2) per molecule of conjugated diene-based graft copolymer (A2)) / [(Number average molecular weight of main chain (a2) Mn) / (Molecular weight of styrene unit) ] ⁇ 100 (2) That is, the amount of the organic lithium compound used is such that the target side chain density is obtained with the number average molecular weight Mn of the main chain (a2) and the side chain (b2) per molecule of the conjugated diene graft copolymer (A2). ) Can be determined by designing the average number.
  • the polar compound used for the lithiolysis of the polymer (M) in the above step (A'-1) is used to promote the lithiolysis reaction.
  • the polar compound 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.
  • 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 alkali metal alkoxides and phosphine compounds.
  • tertiary amines are preferable, and tetramethylethylenediamine is particularly preferable.
  • the amount of the polar compound used is preferably 0.01 mol or more, more preferably 0.05 mol or more, and particularly preferably 0.1 mol or more with respect to 1 mol of the organic alkali metal compound. Further, 100 mol or less is preferable, 50 mol or less is more preferable, and 10 mol or less is particularly preferable. If it is less than 0.01 mol, the reaction rate tends to be inferior, and if it exceeds 100 mol, it tends to be inferior in economic efficiency.
  • Lithioization in the above step (A'-1) is usually carried out in a state where the polymer (M) is dissolved in a solvent.
  • the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene. , Aromatic hydrocarbons such as toluene and xylene.
  • the reaction temperature for lithiolation in the above step (A'-1) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and particularly preferably 20 ° C. or higher. Further, 100 ° C. or lower is preferable, 80 ° C. or lower is more preferable, and 60 ° C. or lower is particularly preferable. If the temperature is lower than 0 ° C., the reaction rate tends to be inferior, and if the temperature exceeds 100 ° C., side reactions such as decomposition tend to increase.
  • the reaction time for lithiolysis in the above step (A'-1) can be appropriately set according to the progress of the reaction, but is preferably 0.01 to 100 hours, more preferably 0.1 to 50 hours, and 0.2 to 0.2 to 50 hours. 20 hours is particularly preferred.
  • the peak area in the range of 4.0 to 5.7 ppm is set to 100, 5.7 to 6.
  • the peak area in the range of 4 ppm is preferably in the range of 0.1 to 10, more preferably in the range of 0.3 to 5, and particularly preferably in the range of 0.5 to 4.
  • the peak area is in this range, it can be said that the lithiolysis reaction is proceeding properly, and the average number of side chains (b2) of the obtained conjugated diene-based graft copolymer (A2) is in the proper range. ..
  • the Lewis acid is added to reduce the action of the polar compound added to promote the lithiolysis reaction and to adjust the vinyl content of the side chain in the step (B') described later to a desired range.
  • an alkyl metal compound that does not inactivate the lithium formation point produced in the above step (A'-1) is preferable, and for example, trimethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, and tri.
  • Alkyl aluminum compounds such as isobutyl aluminum, tri-n-hexyl aluminum, and trioctyl aluminum
  • alkyl magnesium compounds such as butyl ethyl magnesium, di-n-butyl magnesium, and di-n-hexyl magnesium
  • dimethyl zinc, diethyl examples thereof include alkyl zinc compounds such as zinc, di-n-propyl zinc, diisobutyl zinc, and di-n-butyl zinc.
  • alkylaluminum compound or an alkylzinc compound is preferable, an alkylaluminum compound is more preferable, and triisobutylaluminum is particularly preferable.
  • the amount of the Lewis acid used can be appropriately adjusted depending on the vinyl content of the desired side chain (b2). For example, 0.01 mol with respect to 1 mol of the organic alkali metal compound used in the above step (A'-1). The above is preferable, 0.05 mol or more is more preferable, and 0.1 mol or more is particularly preferable. Further, 10 mol or less is preferable, 5 mol or less is more preferable, and 1 mol or less is particularly preferable. If it is less than 0.01 mol, the effect of adding Lewis acid is poor and it is difficult to adjust to the desired degree of vinylization, and if it is more than 10 mol, the polymerization rate of side chain polymerization tends to decrease, and the degree of polymerization tends to decrease.
  • 0.02 mol or more is preferable, 0.1 mol or more is more preferable, and 0.2 mol or more is particularly preferable. Further, 20 mol or less is preferable, 10 mol or less is more preferable, and 2 mol or less is particularly preferable. If it is less than 0.02 mol, the effect of adding Lewis acid is poor and it is difficult to adjust to the desired degree of vinylization, and if it is more than 20 mol, the polymerization rate of side chain polymerization tends to decrease, and the polymerization rate tends to decrease. It tends to be inferior in economic efficiency.
  • the timing of adding the Lewis acid is after the step (A'-1), before the step (B') described later, or at any timing during the step (B'). It may be present and can be arbitrarily selected depending on the vinyl content of the desired side chain (b2).
  • the method for producing the conjugated diene-based graft copolymer (A2) of the present invention is as follows. At least one monomer selected from the group consisting of (B') conjugated diene and aromatic vinyl compound is added and polymerized from the lithiotized moiety in the polymer (M) to form a heavy main chain.
  • the monomer polymerized in the above step (B') becomes the side chain (b2) of the conjugated diene-based graft copolymer (A2) of the present invention.
  • Specific examples, preferred examples, and suitable contents of conjugated diene which is a monomer unit constituting the polymer polymerized in the step (B'), and other monomers (aromatic vinyl) other than the conjugated diene.
  • the description of the weight average molecular weight (Mw), vinyl content, preferred embodiment of Tg and the like of the polymer polymerized in the step (B') relates to the side chain (b2) of the conjugated diene-based graft copolymer (A2). Same as the description.
  • a polar compound may be further added in order to adjust the vinyl content of the side chain (b2) to a desired range.
  • Lewis acid may be added as described above in order to adjust the vinyl content to a desired range.
  • the solvent that can be used in the above step (B') is the same as the preferred example of the solvent in the above step (A'-1). If necessary, the solvent may be further added at any time after the step (A'-1).
  • the polymerization temperature in the above step (B') is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and particularly preferably 20 ° C. or higher. Further, 100 ° C. or lower is preferable, 80 ° C. or lower is more preferable, and 60 ° C. or lower is particularly preferable. If the temperature is lower than 0 ° C., the polymerization rate tends to be inferior, and if the temperature exceeds 100 ° C., side reactions such as decomposition tend to increase.
