Hydrogenated conjugated diene polymer and method for preparing hydrogenated conjugated diene polymer

Abstract

A hydrogenated conjugated diene polymer satisfying the following conditions (i) to (iii). It contains conjugated diene monomer units and may contain aromatic vinyl monomer units; if it contains aromatic vinyl monomer units, it is a random polymer, and the content of aromatic vinyl monomer blocks is less than 10 mass% of the hydrogenated conjugated diene polymer. The weight average molecular weight is 10×10⁴ or more and 200×10⁴ or less. The full width at half maximum temperature of the elution amount peak measured by temperature gradient interaction chromatography is in the range of 20 to 80°C.

Description

Technology Field

[0001] The present invention relates to a hydrogenated conjugated diene polymer and a method for manufacturing a hydrogenated conjugated diene polymer. Background Technology

[0002] Conventionally, rubber products, including tires, have been required to have improved durability, such as ozone resistance and rupture strength, or excellent low hysteresis loss.

[0003] For example, Patent Document 1 or Patent Document 2 proposes a technology regarding a rubber composition incorporating a hydrogenated conjugated diene polymer and a rubber composition having good ozone resistance. Prior art literature

[0004] International Publication No. 2017 / 014282 Japanese Patent No. 6845679 The problem to be solved

[0005] However, as described in the above patent documents 1 and 2, when the hydrogenation process of a conjugated diene polymer is performed in a batch format, if the hydrogenation rate of the conjugated diene polymer is increased to improve the ozone resistance of the rubber composition, the viscosity of the resulting hydrogenated conjugated diene polymer increases significantly due to the entanglement of the polymer chains, and thus the processability of the hydrogenated conjugated diene polymer and the rubber composition is greatly deteriorated.

[0006] If the molecular weight of the conjugated diene polymer is lowered to improve the aforementioned processability, cold flow resistance deteriorates, and fracture properties are reduced. Furthermore, if the hydrogenation rate is lowered, processability improves, but ozone resistance, fracture properties, and cold flow resistance deteriorate.

[0007] Meanwhile, introducing a small amount of aromatic vinyl monomer blocks into conjugated diene polymers can improve the cold flow resistance (flowability) or fracture properties of hydrogenated conjugated diene polymers and rubber compositions, but this has the problem that low hysteresis loss properties are deteriorated.

[0008] In other words, the aforementioned conventional hydrogenated conjugated diene polymers and rubber compositions have the problem that it is difficult to achieve excellent ozone resistance, fracture properties, and low hysteresis loss while ensuring good processability and cold flow resistance.

[0009] Accordingly, the present invention aims to provide a hydrogenated conjugated diene polymer that, in consideration of the problems of the prior art described above, ensures good processability and cold flow resistance, while achieving excellent processability, ozone resistance, breakage properties, and low hysteresis loss when used as a rubber composition. means of solving the problem

[0010] The inventors, after careful consideration to solve the problem of the prior art described above, discovered that a hydrogenated conjugated diene polymer having a specific aromatic vinyl monomer block amount, a weight-average molecular weight, and a half-width temperature of the elution amount peak measured by temperature gradient interaction chromatography (hereinafter referred to as "TGIC") can solve the problem, and thus completed the present invention.

[0011] That is, the present invention is as follows.

[0012] [1]

[0013] A hydrogenated conjugated diene polymer satisfying the following conditions (i) to (iii).

[0014] <condition (i)>

[0015] It contains conjugated diene monomer units and may also contain aromatic vinyl monomer units, and in the case of containing said aromatic vinyl monomer units, it is a random polymer.

[0016] The content of the aromatic vinyl monomer block is less than 10 mass% of the hydrogenated conjugated diene polymer.

[0017] <Condition (ii)>

[0018] Weight-average molecular weight is 10×10 4 More than 200×10 4 It is as follows.

[0019] <Condition (iii)>

[0020] The full width at half maximum temperature of the elution amount peak measured by temperature gradient interaction chromatography is in the range of 20 to 80°C.

[0021] [2]

[0022] A hydrogenated conjugated diene polymer described in [1] above, having a hydrogenation rate of 97 mol% or less.

[0023] [3]

[0024] A hydrogenated conjugated diene polymer described in [1] or [2] above, having a hydrogenation rate of 50 mol% or more.

[0025] [4]

[0026] Having an ethylene structure,

[0027] A hydrogenated conjugated diene polymer described in any one of [1] to [3], having an ethylene structure of 1 mass% or more.

[0028] [5]

[0029] A hydrogenated conjugated diene polymer described in any one of [1] to [4] containing an aromatic vinyl monomer unit.

[0030] [6]

[0031] A method for manufacturing a hydrogenated conjugated diene polymer as described in any one of [1] to [5] above,

[0032] Weight-average molecular weight is 10×10 4 More than 200×10 4 A polymerization process for obtaining a conjugated diene polymer having an aromatic vinyl monomer block content of less than 10 mass% and less than or equal to the amount of aromatic vinyl monomer blocks, and

[0033] A hydrogenation process for obtaining multiple types of hydrogenated conjugated diene polymers with different hydrogenation rates, and

[0034] A mixing process of mixing the above multiple types of hydrogenated conjugated diene polymers to obtain a hydrogenation rate distribution HWD represented by the following formula (1) of 1.005 or higher

[0035] A method for manufacturing a hydrogenated conjugated diene polymer having

[0036]

[0037] In Equation (1), n ​​represents the total number of components of hydrogenated conjugated diene polymers having different hydrogenation rates, and w i is a specific hydrogenation rate H among them i The hydrogenated conjugated diene polymer having [this] represents the mass fraction of the total hydrogenated conjugated diene polymer.

[0038] [7]

[0039] A method for manufacturing a hydrogenated conjugated diene polymer as described in any one of [1] to [5] above,

[0040] Weight-average molecular weight is 10×10 4 More than 200×10 4 A polymerization process for obtaining a conjugated diene polymer having an aromatic vinyl monomer block content of less than 10 mass% and less than or equal to the amount of aromatic vinyl monomer blocks, and

[0041] Hydrogenation process for adding hydrogen to the above conjugated diene polymer

[0042] having,

[0043] The above hydrogenation process is a continuous process, and the number of complete mixing heat N is 1.0 to 2.5 when the residence time distribution in the reactor is fitted to a complete mixing heat model using the impulse response method.

[0044] Method for manufacturing hydrogenated conjugated diene polymers.

[0045] [8]

[0046] In the reactor of the above hydrogenation process, hydrogen and the conjugated diene polymer are supplied from opposing directions, or hydrogen and / or the conjugated diene polymer are supplied from multiple locations, respectively.

[0047] A method for manufacturing a hydrogenated conjugated diene polymer as described in [7] above.

[0048] [9]

[0049] In the above continuous process, a stirred tank reactor is used to supply the conjugated diene polymer and hydrogenation catalyst from the top of the tank of the stirred tank reactor, and to supply hydrogen from the bottom of the tank of the stirred tank reactor while stirring.

[0050] Extruding a hydrogenated conjugated diene polymer from the bottom of the above-mentioned stirred-type reactor,

[0051] A method for manufacturing a hydrogenated conjugated diene polymer as described in [7] above. Effects of the invention

[0052] According to the present invention, a hydrogenated conjugated diene polymer having good processability and cold flow resistance can be provided, and also a hydrogenated conjugated diene polymer having excellent processability, ozone resistance, breakage properties and low hysteresis loss when used as a rubber composition. Specific details for implementing the invention

[0053] Hereinafter, an embodiment for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail.

[0054] Furthermore, the following embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments. The present invention may be implemented with appropriate modifications within the scope of its gist.

[0055] [Hydrogenated Conjugated Diene Polymers]

[0056] The hydrogenated conjugated diene polymer of the present embodiment satisfies the following conditions (i) to (iii).

[0057] <condition (i)>

[0058] It contains conjugated diene monomer units and may also contain aromatic vinyl monomer units, and in the case of containing said aromatic vinyl monomer units, it is a random polymer.

[0059] The content of the aromatic vinyl monomer block is less than 10 mass% of the hydrogenated conjugated diene polymer.

[0060] <Condition (ii)>

[0061] Weight-average molecular weight is 10×10 4 More than 200×10 4 It is as follows.

[0062] <Condition (iii)>

[0063] The half-width temperature of the elution amount peak measured by temperature gradient interaction chromatography (hereinafter referred to as TGIC) is in the range of 20 to 80°C.

[0064] According to the above composition, processability and cold flow resistance are good, and as described below, when a rubber composition is made by appropriately combining other polymers, filler components, plasticizer components, crosslinking agent components, etc. with the hydrogenated conjugated diene-based polymer of the present embodiment, the processability, ozone resistance, breakage properties, and low hysteresis loss are excellent.

[0065] The hydrogenated conjugated diene polymer of the present embodiment has a structure in which hydrogen is added to a portion polymerized using a conjugated diene compound as a monomer, and a conjugated diene monomer unit based on a conjugated diene compound (hereinafter also referred to as a "conjugated diene monomer unit"). The hydrogenated conjugated diene polymer of the present embodiment preferably includes a conjugated unit based on an aromatic vinyl compound (an aromatic vinyl monomer unit).

[0066] The hydrogenated conjugated diene polymer of the present embodiment may have a constituent unit based on ethylene (hereinafter referred to as "ethylene structure"). The ethylene structure is formed by making a part of the double bond portion into an ethylene structure by performing a hydrogenation reaction on a conjugated diene monomer unit, or by copolymerizing a conjugated diene compound with ethylene.

[0067] From the perspective of manufacturing costs, the ethylene structure of the hydrogenated conjugated diene polymer of the present embodiment is preferably obtained by providing the conjugated diene polymer to a hydrogenation reaction. By controlling the hydrogenation rate to a high level, the content of the ethylene structure can be increased.

[0068] In addition, in the hydrogenated conjugated diene polymer of the present embodiment, the hydrogen added to the polymer chains formed at both ends of the main chain of the conjugated diene monomer unit (e.g., 1,4- bonds of a polymer with 1,3-butadiene as the monomer) is formed into an ethylene structure, and the hydrogen added to other forms (e.g., 1,2-vinyl bonds of a polymer with 1,3-butadiene as the monomer) is not included in the ethylene structure.

