Hydrogenated modified conjugated diene-based polymer and rubber composition

Abstract

To provide a hydrogenated modified diene-based polymer that yields a rubber composition featuring enhanced balance in terms of processability, tensile characteristics, and viscoelastic characteristics.SOLUTION: A hydrogenated modified conjugated diene-based polymer comprises: a repeating unit derived from a conjugated diene compound; and a functional group derived from a modifying agent, wherein gel permeation chromatography (GPC) shows a unimodal molecular weight distribution curve, and the molecular weight distribution (PDI: MWD) is less than 1.7.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a hydrogenated modified conjugated diene polymer and a rubber composition.

Background Art

[0002] In recent years, from the perspective of environmental impact, the demand for lower fuel consumption in automobiles has been increasing. In particular, for automobile tires, improvement in fuel efficiency is required for the rubber material used in the tread portion that directly contacts the ground. At the same time, there is a trend towards lighter tires. To reduce the weight of a tire, it is necessary to reduce the thickness of the tread portion that contacts the road surface, and a rubber material having excellent tensile properties more than ever is required to maintain the strength characteristics. In response to such demands, conventionally, a modified conjugated diene polymer produced by continuous polymerization, having excellent processability, excellent strength characteristics such as tensile properties, and excellent viscoelastic properties has been proposed (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the modified conjugated diene polymer disclosed in Patent Document 1 has a problem that there is still room for improvement in terms of the balance of processability, tensile properties, and viscoelastic properties of the rubber composition using the modified conjugated diene polymer.

[0005] Therefore, an object of the present invention is to provide a hydrogenated modified conjugated diene polymer capable of obtaining a rubber composition excellent in the balance of processability, tensile properties, and viscoelastic properties.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that a hydrogenated modified conjugated diene polymer having a predetermined structure and a predetermined molecular weight distribution can solve the above-described problems, and have completed the present invention. That is, the present invention is as follows.

[0007] 〔1〕 A hydrogenated modified conjugated diene polymer containing a repeating unit derived from a conjugated diene compound and a functional group derived from a modifier, wherein the molecular weight distribution curve by gel permeation chromatography (GPC) is unimodal, and the molecular weight distribution (PDI: MWD) is less than 1.7. 〔2〕 The hydrogenated modified conjugated diene polymer according to the above 〔1〕, wherein the modifier is an alkoxysilane-based modifier. 〔3〕 The hydrogenated modified diene polymer according to the above 〔1〕 or 〔2〕, containing an aromatic vinyl monomer unit in an amount of more than 0% by mass and 45% by mass or less. 〔4〕 The hydrogenated modified diene polymer according to any one of the above 〔1〕 to 〔3〕, wherein the vinyl bond amount of the conjugated diene monomer unit before hydrogenation is 10 mol% or more and 60 mol% or less. 〔5〕 The hydrogenated modified diene polymer according to any one of the above 〔1〕 to 〔4〕, wherein the Mooney viscosity at 100 ° C. is 30 or more and 130 or less. 〔6〕 A rubber composition containing the hydrogenated modified conjugated diene polymer according to any one of the above 〔1〕 to 〔5〕, a filler,

Advantages of the Invention

[0008] According to the present invention, a hydrogenated modified diene polymer capable of obtaining a rubber composition excellent in the balance of processability, tensile properties, and viscoelastic properties can be provided.

Embodiments for Carrying Out the Invention

[0009] Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as "the present embodiments") will be described in detail. It should be noted that the following present embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments. The present invention can be appropriately modified and implemented within the scope of its gist.

[0010] 〔Hydrogenated Modified Conjugated Diene Polymer〕 The hydrogenated modified conjugated diene polymer of the present embodiment contains a repeating unit derived from a conjugated diene compound and a functional group derived from a modifier, and the molecular weight distribution curve by gel permeation chromatography (GPC Gel permeation chromatography, hereinafter may be referred to as GPC) is unimodal, and the molecular weight distribution (PDI: MWD) is less than 1.7.

[0011] The repeating unit derived from the conjugated diene compound means the repeating unit formed by the conjugated diene compound during polymerization. The functional group derived from the modifier means a functional group derived from the modifier present at one terminal of the living polymer by the reaction or coupling of the living polymer and the modifier. The hydrogenated modified conjugated diene polymer of the present embodiment may be a hydrogenated product of a homopolymer of a conjugated diene compound that does not contain a repeating unit derived from an aromatic vinyl compound, or may be a hydrogenated product of a copolymer that contains a repeating unit derived from an aromatic vinyl compound.

[0012] Examples of the conjugated diene compound used in the hydrogenated modified conjugated diene polymer of the present embodiment include, but are not limited to, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene, and 2-halo-1,3-butadiene (halo means a halogen atom). These may be used alone or in combination of two or more.

[0013] On the other hand, as described above, the hydrogenated modified conjugated diene polymer of the present embodiment may be a copolymer containing an aromatic vinyl monomer unit derived from an aromatic vinyl compound. In this case, from the viewpoint of tensile properties, the hydrogenated conjugated diene polymer preferably contains the aromatic vinyl monomer unit in an amount of more than 0% by mass and 45% by mass or less, more preferably 4% by mass or more and 40% by mass or less, and even more preferably 8% by mass or more and 36% by mass or less.

[0014] Examples of the aromatic vinyl compound include, but are not limited to, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidinoethyl)styrene, 4-(2-pyrrolidinoethyl)styrene, and 3-(2-pyrrolidino-1-methylethyl)-α-methylstyrene. These may be used alone or in combination of two or more.

[0015] Further, the hydrogenated modified conjugated diene polymer of the present embodiment may be a hydrogenated product of a copolymer further containing a repeating unit derived from another diene compound having 1 to 10 carbon atoms together with the repeating unit derived from the conjugated diene compound. The repeating unit derived from the diene compound is a repeating unit derived from a diene compound different from the conjugated diene compound. Examples of diene compounds different from the conjugated diene compound include, but are not limited to, 1,2-butadiene. When the hydrogenated modified conjugated diene polymer of the present embodiment is a hydrogenated product of a copolymer further containing a repeating unit derived from a diene compound different from the conjugated diene compound, the polymer before hydrogenation of the hydrogenated modified conjugated diene polymer of the present embodiment preferably contains more than 0% by mass to 1% by mass of a repeating unit derived from a diene compound different from the repeating unit derived from the conjugated diene compound, more preferably 0% by mass to 0.1% by mass, still more preferably more than 0% by mass to 0.01% by mass, and still more preferably more than 0% by mass to 0.001% by mass. When within this range, there is a tendency to prevent the formation of gels.

[0016] The hydrogenated modified conjugated diene polymer of the present embodiment may be a random copolymer. In this case, the rubber composition of the hydrogenated modified conjugated diene polymer of the present embodiment tends to have an excellent balance among various physical properties. The random copolymer means a copolymer in which the repeating units constituting the copolymer are arranged in a disordered manner.

[0017] The hydrogenated modified conjugated diene polymer of the present embodiment is obtained by hydrogenating (hydrogenating) the conjugated diene moiety of a conjugated diene polymer or a modified conjugated diene polymer. The method for hydrogenating the conjugated diene moiety is not particularly limited, and known methods can be used. Suitable hydrogenation methods include, for example, a method of hydrogenating by blowing gaseous hydrogen into a polymer solution in the presence of a catalyst. Examples of the catalyst include, but are not limited to, heterogeneous catalysts such as a catalyst in which a noble metal is supported on a porous inorganic substance; catalysts obtained by solubilizing salts of nickel, cobalt, etc. and reacting them with organoaluminum, etc.; homogeneous catalysts such as catalysts using metallocenes such as titanocene. Among these, from the viewpoint of being able to select mild hydrogenation conditions, titanocene catalysts are preferred. The hydrogenation reaction may be either a batch process or a continuous process, or a combination thereof.