  • the polymerization time of the above step (B') can be appropriately set according to the progress of the reaction, but is preferably 0.01 to 100 hours, more preferably 0.1 to 50 hours, and particularly 0.2 to 20 hours. preferable.
  • the polymerization reaction in the above step (B') can be stopped by adding a polymerization terminator.
  • the polymerization terminator include alcohols such as methanol and isopropanol.
  • the method for producing the conjugated diene-based graft copolymer (A2) of the present invention is as follows. (C') Step of recovering the obtained conjugated diene-based graft copolymer (A2); including.
  • the obtained conjugated diene-based graft copolymer (A2) of the present invention is recovered.
  • the method for recovering the conjugated diene-based graft copolymer (A2) is not particularly limited, but when a solution containing the conjugated diene-based graft copolymer (A2) is obtained in the step (B'), for example, it can be obtained.
  • the solution is poured into a poor solvent such as methanol to precipitate the conjugated diene-based graft copolymer (A2), or the polymerization reaction solution is washed with water, separated, and dried to obtain the same weight of the conjugated diene-based graft copolymer. It can be recovered by isolating the coalescence (A2).
  • the rubber composition of the present invention may further contain a solid rubber (B).
  • the solid rubber (B) used in the present invention refers to a rubber that can be handled in a solid state at 20 ° C., and the solid rubber (B) does not include the conjugated diene-based branched copolymer (A).
  • the Mooney viscosity ML 1 + 4 of the solid rubber (B) at 100 ° C. is usually in the range of 20 to 200.
  • solid rubber (B) examples 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, and butadiene acrylonitrile copolymer. Examples thereof include rubber, chloroprene rubber, acrylic rubber, fluororubber, and urethane rubber. Among these solid rubbers (B), natural rubber, SBR, butadiene rubber, and isoprene rubber are preferable, and natural rubber and SBR are more preferable. These solid rubbers (B) may be used alone or in combination of two or more.
  • SBR styrene-butadiene rubber
  • the number average molecular weight (Mn) of the solid rubber (B) is preferably 80,000 or more, preferably 100 or more, from the viewpoint of fully exhibiting the characteristics of the obtained rubber composition and the crosslinked product obtained from the composition. More preferably, it is in the range of 000 to 3,000,000.
  • the number average molecular weight in the present specification is a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (GPC).
  • the natural rubber is generally used in the tire industry such as TSR (Technically Specialized Rubber) such as SMR (Malaysia TSR), SIR (Indonesia TSR), STR (Thai TSR) and RSS (Ribbed Smoked Sheet).
  • TSR Technicalnically Specialized Rubber
  • SMR Manufacturing Rilaysia TSR
  • SIR Indonesia TSR
  • STR Thai TSR
  • RSS Rabbed Smoked Sheet
  • modified natural rubbers such as natural rubbers used, high-purity natural rubbers, epoxidized natural rubbers, hydroxylated natural rubbers, hydrogenated natural rubbers, and grafted natural rubbers.
  • SMR20, STR20 and RSS # 3 are preferable from the viewpoint of less variation in quality and easy availability.
  • These natural rubbers may be used alone or in combination of two or more.
  • SBR general ones used for tire applications can be used, but specifically, those having a styrene content of 0.1 to 70% by mass are preferable, those having a styrene content of 5 to 50% by mass are more preferable, and 15 It is more preferably from ⁇ 35% by mass. Further, a vinyl content of 0.1 to 60 mol% is preferable, and a vinyl content of 0.1 to 55 mol% is more preferable.
  • the "vinyl content” refers to 1,2-bonds, 3,4-bonds (in the case of other than farnesene), and 3,13-bonds in a total of 100 mol% of conjugated diene units contained in the polymer.
  • the vinyl content is derived from conjugated diene units that are bonded in 1,2-bond, 3,4-bond (for non-farnesene), and 3,13-bond (for farnesene) using 1 H-NMR. It can be calculated from the area ratio of the peak derived from the conjugated diene unit that is bonded to the peak of 1,4-bond (in the case of other than farnesene) and 1,13- bond (in the case of farnesene).
  • 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 200,000 to 1,500,000. It is more preferable to have. Within the above range, both workability and mechanical strength can be achieved.
  • the weight average molecular weight in the present specification is a polystyrene-equivalent weight average molecular weight obtained from the measurement of gel permeation chromatography (GPC).
  • the glass transition temperature determined by the differential thermal analysis method of SBR used in the present invention is preferably ⁇ 95 to 0 ° C., more preferably ⁇ 95 to ⁇ 5 ° C. By setting the glass transition temperature in the above range, the viscosity of SBR can be set in a range that is easy to handle.
  • the SBR that can be used in the present invention is obtained by copolymerizing styrene and butadiene.
  • the method for producing SBR is not particularly limited, and any of an emulsion polymerization method, a solution polymerization method, a gas phase polymerization method, and a bulk polymerization method can be used, but among these production methods, the emulsion polymerization method and the solution polymerization method are preferable. ..
  • Emulsion-polymerized styrene-butadiene rubber (hereinafter, also referred to as E-SBR) can be produced by a known or ordinary emulsion polymerization method. For example, it is obtained by emulsifying and dispersing a predetermined amount of styrene and butadiene monomer in the presence of an emulsifier and emulsion polymerization with a radical polymerization initiator.
  • Solution-polymerized styrene-butadiene rubber (hereinafter, also referred to as S-SBR) can be produced by a usual solution polymerization method, for example, using an active metal anionically polymerizable in a solvent, preferably in the presence of a polar compound. Polymerize styrene and butadiene.
  • the solvent examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, Examples include aromatic hydrocarbons such as toluene. These solvents are usually preferably used in a range where the monomer concentration is 1 to 50% by mass.
  • anionic polymerizable active metals examples 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 preferable, and alkali metals are more preferable.
  • organic alkali metal compounds are more preferably used.
  • organic alkali metal compound examples include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stillbenlithium; dilithiomethane, 1,4-dilithiobutane, 1,4.
  • Polyfunctional organic lithium compounds such as -dilithio-2-ethylcyclohexane and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like can be mentioned. Of these, an organic lithium compound is preferable, and an organic monolithium compound is more preferable.
  • the amount of the organic alkali metal compound used is appropriately determined depending on the required molecular weight of S-SBR.