[0069] The conjugated diene compounds used to form the conjugated diene monomer units constituting the hydrogenated conjugated diene-based polymer of the present embodiment are not limited to the following, but examples include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, etc. These may be used individually or in combination of two or more types. Among these, 1,3-butadiene and isoprene are preferred from the perspective of practical aspects such as ease of obtaining monomers, and 1,3-butadiene is more preferred.

[0070] (Condition (i) Content of aromatic vinyl monomer units)

[0071] The hydrogenated conjugated diene polymer of the present embodiment may contain aromatic vinyl monomer units, and if said aromatic vinyl monomer units are contained, it is a random polymer, and the content of aromatic vinyl monomer units in said hydrogenated conjugated diene polymer is preferably 2 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more with respect to the total amount of hydrogenated conjugated diene polymer, in terms of the breaking strength of the rubber composition of the present embodiment described later.

[0072] In addition, the content of aromatic vinyl monomer units is preferably 50 mass% or less, more preferably 45 mass% or less, and even more preferably 40 mass% or less, with respect to the total amount of hydrogenated conjugated diene polymer of the present embodiment, in terms of the low hysteresis loss of the rubber composition of the present embodiment.

[0073] In addition, the content of aromatic vinyl monomer units can be measured by the method described in the examples below, and the content of aromatic vinyl monomer units can be controlled to the above-described numerical range by adjusting the timing, amount, and polymerization time of adding the aromatic vinyl compound in the polymerization process of the conjugated diene polymer.

[0074] Aromatic vinyl compounds forming aromatic vinyl monomer units are not limited to the following, but examples include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2,4,6-trimethylstyrene, etc. These may be used individually or in combination of two or more. Among these, styrene is particularly preferred from the perspective of practical aspects such as the ease of obtaining monomers.

[0075] (Condition (i) Content of aromatic vinyl monomer blocks)

[0076] In the hydrogenated conjugated diene polymer of the present embodiment, with respect to the low hysteresis loss of the rubber composition of the present embodiment, the content of the long chain ratio of an aromatic vinyl monomer block, that is, a constituent unit based on an aromatic vinyl compound, with respect to the total mass of the hydrogenated conjugated diene polymer of the present embodiment is less than 10 mass%, preferably 7 mass% or less, and more preferably 5 mass% or less. The low hysteresis loss of the rubber composition contributes to the fuel efficiency of the tire when used as rubber for tires, and also contributes to the characteristic of having little stress change during repeated deformation when used for industrial products such as cushion rubber.

[0077] The content of the aromatic vinyl monomer block in the hydrogenated conjugated diene polymer of the present embodiment can be controlled to the above numerical range by adjusting, for example, the amount of aromatic vinyl compound added, the timing of addition, the amount of randomizer added, etc., in the polymerization process.

[0078] (Condition (i) Random polymer)

[0079] The hydrogenated conjugated diene polymer of the present embodiment is a random polymer when it contains aromatic vinyl monomer units, in terms of the low hysteresis loss of the rubber composition of the present embodiment.

[0080] In addition, in this specification, "random polymer" refers to a polymer in which the ratio of long chains of aromatic vinyl monomer units is less than 10 mass% with respect to the total mass of a hydrogenated conjugated diene polymer. Here, the ratio of long chains is the ratio of a chain (long chain) in which eight or more structural units are consecutive to the total of a structural unit. In addition, if the "random polymer" in this specification is a polymer using two or more types of monomer units, the two or more types of monomer units may be uniformly distributed in the polymer, or may be distributed in a tapered, stepped, convex, or concave shape.

[0081] Here, the long chain ratio of aromatic vinyl monomer units is measured using the hydrogenated conjugated diene polymer of the present embodiment as a measurement sample and dichloroform as a solvent. 1 It is obtained by calculating the ratio of the integral values ​​of each chemical shift range of (X) below using an H-NMR spectrum. Using this measurement, the content of aromatic vinyl monomer blocks included in the hydrogenated conjugated diene polymer was determined. For example, when the aromatic vinyl monomer is styrene, a chain of 8 or more consecutive styrene structural units is considered as a long chain of styrene, and the amount of styrene blocks can be determined.

[0082] Chain of aromatic vinyl monomer units 8 or more: 6.00≤X<6.68

[0083] As described above, with respect to the low hysteresis loss of the rubber composition, the hydrogenated conjugated diene-based polymer of the present embodiment is a random polymer when containing the aromatic vinyl monomer unit.

[0084] In addition, the hydrogenated conjugated diene polymer of the present embodiment may be modified or unmodified, but it is preferable that it be a modified random polymer from the perspective of reinforcement and wear resistance due to the filler component of the rubber composition.

[0085] Although the modification method will be described later, a modified hydrogenated conjugated diene polymer can be, for example, one in which a functional group is introduced by a modifying agent at the polymerization end of the polymer.

[0086] (Amount of ethylene structure and hydrogenation rate)

[0087] The hydrogenated conjugated diene polymer of the present embodiment preferably has an ethylene structure of 1 mass% or more, more preferably 2 mass% or more, and even more preferably 5 mass% or more, from the perspective of ozone resistance and tensile strength of a rubber composition containing the hydrogenated conjugated diene polymer of the present embodiment. In addition, regarding the upper limit of the ethylene structure, depending on the content of aromatic vinyl monomer units before hydrogenation or the amount of 1,2-vinyl bonds, it is preferably 95 mass% or less, and more preferably 90 mass% or less, from the perspective of processability.

[0088] The amount of ethylene structure in the hydrogenated conjugated diene polymer of the present embodiment can be controlled by adjusting, for example, the ratio of styrene to 1,3-butadiene, the ratio of 1,4-links to 1,2-vinyl linkages of the butadiene portion, and the hydrogenation rate in the case of a polymer having styrene and 1,3-butadiene as monomers.

[0089] Methods to increase the amount of ethylene structure include reducing the styrene ratio and increasing the butadiene ratio, increasing the 1,4- linkage ratio of the butadiene part, and increasing the hydrogenation rate.

[0090] Conversely, the amount of ethylene structure can be reduced by increasing the styrene ratio and lowering the butadiene ratio, lowering the 1,4-linkage ratio of the butadiene part, and lowering the hydrogenation rate.

[0091] For example, in the case of a polymer with 1,3-butadiene as the monomer, 1,4- bonds and 1,2-vinyl bonds are formed by polymerization. However, when hydrogen is added to a polymer containing both, the hydrogenation reaction proceeds more rapidly in the 1,2-vinyl bonds, and hydrogen tends to be added preferentially. Therefore, in order to achieve the condition of "having an ethylene structure of 1 mass% or more," it is desirable to polymerize such that 1,4- bonds are formed in excess of 1 mass% of the conjugated diene polymer before hydrogenation, and then hydrogenate such that most of the 1,2-vinyl bonds are consumed and additionally 1 mass% or more of the 1,4- bonds are hydrogenated, so that an ethylene structure is formed in excess of 1 mass% of the hydrogenated conjugated diene copolymer.

[0092] Specifically, it is desirable to make the hydrogenation rate value at least 1% higher than the value of the 1,2-vinyl bond proportion in the ratio of conjugated diene monomer units, and more desirable to make it at least 2% higher; however, as described below, when the hydrogenation rate has a distribution, even if the hydrogenation rate value is less than the value of the 1,2-vinyl bond amount, there may be cases where 1,4- bonds are hydrogenated at least 1 mass% in the conjugated diene polymer before hydrogenation. The hydrogenation rate (the ratio of hydrogenation to the conjugated diene portion) is preferably a hydrogenation rate in which 1,4- bonds are hydrogenated so that the ethylene structure has at least 1 mass% in the hydrogenated conjugated diene polymer, and depends on the 1,2-vinyl bond amount before hydrogenation, but the preferred hydrogenation rate is 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more. In addition, the hydrogenated conjugated diene polymer of the present embodiment has a hydrogenation rate of preferably 97 mol% or less, more preferably 93 mol% or less, even more preferably 90 mol% or less, even more preferably 88 mol% or less, and even more preferably 85 mol% or less, in order to fully exhibit the effect of the hydrogenation rate distribution described below.

[0093] The hydrogen addition rate is, 1 It can be calculated from the spectral reduction rate of the unsaturated bonding portion of the spectrum obtained by measuring H-NMR, and corresponds to the average hydrogen addition rate when the hydrogen conversion rate has a distribution as described below.

[0094] (Condition (ii) Weight-average molecular weight)

[0095] The hydrogenated conjugated diene polymer of the present embodiment has a weight-average molecular weight (Mw) of 10×10 in terms of the tensile strength of the rubber composition. 4 This is the ideal, and preferably 15×10 4 This is the extent, and more preferably 20×10 4That is all. In addition, the weight average molecular weight of the hydrogenated conjugated diene polymer is 200×10 in terms of the processability of the hydrogenated conjugated diene polymer and rubber composition of the present embodiment. 4 Less than or equal to, preferably 100×10 4 Less than, and more preferably 70×10 4 It is as follows.

[0096] (Molecular weight distribution)

[0097] The hydrogenated conjugated diene polymer of the present embodiment has a molecular weight distribution (Mw / Mn) that is preferably 1.1 or higher, more preferably 1.2 or higher, and even more preferably 1.3 or higher, in terms of processability of the hydrogenated conjugated diene polymer and the rubber composition. In addition, the molecular weight distribution of the hydrogenated conjugated diene polymer of the present embodiment is preferably 4.0 or lower, more preferably 3.5 or lower, and even more preferably 3.0 or lower, in terms of low hysteresis loss of the rubber composition.

[0098] In addition, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be measured by the method described in the examples below.

[0099] (Condition (iii) Temperature at half width of the elution peak measured by temperature gradient interaction chromatography (TGIC))

[0100] The hydrogenated conjugated diene polymer of the present embodiment has a full width temperature of the elution amount peak measured by temperature gradient interaction chromatography (TGIC) in the range of 20 to 80°C.