[0018] (Degree of hydrogenation) In the hydrogenated modified conjugated diene polymer of the present embodiment, the hydrogenation rate of the structural unit derived from the conjugated diene compound (for example, butadiene) is preferably 30 mol% or more and less than 99 mol%, more preferably 30 mol% or more and less than 96 mol%, still more preferably 30 mol% or more and less than 93 mol%, even more preferably 30 mol% or more and less than 90 mol%, and even more preferably 32 mol% or more and less than 90 mol%. When the hydrogenation rate of the structural unit derived from the conjugated diene compound in the hydrogenated modified conjugated diene polymer of the present embodiment is 30 mol% or more, it tends to be excellent in terms of breaking strength and elongation at break when vulcanized. When the hydrogenation rate of the structural unit derived from the conjugated diene compound is 99 mol% or less, the crosslink density after vulcanization increases, and it tends to be excellent in breaking strength when vulcanized. On the other hand, from the viewpoint of processability, the hydrogenation rate of the structural unit derived from the conjugated diene compound in the hydrogenated modified conjugated diene polymer of the present embodiment is preferably 97 mol% or less, more preferably 95 mol% or less, still more preferably 90 mol% or less, and even more preferably 80 mol% or less. Also, from the viewpoint of strength such as breaking strength and elongation at break, the hydrogenation rate is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 45 mol% or more, even more preferably 50 mol% or more, and even more preferably 55 mol% or more. When the hydrogenation rate is in the range of 30 to 99 mol%, it tends to be able to improve processability while maintaining good strength.

[0019] When the hydrogenated modified conjugated diene polymer of the present embodiment is used as a tire material, various required functions are involved in relation to other components compounded in the tire, and the molecular weight, hydrogenation rate, aromatic vinyl monomer unit content, etc. may be adjusted according to the required performance. For example, when determining strength such as breaking strength and breaking elongation, the hydrogenated modified conjugated diene polymer of the present embodiment preferably has a hydrogenation rate of 65 mol% or more, more preferably 70 mol% or more, still more preferably 75 mol% or more, and even more preferably 80 mol% or more. On the other hand, when the hydrogenation rate is extremely high exceeding 95 mol%, depending on the composition of other materials constituting the tire, it tends to be difficult to exhibit the desired fuel efficiency performance. Therefore, from the viewpoint of designing for a balance between fuel efficiency and strength, it is preferable to set the hydrogenation rate to 30 to 95 mol%. The hydrogenation rate can be controlled by adjusting the amount of hydrogen added to the structural unit derived from the conjugated diene compound, the hydrogen pressure, the reaction time, the addition amount of the hydrogenation catalyst, and the solution viscosity. The temperature of the hydrogenation reaction is not particularly limited, but is preferably 60 to 105°C, more preferably 70 to 100°C.

[0020] The hydrogenated modified conjugated diene polymer of the present embodiment contains a structural unit derived from a conjugated diene compound. When the composition ratios (mol%) of the structural unit represented by the following formula (1), the structural unit represented by the following formula (2), the structural unit represented by the following formula (3), and the structural unit represented by the following formula (4) are a, b, c, and d in order, it preferably satisfies the following mathematical formula (S). Note that the structural unit represented by formula (4) includes a 1,4-trans bond and a 1,4-cis bond. Mathematical formula (S): 20 ≤ (a + b) / (a + b + c + d)×100 ≤ 65

[0021]

Chemical formula

[0022] The formula (S) represents the mass ratio of 1,2-vinyl bonds and hydrogenated 1,2-vinyl bonds in the hydrogenated modified conjugated diene polymer. The hydrogenated conjugated diene polymer of the present embodiment has an excellent balance of processability, fuel efficiency performance, and wet grip performance when the formula (S) is within the above range.

[0023] The ratios of a, b, c, and d can be controlled by the type and addition amount of the polar substance, the polymerization temperature, and the amount of hydrogen to be reacted when polymerizing the conjugated diene polymer before hydrogenation. When controlling the hydrogenation rate to be 30 mol% or more and 95 mol% or less, it is preferable from the viewpoint of heat resistance that the content of 1,2-vinyl bonds is small. More specifically, the composition ratio of b is preferably 10 mol% or less, more preferably 8 mol% or less, and even more preferably 5 mol% or less.

[0024] The hydrogenated modified conjugated diene polymer of the present embodiment contains a structural unit derived from a conjugated diene compound, and when the composition ratios (mol%) of the structural unit represented by the formula (1) and the structural unit represented by the formula (2) are a and b in this order, respectively, it preferably satisfies the following formula (T). Formula (T): 90 ≦ (a) / (a + b)×100 ≦ 100 The formula (T) represents the hydrogenation rate of the structure derived from 1,2-vinyl bonds, and the value approaches 100 as the 1,2-vinyl bonds are hydrogenated. The hydrogenated modified conjugated diene polymer of the present embodiment tends to have excellent heat resistance when the formula (T) is 90 or more. The ratios of a and b can be controlled by adjusting the type of hydrogenation catalyst, the hydrogenation reaction temperature, and the amount of hydrogen to be reacted. The ratios of a, b, c, and d can be measured by the method described in the examples below.

[0025] (Molecular weight distribution) The hydrogenated modified conjugated diene polymer of the present embodiment has a molecular weight distribution (PDI; MWD; Mw / Mn) of less than 1.7, preferably 1.0 or more and less than 1.7, and more preferably 1.1 or more and less than 1.7. When within this range, the rubber composition using the hydrogenated modified conjugated diene polymer of the present embodiment has excellent tensile properties and viscoelastic properties, and also has an excellent effect in terms of property balance. In addition, the hydrogenated modified conjugated diene polymer of the present embodiment has a unimodal molecular weight distribution curve by GPC. This is the molecular weight distribution that appears in the polymer polymerized by continuous polymerization, which means that the hydrogenated modified conjugated diene polymer of the present embodiment has uniform properties. That is, the hydrogenated modified conjugated diene polymer of the present embodiment is produced by continuous polymerization, has a unimodal molecular weight distribution curve, and has a molecular weight distribution of less than 1.7. The molecular weight distribution of the hydrogenated modified conjugated diene polymer of the present embodiment can be measured by the method described in the examples below. Also, in the polymerization process, it can be controlled within the above numerical range by controlling the first reactor polymerization conversion rate, the type and addition amount of the modifier.

[0026] (Mooney viscosity) The hydrogenated modified conjugated diene polymer of the present embodiment preferably has a Mooney viscosity at 100 °C of 30 to 130, more preferably 40 to 120, and even more preferably 45 to 110. When the Mooney viscosity is within the above range, it tends to be excellent in processability and productivity. The Mooney viscosity of the hydrogenated modified conjugated diene polymer can be measured by the method described in the examples below. The Mooney viscosity of the hydrogenated modified conjugated diene polymer of the present embodiment can be controlled within the above numerical range by controlling the molecular weight and molecular weight distribution.

[0027] (Vinyl bond content) From the viewpoints of productivity and processability, the hydrogenated modified conjugated diene polymer of the present embodiment preferably has a vinyl bond amount before hydrogenation of 5 mol% or more, more preferably 10 mol% or more, and even more preferably 10 mol% or more and 60 mol% or less in the structural units derived from the conjugated diene compound. The vinyl bond amount means the ratio of the content of the 1,2-addition conjugated diene monomer unit, rather than the 1,4-addition, in the conjugated diene bond units in the conjugated diene polymer containing monomer units having vinyl groups. The vinyl bond amount can be measured by the method described in the examples below, and can be controlled within the above numerical range by the polymerization temperature and the addition amount of the polar additive.

[0028] (Functional groups derived from the modifier) The hydrogenated modified conjugated diene polymer of the present embodiment has functional groups derived from the modifier. The modifier is a modifier for modifying the terminal of the conjugated diene polymer. Examples of the modifier used in the present embodiment include alkoxysilane-based modifiers. Further, alkoxysilane-based modifiers containing a nitrogen atom are preferred. When the alkoxysilane-based modifier is used as the modifier, the modification is carried out in such a form that one terminal of the living polymer is bonded to a silyl group by a substitution reaction between the anionic active site located at one terminal of the living polymer and the alkoxy group of the alkoxysilane-based modifier. Thereby, the affinity with an inorganic filler or the like is improved from the functional groups derived from the modifier present at one terminal of the hydrogenated modified conjugated diene polymer of the present embodiment, and the mechanical physical properties of the rubber composition containing the hydrogenated modified conjugated diene polymer of the present embodiment tend to be improved. When the alkoxysilane-based modifier contains a nitrogen atom, in addition to the effect caused by the silyl group, an additional effect of increasing physical properties caused by the nitrogen atom tends to be obtained. According to the present embodiment, the modifier may contain a compound represented by the following (Chemical Formula I).