  • the organic alkali metal compound can also be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine, or dibenzylamine.
  • the polar compound is not particularly limited as long as it does not inactivate the reaction in anionic polymerization and is usually used for adjusting the microstructure of the butadiene site and the distribution in the copolymer segment of styrene.
  • the polar compound is not particularly limited.
  • Ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides, phosphine compounds and the like can be mentioned.
  • 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 mode may be either a batch type or a continuous type.
  • styrene and butadiene are continuously or intermittently supplied into the reaction solution so that the composition ratio of styrene and butadiene in the polymerization system is within a specific range. Is preferable.
  • the polymerization reaction can be stopped by adding an alcohol such as methanol or isopropanol as a polymerization terminator.
  • an alcohol such as methanol or isopropanol
  • the solvent can be separated from the polymerization solution by direct drying, steam stripping, or the like, and the desired S-SBR can be recovered.
  • the polymerization solution and the spreading oil may be mixed in advance and recovered as an oil spreading rubber.
  • a modified SBR in which a functional group is introduced into the SBR may be used as long as the effect of the present invention is not impaired.
  • the functional group include an amino group, an alkoxysilyl group, a hydroxyl group, an epoxy group, a carboxyl group and the like.
  • Examples of the method for producing the modified SBR include tin tetrachloride, tetrachlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, tetramethoxysilane, and tetraethoxysilane, which can react with the polymerization active terminal before adding the polymerization terminator.
  • Coupling agents such as 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolylenediisocyanate, 4,4'-bis (diethylamino) benzophenone, N-vinylpyrrolidone, etc.
  • Examples thereof include a method of adding a polymerization terminal modifier of the above, or another modifier described in JP-A-2011-132298.
  • the position of the polymer into which the functional group is introduced may be the polymerization terminal or the side chain of the polymer segment.
  • butadiene rubber examples include Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel; triethyl.
  • Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel; triethyl.
  • a commercially available butadiene rubber polymerized with a lanthanoid-based rare earth metal catalyst such as aluminum-organic acid neodymium-Lewis acid or an organic alkali metal compound similar to S-SBR can be used.
  • a butadiene rubber polymerized by a Ziegler-based catalyst is preferable because of its high cis-form content
  • the vinyl content of the butadiene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. If the vinyl content exceeds 50% by mass, the rolling resistance performance tends to deteriorate.
  • the lower limit of the vinyl content is not particularly limited.
  • the glass transition temperature varies depending on the vinyl content, but is preferably ⁇ 40 ° C. or lower, more preferably ⁇ 50 ° C. or lower.
  • the weight average molecular weight (Mw) of the butadiene rubber is preferably 90,000 to 2,000,000, more preferably 150,000 to 1,500,000. When Mw is in the above range, workability and mechanical strength are good.
  • the butadiene rubber contains a polyfunctional modifier, for example, tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in the molecule, or an amino group as long as the effect of the present invention is not impaired. It may have a branched structure or a polar functional group by using a modifier such as alkoxysilane.
  • a polyfunctional modifier for example, tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in the molecule, or an amino group as long as the effect of the present invention is not impaired. It may have a branched structure or a polar functional group by using a modifier such as alkoxysilane.
  • isoprene rubber examples include Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel; triethyl.
  • a lanthanoid-based rare earth metal catalyst such as aluminum-organic acid neodymium-Lewis acid, or a commercially available isoprene rubber polymerized using an organic alkali metal compound similar to S-SBR can be used.
  • Isoprene rubber polymerized by a Ziegler-based catalyst is preferable because of its high cis-form content. Further, isoprene rubber having an ultra-high cis form content obtained by using a lanthanoid-based rare earth metal catalyst may be used.
  • the vinyl content of the isoprene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. If the vinyl content exceeds 50% by mass, the rolling resistance performance tends to deteriorate.
  • the lower limit of the vinyl content is not particularly limited.
  • the glass transition temperature varies depending on the vinyl content, but is preferably ⁇ 20 ° C. or lower, more preferably ⁇ 30 ° C. or lower.
  • the weight average molecular weight (Mw) of the isoprene rubber is preferably 90,000 to 2,000,000, more preferably 150,000 to 1,500,000. When Mw is in the above range, workability and mechanical strength are good.
  • the isoprene rubber contains a polyfunctional modifier, for example, tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in the molecule, or an amino group as long as the effect of the present invention is not impaired. It may have a branched structure or a polar functional group by using a modifier such as alkoxysilane.
  • a polyfunctional modifier for example, tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in the molecule, or an amino group as long as the effect of the present invention is not impaired. It may have a branched structure or a polar functional group by using a modifier such as alkoxysilane.
  • the rubber composition of the present invention (for example, a rubber composition for a tire or a rubber composition for a sole) contains a solid rubber (B), the above-mentioned conjugated diene-based branching with respect to 100 parts by mass of the solid rubber (B) is carried out.
  • the content of the polymer (A) is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 60 parts by mass, further preferably 1 to 50 parts by mass, still more preferably 2 to 40 parts by mass.
  • the content of the conjugated diene-based branched copolymer (A) is within the above range, the rubber composition of the present invention or an article such as a tire or sole obtained from a crosslinked product of the composition has ice grip performance. Abrasion resistance becomes even better.
  • the rubber composition of the present invention may further contain a filler (C).
  • a filler (C) used in the rubber composition of the present invention include carbon black, silica, clay, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium oxide, glass fiber, and fibrous filler.
  • Inorganic fillers such as glass balloons; organic fillers such as resin particles, wood powder, and cork powder can be mentioned.
  • a filler in a rubber composition (for example, a rubber composition for a tire or a rubber composition for a sole), physical properties such as mechanical strength, heat resistance, or weather resistance can be improved, hardness can be adjusted, and rubber You can increase the amount.
  • a filler for example, a rubber composition for a tire or a rubber composition for a sole
  • carbon black and silica are preferable from the viewpoint of improving physical properties such as improvement of mechanical strength in rubber compositions, particularly rubber compositions for tires.
  • silica is preferable among the fillers (C).
  • Examples of the carbon black include furnace black, channel black, thermal black, acetylene black, and Ketjen black.
  • furnace black is preferable from the viewpoint of improving the cross-linking speed and mechanical strength.
  • These carbon blacks may be used alone or in combination of two or more.