[0101] "The half-width temperature of the elution peak" refers to the difference in temperature (the difference between the high-temperature side temperature and the low-temperature side temperature) at the point where a straight line parallel to the baseline is drawn from the half-width value of the elution peak height measured by the temperature gradient interaction chromatography (TGIC) described later, and intersects the elution distribution graph of the hydrogenated conjugated diene polymer.

[0102] The hydrogenated conjugated diene polymer of the present embodiment preferably has a hydrogenation rate distribution that is highly balanced with processability, cold flow resistance, ozone resistance of the rubber composition, and tensile strength.

[0103] When the hydrogenation rate distribution of a hydrogenated conjugated diene polymer is narrow—that is, when the hydrogenation rate is single or the frequency distribution for the hydrogenation rate shows a sharp peak—a method to improve ozone resistance or tensile strength of a rubber composition using the hydrogenated conjugated diene polymer of the present embodiment may be to increase the hydrogenation rate, for example, as described in International Publication No. 2014 / 133097. On the other hand, when the hydrogenation rate of the hydrogenated conjugated diene polymer increases, the Mooney viscosity of the hydrogenated conjugated diene polymer becomes excessively high, and processability tends to deteriorate. To ensure good processability, one might consider lowering the molecular weight, but since lowering the molecular weight leads to a decrease in tensile strength when used in a rubber composition, it tends to be difficult to achieve these properties in harmony.

[0104] Meanwhile, when there is a spreading in the hydrogenation rate distribution of a hydrogenated conjugated diene polymer, that is, when the frequency distribution for the hydrogenation rate shows a broad peak, a low hydrogenation rate component with excellent processability and crosslinkability coexists with a high hydrogenation rate component with excellent ozone resistance and tensile properties when made into a rubber composition, so these properties can be highly balanced.

[0105] Additionally, hydrogenated conjugated diene polymers with a spread in the hydrogenation rate distribution tend to have superior ozone resistance in rubber compositions when compared at the same average hydrogenation rate compared to hydrogenated conjugated diene polymers with a narrow hydrogenation rate distribution. This is thought to be because components having many units derived from the ethylene structure in their molecular chains, such as high hydrogenation rate components, have lower surface free energy compared to low hydrogenation rate components, and thus tend to segregate on the surface of the rubber composition when hydrogenated conjugated diene polymers are used as rubber compositions. When used as a vulcanized product, this acts as a protective film for the vulcanized product, preventing ozone from penetrating into the vulcanized product and preventing the deterioration of the vulcanized product.

[0106] The hydrogenation rate distribution of a hydrogenated conjugated diene polymer can be indirectly evaluated by the following method. Specifically, the hydrogenation rate distribution of a hydrogenated conjugated diene polymer can be evaluated by analyzing the full width at half maximum temperature of the elution amount peak from the elution distribution of the hydrogenated conjugated diene polymer obtained by temperature gradient interaction chromatography (TGIC).

[0107] Specifically, since the porous graphite carbon column used in TGIC exhibits strong interaction with the ethylene structure, the higher the amount of the component with the ethylene structure, the higher the temperature required to elute from the column. This will be explained in the case where styrene is used as the aromatic vinyl compound and butadiene is used as the conjugated diene compound. That is, when a random copolymer of butadiene and styrene is assumed as the hydrogenated conjugated diene polymer of this embodiment, the amount of the ethylene structure generated by the hydrogenation of the 1,4- bond of the butadiene unit, which is the conjugated diene monomer unit in the conjugated diene polymer, is correlated with the elution temperature measured by TGIC. Thus, the higher the hydrogenation rate and the greater the amount of the ethylene structure, the higher the elution temperature, and the lower the hydrogenation rate and the less the amount of the ethylene structure, the lower the elution temperature. Therefore, the wider the hydrogenation rate distribution of the hydrogenated conjugated diene polymer, the broader the elution distribution obtained by TGIC becomes, and the half-width temperature of the elution amount peak increases. In addition, for components with a small amount of ethylene structure and weak interaction with the porous graphite-carbon column, the elution temperature becomes less than 0°C. For components with a large amount of ethylene structure and strong interaction with the porous graphite-carbon column, although not specifically limited, the elution temperature becomes 0°C or higher and 160°C or lower, and the temperature of the elution amount peak becomes 0°C or higher and 160°C or lower. Furthermore, when the conjugated diene polymer has 1,2-vinyl bonds derived from butadiene (conjugated diene compound), the structure generated by the hydrogenation of the butadiene-derived 1,2-vinyl bonds (hereinafter referred to as butylene structure) has a relatively low interaction with the porous graphite-carbon column used in TGIC compared to the ethylene structure, or does not appear. For this reason, the hydrogenation rate distribution analyzed by TGIC is estimated to represent, more specifically, the distribution of the ethylene structure.

[0108] In addition, aromatic vinyl compounds are not limited to styrene, and conjugated diene compounds are not limited to butylene, and the distribution of hydrogenation rates or the distribution of ethylene structures can be evaluated by TGIC.

[0109] When the hydrogenation rate distribution of the hydrogenation conjugated diene polymer of the present embodiment is evaluated at the half-width temperature of the elution amount peak measured by the TGIC described above, the half-width temperature of the elution amount peak measured by the TGIC is 20°C or higher, preferably 22°C or higher, more preferably 24°C or higher, even more preferably 27°C or higher, and even more preferably 30°C or higher, from the perspective of highly balancing the processability, cold flow resistance, ozone resistance, and tensile strength of the hydrogenation conjugated diene polymer and rubber composition of the present embodiment.

[0110] The half-width temperature of the elution amount peak measured by TGIC being 20°C or higher means that the hydrogenation rate distribution of the hydrogenated conjugated diene polymer of the present embodiment is somewhat wide, and the processability, cold flow resistance, ozone resistance, and tensile strength of the rubber composition and the hydrogenated conjugated diene polymer of the present embodiment can be balanced.

[0111] In addition, the half-width temperature of the leaching amount peak measured by TGIC is 80°C or lower, preferably 75°C or lower, more preferably 70°C or lower, even more preferably 65°C or lower, and even more preferably 60°C or lower, from the perspective of sufficiently exhibiting ozone resistance or tensile strength of the rubber composition.

[0112] By setting the half-width temperature of the leaching amount peak measured by TGIC to 80°C or lower, it is difficult to include components with extremely low hydrogenation rates, so the ozone resistance and tensile strength of the rubber composition can be sufficiently expressed.

[0113] The molecular weight distribution of the hydrogenated conjugated diene polymer has almost no effect on the half-width temperature of the elution amount peak measured by the TGIC described above. This is because the hydrogenated conjugated diene polymer of the present embodiment is a random polymer when it contains the aromatic vinyl monomer unit, and the molecular weight itself has no or little effect on the elution temperature.

[0114] The half-width temperature of the elution amount peak measured by TGIC can be controlled to the above-described numerical range by adjusting, for example, the distribution of 1,2-bonds or 1,4-bonds and the distribution of the hydrogenation rate of the hydrogenated conjugated diene polymer of the present embodiment. Specifically, methods such as a method of imparting a distribution to 1,2-bonds or 1,4-bonds, or a method of imparting a distribution to the hydrogenation rate in the hydrogenated conjugated diene polymer of the present embodiment as described below, may be cited.

[0115] [Method for Manufacturing Hydrogenated Conjugated Diene Polymers]

[0116] The hydrogenated conjugated diene polymer of the present embodiment can be prepared by a method having, for example, a polymerization process of polymerizing a conjugated diene compound and an aromatic vinyl compound, and a hydrogenation process of providing the conjugated diene polymer obtained by the polymerization process to a hydrogenation reaction.

[0117] In the case where the hydrogenated conjugated diene polymer of the present embodiment has an ethylene structure, a hydrogenation process may be performed to form the ethylene structure, or ethylene may be copolymerized during the polymerization process. In addition, even when ethylene is copolymerized during the polymerization process, a hydrogenation process may be performed.

[0118] In addition, the modification process described below may be performed as necessary.

[0119] (Polymerization process)

[0120] In the polymerization process, the weight-average molecular weight is 10×104 More than 200×10 4 A conjugated diene polymer is polymerized having an aromatic vinyl monomer block content of less than 10 mass%.

[0121] The weight-average molecular weight can be controlled to the above numerical range by adjusting polymerization conditions such as the amount of polymerization initiator added, the amount of monomer added, and the polymerization time during the polymerization process.

[0122] The content of the aromatic vinyl block can be controlled to the above numerical range by adjusting the timing and amount of addition of the aromatic vinyl compound and the amount of addition of the randomizer in the polymerization process.

[0123] The polymerization process can be carried out by solution polymerization. The monomer concentration in the solution is preferably 5 mass% or more, and more preferably 10 mass% or more. When the monomer concentration in the solution is 5 mass% or more, the amount of conjugated diene polymer obtained increases, and there is a tendency for costs to decrease. In addition, the monomer concentration in the solution is preferably 50 mass% or less, and more preferably 30 mass% or less. When the monomer concentration in the solution is 50 mass% or less, the viscosity of the solution decreases further, stirring efficiency improves, and there is a tendency for polymerization to become easier.

[0124] When anionic polymerization is performed in the polymerization process, there are no particular restrictions on the polymerization initiator, but an organic lithium compound is preferably used.

[0125] Examples of organic lithium compounds include, but are not limited to the following: ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, tert-octyllithium, n-decyllithium, phenyllithium, 2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, cyclopentyllithium, and reaction products of diisopropenphenylbenzene and butyllithium. Among these, it is preferable to have an alkyl group having 2 to 20 carbon atoms, and n-butyllithium or sec-butyllithium is preferred from the viewpoint of ease of availability and safety.

[0126] In addition, when performing coordination polymerization in the polymerization process, it is preferable to use the polymerization catalyst composition described in Japanese Patent Publication No. 2020-45500 as the polymerization initiator.