[0029]

Chemical formula

[0030] In the above (Chemical Formula I), R 1 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms, and R 4 is hydrogen, an alkyl group having 1 to 10 carbon atoms, a divalent, trivalent or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms, and R 21 is a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R 42 O] j -, and R 42 is an alkylene group having 1 to 10 carbon atoms, a and m are each independently an integer selected from 1 to 3, n is an integer of 0, 1 or 2, and j is an integer selected from 1 to 30. Specifically, in the above (Chemical Formula I), R 1 is a single bond or an alkylene group having 1 to 5 carbon atoms, and R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, and R 4 is hydrogen, an alkyl group having 1 to 5 carbon atoms, a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, or a heterocyclic group having 2 to 5 carbon atoms, and R 21 is a single bond, or an alkylene group having 1 to 5 carbon atoms, or -[R 42 O] j -, and R 42 is an alkylene group having 1 to 5 carbon atoms, a is an integer of 2 or 3, m is an integer selected from 1 to 3, n is an integer of 0, 1 or 2, m + n = 3, and j is preferably an integer selected from 1 to 10.

[0031] In the above (Chemical Formula I), R 4When it is a heterocyclic group, the heterocyclic group may or may not be substituted with a trisubstituted alkoxysilyl group. When the heterocyclic group is substituted with a trisubstituted alkoxysilyl group, the trisubstituted alkoxysilyl group may be one that is linked to and substituted on the heterocyclic group by an alkylene group having 1 to 10 carbon atoms. The trisubstituted alkoxysilyl group may mean an alkoxysilyl group substituted with an alkoxy group having 1 to 10 carbon atoms.

[0032] Examples of the compound represented by the above (Chemical Formula I) include, but are not limited to, N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine), N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine, N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine, N,N-diethyl-3-(trimethoxysilyl)propane-1-amine, N,N-diethyl-3-(triethoxysilyl)propane-1-amine, tris(trimethoxysilyl)amine, tris(3-(trimethoxysilyl)propyl)amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilaneamine, N,N-bis(3-(1H-imidazol-1-yl)propyl)-(triethoxysilyl)methane-1-amine, N-(3-(1H-1,2,4-triazol-1-yl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propane-1-amine, 3-(trimethoxysilyl)-N-(3-trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazol-3-yl)propyl)propane-1-amine, N,N-bis(2-(2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propane-1-amine, N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecane-16-amine, N-(2,5,8,11,14-pentaoxahexadecane-16-yl)-N-(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecane-16-amine, and N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecane-1-amine, etc.

[0033] Furthermore, as the modifier, a compound represented by the following (Chemical Formula II) can be used.

[0034]

Chemical Structure

[0035] In the above (Chemical Formula II), R 5 , R 6 , and R 9 are each independently an alkylene group having 1 to 10 carbon atoms, and R 7 , R 8 , R 10 , and R 11 are each independently an alkyl group having 1 to 10 carbon atoms, R 12 is hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c are each independently 0, 1, 2, or 3, with b + c ≥ 1, and A is the following (Formula a) or (Formula b), and R 13 , R 14 , R 15 , and R 16 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.

[0036] [Chemical Formula]

[0037] [Chemical Formula]

[0038] Examples of the compound represented by the above (Chemical Formula II) include, but are not limited to, N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propane-1-amine, and 3-(4,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propane-1-amine.

[0039] Furthermore, as the modifier, a compound represented by the following (Chemical Formula III) can be used.

[0040] [Chemical Formula]

[0041] In the above (Chemical Formula III), A 1 and A 2 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, which may or may not contain an oxygen atom, and R 17 ~R 20 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, and L 1 ~L 4 are each independently a divalent, trivalent, or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or L 1 and L 2 and L 3 and L 4 may be linked to each other to form a ring having 1 to 5 carbon atoms, and L 1 and L 2 and L 3 and L 4 When they are linked to each other to form a ring, the formed ring may contain 1 to 3 heteroatoms selected from the group consisting of N, O, and S.

[0042] As a specific embodiment of the above (Chemical Formula III), A 1 and A 2 are each independently an alkylene group having 1 to 10 carbon atoms, and R 17 ~R 20 are each independently an alkyl group having 1 to 10 carbon atoms, and L 1 ~L 4 are each independently a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or L 1 and L 2 and L 3 and L 4 may be linked to each other to form a ring having 1 to 3 carbon atoms, and L 1 and L 2 and L 3 and L 4When they are connected to each other to form a ring, the formed ring may contain 1 to 3 heteroatoms selected from the group consisting of N, O, and S.

[0043] Examples of the compound represented by the above (Chemical Formula III) include, but are not limited to, 3,3'-(1,1,3,3-Tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-Tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-Tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-Tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-Tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-Tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-Tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-Tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-Tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-Tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-Tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-Tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-Tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine), 3,3'-(1,1,3,3-Tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-Tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine), 3,3'-(1,1,3,3-Tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-Tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine, N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine, N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine, N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine, N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine, N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine, 1,3-bis(3-(1H-imidazol-1-yl)propyl)1,1,1,3,3-tetramethoxydisiloxane, 1,3-bis(3-(1H-imidazol-1-yl)propyl)1,1,3,3-tetraethoxydisiloxane, and 1,3-bis(3-(1H-imidazol-1-yl)propyl)1,1,3,3-tetrapropoxydisiloxane, etc. may be mentioned.,

[0044] Furthermore, as the modifier, a compound represented by the following (Chemical Formula IV) can be used.

[0045]

Chemical formula

[0046] In the above (Chemical Formula IV), R 22 and R23 is, independently of each other, an alkylene group having 1 to 20 carbon atoms, or -R 28 [OR 29 f -, where R 24 ~R 27 are, independently of each other, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 28 and R 29 are, independently of each other, an alkylene group having 1 to 20 carbon atoms, and R 47 and R 48 are, independently of each other, a divalent hydrocarbon group having 1 to 6 carbon atoms, and d and e are, independently of each other, an integer selected from 0 or 1 to 3, and d + e is an integer of 1 or more, and f is an integer of 1 to 30.

[0047] As a specific embodiment of the above (Chemical Formula IV), R 22 and R 23 are, independently of each other, an alkylene group having 1 to 10 carbon atoms, or -R 28 [OR 29 f -, where R 24 ~R 27 are, independently of each other, an alkyl group having 1 to 10 carbon atoms, and R 28 and R 29 are, independently of each other, an alkylene group having 1 to 10 carbon atoms, and d and e are, independently of each other, an integer selected from 0 or 1 to 3, and d + e is an integer of 1 or more, and f is an integer selected from 1 to 30.

[0048] The compound represented by the above (Chemical Formula IV) can be a compound represented by the following (Chemical Formula IV-a), (Chemical Formula IV-b), or (Chemical Formula IV-c).

[0049]

Chemical Formula

[0050]

Chemical Formula

[0051]

Chem.

[0052] In the above (Chemical Formula IV-a), (Chemical Formula IV-b), and (Chemical Formula IV-c), R 22 ~R 27 , d, and e are as described above.

[0053] The compounds represented by the above (Chemical Formula IV) include, but are not limited to, for example, 1,4-bis(3-(3-(triethoxysilyl)propoxy)propyl)piperazine, 1,4-bis(3-(trimethoxysilyl)propyl)piperazine, 1,4-bis(3-(dimethoxymethylsilyl)propyl)piperazine, 1-(3-(ethoxydimethylsilyl)propyl)-4-(3-(triethoxysilyl)propyl)piperazine, 1-(3-(ethoxydimethyl)propyl)-4-(3-(triethoxysilyl)methyl)piperazine, 1-(3-(ethoxydimethyl)methyl)-4-(3-(triethoxysilyl)propyl)piperazine, 1,3-bis(3-(triethoxysilyl)propyl)imidazolidine, 1,3-bis(3-(dimethoxyethylsilyl)propyl)imidazolidine, 1,3-bis(3-(trimethoxysilyl)propyl)hexahydropyrimidine, 1,3-bis(3-(triethoxysilyl)propyl)hexahydropyrimidine, and 1,3-bis(3-(tributoxysilyl)propyl)-1,2,3,4-tetrahydropyrimidine, etc.

[0054] Furthermore, examples of the modifier include compounds represented by the following (Chemical Formula V).

[0055]

Chem.

[0056] In the above (Chemical Formula V), R 30is a monovalent hydrocarbon group having 1 to 30 carbon atoms, R 31 ~R 33 are each independently an alkylene group having 1 to 10 carbon atoms, R 34 ~R 37 are each independently an alkyl group having 1 to 10 carbon atoms, and g and h are each independently an integer selected from 0 or 1 to 3, and g + h is an integer of 1 or more.