  • the average particle size of the carbon black is preferably 5 to 100 nm, more preferably 5 to 80 nm, and even more preferably 5 to 70 nm from the viewpoint of improving dispersibility, mechanical strength, hardness and the like.
  • the average particle size of carbon black can be obtained by measuring the diameter of the particles with a transmission electron microscope and calculating the average value.
  • Examples of commercially available products of the above-mentioned furnace black include “Dia Black” manufactured by Mitsubishi Chemical Corporation and “Seast” manufactured by Tokai Carbon Co., Ltd.
  • Examples of commercially available products of acetylene black include “Denka Black” manufactured by Denki Kagaku Kogyo Co., Ltd.
  • Examples of commercially available products of Ketjen Black include “ECP600JD” manufactured by Lion Corporation.
  • the carbon black can be treated with an acid such as nitric acid, sulfuric acid, hydrochloric acid or a mixed acid thereof.
  • the surface oxidation treatment by heat treatment in the presence of air may be performed.
  • heat treatment is performed at 2,000 to 3,000 ° C. in the presence of a graphitizing catalyst. May be done.
  • Examples of the graphitization catalyst include boron, boron oxide (for example, B 2 O 2 , B 2 O 3 , B 4 O 3 , B 4 O 5, etc.), and boron oxo acid (for example, orthoboric acid, metaboric acid, etc.).
  • boron carbides for example, B 4 C, B 6 C, etc.
  • BN boron nitride
  • the above carbon black can also be used after adjusting the particle size by pulverization or the like.
  • high-speed rotary crushers hammer mills, pin mills, cage mills
  • various ball mills rolling mills, vibration mills, planetary mills
  • stirring mills be used for crushing carbon black.
  • silica examples include wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate and the like.
  • wet silica is preferable from the viewpoint of further improving workability, mechanical strength and wear resistance.
  • These silicas (C1) may be used alone or in combination of two or more.
  • the average particle size of silica (C1) is preferably 0.5 to 200 nm, more preferably 5 to 150 nm, further preferably 10 to 100 nm, from the viewpoint of improving workability, rolling resistance performance, mechanical strength, and wear resistance. preferable.
  • the average particle size of silica (C1) can be obtained by measuring the diameter of the particles with a transmission electron microscope and calculating the average value thereof.
  • the filler (C) contains silica (C1) from the viewpoint of improving physical properties such as the obtained rubber composition (for example, a rubber composition for tires and a rubber composition for soles) and the rolling resistance performance of the crosslinked product thereof. Is more preferable.
  • the rubber composition of the present invention for example, a rubber composition for a tire or a rubber composition for a sole
  • the amount of silica (C1) to 100 parts by mass of the solid rubber (B) is The content is preferably 5 to 200 parts by mass, more preferably 20 to 200 parts by mass, and even more preferably 30 to 100 parts by mass.
  • the rubber composition of the present invention or an article such as a tire or shoe obtained from a crosslinked product obtained from the composition has ice grip performance. Abrasion resistance becomes even better.
  • the rubber composition of the present invention (for example, a rubber composition for tires and a rubber composition for soles) contains solid rubber (B) and silica (C1), and the filler (C) is a filler other than silica and carbon black.
  • the content thereof is preferably 20 to 120 parts by mass, more preferably 20 to 90 parts by mass, and even more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the solid rubber (B).
  • These fillers (C) may be used alone or in combination of two or more.
  • the rubber composition of the present invention may further contain a cross-linking agent (D) in order to cross-link the rubber.
  • a cross-linking agent (D) include sulfur, sulfur compounds, oxygen, organic peroxides, phenol resins, amino resins, quinone and quinone dioxime derivatives, halogen compounds, aldehyde compounds, alcohol compounds, epoxy compounds, and metal halides. And organic metal halides, silane compounds and the like.
  • the sulfur compound include morpholine disulfide and alkylphenol disulfide.
  • organic peroxide examples include cyclohexanone peroxide, methylacetate acetate peroxide, t-butylperoxyisobutyrate, t-butylperoxybenzoate, benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, and dit.
  • -Butyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene and the like can be mentioned.
  • These cross-linking agents (D) may be used alone or in combination of two or more.
  • the cross-linking agent (D) is usually 0.1 to 10 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the solid rubber (B). It is contained in an amount of 0.8 to 5 parts by mass.
  • the rubber composition of the present invention (for example, a rubber composition for a tire, a rubber composition for a sole) contains sulfur, a sulfur compound, or the like as a cross-linking agent (D) for cross-linking (vulcanizing) rubber, for example.
  • the vulcanization accelerator (E) may be further contained.
  • the sulfide accelerator (E) include guanidine compounds, sulfenamide compounds, thiazole compounds, thiuram compounds, thiourea compounds, dithiocarbamic acid compounds, aldehyde-amine compounds, and aldehyde-ammonia compounds. , Imidazoline compounds, xanthate compounds and the like.
  • vulcanization accelerators (E) may be used alone or in combination of two or more.
  • the vulcanization accelerator (E) is usually contained in an amount of 0.1 to 15 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the solid rubber (B).
  • the rubber composition of the present invention (for example, a rubber composition for a tire, a rubber composition for a sole) contains sulfur, a sulfur compound, or the like as a cross-linking agent (D) for cross-linking (vulcanizing) rubber, for example.
  • a vulcanization aid (F) may be further contained.
  • the vulcanization aid (F) 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.
  • the vulcanization aid (F) is usually contained in an amount of 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the solid rubber (B).
  • silica (C1) when silica (C1) is contained as the filler (C), it is preferable to contain a silane coupling agent.
  • the silane coupling agent include sulfide compounds, mercapto compounds, vinyl compounds, amino compounds, glycidoxy compounds, nitro compounds, chloro compounds and the like.
  • sulfide compound examples include bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, and bis (2-trimethoxy).
  • Cyrilethyl) tetrasulfide bis (3-triethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) Disulfide, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 2-trimethoxysilylethyl-N, N-dimethylthiocarbamoyl Tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilyl
  • Examples of the mercapto-based compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane.
  • Examples of the vinyl compound include vinyltriethoxysilane and vinyltrimethoxysilane.
  • Examples of amino compounds include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, and 3- (2-aminoethyl) aminopropyltri. Examples thereof include methoxysilane.
  • Examples of the glycidoxy-based compound include ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and ⁇ -glycidoxypropylmethyldimethoxysilane. Can be mentioned.