[0127] The method for preparing a conjugated diene polymer by anionic polymerization or coordination polymerization using a polymerization initiator is not particularly limited, and conventionally known methods may be used. Specifically, a desired conjugated diene polymer can be obtained by polymerizing styrene, 1,3-butadiene, ethylene, etc., in the presence of a predetermined randomizer, using, for example, butyllithium as a polymerization initiator in an organic solvent that is inert to the reaction, such as a hydrocarbon solvent including aliphatic, alicyclic, or aromatic hydrocarbon compounds.

[0128] As a hydrocarbon solvent, a hydrocarbon solvent having 3 to 8 carbon atoms is preferred. Examples include, but are not limited to, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene, etc.

[0129] These may be used as a single type or in combination of two or more types.

[0130] The above randomizer refers to a compound having the function of controlling the microstructure of the conjugated diene portion in a conjugated diene polymer, for example, increasing 1,2-vinyl bonds in butadiene or 3,4-bonds in isoprene, or controlling the compositional distribution of monomer units in a conjugated diene polymer, for example, randomizing styrene units and butadiene units in a styrene-butadiene copolymer.

[0131] The above randomizer is not particularly limited, and any known compound generally used as a conventional randomizer may be used.

[0132] The above randomizers are not limited to the following, but examples include ethers such as dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-di(2-tetrahydrofuryl)propane, triethylamine, pyridine, N-methylmorpholine, N,N,N',N'-tetramethylethylenediamine, 1,2-dipiperidinoethane, and tertiary amines. In addition, potassium salts such as potassium-t-amylate and potassium-t-butoxide, and sodium salts such as sodium-t-amylate may also be used.

[0133] These randomizers may be used as a single type or in combination of two or more types.

[0134] In addition, the amount of randomizer used is preferably 0.01 molar equivalent or more per mole of polymerization initiator, and more preferably 0.05 molar equivalent or more. When the amount of randomizer used is 0.01 molar equivalent or more per mole of polymerization initiator, there is a tendency for it to be more randomized. In addition, the amount of randomizer used is preferably 1,000 molar equivalent or less per mole of polymerization initiator, and more preferably 500 molar equivalent or less. When the amount of randomizer used is 1,000 molar equivalent or less per mole of polymerization initiator, the change in the reaction rate of the monomer is small, and there is a tendency for it to become difficult to randomize to be suppressed.

[0135] The reaction temperature during the polymerization process is not particularly limited as long as the reaction proceeds suitably, but it is generally preferred to be 10°C to 130°C, and more preferably 25°C to 110°C.

[0136] (Deformation process)

[0137] Additionally, in the method for manufacturing a hydrogenated conjugated diene polymer of the present embodiment, a modification process for modifying the obtained conjugated diene polymer may be included after the polymerization process described above.

[0138] When performing a modification process, it is preferable to make the polymerization end units into conjugated diene monomer units by adding a conjugated diene compound at the end of the polymerization process. By doing so, the reaction with the modification agent tends to proceed more appropriately.

[0139] A modification process is a process of reacting, for example, the active end of a conjugated diene polymer obtained by a polymerization process with a compound having a functional group that interacts with silica and / or carbon black.

[0140] By a modification process, functional groups interacting with silica and / or carbon black can be introduced to the polymerization end of a conjugated diene polymer, and a conjugated diene polymer with modified polymerization end is obtained. Furthermore, the term "end" refers to a portion other than the structure derived from a monomer having a carbon-carbon double bond, present at the end of the molecular chain.

[0141] In the modification process, the active end of the conjugated diene polymer obtained by the polymerization process is reacted with a compound having a functional group that interacts with silica and / or carbon black. Additionally, by performing polymerization using a polymerization initiator having a functional group in its molecule that interacts with silica and / or carbon black, a functional group can be introduced to the starting end of the conjugated diene polymer. Furthermore, if necessary, functional groups may be introduced to both the starting end and the ending end.

[0142] The conjugated diene polymer used in the modification reaction (hereinafter also referred to as the "terminal modification reaction") may have an unmodified polymerization initiation end or a modified polymerization initiation end, as long as it has an active end. Furthermore, the compound having the above functional group is not particularly limited as long as it has a functional group that interacts with silica and / or carbon black and can react with the active end of the conjugated diene polymer; however, regarding the specific modification reaction using these conjugated diene polymers and the compound having the functional group, a method of introducing the functional group into the conjugated diene polymer using a terminal modifying agent containing a tin atom or a nitrogen atom is preferred, and a method of introducing the functional group into the conjugated diene polymer using a terminal modifying agent containing a nitrogen atom is more preferred.

[0143] As for the terminal modifying agent containing the nitrogen atom mentioned above, examples such as isocyanate compounds, isothiocyanate compounds, isocyanuric acid derivatives, nitrogen-containing carbonyl compounds, nitrogen-containing vinyl compounds, nitrogen-containing epoxy compounds, nitrogen-containing alkoxysilane compounds, and cyclic urea compounds are preferred in terms of polymerization productivity or high modification rate. In particular, nitrogen-containing alkoxysilane compounds or cyclic urea compounds are more preferred in terms of polymerization productivity, high modification rate, and reinforcement by fillers.

[0144] These modifying agents may be used as a single type or in combination of two or more types.

[0145] As nitrogen group-containing alkoxysilane compounds, examples include, but are not limited to the following: 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclohexane, 2,2-dimethoxy-1-(5-trimethoxysilylpentyl)-1-aza-2-silacycloheptane, 2,2-dimethoxy-1-(3-dimethoxymethylsilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3-diethoxyethylsilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-ethyl-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(3-dimethoxymethylsilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-ethyl-1-(3-diethoxyethylsilylpropyl)-1-aza-2-silacyclopentane, tris(3-trimethoxysilylpropyl)amine, tris(3-methyldimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl)amine, Examples include tris(3-methyldiethoxysilylpropyl)amine, tris(trimethoxysilylmethyl)amine, tris(2-trimethoxysilylethyl)amine, tris(4-trimethoxysilylbutyl)amine, tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane and N-(3-(bis(3-(trimethoxysilyl)propyl)amino)propyl)-N-methyl-N'-(3-(methyl(3-(trimethoxysilyl)propyl)amino)propyl)-N'-(3-(trimethoxysilyl)propyl)-1,3-propanediamine.

[0146] As cyclic element compounds, examples include, but are not limited to: 1,3-diethyl-2-imidazolinone, 1,3-dimethyl-2-imidazolinone, 1,3-dipropyl-2-imidazolinone, 1-methyl-3-ethyl-2-imidazolinone, 1-methyl-3-propyl-2-imidazolinone, 1-methyl-3-butyl-2-imidazolinone, 1,3-dihydro-1,3-dimethyl-2H-imidazole-2-one, 1,3-diethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-propyl-2-imidazolidinone, Examples include 1-methyl-3-butyl-2-imidazolidinone.

[0147] The terminal modification reaction of a conjugated diene polymer can be carried out, for example, as a solution reaction. This solution reaction may be performed using a solution containing unreacted monomers after the completion of the polymerization reaction in the polymerization process, or by isolating the conjugated diene polymer contained in said solution and dissolving it in a specified solvent such as cyclohexane. Furthermore, the terminal modification reaction may be carried out using either a batch method, a continuous method, or a combination thereof. At this time, the method of adding the terminal modifying agent is not particularly limited and may be any of the methods, such as adding it all at once, adding it in divided portions, or adding it continuously.

[0148] The amount of terminal modifier used in the terminal modification reaction can be appropriately set according to the type of terminal modifier used in the reaction, but with respect to the metal atom involved in the polymerization reaction of the polymerization initiator, it is preferably 0.1 molar equivalent or more, more preferably 0.3 molar equivalent or more. By making it 0.1 molar equivalent or more, the modification reaction can be sufficiently carried out, and it can interact suitably with filler components such as silica or carbon black, thereby suitably improving the dispersibility of the filler components.

[0149] The temperature of the terminal modification reaction is typically the same as the temperature of the polymerization reaction described above, and is preferably -20 to 150°C, more preferably 0 to 120°C, and even more preferably 20 to 100°C. As the temperature of the modification reaction increases, the viscosity of the conjugated diene polymer after modification tends to decrease. On the other hand, as the temperature of the modification reaction decreases, the active terminal tends to be less deactivated. The reaction time of the modification reaction is preferably 5 seconds to 1 hour, more preferably 10 seconds to 45 minutes, and even more preferably 15 seconds to 30 minutes.

[0150] (Stopping the reaction in the polymerization process)

[0151] The polymerization process in the method for manufacturing the hydrogenated conjugated diene polymer described above can be stopped by adding a reaction stopping agent commonly used in this field. Examples of such reaction stopping agents include alcohols such as methanol, ethanol, and isopropanol; polar solvents having active protons such as acetic acid; and mixtures thereof, or mixtures of the polar solvents and non-polar solvents such as hexane and cyclohexane.

[0152] The amount of reaction stopping agent added is typically preferred to be equal to or twice the molar amount relative to the polymerization initiator.

[0153] (Hydrogenation process)

[0154] In the method for manufacturing a hydrogenated conjugated diene-based polymer of the present embodiment, the hydrogenation process is not particularly limited with respect to the hydrogenation method or reaction conditions and can be carried out using known methods and known conditions.

[0155] Typically, a hydrogenation reaction can be carried out at 20 to 150°C, under hydrogen pressure of 0.1 to 10 MPa, in the presence of a hydrogenation catalyst. Additionally, the hydrogenation rate of the hydrogenation conjugated diene polymer of the present embodiment can be controlled by adjusting the amount and type of the hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, the reaction time, etc.

[0156] As for the reaction process for hydrogenation, either batch or continuous, or a combination thereof, may be used, but in order to control the half-width temperature of the elution amount peak measured by TGIC of the hydrogenated conjugated diene polymer of the present embodiment to a range of 20 to 80°C, it is necessary to provide a distribution to the hydrogenation rate.

[0157] Methods for imparting a distribution to the hydrogenation rate distribution include, for example, obtaining multiple types of hydrogenated conjugated diene polymers with different hydrogenation rates and additionally mixing these multiple types of hydrogenated conjugated diene copolymers, or making the hydrogenation process a continuous process and controlling the residence time distribution within the reactor in which the hydrogenation process is carried out.