[0057] In addition, examples of the modifier include compounds represented by the following (Chemical Formula VI).

[0058]

Chemical Formula

[0059] In the above (Chemical Formula VI), A 3 and A 4 are each independently an alkylene group having 1 to 10 carbon atoms, R 38 ~R 41 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and i is an integer selected from 1 to 30.

[0060] Furthermore, examples of the modifier include 3,4-bis(2-methoxyethoxy)-N-(4-(triethoxysilyl)butyl)aniline, N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl)propan-1-amine, 2,4-bis(2-methoxyethoxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine, and 3,13-dimethoxy-3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilapentadecane, etc.

[0061] As the modifier, a compound represented by the following (Chemical Formula VII) may also be used.

[0062]

Chemical Formula

[0063] In the above (Chemical Formula VII), R 43 , R 45 , and R 46 are each independently an alkyl group having 1 to 10 carbon atoms, R 44 is an alkylene group having 1 to 10 carbon atoms, and k is an integer selected from 1 to 4.

[0064] Examples of the compound represented by the above (Chemical Formula VII) include, but are not limited to, 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane, 8,8-dimethyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane, 8,8-dibutyl-3,3,13,13-tetramethoxy-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane, and 8-butyl-3,3,13,13-tetramethoxy-8-((3-(trimethoxysilyl)propyl)thio)-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane.

[0065] As used herein, the term "monovalent hydrocarbon group" can mean a monovalent atomic group in which carbon and hydrogen are bonded, such as a monovalent alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkyl group containing one or more unsaturated bonds, and aryl group. The minimum number of carbon atoms of the substituent represented by the monovalent hydrocarbon can be determined by the type of each substituent. As used herein, the term "divalent hydrocarbon group" can mean a divalent atomic group in which carbon and hydrogen are bonded, such as a divalent alkylene group, alkenylene group, alkynylene group, cycloalkylene group, cycloalkylene group containing one or more unsaturated bonds, and arylene group. The minimum number of carbon atoms of the substituent represented by the divalent hydrocarbon can be determined by the type of each substituent. As used herein, the term "alkyl group" means a monovalent aliphatic saturated hydrocarbon, and can include both linear alkyl groups such as methyl, ethyl, propyl, and butyl, and branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neopentyl.

[0066] As used herein, the term "alkylene group" can mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene. As used herein, the term "alkenyl group" can mean an alkyl group containing one or more double bonds. As used herein, the term "alkynyl group" can mean an alkyl group containing one or more triple bonds. As used herein, the term "cycloalkyl group" can include both cyclic saturated hydrocarbons and cyclic unsaturated hydrocarbons containing one or more unsaturated bonds. As used herein, the term "aryl group" means a cyclic aromatic hydrocarbon, and can include both monocyclic aromatic hydrocarbons formed by one ring and polycyclic aromatic hydrocarbons formed by bonding two or more rings.

[0067] 〔Method for Producing Hydrogenated Modified Conjugated Diene Polymer〕 The hydrogenated modified conjugated diene polymer of the present embodiment includes a step (S1) of producing an active polymer bonded with an organometal by polymerizing or copolymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound in a hydrocarbon solvent in the presence of an organometallic compound, and a step (S2) of reacting or coupling the active polymer produced in the step (S1) with a modifier. After the step (S2), a hydrogenation step can be carried out. The step (S1) is preferably carried out continuously in two or more polymerization reactors, and the polymerization conversion rate in the first reactor among the polymerization reactors may be 50% or less. Examples of the hydrocarbon solvent include, but are not limited to, n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, xylene, and the like.

[0068] The addition amount of the organometallic compound is preferably 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 to 0.8 mmol based on 100 g of the total monomers used in the polymerization. Examples of the organometallic compound include, but are not limited to, methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthylsodium, naphthylpotassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium isopropylamide.

[0069] The polymerization in the step (S1) may be, for example, anionic polymerization, specifically, living anionic polymerization having an anionic active site at the polymerization terminal by a growth polymerization reaction by an anion. Further, the polymerization in the step (S1) may be temperature-rising polymerization, isothermal polymerization, or isothermal polymerization (adiabatic polymerization). The isothermal polymerization means a polymerization method including a step of polymerizing with the heat of its own reaction without arbitrarily adding heat after adding the organometallic compound, and the temperature-rising polymerization means a polymerization method of arbitrarily adding heat after adding the organometallic compound to increase the temperature. The isothermal polymerization means a polymerization method in which, after the organometallic compound is charged, heat is applied to increase or remove heat to maintain the temperature of the polymer constant.

[0070] In addition, the polymerization in the step (S1) may be carried out by further adding a diene compound having 1 to 10 carbon atoms in addition to the conjugated diene compound. In this case, there is an effect of preventing the formation of gel on the wall surface of the reactor during long-term operation. Examples of the diene monomer having 1 to 10 carbon atoms include 1,2-butadiene.

[0071] The polymerization in the step (S1) can be carried out, for example, in a temperature range of 80°C or lower, -20°C to 80°C, 0°C to 80°C, 0°C to 70°C, or 10°C to 70°C. When within this temperature range, the molecular weight distribution of the polymer can be adjusted narrowly, and there is a tendency to be excellent in improving the physical properties of the hydrogenated modified conjugated diene polymer and its rubber composition of the present embodiment. The living polymer produced by the step (S1) is a polymer in which a polymer anion and an organometallic cation are bonded. The living polymer produced by the polymerization in the step (S1) may be a random copolymer. In this case, the hydrogenated modified conjugated diene polymer and its rubber composition of the present embodiment tend to have an excellent balance among various physical properties. The random copolymer means one in which the repeating units constituting the copolymer are arranged disorderly. In the method for producing the hydrogenated modified conjugated diene polymer of the present embodiment, it is preferably carried out by a continuous polymerization method in a plurality of reactors including two or more polymerization reactors and modification reactors. Specifically, the step (S1) may be continuously carried out in two or more polymerization reactors, and the number of the polymerization reactors can be determined elastically according to the reaction conditions and environment. The continuous polymerization method means a reaction process in which reactants are continuously supplied to the reactor and the produced reaction products are continuously discharged. When using the continuous polymerization method, it is excellent in productivity and processability, and tends to be excellent in the uniformity of the produced polymer.

[0072] Also, when continuously producing an active polymer in the polymerization reactor, the polymerization conversion rate in the first reactor can be 50% or less, 10% - 50%, or 20% - 50%. When within this range, after the polymerization reaction is initiated, side reactions that occur while the polymer is being formed can be suppressed, and a polymer with a linear structure can be induced during polymerization. As a result, the molecular weight distribution of the polymer can be narrowly controlled, and there is a tendency to be excellent in improving the physical properties of the hydrogenated modified conjugated diene polymer and its rubber composition of the present embodiment. At this time, the polymerization conversion rate can be controlled by adjusting the reaction temperature, reactor residence time, etc. The polymerization conversion rate may be determined, for example, by measuring the solid concentration in the polymer solution containing the polymer during the polymerization of the polymer. For example, in order to secure the polymer solution, a cylinder-shaped container is attached to the outlet of each polymerization reactor to fill the cylinder-shaped container with a certain amount of polymer solution, the cylinder-shaped container is separated from the reactor, and after measuring the mass (A) of the cylinder filled with the polymer solution, the polymer solution filled in the cylinder-shaped container is transferred to an aluminum container, for example, an aluminum dish, and the mass (B) of the cylinder-shaped container from which the polymer solution has been removed is measured. The aluminum container containing the polymer solution is dried in an oven at 140°C for 30 minutes, and after measuring the mass (C) of the dried polymer, it may be calculated by the following mathematical formula.

[0073]

Equation

[0074] On the other hand, the polymer polymerized in the first reactor may be sequentially transferred to the polymerization reactors before the modification reactor, and polymerization may be finally performed until the polymerization conversion rate reaches 95% or more. After being polymerized in the first reactor, the polymerization conversion rate for each reactor from the second reactor or from the second reactor to the polymerization reactors before the modification reactor may be appropriately adjusted for each reactor in order to control the molecular weight distribution.