  • Examples of the nitro compound include 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane.
  • Examples of the chloro compound include 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, and 2-chloroethyltriethoxysilane.
  • Examples of other compounds include octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, hexadecyltrimethoxysilane and the like.
  • 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 from the viewpoint of large addition effect and cost. Is preferable.
  • the silane coupling agent is preferably contained in an amount of 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and further preferably 1 to 15 parts by mass with respect to 100 parts by mass of silica (C1).
  • silica C1
  • the rubber composition of the present invention (for example, a rubber composition for a tire, a rubber composition for a shoe sole) is made of silicon as necessary for the purpose of improving workability, fluidity, etc. within a range that does not impair the effects of the present invention.
  • Process oils such as oils, aroma oils, TDAE (Treated Distilled Aromatic Extracts), MES (Mild Extracted Solves), RAE (Residual Aromatic Extracts), RAE (Residual Aromatic Industries), paraffin oils, naphthenic oils, and other process oils.
  • a resin component such as a C9-based resin, a rosin-based resin, a kumaron-inden-based resin, or a phenol-based resin may be contained as a softening agent.
  • the rubber composition of the present invention for example, a rubber composition for a tire or a rubber composition for a sole
  • contains the process oil as a softener the content thereof is based on 100 parts by mass of the solid rubber (B). It is preferably less than 50 parts by mass.
  • the rubber composition of the present invention (for example, a rubber composition for a tire, a rubber composition for a shoe sole) is necessary for the purpose of improving weather resistance, heat resistance, oxidation resistance, etc. within a range that does not impair the effects of the present invention.
  • antioxidant examples include hindered phenol compounds, phosphorus compounds, lactone compounds, hydroxyl compounds and the like.
  • examples of the antiaging agent 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 of the present invention is not particularly limited as long as each of the above components can be uniformly mixed.
  • the device used for manufacturing the rubber composition include a tangential or meshing closed kneader such as a kneader ruder, a brabender, a Banbury mixer, and an internal mixer, a single-screw extruder, a twin-screw extruder, and mixing. Examples include rolls and rollers.
  • the rubber composition can usually be produced in a temperature range of 70 to 270 ° C.
  • a crosslinked product can be obtained by cross-linking the rubber composition of the present invention (for example, a rubber composition for a tire or a rubber composition for a sole).
  • the cross-linking conditions of the rubber composition can be appropriately set according to the application and the like. For example, when sulfur or a sulfur compound is used as a cross-linking agent and the above rubber composition is cross-linked (vulcanized) by a mold, the cross-linking temperature is usually 120 to 200 ° C. and the pressurizing condition is usually 0.5 to 2.0 MPa. And can be crosslinked (vulcanized).
  • the extraction rate of the conjugated diene-based branched copolymer (A) from the crosslinked product is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.
  • the extraction rate can be calculated from the amount of the conjugated diene-based branched copolymer (A) extracted in toluene after 48 hours at 23 ° C. by immersing 2 g of the crosslinked product in 400 mL of toluene.
  • the rubber composition for a tire of the present invention or a crosslinked product of the rubber composition can also be used as at least a part of a tire.
  • the tire thus obtained has an ideal state in which the filler (C) is dispersed (for example, the pane effect is sufficiently reduced), so that the tire has excellent rolling resistance and wear resistance. Is good.
  • Examples of tire parts where the rubber composition for tires or a crosslinked product of the rubber composition can be used include treads (cap treads, under treads), sidewalls, rubber reinforcing layers for run-flat tires (liners, etc.), and rims.
  • Examples include cushions, bead fillers, bead insulation, bead apex, clinch apex, belts, belt cushions, breakers, breaker cushions, chafers, chafer pads, strip apex and the like.
  • the rubber composition for soles of the present invention or a crosslinked product of the rubber composition can also be used as at least a part of the soles. Specifically, it can be used as a sole for footwear such as hiking boots, sandals, safety shoes, hiking shoes, marathon shoes, jikatabi, and boots.
  • Conjugated diene-based branched copolymer (A) Conjugated diene graft copolymers (A1-1) to (A1-5), (A'1-6) to (A'1-7), (A1) obtained in Production Examples 1 to 5 and 6 to 7 below.
  • Solid rubber (B) Solid rubber (B-1) Emulsified polymerized styrene-butadiene rubber: SBR1500 (manufactured by JSR Corporation, styrene content: 23.5% by mass, vinyl content: 15 mol%, Tg: -53 ° C.) Solid rubber (B-2) Natural rubber: STR20 (Thailand): VON BUNDIT (Tg-63 ° C) [Silica (C1)] Silica: ULTRASIL 7000GR (manufactured by Evonik Japan Co., Ltd., wet silica, average particle size 14 nm) [Filler (C) other than silica (C1)] Carbon black: Diamond black I (N220) (manufactured by Mitsubishi Chemical Corporation, average particle size 20 nm) ⁇ Silane coupling agent ⁇ SI75 (manufactured by Evonik Japan Co., Ltd
  • Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn) By gel permeation chromatography (GPC), the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the conjugated diene-based graft copolymer and the polymer at each stage of its production. was calculated in terms of standard polystyrene.
  • Si atomic weight [(Si content (mass%)) / 100] x [(number average molecular weight Mn) / (molecular weight in styrene units) x (conjugated diene and, if necessary) Average molecular weight of other monomeric units other than the contained conjugated diene)] / Si atomic weight
  • the average number (X / Y) of functional groups (c) (at least one selected from the group consisting of alkoxy groups and hydroxyl groups) per Si atom (branch point) contained in the conjugated diene-based graft copolymer is the conjugated diene. It is obtained from the results of measuring 29 Si-NMR of the system-grafted copolymer. Specifically, the integral value of Si having one functional group (c) bonded, Si having two functional groups (c) bonded, etc. multiplied by the average number of functional groups is summed up. Calculated by comparing with the simple sum of the integrated values.
  • Average number of functional groups (c) per molecule of conjugated diene-based graft copolymer X The average number X of the functional groups (c) per molecule of the conjugated diene-based graft copolymer is the average number of functional groups (c) per Si atom (branch point) contained in the conjugated diene-based graft copolymer and the above. It is calculated from the following formula using the number of Si atoms per molecule of the conjugated diene-based graft copolymer.