[0158] When multiple types of hydrogenated conjugated diene polymers with different hydrogenation rates are obtained and mixed, the hydrogenation rate distribution HWD of the obtained hydrogenated conjugated diene polymer can be expressed by the following equation (1).

[0159]

[0160] In the above formula (1), n ​​represents the total number of components of hydrogenated conjugated diene polymers having different hydrogenation rates, and w i is a specific hydrogenation rate H among them i It represents the mass fraction of the hydrogenated conjugated diene polymer having [the component] in the total hydrogenated conjugated diene polymer.

[0161] (Mixing process)

[0162] In the method for manufacturing a hydrogenated conjugated diene polymer of the present embodiment, hydrogenated conjugated diene polymers of multiple types with different hydrogenation rates are mixed.

[0163] The hydrogenation rate distribution HWD of the obtained hydrogenated conjugated diene polymer and the half-width temperature of the elution peak measured by TGIC depend on the microstructure, the hydrogenation rate of a reference value, and the mixing ratio of multiple types of hydrogenated conjugated diene polymers with different hydrogenation rates. For example, when a conjugated diene polymer with a styrene content of 8 mass% and a 1,2-vinyl bond content of 40% is hydrogenated, and hydrogenated conjugated diene polymers having a hydrogenation rate of 20% different from the reference hydrogenation rate are mixed in equal proportions on the high hydrogenation side and the low hydrogenation side, respectively, the hydrogenation rate distribution HWD becomes 1.02 to 1.1, and the half-width temperature of the elution peak measured by TGIC becomes about 25 to 50°C. In addition, when a hydrogenated conjugated diene polymer similar to the one described above is hydrogenated, and hydrogenated conjugated diene polymers having hydrogenation rates of 10% each on the high hydrogenation side and the low hydrogenation side are mixed in equal proportions with respect to a reference hydrogenation rate of a predetermined value, the hydrogenation rate distribution HWD becomes 1.005 to 1.02, and the half-width temperature of the elution amount peak measured by TGIC becomes approximately 21 to 40°C. By adopting a method that widens the hydrogenation rate distribution, the half-width temperature of the elution amount peak measured by TGIC of the hydrogenated conjugated diene polymer can be controlled to 20 to 80°C.

[0164] Specifically, the standard hydrogenation rate is set to 75%, and hydrogenation conjugated diene polymers having a hydrogenation rate of 20% each are mixed in equal proportions on the high hydrogenation side and the low hydrogenation side with respect to this standard hydrogenation rate, and by widening the hydrogenation rate distribution by the method described below, the hydrogenation rate distribution HWD can be set to 1.005 or higher, and the half-width temperature of the elution amount peak measured by TGIC can be controlled to 20 to 80°C.

[0165] By setting the above hydrogenation rate distribution HWD to 1.005 or higher and controlling the half-width temperature of the elution amount peak measured by TGIC of the hydrogenated conjugated diene polymer to a numerical range of 20 to 80°C, there is a tendency to obtain a hydrogenated conjugated diene polymer with highly balanced cold flow resistance, ozone resistance, and tensile strength.

[0166] When the hydrogenation process is carried out as a continuous process, the distribution range of the hydrogenation rate of the generated hydrogenated conjugated diene polymer can be controlled by adjusting the solution viscosity, the amount of solution in the reactor, or the stirring conditions, or by changing the number of feed ports of the conjugated diene polymer to the continuous hydrogenation reactor, or by changing the flow path through which the conjugated diene polymer passes, thereby adjusting the reaction time distribution (residence time distribution).

[0167] As an indicator of the reaction time distribution (retention time distribution), there is a value of N when the degree of mixing is represented by a complete mixing tank series model assuming that N complete mixing tanks of equal volume are connected in series. It is desirable to make the value of N small to approximate complete mixing. Specifically, the value of N can be made small to approximate complete mixing by lowering the viscosity of the solution, increasing the stirring speed, and lowering the value of H / D, which is the ratio of the height of the liquid level (H) to the diameter (D) of the reactor.

[0168] More specifically, when a hydrogenation process is carried out as a continuous process, the number N of the complete mixing heat when fitting the residence time distribution in the reactor to the complete mixing heat model using the impulse response method is set to 1.0 to 2.5, thereby making the hydrogenation rate distribution HWD of the generated hydrogenated conjugated diene polymer 1.005 or higher, and controlling the half-width temperature of the elution amount peak measured by TGIC of the hydrogenated conjugated diene polymer to a numerical range of 20 to 80°C, so that a hydrogenated conjugated diene polymer with highly balanced cold flow resistance, ozone resistance, and tensile strength can be obtained.

[0169] In addition to the above method, methods to increase the value of the hydrogen addition rate distribution HWD by adjusting the reaction time distribution can be given as examples of (1) and (2).

[0170] (1) Method of supplying hydrogen and a conjugated diene polymer from opposite directions to a reactor that performs a hydrogenation process.

[0171] (2) Method of supplying hydrogen and / or conjugated diene polymers from multiple locations.

[0172] In the case of the method of (1) above, for example, in a continuous process, a conjugated diene polymer solution and a hydrogenation catalyst are supplied from the top of the stirred-type reactor, hydrogen is supplied continuously from the bottom of the stirred-type reactor while stirring, and extruded from the bottom of the stirred-type reactor by the continuous supply, etc., can be cited as a more desirable method to widen the reaction time distribution of the hydrogenation reaction so that the hydrogenation rate distribution HWD is widened.

[0173] In the case of the method of (2) above, for example, to widen the reaction time distribution of the hydrogenation reaction, a plurality of supply ports for the conjugated diene polymer to the reactor in the continuous reaction process of hydrogenation may be provided, 80% of the total amount of polymer may be continuously supplied from the top of the reactor, 20% of the total amount may be continuously supplied from the middle of the reactor, and the total amount of polymer after the hydrogenation reaction may be continuously discharged from the bottom of the reactor.

[0174] In the case of the above methods (1) and (2), the value of N of the above-described complete mixing heat model is approximately 1.0 to 1.8, depending on the L / D (L: height of the reactor, D: diameter of the reactor) of the reactor carrying out the hydrogenation reaction, the shape and rotation speed of the stirring blade, and the viscosity of the solution, and the half-width temperature of the elution amount peak measured by TGIC of the obtained hydrogenated conjugated diene polymer is approximately 25 to 80°C, depending on the microstructure and the standard hydrogenation rate.

[0175] In addition, in the continuous process of the above hydrogenation process, a method may be employed in which a hydrogenated conjugated diene polymer solution, a homogeneous hydrogenation catalyst, and hydrogen are continuously supplied to the bottom of the stirred reactor while stirring to fill the inside of the stirred reactor, and a hydrogenated conjugated diene polymer is extruded from the top of the stirred reactor by the continuous supply of these polymer solutions, hydrogenation catalyst, and hydrogen.

[0176] Specific methods for stirring conditions that increase the reaction time distribution of the hydrogenation reaction include using a stirred reactor and employing a backmix reactor in which vigorous mixing is performed with a stirrer, preferably using a fully mixed reactor. According to this method, when the continuous reaction process of hydrogenation is represented as a fully mixed reactor, the number of N can be reduced, and by increasing the reaction time distribution, a hydrogenated conjugated diene polymer with a wide hydrogenation rate distribution can be obtained.

[0177] As a fitting method for calculating the number N of the total mixing heats, known methods such as the impulse response method or the step response method described in the Chemical Engineering Handbook can be used.

[0178] As a hydrogenation catalyst, a compound containing any one of the metals of Groups 4 to 11 of the periodic table can be used. For example, a compound containing atoms of Ti, V, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re, and Pt can be used as a hydrogenation catalyst. More specific hydrogenation catalysts include metallocene compounds such as Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, and Re; a supported heterogeneous catalyst in which metals such as Pd, Ni, Pt, Rh, and Ru are supported on a carrier such as carbon, silica, alumina, or diatomite; a homogeneous Ziegler-type catalyst in which an organic salt or acetylacetone salt of a metal element such as Ni or Co is combined with a reducing agent such as an organoaluminum; organometallic compounds or complexes such as Ru or Rh; and fullerenes or carbon nanotubes that have absorbed hydrogen.

[0179] Among these, a metallocene compound containing any one of Ti, Zr, Hf, Co, and Ni is preferred in that it can undergo a hydrogenation reaction in a homogeneous system in an inert organic solvent. Additionally, a metallocene compound containing any one of Ti, Zr, and Hf is preferred.

[0180] Hydrogenation catalysts may be used as a single type or in combination of two or more types.

[0181] A preferred method for obtaining a hydrogenated conjugated diene polymer is to polymerize the solution, use the obtained polymer solution as is to perform a modification treatment, and then provide it to a hydrogenation process as needed. Additionally, since the solution viscosity generally increases due to the hydrogenation reaction, depending on the process being applied, a process of diluting with a solvent before the hydrogenation process to lower the solution viscosity in advance may be added.

[0182] (Solvent removal process)

[0183] The hydrogenated conjugated diene polymer is obtained by removing the solvent from the polymer solution obtained above and isolating the polymer.

[0184] As methods for isolating hydrogenated conjugated diene polymers, known desolvation methods such as steam stripping and drying operations such as dehydration extruders, drying extruders, and heat treatment using conveyors can be cited.

[0185] [Rubber Composition]

[0186] The hydrogenated conjugated diene polymer of the present embodiment can be combined with other polymers, filler components, plasticizer components, crosslinking agent components, etc., to form a rubber composition having desired characteristics.

[0187] Other polymers include, but are not limited to the following, natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), etc. These may be used individually or in combination of two or more types.

[0188] The filler component is incorporated into the rubber composition for the purpose of reinforcing the rubber, and is not limited to the following, but may include, for example, white fillers (inorganic fillers) such as silica, calcium carbonate, mica, aluminum hydroxide, magnesium oxide, magnesium hydroxide, clay, talc, alumina, titanium oxide, mica, etc., or carbon black, etc.