[0075] In the step (S1), when producing the living polymer, the residence time of the polymer in the first reactor may be 1 minute to 40 minutes, 1 minute to 30 minutes, or 5 minutes to 30 minutes. When within this range, since the polymerization conversion rate is easy to adjust, the molecular weight distribution of the polymer can be narrowly controlled, and thereby, there is an excellent effect in improving the physical properties of the hydrogenated modified conjugated diene-based polymer and its rubber composition of the present embodiment.

[0076] The molecular weight distribution (PDI, polydispersed index; MWD, molecular weight distribution; Mw / Mn) of the living polymer produced in the step (S1) may be less than 1.5, 1.0 or more to less than 1.5, or 1.1 or more to less than 1.5. When within this range, the molecular weight distribution of the modified hydrogenated conjugated diene-based polymer produced by the modification reaction with the modifier or coupling can be made less than 1.7, and there is an excellent effect in improving the physical properties.

[0077] The polymerization in the step (S1) may be carried out in the presence of a polar additive. The polar additive is preferably added in a proportion of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g based on 100 g of the total monomers. As another example, the polar additive may be added in a proportion of 0.001 g to 10 g, 0.005 g to 5 g, or 0.005 g to 4 g based on 1 mmol of the total organometallic compounds.

[0078] Examples of the polar additive include, but are not limited to, tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethylethylenediamine, sodium mentholate, and 2-ethyltetrahydrofurfuryl ether. In particular, triethylamine, tetramethylethylenediamine, sodium mentholate, and 2-ethyltetrahydrofurfuryl ether are preferred. When the polar additive is included, when copolymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound, by complementing the difference in their reaction rates, there is an effect of inducing the easy formation of a random copolymer.

[0079] The reaction or coupling in the step (S2) may be carried out in a modification reactor. At this time, the modifier may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomers. As another example, the modifier may be used in a molar ratio of 1:0.1 to 10, 1:0.1 to 5, or 1:0.1 to 1:3 based on 1 mol of the organometallic compound in the step (S1). Also, the modifier may be charged into the modification reactor, and the step (S2) may be carried out in the modification reactor. As another example, the modifier may be charged into the transfer section for transferring the living polymer produced in the step (S1) to the modification reactor for carrying out the step (S2), and in the transfer section, the reaction or coupling can proceed by mixing the living polymer and the modifier.

[0080] The hydrogenation reaction is generally carried out by maintaining a conjugated diene polymer at a predetermined temperature in hydrogen or an inert atmosphere, adding a hydrogenation catalyst with stirring or without stirring, and then introducing hydrogen gas to pressurize to a predetermined pressure. The inert atmosphere means an atmosphere that does not react with substances involved in the hydrogenation reaction. For example, an atmosphere such as helium, neon, argon, etc. can be mentioned. Air and oxygen are not preferred because they oxidize the catalyst and cause deactivation of the catalyst. The hydrogen reaction process can be used in any of a batch process, a continuous process, and combinations thereof. Also, when using a titanocene diaryl-based compound as the hydrogenation catalyst, it may be added directly to the reaction solution alone, or added as a solution in an inert organic solvent. As the inert organic solvent used when using the catalyst as a solution, various solvents that do not react with substances involved in the hydrogenation reaction can be used. Preferably, it is a solvent that is uniform with the solvent used in the hydrogenation reaction.

[0081] A preferred method for obtaining a hydrogenated modified conjugated diene polymer is to solution polymerize a monomer containing 1,3-butadiene in the presence of a polymerization initiator, perform a coupling reaction on the obtained polymer solution, then add a terminal modifier as necessary, and then subject it to a hydrogenation step, which is industrially useful. In this case, a hydrogenated modified conjugated diene polymer is obtained by removing the solvent from the solution obtained above. To isolate the polymer, it can be carried out by known solvent removal methods such as steam stripping and drying operations such as heat treatment.

[0082] 〔Rubber Composition〕 The rubber composition of this embodiment contains the hydrogenated modified conjugated diene polymer of this embodiment described above and a filler. The rubber composition of this embodiment preferably contains 10% by mass or more, 10% by mass to 100% by mass, or 20% by mass to 90% by mass of the hydrogenated modified conjugated diene polymer of this embodiment described above. When within this range, it is excellent in mechanical physical properties such as tensile strength and abrasion resistance, and tends to be excellent in the balance between various physical properties.

[0083] In addition to the hydrogenated conjugated diene polymer, the rubber composition of this embodiment may further contain other rubber components as needed. The other rubber components may be contained in an amount of 90% by mass or less based on the total mass of the rubber composition of this embodiment. That is, the other rubber components may be contained in an amount of 1 part by mass to 900 parts by mass with respect to 100 parts by mass of the hydrogenated conjugated diene polymer of this embodiment.

[0084] The other rubber components may be natural rubber or synthetic rubber. Although not limited to the following, for example, natural rubber (NR) containing cis-1,4-polyisoprene; modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or purifying the general natural rubber; styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, isobutylene-isoprene copolymer, neoprene, ethylene-propylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isoprene-butadiene copolymer, isoprene-butadiene copolymer, ethylene-propylene-diene copolymer, polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber, etc. These may be used alone or in combination of two or more.

[0085] The rubber composition of this embodiment contains a filler. Preferably, the filler is contained in an amount of 0.1 to 200 parts by mass, more preferably 10 to 120 parts by mass, with respect to 100 parts by mass of the hydrogenated conjugated diene polymer of this embodiment. As the filler, for example, a silica-based filler can be used. Although not limited to the following, for example, wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, colloidal silica, etc. are mentioned. Wet silica, which has the highest effect of improving the fracture properties and the dual effect of wet grip properties of the rubber composition of this embodiment, is preferred. In addition, the rubber composition may further contain a carbon-based filler, if necessary.

[0086] When silica is used as the filler, a silane coupling agent may be used together to improve the reinforcing property and low heat generation property. Examples of the silane coupling agent include, but are not limited to, bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, and dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide. These may be used alone or in combination of two or more. In consideration of the effect of improving the reinforcing property, bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide is preferable.

[0087] In addition, in the rubber composition of the present embodiment, as the rubber component, a hydrogenated modified conjugated diene polymer having a functional group with high affinity for silica introduced into the active site is used. Therefore, the blending amount of the silane coupling agent can be reduced compared to the normal case. Accordingly, the silane coupling agent may be used in an amount of 1 to 20 parts by mass, or 5 to 15 parts by mass, per 100 parts by mass of silica. When within this range, while the effect as a coupling agent is sufficiently exhibited, there is an effect of preventing gelation of the rubber component.

[0088] The rubber composition of the present embodiment may be sulfur-crosslinkable and may further contain a vulcanizing agent. Specifically, the vulcanizing agent may be sulfur powder and may be contained in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the rubber component. When within this range, while ensuring the elastic modulus and strength required for the vulcanized rubber composition, there is an effect of excellent low fuel consumption.

[0089] In addition to the above components, the rubber composition of the present embodiment can contain various additives commonly used in the rubber industry. Examples of the additives include vulcanization accelerators, process oils, antioxidants, plasticizers, anti-aging agents, scorch inhibitors, zinc white, stearic acid, thermosetting resins, and thermoplastic resins. The vulcanization accelerator is not limited to the following. For example, thiazole-based compounds such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), or guanidine-based compounds such as DPG (diphenylguanidine) can be used and may be contained in an amount of 0.1 to 5 parts by mass per 100 parts by mass of the rubber component. The process oil acts as a softening agent in the rubber composition and includes, but is not limited to, for example, paraffinic, naphthenic, and aromatic compounds. Considering tensile strength and abrasion resistance, aromatic process oils are preferred, while considering hysteresis loss and low-temperature properties, naphthenic and paraffinic process oils are preferred. The process oil may be included, for example, in an amount of 100 parts by mass or less per 100 parts by mass of the rubber component. When within this range, it has the effect of preventing a decrease in the tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber. Examples of the antioxidant include, but are not limited to, 2,6-di-t-butyl-p-cresol, di-butyl-hydroxy-toluenyl, 2,6-bis((dodecylthio)methyl)-4-nonylphenol, and 2-methyl-4,6-bis((octylthio)methyl)phenol, and it may be used in an amount of 0.1 to 6 parts by mass per 100 parts by mass of the rubber component. Examples of the anti-aging agent include, but are not limited to, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, and high-temperature condensates of diphenylamine and acetone, etc., and it may be used in an amount of 0.1 to 6 parts by mass per 100 parts by mass of the rubber component.