  • the average number W of side chains (b) per molecule of the conjugated diene-based graft copolymer is the active terminal weight which is a component of the side chain (b) of the conjugated diene-based graft copolymer in the above-mentioned coupling step. It is calculated from the following formula using the charge amount (number of moles) per active terminal of the coalescence (I) and the charge amount (number of moles) of the functional group-modified conjugated diene polymer (F).
  • (Average number of side chains (b) per molecule of conjugated diene-based graft copolymer) (Amount of active terminal polymer (I), which is a component of the side chain (b), charged per active end (number of moles) )) / (Amount of functional group-modified conjugated diene polymer (F) charged (number of moles))
  • Average number of side chains (b) per Si atom (branch point) contained in the conjugated diene-based graft copolymer (W / Y)
  • the average number (W / Y) of side chains (b) per Si atom (branch point) contained in the conjugated diene-based graft copolymer is the side chain (b) per molecule of the conjugated diene-based graft copolymer. It is calculated from the following formula using the average number of Si atoms per molecule of the conjugated diene-based graft copolymer.
  • the main chain is lithiated by reacting a pre-synthesized conjugated diene polymer with an organic alkali metal compound in the presence of tetramethylethylenediamine, and then the monomer that is the constituent unit of the side chain is polymerized. In the case, it was calculated from the charging ratio of the organic alkali metal compound used in the lithiolysis reaction and the conjugated diene polymer which is the constituent unit of the main chain.
  • the side chain density of the side chain (b2) is the average number of side chains (b2) per molecule of the conjugated diene graft copolymer (A2) and the main chain (a2). It was calculated from the following formula (2') using the standard polystyrene-equivalent number average molecular weight (Mn) of.
  • Side chain density (Average number of side chains (b2) per molecule of conjugated diene-based graft copolymer (A2)) / [(Number average molecular weight of main chain (a2) Mn) / (Molecular weight of styrene unit) ] X 100 (2')
  • Step (1) A sufficiently dried 5 L autoclave is replaced with nitrogen, 1580 g of cyclohexane and 56 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, and the temperature is raised to 50 ° C. While controlling in this manner, 2.9 g of tetrahydrofuran and 1250 g of butadiene were sequentially added and polymerized for 1 hour. Then, 3.3 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water.
  • Step (2) Subsequently, 700 g of the unmodified conjugated diene polymer (F'-1) obtained in the step (1) was charged into an autoclave having a capacity of 1 L, and nitrogen degassed while stirring at 60 ° C. for 3 hours. 0.9 g of t-butylperoxypivalate and 51 g of 3-mercaptopropyltriethoxysilane were added and reacted at 80 ° C. for 8 hours to obtain a functional group-modified conjugated diene polymer (F-1).
  • the weight average molecular weight of the obtained functional group-modified conjugated diene polymer (F-1) is 26,000, the 1,4-bond content is 70 mol%, the styrene unit content is 0% by mass, and each polymer molecule.
  • the average number of Si atoms in was four.
  • Step (3) A sufficiently dried 5 L autoclave is replaced with nitrogen, 700 g of cyclohexane and 78 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is 50 ° C. under stirring conditions. While controlling in this manner, 340 g of butadiene was sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-1).
  • the weight average molecular weight of the obtained active terminal polymer (I-1) was 5,000, the 1,4-bond content was 90 mol%, and the styrene unit content was 0% by mass.
  • Step (4) Subsequently, 7.0 g of tetrahydrofuran and the functional group-modified conjugated diene polymer (F-1) obtained in step (2) were added to the solution containing the active terminal polymer (I-1) obtained in step (3). 1480 g of the diluted solution was added, and the coupling reaction was carried out at 50 ° C. for 2 hours. Then, 190 g of sec-butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours to seal a part of the remaining alkoxy groups. Then, 21 g of methanol was added to stop the polymerization reaction to obtain a polymer solution.
  • Step (5) Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. After the washing was completed, the polymer solution was vacuum dried at 70 ° C. for 24 hours to obtain a conjugated diene-based graft copolymer (A1-1).
  • the weight average molecular weight of the obtained conjugated diene-based graft copolymer (A1-1) is 46,000, Mw / Mn is 1.5, the styrene unit content is 0% by mass, and Si atoms per polymer molecule (Si atom per polymer molecule).
  • the average number of functional groups (branch points) is 4, the average number of functional groups (c) per polymer molecule is 0.4, and the average number of functional groups (c) per Si atom (branch point) is 0.1.
  • the average number of side chains (b) per molecule of the polymer was 4, and the average number of side chains (b) per Si atom (branch point) was 1.
  • Table 1 shows the types and amounts of each reagent used in Example 1
  • Table 2 shows the molecular specifications and physical properties of the obtained conjugated diene-based graft copolymer (A1-1).
  • the conjugated diene-based graft copolymer (A1-) was produced by the same method as in Production Example 1 except that the types and amounts of the reagents used in steps (1) to (5) were changed as shown in Table 1. 2) to (A1-5) and (A'1-6) to (A'1-7) were obtained.
  • Table 2 shows the molecular specifications and physical properties of the obtained conjugated diene-based graft copolymers (A1-2) to (A1-5) and (A'1-6) to (A'1-7).
  • the conjugated diene-based graft copolymer (A1-) was produced by the same method as in Production Example 1 except that the types and amounts of the reagents used in steps (1) to (5) were changed as shown in Table 3. 8)-(A1-12) were obtained.
  • Table 4 shows the molecular specifications and physical properties of the obtained conjugated diene-based graft copolymers (A1-8) to (A1-12).
  • Step (1) A fully dried 5 L autoclave is replaced with nitrogen, 1590 g of cyclohexane and 60 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is 50 ° C. under stirring conditions. 1350 g of 1,3-butadiene was sequentially added and polymerized for 1 hour. Then, 3.5 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water.
  • conjugated diene polymer (M-1) was 26,000, and the 1,4-bond content was 90 mol%.
  • Step (2) Subsequently, 51 g of the conjugated diene polymer (M-1) obtained in the step (1) was charged in a sufficiently dried 5 L autoclave, and the polymer was degassed with nitrogen while stirring at 60 ° C. for 3 hours. And nitrogen substitution in the autoclave. After charging 570 g of cyclohexane and heating to 40 ° C., 42 g of sec-butyllithium (10.5 mass% cyclohexane solution) and 4.1 g of N, N, N', N'-tetramethylethylenediamine were sequentially added. The lithium reaction was carried out at 40 ° C. for 1 hour.