[0189] These may be used as a single type or in combination of two or more types. In particular, silica and carbon black are preferred.

[0190] The content of the filler is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, with respect to 100 parts by mass of the rubber component including the hydrogenated conjugated diene polymer and other polymers of the present embodiment, in terms of the tensile strength of the rubber composition. In addition, when silica is used as a filler, the content of silica is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, in terms of processability or low hysteresis loss.

[0191] Silica is not particularly limited and, for example, dry method silica (anhydrous silica) and wet method silica (hydrated silica) can be used, but wet method silica is preferred because it has many silanol groups.

[0192] The silica has a nitrogen adsorption specific surface area (N2SA) that is preferably 60 m² / g or more, more preferably 120 m² / g or more, in terms of the wear resistance of the rubber composition, and preferably 300 m² / g or less, more preferably 200 m² / g or less, in terms of the low fuel consumption of the rubber composition. In addition, the nitrogen adsorption specific surface area of ​​the silica is a value measured by the BET method in accordance with ASTM D3037-81.

[0193] Examples of carbon black include, but are not limited to, furnace black (furnace carbon black) such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF, and ECF; acetylene black (acetylene carbon black); thermal black (thermal carbon black) such as FT and MT; channel black (channel carbon black) such as EPC, MPC, and CC; graphite, etc. These may be used individually or in combination of two or more types.

[0194] The nitrogen adsorption specific surface area (N2SA) of carbon black is typically 5 to 200 m² / g, and, from the perspective of the wear resistance of the rubber composition, preferably 30 m² / g or more, more preferably 50 m² / g or more, and also from the perspective of the low fuel consumption of the rubber composition, preferably 150 m² / g or less, more preferably 120 m² / g or less. The nitrogen adsorption specific surface area of ​​carbon black is measured according to ASTM D4820-93.

[0195] In addition, the dibutyl phthalate (DBP) absorption amount of carbon black is typically 5 to 300 mL / 100 g, and preferably has a lower limit of 80 mL / 100 g or more and an upper limit of 180 mL / 100 g or less. The DBP absorption amount of carbon black is measured according to ASTM D2414-93.

[0196] It is preferable to use silica in combination with a silane coupling agent.

[0197] As for the silane coupling agent, conventionally known ones may be used. But not limited to the following, for example, bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-trimethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzothiazoltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, Sulfide-based silane coupling agents such as 3-trimethoxysilylpropyl methacrylate monosulfide; mercapto-based compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane; vinyl-based silane coupling agents such as vinyltriethoxysilane and vinyltrimethoxysilane; amino-based silane coupling agents such as 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane; Examples include glycidoxy-based silane coupling agents such as γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane; nitro-based silane coupling agents such as 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane; and chloro-based silane coupling agents such as 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, and 2-chloroethyltriethoxysilane.

[0198] Meanwhile, a silane coupling agent may be used alone or in combination of two or more types. In particular, sulfide-based silane coupling agents are preferred in terms of coupling effect, processability, and cost, and bis(3-triethoxysilylpropyl)tetrasulfide and bis(3-triethoxysilylpropyl)disulfide are more preferred.

[0199] The content of the silane coupling agent is preferably 3 parts by mass or more and more preferably 5 parts by mass or more per 100 parts by mass of silica, in terms of low fuel consumption and wear resistance of the rubber composition. In addition, the content of the silane coupling agent is preferably 15 parts by mass or less and more preferably 10 parts by mass or less per 100 parts by mass of silica, in terms of processability or cost of the rubber composition.

[0200] Examples of plasticizer components include, but are not limited to the following: new oils, resins other than the polymers mentioned above, anti-aging agents, waxes, stearic acid, vulcanization accelerators, etc. These may be used individually or in combination of two or more types.

[0201] Examples of new oils include, but are not limited to the following: aromatic mineral oil (viscosity specific gravity constant (VGC value) 0.900 to 1.049), naphthenic mineral oil (VGC value 0.850 to 0.899), paraffinic mineral oil (VGC value 0.790 to 0.849), etc.

[0202] The polycyclic aromatic content of the new oil is preferably less than 3 mass%, and more preferably less than 1 mass%. The polycyclic aromatic content of the new oil can be measured according to the British Petroleum Institute 346 / 92 method. In addition, the aromatic compound content (CA) of the new oil is preferably 20 mass% or more. The new oil may be used as a single type or in combination of two or more types.

[0203] The content of the extensor oil is preferably 5 parts by mass or more and more preferably 10 parts by mass or more per 100 parts by mass of the rubber component, in terms of the Mooney viscosity of the rubber composition. In addition, the content of the extensor oil is preferably 50 parts by mass or less and more preferably 40 parts by mass or less per 100 parts by mass of the rubber component, in terms of the low hysteresis loss or hardness of the rubber composition.

[0204] Resins other than the polymers described above are not limited to the following, but examples include C5-based petroleum resin, C9-based petroleum resin, coumarone-indene resin, indene resin, phenolic resin, copolymer of α-methylstyrene and / or styrene, etc.

[0205] These may be used as a single type or in combination of two or more types. In particular, a copolymer of coumarone-indene resin, a phenolic resin (especially a terpene-phenol resin), and α-methylstyrene and / or styrene is preferred, and a copolymer of α-methylstyrene and styrene is more preferred.

[0206] The resin content is preferably 1 part by mass or more and more preferably 3 parts by mass or more per 100 parts by mass of the rubber component, in terms of wet grip performance of the rubber composition. In addition, the resin content is preferably 20 parts by mass or less and more preferably 10 parts by mass or less per 100 parts by mass of the rubber component, in terms of low hysteresis loss of the rubber composition.

[0207] As anti-aging agents, examples include, but are not limited to: naphthylamine-based anti-aging agents such as phenyl-α-naphthylamine; diphenylamine-based anti-aging agents such as octylated diphenylamine and 4,4'-bis(α,α'-dimethylbenzyl)diphenylamine; p-phenylenediamine-based anti-aging agents such as N-phenyl-N'-isopropyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, and N,N'-di-2-naphthyl-p-phenylenediamine; quinoline-based anti-aging agents such as polymers of 2,2,4-trimethyl-1,2-dihydroquinoline; and monophenol-based anti-aging agents such as 2,6-di-t-butyl-4-methylphenol and styrene phenol. Examples include bis, tris, and polyphenol-based anti-aging agents such as tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane.

[0208] These may be used as a single type or in combination of two or more types. In particular, p-phenylenediamine-based anti-aging agents are preferred, and N-phenyl-N'-isopropyl-p-phenylenediamine is more preferred.

[0209] The content of the anti-aging agent is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, per 100 parts by mass of the rubber component.

[0210] Examples of waxes include, but are not limited to, petroleum-based waxes such as paraffin wax and microcrystalline wax; natural waxes such as plant-based wax and animal-based wax; and synthetic waxes such as polymers of ethylene and propylene.

[0211] These may be used as a single type or in combination of two or more types. In particular, petroleum-based wax is preferred, and paraffin wax is more preferred.

[0212] The wax content is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, per 100 parts by mass of the rubber component.

[0213] As for stearic acid, conventionally known types may be used, and are not limited to the following, examples include products from Nichiyu Co., Ltd., NOF Co., Ltd., Kao Co., Ltd., Wako Junyaku Kogyo Co., Ltd., Chiba Shibosan Co., Ltd. These may be used as a single type or in combination of two or more types.

[0214] The content of stearic acid is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, per 100 parts by mass of the rubber component.

[0215] Examples of vulcanization promoters include, but are not limited to the following: thiazole-based vulcanization promoters such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and N-cyclohexyl-2-benzothiazylsulfenamide; thiuram-based vulcanization promoters such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; sulfenamide-based vulcanization promoters such as N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, and N,N'-diisopropyl-2-benzothiazole sulfenamide; and guanidine-based vulcanization promoters such as diphenylguanidine, diortotolylguanidine, and orthotolyl biguanidine.

[0216] These may be used as a single type or in combination of two or more types. In particular, sulfenamide-based vulcanization accelerators are preferred because the effects of the present embodiment are more suitably obtained, and N-cyclohexyl-2-benzothiazolesulfenamide is more preferred. Additionally, it is also desirable to use a guanidine-based vulcanization accelerator in combination.

[0217] The content of the vulcanization accelerator is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, per 100 parts by mass of the rubber component.

[0218] As for the crosslinking agent component, it is not limited to the following but can be appropriately selected according to the purpose, and examples include sulfur-based crosslinking agents, organic peroxide-based crosslinking agents, inorganic crosslinking agents, polyamine crosslinking agents, resin crosslinking agents, sulfur compound-based crosslinking agents, oxime-nitrosamine-based crosslinking agents, etc. These may be used individually or in combination of two or more types. In particular, sulfur-based crosslinking agents are preferred, and sulfur is more preferred, because the effect of the present embodiment is obtained more suitably. The content of the crosslinking agent in the rubber composition of the present embodiment is preferably 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the rubber component. 0.1 parts by mass or more is preferred, 0.5 parts by mass or more is more preferred, and 1.5 parts by mass or more is even more preferred. Additionally, 20 parts by mass or less is preferred, 5 parts by mass or less is more preferred, and 3 parts by mass or less is even more preferred. By doing so, the effect of the present embodiment is more appropriately obtained.

[0219] In addition, the rubber composition of the present embodiment may contain various additives such as other softeners and fillers, heat stabilizers, antistatic agents, weather stabilizers, anti-aging agents, colorants, and lubricants, in addition to the various components described above.

[0220] As other softening agents, known softening agents may be used. Examples of other fillers include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate. As for the above-mentioned heat stabilizers, antistatic agents, weather stabilizers, anti-aging agents, coloring agents, and lubricants, known materials may be used, respectively.

[0221] (Method for manufacturing a rubber composition)

[0222] The rubber composition containing the hydrogenated conjugated diene polymer of the present embodiment can be manufactured by a general method. For example, it can be manufactured by mixing each component with a Banbury mixer, a kneader, an open roll, etc., and then vulcanizing.