[0090] The rubber composition of this embodiment can be obtained by kneading using a kneader such as a Banbury mixer, roll, internal mixer, etc. according to the above formulation. After molding, a rubber composition excellent in low heat generation and wear resistance can be obtained through a vulcanization process. Thereby, the rubber composition is useful in the manufacture of various members of a tire such as a tire tread, under tread, sidewall, carcass coating rubber, belt coating rubber, bead filler, chafer, or bead coating rubber, and various industrial rubber products such as dust rubber, belt conveyor, and hose.

Examples

[0091] Hereinafter, the present embodiment will be described in more detail with specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples in any way. Various physical properties in the examples and comparative examples were measured by the following methods.

[0092] [[1: Hydrogenated modified conjugated diene polymer]] In the examples and comparative examples described below, hydrogenated modified conjugated diene polymers were prepared and their physical properties were measured. ((1-1) Styrene unit content, vinyl bond amount, hydrogenation rate of pre-hydrogenated polymer) The bound styrene amount (mass %) in the pre-hydrogenated polymer, the vinyl bond amount (mol %) in the conjugated diene monomer, and the hydrogenation rate (mol %) in the hydrogenated conjugated diene polymer were measured using JNM-LA400 (manufactured by JEOL), and deuterated chloroform was used as the solvent. The composition ratios (mol %) of the structural units represented by the above formula (1), the structural units represented by the above formula (2), the structural units represented by the above formula (3), and the structural units represented by the above formula (4) were measured, and the hydrogenation rate of the double bond of the structural unit derived from 1,3-butadiene (hereinafter simply referred to as "hydrogenation rate") was measured and analyzed.

[0093] ((1-2) Molecular weight distribution (PDI; MWD)) The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by GPC (Gel permeation Chromatography) analysis, and the molecular weight distribution (PDI; MWD; Mw / Mn) was calculated from the measured molecular weights. Specifically, as the GPC, two PLgel Olexis (manufactured by Polymer Laboratories) columns and one PLgel mixed-C (manufactured by Polymer Laboratories) column were used in combination, and all the newly alternating columns were mixed bed type columns. When calculating the molecular weight, PS (polystyrene) was used as the GPC standard material. The GPC measurement solvent was prepared by mixing 1% by mass of an amine compound with tetrahydrofuran.

[0094] ((1-3) Mooney viscosity) The Mooney viscosity ((ML 1+4 , @100 °C) MU) was measured using a VR1132 (manufactured by Ueshima Seisakusho Co., Ltd.) in accordance with ISO 289 using an L-shaped rotor. The measurement temperature was 100 °C when the hydrogenated conjugated diene polymer was used as the sample. Specifically, first, the sample was preheated at the test temperature for 1 minute, then the rotor was rotated at 2 rpm, and the torque of the sample after 4 minutes was measured, and the measured value was taken as the Mooney viscosity (ML (1+4) ).

[0095] 〔Production of hydrogenated modified conjugated diene polymer〕 (Production Example 1: Production of modifier initiator) Two 4 L stainless steel pressure vessels dried under vacuum were prepared. 944 g of cyclohexane, 161 g of the compound represented by the following chemical formula (1-1), and 86 g of tetramethylethylenediamine were charged into the first pressure vessel to prepare a first reaction solution. At the same time, 318 g of liquid 20% by mass of n-butyllithium and 874 g of cyclohexane were charged into the second pressure vessel to prepare a second reaction solution. At this time, the molar ratio of the compound represented by Chemical Formula 1-1, n-butyllithium, and tetramethylethylenediamine was 1:1:1 in this order. While maintaining the pressure in each pressure vessel at 7 bar, using a mass flow meter, the first reaction solution was injected into the continuous reactor into the first continuous channel at an injection rate of 1.0 g / min, and the second reaction solution was injected into the second continuous channel at an injection rate of 1.0 g / min. At this time, the temperature of the continuous reactor was maintained at -10 °C, the internal pressure was maintained at 3 bar using a backpressure regulator, and the residence time in the reactor was adjusted to be within 10 minutes. The reaction was terminated to obtain a modified initiator solution.

[0096]

Chemical formula

[0097] (Production Example 2: Production of Hydrogenation Catalyst) In the Examples and Comparative Examples described below, the hydrogenation catalyst (TC) used for preparing the hydrogenated conjugated diene polymer was prepared by the following method. A reaction vessel equipped with a stirrer was purged with nitrogen, and 1 L of dried and purified cyclohexane was charged therein. Next, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added. While stirring this well, an n-hexane solution containing 200 mmol of trimethylaluminum was added to obtain a hydrogenation catalyst (TC).

[0098] (Production Example 3: Production of Ziegler Catalyst as Hydrogenation Catalyst) In the Examples and Comparative Examples described below, the hydrogenation catalyst (NA) used for preparing the hydrogenated conjugated diene polymer was prepared by the following method. 1 L of dried and purified cyclohexane was charged into a reaction vessel purged with nitrogen, and 100 mmol of nickel octylate and 200 mmol of trimethylaluminum were added to obtain a Ziegler catalyst (NA) as a hydrogenation catalyst.

[0099] (Example 1) Into the first reactor of a continuous reactor in which three reactors are connected in series, a 1,3-butadiene solution in which 1,3-butadiene is dissolved at 60% by mass in n-hexane was injected at a rate of 14.2 kg / h, n-hexane was injected at a rate of 49.0 kg / h, a 1,2-butadiene solution in which 1,2-butadiene is dissolved at 2.0% by mass in n-hexane was injected at a rate of 40.0 g / h, and as a polar additive, a solution in which 2,2-bis(2-tetrahydrofuryl)propane is dissolved at 10% by mass in n-hexane was injected at a rate of 27.0 g / h, and an initiator solution in which n-butyllithium is dissolved at 10% by mass in n-hexane was injected at a rate of 38.0 g / h. At this time, the temperature of the first reactor was maintained at 65°C, and when the polymerization conversion rate reached 47%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe. Next, a 1,3-butadiene solution in which 1,3-butadiene is dissolved at 60% by mass in n-hexane was injected into the second reactor at a rate of 0.8 kg / h, and the temperature of the second reactor was maintained at 70°C to continue the polymerization. When the polymerization conversion rate reached 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe. Thereafter, in the third reactor, as the first modifier, a solution in which N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propane-1-amine is dissolved at 20% by mass in n-hexane, and as the second modifier, a solution in which 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropane-1-amine) is dissolved at 20% by mass in n-hexane were continuously supplied in the above order in an equivalent ratio of 0.3:0.7 to proceed with the modification reaction (n-butyllithium:total amount of modifiers = 1:1 molar ratio). The temperature of the third reactor was maintained at 70°C. Thereafter, in the hydrogenation reactor, the conjugated diene polymer solution discharged from the third reactor was supplied at a rate of 64.1 kg / h, the hydrogenation catalyst (TC) produced in the above (Production Example 2) was supplied at a rate of 1.1 kg / h, and hydrogen was injected at a rate of 4.3 Nm 3 / h to carry out the hydrogenation reaction. The temperature of the hydrogenation reactor was maintained at 90°C. Thereafter, to the polymerization solution discharged from the hydrogenation reactor, as an antioxidant, an IR1520 (manufactured by BASF) solution dissolved at 30% by weight in n-hexane was injected at a rate of 167 g / h and stirred. The resulting polymer was put into warm water heated by steam and stirred to remove the solvent, thereby producing a hydrogenated modified conjugated diene polymer.

[0100] (Examples 2 to 19, Comparative Example 1) Except for the points where the polymerization formulation was changed as described in Tables 1 to 2 below and the points where the hydrogenation rate was changed as described in Tables 1 to 2 below, a hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 1). Various physical property values, etc. of the obtained hydrogenated modified conjugated diene polymer are shown in Tables 1 to 2.

[0101] (Examples 20 to 38, Comparative Example 2) Except for the points where the polymerization formulation was changed as described in Tables 3 to 4 below and the points where the hydrogenation rate was changed as described in Tables 3 to 4 below, a hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 1). Various physical property values, etc. of the obtained hydrogenated modified conjugated diene polymer are shown in Tables 3 to 4.

[0102] (Examples 39 to 57, Comparative Example 3) Except for the points where the polymerization formulation was changed as described in Tables 5 to 6 below and the points where the hydrogenation rate was changed as described in Tables 5 to 6 below, a hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 1). Various physical property values, etc. of the obtained hydrogenated modified conjugated diene polymer are shown in Tables 5 to 6.