  • Step (3) While controlling the polymerization temperature to 40 ° C., 550 g of 1,3-butadiene was sequentially added and polymerized for 2 hours. Then, 11 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Based on the amount of reagent charged in step (3) and the analysis of the polymer solution in step (3), the number average molecular weight of the side chain (b2) of the conjugated diene-based graft copolymer (A2-13) described later, 1, 4-The bond content and styrene unit content can be determined.
  • the number average molecular weight of the side chain (b2) of the conjugated diene-based graft copolymer (A2-13) was 15,000, the 1,4-bond content was 70 mol%, and the styrene unit content was 0% by mass.
  • Step (4) Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. After the washing was completed, the polymer solution was vacuum dried at 70 ° C. for 24 hours to obtain a conjugated diene-based graft copolymer (A2-13).
  • the weight average molecular weight of the obtained conjugated diene-based graft copolymer (A2-13) is 326,000, Mw / Mn is 1.5, and the average side chain (b) per molecule of the conjugated diene-based graft copolymer is average.
  • Examples 1 to 5 and Comparative Examples 1 to 3 Conjugated diene-based branched copolymer (A), solid rubber (B), filler (C), vulcanization aid, silane coupling agent and other components were added according to the compounding ratio (parts by mass) shown in Table 7. After being put into a closed rubbery mixer and kneaded for 6 minutes so that the starting temperature was 60 ° C. and the resin temperature was 140 ° C., they were taken out of the mixer and cooled to room temperature. Next, this mixture is put into a closed Banbury mixer again, a vulcanizing agent and a vulcanization accelerator are added, and the mixture is kneaded for 75 seconds so that the starting temperature is 50 ° C.
  • the rubber composition obtained in the same manner as above was press-molded (press conditions: 160 ° C., 60 minutes) and vulcanized to prepare a tire-shaped vulcanized rubber sample having a diameter of 80 mm and a width of 16 mm.
  • the coefficient of friction on ice ( ⁇ ) was evaluated based on the method of. The results are shown in Table 7.
  • the wear resistance of the vulcanized rubber sample was evaluated.
  • the amount of wear of the vulcanized rubber samples obtained in Examples 1 to 5 and Comparative Examples 1 to 3 was used for measurement.
  • the measuring device and conditions are as follows. The smaller the value, the smaller the amount of wear and the better the wear resistance.
  • [Measuring equipment and measurement conditions] ⁇ Equipment: FPS wear tester manufactured by Ueshima Seisakusho Co., Ltd. ⁇ Measurement temperature: 35 ° C ⁇ Road surface: Safety walk No. 240 ⁇ Speed: Sample rotation speed fixed at 80m / min ⁇ Load: 40N ⁇ Slip ratio: 10% ⁇ Talc feed amount: 0.04cm 3 / sec
  • the rubber compositions of Examples 1 to 5 (rubber composition for tires, rubber composition for shoe sole) have a polymer segment having a high 1,4-bond content and a polymer segment having a low 1,4-bond content. However, it contains a conjugated diene-based branched copolymer in which the difference in 1,4-bond content of these polymer segments satisfies the requirements of the present invention.
  • the crosslinked products obtained from the rubber compositions of Examples 1 to 5 do not contain any conjugated diene-based branched copolymer (rubber composition of Comparative Example 3).
  • the wear resistance is about the same or superior, and it can be seen that the ice grip performance evaluated by the friction coefficient on ice is excellent. ..
  • the 1,4-bond content of the polymer segment contained in the conjugated diene-based branched copolymer is relatively low, and the difference in the 1,4-bond content is the present.
  • the crosslinked product obtained from the rubber composition of Comparative Example 2 (rubber composition for tires, rubber composition for soles) containing a conjugated diene-based branched copolymer that does not satisfy the requirements of the present invention is the crosslinked product obtained in Comparative Example 3. It can be seen that although the ice grip performance is superior to that of the product, the wear resistance is inferior. In addition, although it contains a conjugated diene-based branched copolymer, the 1,4-bond content of the polymer segment contained in the conjugated diene-based branched copolymer is relatively high, and the difference in the 1,4-bond content is the present.
  • the crosslinked product obtained from the rubber composition of Comparative Example 1 (rubber composition for tires, rubber composition for soles) containing a conjugated diene-based branched copolymer that does not satisfy the requirements of the present invention is the crosslinked product obtained in Comparative Example 3. It can be seen that although the abrasion resistance is superior to that of the product, the ice grip performance is inferior. From these facts, it can be seen that the crosslinked products obtained from the rubber compositions of Examples 1 to 5 (rubber composition for tires, rubber composition for soles) have both wear resistance and ice grip performance. ..
  • Examples 6 to 19 and Comparative Examples 4 to 6 Conjugated diene-based branched copolymer (A), solid rubber (B), filler (C), vulcanization aid, silane coupling agent and others according to the compounding ratios (parts by mass) shown in Tables 8 to 10.
  • the components were put into a sealed rubbery mixer and kneaded for 6 minutes so that the starting temperature was 60 ° C. and the resin temperature was 140 ° C., and then taken out of the mixer and cooled to room temperature. Next, this mixture is put into a closed Banbury mixer again, a vulcanizing agent and a vulcanization accelerator are added, and the mixture is kneaded for 75 seconds so that the starting temperature is 50 ° C.
  • the reaching temperature is 100 ° C. to obtain a rubber composition (for tires).
  • a rubber composition and a rubber composition for soles) were obtained.
  • the obtained rubber composition was press-molded (pressing conditions: 160 ° C., 30 minutes) to prepare a tire-shaped vulcanized rubber sample having a diameter of 50 mm and a width of 10 mm, and the wear resistance was evaluated based on the following method. .. The evaluation results are shown in Tables 8 and 10.
  • the rubber composition obtained in the same manner as above was press-molded (press conditions: 160 ° C., 60 minutes) and vulcanized to prepare a tire-shaped vulcanized rubber sample having a diameter of 80 mm and a width of 16 mm.
  • the coefficient of friction on ice ( ⁇ ) was evaluated based on the method of. The evaluation results are shown in Tables 8 and 9.
  • the rubber composition obtained in the same manner as above was press-molded (160 ° C., 20 minutes) to prepare a vulcanized rubber sheet (thickness 2 mm), and the wet grip performance was evaluated based on the following method.