[0223] Examples

[0224] The present embodiment will be described in more detail below with reference to specific examples and comparative examples, but the present invention is not limited in any way by the following examples and comparative examples.

[0225] Various physical properties in the examples and comparative examples were measured by the method shown below, and additionally evaluated by the method described later.

[0226] [Methods for Measuring Physical Properties]

[0227] (Amount of bound styrene in conjugated diene polymers)

[0228] A conjugated diene polymer prior to hydrogenation was used as a sample, and 100 mg of the sample was dissolved in 100 mL of chloroform to be used as a measurement sample. The amount of bound styrene (mass%) relative to 100 mass% of the conjugated diene polymer sample was measured by the amount of absorption of ultraviolet light at the wavelength (around 254 nm) by the phenyl group of styrene.

[0229] As a measuring device, the spectrophotometer "UV-2450" manufactured by Shimadzu Seisakusho was used.

[0230] (Amount of 1,2-vinyl bonds in the butadiene moiety of conjugated diene polymers)

[0231] A conjugated diene polymer before hydrogenation was used as a sample, and 50 mg of the sample was dissolved in 10 mL of carbon disulfide to be used as a measurement sample.

[0232] Using a solution cell, the infrared spectrum from 600 to 1000 cm -1 The microstructure of the butadiene portion, i.e., the amount of 1,2-vinyl bonds (mol%), was determined by measuring within the range and using the absorbance at a given wavenumber according to the formula of Hampton's method (the method described in R-Hampton, Analytical Chemistry 21, 923 (1949)). As the measuring device, a Fourier transform infrared spectrophotometer "FT-IR230" manufactured by Nihon Bunko was used.

[0233] (Temperature at half width of the elution peak measured by TGIC of hydrogenated conjugated diene polymers)

[0234] A hydrogenated conjugated diene polymer was dissolved in orthodichlorobenzene, and the solution sample was injected into a graphite-carbon column as described below to calculate the elution amount (mass%) and the column temperature (°C) at that time. From the elution temperature-elution amount curve obtained from these values, the elution amount at each temperature was determined.

[0235] First, the column containing the packing material was heated to 140°C, and 0.2 mL of a sample solution in which a hydrogenated conjugated diene polymer was dissolved in orthodichlorobenzene was introduced, and the column temperature was lowered to -20°C at a cooling rate of 2°C / min. Then, the column temperature was heated to 165°C at a cooling rate of 2°C / min, and the mobile phase flow rate was set to 0.5 mL / min to detect the concentration of the sample eluted at each temperature. Then, the elution temperature-elution amount curve was measured, and the elution amount at each temperature was calculated.

[0236] · Device: High-throughput compositional distribution analyzer, CEF (manufactured by Polymer Char)

[0237] · Detector: IR5 MCT infrared spectrophotometer (manufactured by Polymer Char)

[0238] · Detection wavelength: Concentration sensor CH2v3.42㎛ (2920㎝) -1 ), methyl sensor CH3v3.38㎛(2960㎝ -1 )

[0239] · Column: Porous graphite carbon column, Hypercarb high-temperature type (Thermo Scientific), inner diameter 4.6 mm, length 100 mm, particle size 5 µm

[0240] · Mobile phase: Orthodichlorobenzene, BHT added

[0241] · Sample concentration: 8 mg / 8 mL

[0242] · Dissolution conditions: 150℃ for 60 minutes (under a nitrogen atmosphere)

[0243] · Sample filtration: 10㎛ inline filter

[0244] · Infusion volume: 0.2mL

[0245] · Temperature conditions: 140℃ to -20℃ (2℃ / min), flow rate 0.0mL / min

[0246] · Temperature rise conditions: -20℃ to -165℃ (2℃ / min), flow rate 0.5mL / min

[0247] From the obtained elution temperature-elution amount curve, the half-width temperature of the elution amount peak and the temperature of the elution amount peak in the range of 0°C to 160°C were determined.

[0248] (If there are multiple elution peaks, the highest peak is used as the reference.)

[0249] Tables 3 to 6 below show the half-width temperatures of the elution amount peaks. In addition, in the tables, "-" indicates that no peak area was detected.

[0250] (Hydrogenation rate of hydrogenated conjugated diene polymers)

[0251] 1 The integrated value of the unsaturated bonds of the conjugated diene polymer prior to hydrogenation was obtained by H-NMR measurement. Subsequently, the hydrogenated conjugated diene polymer was precipitated and recovered by adding a large amount of methanol to the reaction solution after the hydrogenation reaction. Subsequently, the hydrogenated conjugated diene polymer was extracted with acetone, and the hydrogenated conjugated diene polymer was vacuum dried. This, 1 The hydrogenation rate was measured using a sample for H-NMR measurement. The measurement conditions are described below.

[0252] <Measurement Conditions>

[0253] Measuring instrument: JNM-LA400 (JEOL)

[0254] Solvent: Deuterium chloroform

[0255] Measurement sample: Extract before and after polymer hydrogenation

[0256] Sample concentration: 50 mg / mL

[0257] Observation frequency: 400 MHz

[0258] Chemical shift standard: TMS (tetramethylsilane)

[0259] Pulse Delay: 2.904 seconds

[0260] Scan count: 64

[0261] Pulse width: 45°

[0262] Measured temperature: 26℃

[0263] (Content of aromatic vinyl monomer blocks of hydrogenated conjugated diene polymers)

[0264] A chain of 8 or more consecutive styrene units was defined as a styrene block, and the content of the styrene block was calculated as follows.

[0265] A hydrogenated conjugated diene polymer, using dichloroform as a solvent at 400 MHz 1 The H-NMR spectrum was measured. The obtained 1 From the H-NMR spectrum, the ratio of the integral values ​​of each chemical shift range of (X) below was calculated, and the content of the styrene block included in the hydrogenated conjugated diene polymer was calculated.

[0266] Styrene unit chain of 8 or more: 6.00≤X<6.68

[0267] (Ethylene structural amount of hydrogenated conjugated diene polymer)

[0268] 1 The amount of ethylene structure of the hydrogenated conjugated diene polymer was measured using a hydrogenated conjugated diene polymer by H-NMR measurement. The conditions are described below.

[0269] <Measurement Conditions>

[0270] Measuring instrument: JNM-LA400 (JEOL)

[0271] Solvent: Deuterium chloroform

[0272] Measurement Sample: Hydrogenated Conjugated Diene Polymer

[0273] Sample concentration: 50 mg / mL

[0274] Observation frequency: 400 MHz

[0275] Chemical shift standard: TMS (tetramethylsilane)

[0276] Pulse Delay: 2.904 seconds

[0277] Scan count: 64

[0278] Pulse width: 45°

[0279] Measured temperature: 26℃

[0280] (Modification rate of hydrogenated conjugated diene polymers)

[0281] The modification rate of the hydrogenated conjugated diene polymers of the examples and comparative examples described below was measured by the column adsorption GPC method as follows.

[0282] It was measured using the adsorption characteristics of conjugated diene polymers modified with nitrogen atom-containing functional groups on the column.

[0283] The modification rate was calculated by measuring the amount of adsorption to the silica column from the difference between the chromatogram measured by the polystyrene-based column and the chromatogram measured by the silica-based column for a sample solution containing the sample and low molecular weight internal standard polystyrene.

[0284] Specifically, as shown below.

[0285] <Preparation of Sample Solution>:

[0286] 10 mg of the sample for measurement and 5 mg of standard polystyrene were dissolved in 20 mL of THF (tetrahydrofuran) to make the sample solution.

[0287] <GPC Measurement Conditions Using Polystyrene Columns>:

[0288] THF containing 5 mmol / L of triethylamine was used as the eluent, and 20 μL of the sample solution was injected into the device for measurement. The columns used were: guard column: Tosoh Corporation’s trade name “TSKguardcolumn SuperH-H”, and columns: Tosoh Corporation’s trade names “TSKgel SuperH5000”, “TSKgel SuperH6000”, and “TSKgel SuperH7000”. Under conditions of a column oven temperature of 40°C and a THF flow rate of 0.6 mL / min, measurements were taken using an RI detector (Tosoh Corporation HLC8020) to obtain a chromatogram.

[0289] <GPC Measurement Conditions Using Silica-Based Columns>:

[0290] The product name “HLC-8320GPC” manufactured by Dosō Co. was used, THF was used as the eluent, 50 μL of the sample solution was injected into the device, and a chromatogram was obtained using an RI detector under conditions of a column oven temperature of 40°C and a THF flow rate of 0.5 ml / min. The columns used were the product names “Zorbax PSM-1000S”, “PSM-300S”, and “PSM-60S”, and the product name “DIOL 4.6×12.5㎜ 5micron” was used as a guard column connected upstream of them.

[0291] <Calculation Method for Modification Rate>:

[0292] The total peak area of ​​the chromatogram using a polystyrene-based column was set to 100, the peak area of ​​the sample was set to P1, the peak area of ​​the standard polystyrene was set to P2, the total peak area of ​​the chromatogram using a silica-based column was set to 100, the peak area of ​​the sample was set to P3, and the peak area of ​​the standard polystyrene was set to P4, and the modification rate (%) was calculated from the following formula.

[0293] Modification Rate (%) = [1 - (P2 × P3) / (P1 × P4)] × 100

[0294] (In the above equation, P1+P2=P3+P4=100)

[0295] (Weight average molecular weight of hydrogenated conjugated diene polymers)

[0296] Measurement condition 1: A conjugated diene polymer or a hydrogenated conjugated diene polymer was used as a sample, and a GPC measuring device (product name “HLC-8320GPC”) with three columns packed with polystyrene gel was used, and a chromatogram was measured using an RI detector (product name “HLC8020”). Based on the calibration curve obtained using standard polystyrene, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the sample were determined.

[0297] The eluent used was 5 mmol / L triethylamine-containing THF (tetrahydrofuran). Three columns of the Toso brand “TSKgel SuperMultipore HZ-H” were connected, and a Toso brand “TSKguardcolumn SuperMP(HZ)-H” was connected as a guard column in front of them.