[0103] (Examples 58 to 76, Comparative Example 4) Except for the points where the polymerization formulation was changed as described in Tables 7 to 8 below and the points where the hydrogenation rate was changed as described in Tables 7 to 8 below, a hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 1). Various physical property values, etc. of the obtained hydrogenated modified conjugated diene polymer are shown in Tables 7 to 8.

[0104] (Examples 77 to 95, Comparative Example 5) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 1), except that the polymerization formulation was changed as described in Tables 9 to 10 below, and the hydrogenation rate was changed as described in Tables 9 to 10 below. Various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer are shown in Tables 9 to 10.

[0105] (Examples 96 to 114, Comparative Example 6) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 1), except that the polymerization formulation was changed as described in Tables 11 to 12 below, and the hydrogenation rate was changed as described in Tables 11 to 12 below. Various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer are shown in Tables 11 to 12.

[0106] (Example 115) Into the first reactor of a continuous reactor in which three reactors were connected in series, a 1,3-butadiene solution in which 1,3-butadiene was dissolved at 60% by mass in n-hexane was fed at a rate of 14.2 kg / h, n-hexane was fed at a rate of 49.0 kg / h, a 1,2-butadiene solution in which 1,2-butadiene was dissolved at 2.0% by mass in n-hexane was fed at a rate of 40.0 g / h, and as a polar additive, a solution in which 2,2-di(2-tetrahydrofuryl)propane was dissolved at 10% by mass in n-hexane was fed at a rate of 27.0 g / h, and the modified initiator solution prepared in the above (Production Example 1) was fed at a rate of 490.0 g / h. At this time, the temperature of the first reactor was maintained at 60°C, and when the polymerization conversion reached 45%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe. Next, a 1,3-butadiene solution in which 1,3-butadiene was dissolved at 60% by mass in n-hexane was fed into the second reactor at a rate of 0.8 kg / h, and the temperature of the second reactor was maintained at 70°C to continue the polymerization. When the polymerization conversion reached 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe. Thereafter, in the third reactor, as the first modifier, a solution in which N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propane-1-amine was dissolved at 20% by mass in n-hexane was continuously supplied to proceed with the modification reaction (modification initiator: total amount of modifier = 1:1 molar ratio). The temperature of the third reactor was maintained at 70°C. Thereafter, in the hydrogenation reactor, the conjugated diene polymer solution discharged from the third reactor was supplied at a rate of 64.1 kg / h, and the hydrogenation catalyst (TC) produced in the above (Production Example 2) was supplied at 1.1 kg / h, and hydrogen was supplied at a rate of 2.5 Nm 3 / h to carry out the hydrogenation reaction. The temperature of the hydrogenation reactor was maintained at 90°C. Thereafter, to the polymerization solution discharged from the hydrogenation reactor, as an antioxidant, an IR1520 (manufactured by BASF) solution dissolved at 30% by weight in n-hexane was injected at a rate of 167 g / h and stirred. The resulting polymer was put into warm water heated by steam and stirred to remove the solvent, thereby producing a hydrogenated modified conjugated diene polymer. Various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer are shown in Table 13.

[0107] (Examples 116 to 118, Comparative Example 7) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation and the modifier were changed as described in Table 13 below. Various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer are shown in Table 13.

[0108] (Examples 119 to 122, Comparative Example 8) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation and the modifier were changed as described in Table 14 below, and the hydrogenation formulation was changed as described in Table 14 below. Various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer are shown in Table 14.

[0109] (Examples 123 to 126, Comparative Example 9) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation, the modifying agent was changed as described in Table 15 below, and the hydrogenation formulation was changed as described in Table 15 below. Table 15 shows various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer.

[0110] (Examples 127 to 130, Comparative Example 10) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation, the modifying agent was changed as described in Table 16 below, and the hydrogenation formulation was changed as described in Table 16 below. Table 16 shows various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer.

[0111] (Examples 131 to 134, Comparative Example 11) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation, the modifying agent was changed as described in Table 17 below, and the hydrogenation formulation was changed as described in Table 17 below. Table 17 shows various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer.

[0112] (Examples 135 to 138, Comparative Example 12) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation, the modifying agent was changed as described in Table 18 below, and the hydrogenation formulation was changed as described in Table 18 below. Table 18 shows various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer.

[0113] (Examples 139 to 142, Comparative Example 13) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation, the modifying agent was changed as described in Table 19 below, and the hydrogenation formulation was changed as described in Table 19 below. Table 19 shows various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer.

[0114] (Examples 143 to 146, Comparative Example 14) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation, the modifier was changed as described in Table 20 below, and the hydrogenation formulation was changed as described in Table 20 below. Table 20 shows various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer.

[0115] (Examples 147 to 150, Comparative Example 15) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation, the modifier was changed as described in Table 21 below, and the hydrogenation formulation was changed as described in Table 21 below. Table 21 shows various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer.

[0116] (Examples 151 to 154, Comparative Example 16) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation, the modifier was changed as described in Table 22 below, and the hydrogenation formulation was changed as described in Table 22 below. Table 22 shows various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer.

[0117] (Examples 155 to 158, Comparative Example 17) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation, the modifier was changed as described in Table 23 below, and the hydrogenation formulation was changed as described in Table 23 below. Table 23 shows various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer.

[0118] (Examples 159 to 162, Comparative Example 18) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation, the modifier was changed as described in Table 24 below, and the hydrogenation formulation was changed as described in Table 24 below. Table 24 shows various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer.

[0119] (Examples 163 to 166, Comparative Example 19) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation, the modifier were changed as described in Table 25 below, and the hydrogenation formulation was changed as described in Table 25 below. Table 25 shows various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer.

[0120] (Examples 167 to 170, Comparative Example 20) A hydrogenated modified conjugated diene polymer was obtained in the same manner as in the above (Example 115), except that the polymerization formulation, the modifier were changed as described in Table 26 below, and the hydrogenation formulation was changed as described in Table 26 below. Table 26 shows various physical property values and the like of the obtained hydrogenated modified conjugated diene polymer.

[0121] The symbols in the following table are shown below. DTP: 2,2 - bis(2 - tetrahydrofuryl)propane TMEDA: N,N,N’,N’ - tetramethylethylenediamine (M:PI): Molar ratio of modifier to initiator A: N-(3-(1H - imidazol - 1 - yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propane - 1 - amine B: 3,3’-(1,1,3,3 - tetramethoxydisiloxane - 1,3 - diyl)bis(N,N - diethylpropane - 1 - amine) C: N,N - bis(3-(diethoxy(methyl)silyl)propyl)-methyl - 1 - amine D: N-(3,6,9,12 - tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12 - tetraoxahexadecane - 1 - amine E: 3,3’-(piperazine - 1,4 - diyl)bis(N,N - bis(3-(triethoxysilyl)propyl)propane - 1 - amine) F: Silicon tetrachloride

[0122]

Table 1

[0123]

Table 2

[0124]

Table 3

[0125]

Table 4

[0126]

Table 5

[0127]

Table 6

[0128]

Table 7

[0129]

Table 8

[0130]

Table 9

[0131]

Table 10

[0132]

Table 11

[0133]

Table 12

[0134]

Table 13

[0135]

Table 14

[0136]

Table 15

[0137]

Table 16

[0138]

Table 17

[0139]

Table 18

[0140]

Table 19

[0141]

Table 20

[0142]

Table 21

[0143]

Table 22

[0144]

Table 23

[0145]

Table 24

[0146]

Table 25

[0147]

Table 26

[0148] 〔2: Rubber Composition〕 In order to comparatively analyze the properties of rubber compositions containing each modified or unmodified conjugated diene copolymer produced in the above Examples and Comparative Examples, and molded articles produced therefrom, viscoelastic properties and abrasion resistance were measured respectively, and the results are shown in Tables 27 to 52 below. In the following tables, the same numbers as those of the Examples and Comparative Examples of the above-described polymers are assigned, and the properties of the rubber compositions using each polymer are shown.