  • the evaluation results are shown in Tables 9 and 10.
  • the rubber compositions of Examples 6 to 13 have a polymer segment having a high 1,4-bond content and a polymer segment having a low 1,4-bond content. However, it contains a conjugated diene-based branched copolymer in which the difference in 1,4-bond content of these polymer segments satisfies the requirements of the present invention.
  • the crosslinked products obtained from the rubber compositions of Examples 6 to 13 do not contain any conjugated diene-based branched copolymer (rubber composition of Comparative Example 4). It can be seen that the wear resistance is about the same or superior to that of the crosslinked product obtained from the rubber composition for tires and the rubber composition for soles), and the ice grip performance evaluated by the friction coefficient on ice is excellent.
  • the rubber compositions of Examples 14 to 17 (rubber compositions for tires, rubber compositions for shoe soles) have a polymer segment having a high 1,4-bond content and a polymer segment having a low 1,4-bond content. However, it contains a conjugated diene-based branched copolymer in which the difference in 1,4-bond content of these polymer segments satisfies the requirements of the present invention.
  • the crosslinked products obtained from the rubber compositions of Examples 14 to 17 do not contain any conjugated diene-based branched copolymer (rubber composition of Comparative Example 5). Compared with the crosslinked product obtained from (rubber composition for tires, rubber composition for soles), the physical properties of the other are improved without deteriorating either the wet grip performance or the friction coefficient on ice. I understand.
  • the rubber compositions of Examples 18 to 19 have a polymer segment having a high 1,4-bond content and a polymer segment having a low 1,4-bond content. However, it contains a conjugated diene-based branched copolymer in which the difference in 1,4-bond content of these polymer segments satisfies the requirements of the present invention.
  • the crosslinked products obtained from the rubber compositions of Examples 18 to 19 do not contain any conjugated diene-based branched copolymer (rubber composition of Comparative Example 6). It can be seen that the wear resistance is about the same and the wet grip performance is excellent as compared with the crosslinked product obtained from the rubber composition for tires and the rubber composition for soles.

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Abstract

L'invention fournit une composition de caoutchouc, une composition de caoutchouc pour pneumatique et une composition de caoutchouc pour semelle de chaussures qui permettent de concilier une amélioration en termes de résistance à l'usure et d'adhérence sur glace d'un article contenant la composition de caoutchouc pour pneumatique, semelle de chaussures, ou similaire, et un produit réticulé de cette composition de caoutchouc.　Plus précisément, l'invention concerne une composition de caoutchouc qui comprend un copolymère ramifié à base de diène conjugué (A). Ledit copolymère ramifié à base de diène conjugué (A) contient au moins deux segments de polymère contenant à leur tour des unités diène conjugué de différentes teneurs en unité diène conjugué liée par une liaison 1,4- (teneur en liaison 1,4-). La différence (Δ14＝Ｄ14（α１）－Ｄ14（α２）) entre le pourcentage en moles de teneur en liaison 1,4- (　Ｄ14（α１）) d'un segment de polymère (α１) contenant l'unité diène conjugué de teneur en liaison 1,4- la plus élevée, et le pourcentage en moles de teneur en liaison 1,4- (Ｄ14（α２）) d'un segment de polymère (α2) contenant l'unité diène conjugué de teneur en liaison 1,4- la plus basse, est supérieure ou égale à 5% en moles.
PCT/JP2020/035409 2019-09-20 2020-09-18 Composition de caoutchouc, composition de caoutchouc pour pneumatique, et composition de caoutchouc pour semelle de chaussures WO2021054429A1 (fr)

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WO2023276741A1 (fr) * 2021-06-30 2023-01-05 株式会社クラレ Polymère greffé de diène conjugué hydrogéné, procédé pour le produire, composition de polymère, article moulé et produit réticulé
WO2023276742A1 (fr) * 2021-06-30 2023-01-05 株式会社クラレ Polymère greffé de diène conjugué, son procédé de production, additif d'huile lubrifiante, améliorant d'indice de viscosité, agent de suppression de frottement et composition d'huile

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JPH01297412A (ja) * 1988-05-24 1989-11-30 Nippon Erasutomaa Kk ジエン系共重合体及びその製造方法
JPH1129660A (ja) * 1996-07-19 1999-02-02 Yokohama Rubber Co Ltd:The タイヤ用ゴム組成物
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JP2018115239A (ja) * 2017-01-17 2018-07-26 横浜ゴム株式会社 タイヤトレッド用ゴム組成物及び空気入りタイヤ
JP2019002028A (ja) * 2015-02-19 2019-01-10 旭化成株式会社 変性共役ジエン系重合体及びその製造方法、ゴム組成物、並びにタイヤ

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Publication number Priority date Publication date Assignee Title
JPS62135506A (ja) * 1985-12-10 1987-06-18 Japan Synthetic Rubber Co Ltd 共役ジオレフィン系重合体の製造方法
JPH01297412A (ja) * 1988-05-24 1989-11-30 Nippon Erasutomaa Kk ジエン系共重合体及びその製造方法
JPH1129660A (ja) * 1996-07-19 1999-02-02 Yokohama Rubber Co Ltd:The タイヤ用ゴム組成物
JP2002012702A (ja) * 2000-06-30 2002-01-15 Nippon Zeon Co Ltd ゴム組成物
WO2008041631A1 (fr) * 2006-10-03 2008-04-10 Zeon Corporation Polymère diène conjugué modifié, procédé de fabrication du polymère, composition de caoutchouc et utilisation de la composition
JP2010126540A (ja) * 2008-11-25 2010-06-10 Jsr Corp 変性共役ジエン系重合体の製造方法、変性共役ジエン系重合体、及びゴム組成物
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JP2018115239A (ja) * 2017-01-17 2018-07-26 横浜ゴム株式会社 タイヤトレッド用ゴム組成物及び空気入りタイヤ

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023276741A1 (fr) * 2021-06-30 2023-01-05 株式会社クラレ Polymère greffé de diène conjugué hydrogéné, procédé pour le produire, composition de polymère, article moulé et produit réticulé
WO2023276742A1 (fr) * 2021-06-30 2023-01-05 株式会社クラレ Polymère greffé de diène conjugué, son procédé de production, additif d'huile lubrifiante, améliorant d'indice de viscosité, agent de suppression de frottement et composition d'huile

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