[0149] (Production of Rubber Test Specimens) Each modified or unmodified conjugated diene polymer produced in the Examples and Comparative Examples was used as a raw rubber and compounded under the compounding conditions shown below. The content of the raw materials in the compounding shown below is in parts by mass based on 100 parts by mass of the raw rubber. Specifically, the rubber test piece was kneaded through primary kneading and secondary kneading. In the primary kneading, using a closed kneader with a temperature control device, raw rubber, fillers (silica, carbon black), a silane coupling agent, SRAE oil, zinc oxide (ZnO), stearic acid, and an anti-aging agent (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine)) were kneaded. At this time, the discharge temperature of the formulation was adjusted to 155°C to 160°C. In the secondary kneading, after cooling the primary formulation to room temperature, the primary formulation, sulfur, and a vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the kneader and mixed at a temperature of 100°C or lower to obtain a secondary formulation. Thereafter, vulcanization was carried out using a vulcanization press at 160°C for 20 minutes to produce a rubber test piece.

[0150] (Mixing conditions) <Primary kneading> Raw rubber: 100 parts by mass Silica: 75 parts by mass Carbon black: 5 parts by mass Silane coupling agent: 6 parts by mass Process oil (SRAE oil): 30 parts by mass Zinc oxide (ZnO): 3 parts by mass Stearic acid: 2 parts by mass Anti-aging agent: 2 parts by mass <Secondary kneading> Sulfur: 1.7 parts by mass Vulcanization accelerator CZ: 1.7 parts by mass

[0151] ((2-1) Viscoelastic properties) The viscoelastic properties were measured using a dynamic mechanical analyzer (Dynamic Mechanical Analyzer: TA Instruments, ARES-G2) in torsional mode at a frequency of 10 Hz, a deformation rate (strain) of 0.5%, and at each measurement temperature (-100°C to 100°C) to measure the viscoelastic behavior with respect to dynamic deformation and confirm the tanδ value. In the measured values, the lower the tanδ value at 50°C, the less the hysteresis loss, which means excellent low rolling resistance (fuel efficiency). In the following table, the reference values of the viscoelastic properties (for Examples 1 to 19, Comparative Example 1; for Examples 20 to 38, Comparative Example 2; for Examples 39 to 57, Comparative Example 3; for Examples 58 to 76, Comparative Example 4; for Examples 77 to 95, Comparative Example 5; for Examples 96 to 114, Comparative Example 6; for Examples 115 to 118, Comparative Example 7; for Examples 119 to 122, Comparative Example 8; for Examples 123 to 126, Comparative Example 9; for Examples 127 to 130, Comparative Example 10; for Examples 131 to 134, Comparative Example 11; for Examples 135 to 138, Comparative Example 12; for Examples 139 to 142, Comparative Example 13; for Examples 143 to 146, Comparative Example 14; for Examples 147 to 150, Comparative Example 15; for Examples 151 to 154, Comparative Example 16; for Examples 155 to 158, Comparative Example 17; for Examples 159 to 162, Comparative Example 18; for Examples 163 to 166, Comparative Example 19; for Examples 167 to 170, Comparative Example 20.) were specified and indexed (%). If the index is 111 or more, it is very good (◎ in the table), if it is 101 - 110, it is good (○ in the table), if it is 91 - 100, there is no practical problem (△ in the table), and if it is 90 or less, deterioration is observed (× in the table), and it was evaluated accordingly.

[0152] ((2 - 2) Tensile properties) For the tensile properties, each test piece was manufactured according to the tensile test method of ASTM 412, and the tensile strength at the time of cutting the test piece was measured. In the following table, the reference values of the tensile strength (for Examples 1 to 19, Comparative Example 1; for Examples 20 to 38, Comparative Example 2; for Examples 39 to 57, Comparative Example 3; for Examples 58 to 76, Comparative Example 4; for Examples 77 to 95, Comparative Example 5; for Examples 96 to 114, Comparative Example 6; for Examples 115 to 118, Comparative Example 7; for Examples 119 to 122, Comparative Example 8; for Examples 123 to 126, Comparative Example 9; for Examples 127 to 130, Comparative Example 10; for Examples 131 to 134, Comparative Example 11; for Examples 135 to 138, Comparative Example 12; for Examples 139 to 142, Comparative Example 13; for Examples 143 to 146, Comparative Example 14; for Examples 147 to 150, Comparative Example 15; for Examples 151 to 154, Comparative Example 16; for Examples 155 to 158, Comparative Example 17; for Examples 159 to 162, Comparative Example 18; for Examples 163 to 166, Comparative Example 19; for Examples 167 to 170, Comparative Example 20.) were specified and indexed (%). If the index is 111 or more, it is very good (◎ in the table), if it is 101 - 110, it is good (○ in the table), if it is 91 - 100, there are no practical problems (△ in the table), and if it is 90 or less, deterioration is observed (× in the table), and it was evaluated accordingly.

[0153] ((2 - 3) Processability) The Mooney viscosity (MV, (ML 1+4 , @100 °C) MU) of the secondary formulation obtained in the above (manufacture of rubber test pieces) was measured, and the processability characteristics of each polymer were comparatively analyzed. In the following table, the Mooney viscosity (MV, (ML 1+4, (@100℃) MU) reference values (for Examples 1 to 19, Comparative Example 1; for Examples 20 to 38, Comparative Example 2; for Examples 39 to 57, Comparative Example 3; for Examples 58 to 76, Comparative Example 4; for Examples 77 to 95, Comparative Example 5; for Examples 96 to 114, Comparative Example 6; for Examples 115 to 118, Comparative Example 7; for Examples 119 to 122, Comparative Example 8; for Examples 123 to 126, Comparative Example 9; for Examples 127 to 130, Comparative Example 10; for Examples 131 to 134, Comparative Example 11; for Examples 135 to 138, Comparative Example 12; for Examples 139 to 142, Comparative Example 13; for Examples 143 to 146, Comparative Example 14; for Examples 147 to 150, Comparative Example 15; for Examples 151 to 154, Comparative Example 16; for Examples 155 to 158, Comparative Example 17; for Examples 159 to 162, Comparative Example 18; for Examples 163 to 166, Comparative Example 19; for Examples 167 to 170, Comparative Example 20) were specified and indexed (%). If the index is 111 or more, it is very good (◎ in the table); if it is 101 - 110, it is good (○ in the table); if it is 91 - 100, there are no practical problems (△ in the table); if it is 90 or less, deterioration is observed (× in the table), and it was evaluated as such.

[0154]

Table 27

[0155]

Table 28

[0156]

Table 29

[0157]

Table 30

[0158]

Table 31

[0159]

Table 32

[0160]

Table 33

[0161]

Table 34

[0162]

Table 35

[0163]

Table 36

[0164]

Table 37

[0165]

Table 38

[0166]

Table 39

[0167]

Table 40

[0168]

Table 41

[0169]

Table 42

[0170]

Table 43

[0171]

Table 44

[0172]

Table 45

[0173]

Table 46

[0174]

Table 47

[0175]

Table 48

[0176]

Table 49

[0177]

Table 50

[0178]

Table 51

[0179]

Table 52

[0180] The hydrogenated modified conjugated diene polymer of the example was found to have practically sufficient processability, tensile properties, and viscoelastic properties, and to be excellent in the balance of these properties.

Industrial Applicability

[0181] The hydrogenated modified conjugated diene polymer of the present invention has industrial applicability in the use of materials for various members of tires such as tire treads, undertreads, sidewalls, carcass coatings, belt coatings, bead fillers, chafers, or bead coatings, and various industrial rubber products such as dust rubbers, belt conveyors, and hoses.

Claims

Claim 1 A hydrogenated modified conjugated diene polymer, comprising a repeating unit derived from a conjugated diene compound and a functional group derived from a modifier, wherein the molecular weight distribution curve by gel permeation chromatography (GPC) is unimodal, and the molecular weight distribution (PDI: MWD) is less than 1.

7. Claim 2 The hydrogenated modified conjugated diene polymer according to claim 1, wherein the modifier is an alkoxysilane-based modifier. Claim 3 The hydrogenated modified diene polymer according to claim 1, containing an aromatic vinyl monomer unit in an amount of more than 0% by mass and 45% by mass or less. Claim 4 The hydrogenated modified diene polymer according to claim 1, wherein the vinyl bond amount of the conjugated diene monomer unit before hydrogenation is 10 mol% or more and 60 mol% or less. Claim 5 The hydrogenated modified diene polymer according to claim 1, having a Mooney viscosity at 100 °C of 30 or more and 130 or less. Claim 6 A rubber composition, comprising the hydrogenated modified conjugated diene polymer according to any one of claims 1 to 5, and a filler. ​

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