[0298] 10 mg of the sample for measurement was dissolved in 10 mL of THF to make the measurement solution, 10 μL of the measurement solution was injected into a GPC measuring device, and measurements were taken under conditions of an oven temperature of 40°C and a THF flow rate of 0.35 mL / min.

[0299] Among the various samples measured under the above measurement condition 1, the samples for which the molecular weight distribution (Mw / Mn) value was less than 1.6 were measured again under the following measurement condition 2, and the results obtained were used as the weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the samples.

[0300] Measurement condition 2: A conjugated diene polymer or a hydrogenated conjugated diene polymer was used as a sample, and a chromatogram was measured using a GPC measuring device consisting of three connected columns filled with a polystyrene gel, and the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the sample were determined based on a calibration curve using standard polystyrene.

[0301] The eluent used was 5 mmol / L triethylamine-containing THF. The columns used were guard column: "TSKguardcolumn SuperH-H" manufactured by Dosoh Co., Ltd., and columns: "TSKgel SuperH5000", "TSKgel SuperH6000", and "TSKgel SuperH7000" manufactured by Dosoh Co., Ltd.

[0302] Under conditions of an oven temperature of 40℃ and a THF flow rate of 0.6 mL / min, an RI detector (product name “HLC8020” manufactured by Tosho Co., Ltd.) was used. 10 mg of the sample to be measured was dissolved in 20 mL of THF to make the measurement solution, and 20 μL of the measurement solution was injected into a GPC measuring device for measurement.

[0303] [Characteristic Evaluation Method]

[0304] (Moony viscosity (ML) of hydrogenated conjugated diene polymers)

[0305] Mooney viscosity was measured in accordance with ISO 289 using a Mooney viscometer (product name "VR1132" manufactured by Seisakusho Uejima). After preheating the sample at 100°C for 1 minute, the L-type rotor was rotated at 2 rpm, and the torque was measured after 4 minutes to determine the Mooney viscosity (ML). (1+4) I obtained ).

[0306] (Cold flow resistance of hydrogenated conjugated diene polymers)

[0307] A sample heated to 60°C was filled into a rectangular container with dimensions of 210 mm for the long side, 105 mm for the short side, and 200 mm for the depth, and a rectangular molded body was obtained by applying a pressure of 3.5 MPa with a cylinder for 10 seconds to compress it. Using the obtained molded body, the change rate (%) of the thickness was calculated from the thickness (H72) after being left for 72 hours under an ambient temperature of 25°C and humidity of 50% with a load of 5 kg, and additionally, the thickness change index was calculated.

[0308] Rate of change in thickness (%) = (H0 - H72) × 100 / H0

[0309] Thickness change index = (Rate of change in thickness of reference hydrogenated conjugated diene polymer) ÷ (Rate of change in thickness of hydrogenated conjugated diene polymer subject to evaluation) × 100

[0310] H0 represents the thickness of the sample immediately after molding.

[0311] The smaller the rate of change in thickness and the larger the index of change in thickness, the smaller the cold flow of the stored sample, indicating excellent handling characteristics.

[0312] The thickness change index of the hydrogenated conjugated diene polymer subject to evaluation was evaluated according to the following criteria.

[0313] In addition, (the standard hydrogenated conjugated diene polymer) is shown in Table 1 below.

[0314] <Evaluation Criteria>

[0315] ◎: Thickness variation index is 140 or higher

[0316] ○: Thickness variation index is 120 or more and less than 140

[0317] △: Thickness variation index is 80 or more and less than 120

[0318] ×: Thickness variation index is less than 80

[0319] [Preparation of Hydrogenated Conjugated Diene Polymers]

[0320] (Preparation of hydrogenation catalysts)

[0321] In the examples and comparative examples described below, the hydrogenation catalyst used when preparing the hydrogenation conjugated diene polymer was prepared by the following method.

[0322] 1 L of dried and purified cyclohexane was added to a nitrogen-substituted reaction vessel, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added, and while stirring sufficiently, an n-hexane solution containing 200 mmol of trimethylaluminum was added and reacted at room temperature for about 3 days to obtain a hydrogenation catalyst.

[0323] (Example 1: Preparation of hydrogenated conjugated diene polymer A1)

[0324] 22,000 g of cyclohexane, 30 mmol of tetrahydrofuran (THF), 7.0 mmol of 2,2-di(2-tetrahydrofuryl)propane, 450 g of styrene, and 2,550 g of 1,3-butadiene were added to a nitrogen-substituted autoclave with a volume of 40 L. The temperature of the reactor contents was adjusted to 43°C, and then a cyclohexane solution containing 40.0 mmol of n-butyllithium was added to start polymerization, and polymerization was carried out under adiabatic conditions.

[0325] 8.0 mmol of 2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1,2-azacillidine was added as a denaturant 2 minutes after the reaction temperature reached a peak, and the reaction was carried out at the active site of the polymer for 20 minutes. Subsequently, 8.0 mmol of methanol was added to this polymer solution as a reaction stopper to obtain a conjugated diene polymer solution before hydrogenation.

[0326] In the subsequent hydrogenation reaction process, a reactor with a volume of 40 L and an L / D ratio (L: height of the reactor, D: diameter of the reactor) of 2.2 was used, equipped with a rotary stirrer with a rotational speed of 114 rpm, and having three nozzles each at the top and bottom (respectively, at the top: nozzles A, B, and C, and at the bottom: nozzles D, E, and F), and additionally one nozzle at the center of the reactor (referred to as nozzle G).

[0327] The temperature of the reactor was adjusted to 90°C, and then the conjugated diene polymer solution (polymer concentration 12 mass%) obtained above was supplied from nozzle A at the top of the reactor at a rate of 1.7 kg / h of polymer. Additionally, a hydrogenation catalyst prepared as described above was added to the polymer solution at a titanium-based amount of 100 ppm relative to the amount of monomer input, and discharged from nozzle D at the bottom of the reactor while adjusting the liquid level inside the reactor to 60%. At this time, the average residence time τ of the polymer was 70 minutes, and H / D (H: height of the liquid level, D: diameter of the reactor) was 1.3.

[0328] After that, hydrogen was instantaneously introduced into the reactor from nozzle E at the bottom of the reactor to a level of 0.6 MPa, and the supply was stopped immediately. Then, the polymer flowing out from the reactor's discharge nozzle D was sampled every 10 minutes to measure the hydrogen addition rate.

[0329] The results of the obtained hydrogen addition rate were plotted against the average residence time τ based on the impulse response method and fitted using the following equation (2), and the number of complete mixing tanks N was found to be an approximate value of 1.1.

[0330]

[0331] Under the same reactor conditions as above, hydrogen was continuously supplied to 0.6 MPa to carry out a hydrogenation reaction.

[0332] Next, 12.6 g of n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants to the obtained hydrogenated conjugated diene polymer solution. Then, an aqueous solution (temperature: 80°C) adjusted to pH 8.5 (pH at 80°C by the glass electrode method, hereinafter the same) using ammonia as a pH adjuster was placed in a desolvation tank, and the hydrogenated conjugated diene polymer solution was additionally added to the desolvation tank (at a ratio of 200 parts by mass of aqueous solution to 100 parts by mass of polymer solution), and desolvation was performed by steam stripping (steam temperature: 190°C) for 2 hours in the liquid phase of the desolvation tank (temperature: 95°C). After that, the remaining water was dried by a dryer to obtain hydrogenated conjugated diene polymer A1.

[0333] The analysis values ​​of hydrogenated conjugated diene polymer A1 are shown in Table 3 below.

[0334] (Comparative Example 1: Preparation of hydrogenated conjugated diene polymer A1')

[0335] 22,000 g of cyclohexane, 30 mmol of tetrahydrofuran (THF), 7.0 mmol of 2,2-di(2-tetrahydrofuryl)propane, 450 g of styrene, and 2,550 g of 1,3-butadiene were added to a nitrogen-substituted autoclave with a volume of 40 L. After adjusting the temperature of the reactor contents to 43°C, a cyclohexane solution containing 40.0 mmol of n-butyllithium was added to initiate polymerization, and polymerization was carried out under adiabatic conditions.

[0336] Two minutes after the reaction temperature reached a peak, 8.0 mmol of 2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1,2-azacillidine was added as a denaturant and reacted at the active site of the conjugated diene polymer for 20 minutes. Subsequently, 8.0 mmol of methanol was added to this conjugated diene polymer solution as a reaction stopper to obtain a conjugated diene polymer solution before hydrogenation.

[0337] In the subsequent hydrogenation reaction process, a reactor with a net volume of 40 L and an L / D ratio of 2.2 was used, equipped with a rotary stirrer with a rotation speed of 114 rpm. After adjusting the temperature of the reactor to 90°C, the conjugated diene polymer solution (polymer concentration 12 mass%) obtained above was fully filled into the reactor. Additionally, a hydrogenation catalyst prepared as described above was added to the conjugated diene polymer solution at a titanium-based concentration of 100 ppm relative to the amount of input monomer, and the hydrogenation reaction was carried out for 70 minutes while filling the reactor with hydrogen to a concentration of 0.6 MPa. Next, 12.6 g of n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added to the obtained polymer solution as antioxidants, and then an aqueous solution (temperature: 80°C) adjusted to pH 8.5 (pH at 80°C by glass electrode method, hereinafter the same) by ammonia, a pH adjuster, was placed in a desolvation tank, and additionally, the hydrogenated conjugated diene polymer solution was added to the desolvation tank (at a ratio of 200 parts by mass of aqueous solution to 100 parts by mass of polymer solution), and desolvation was performed by steam stripping (steam temperature: 190°C) for 2 hours in the liquid phase of the desolvation tank (temperature: 95°C). After that, the remaining water was dried using a dryer to obtain a hydrogenated conjugated diene polymer A1'.

[0338] The analysis values ​​of hydrogenated conjugated diene polymer A1' are shown in Table 3.

[0339] (Example 2: Preparation of hydrogenated conjugated diene polymer A2)

[0340] 22,000 g of cyclohexane, 30 mmol of tetrahydrofuran (THF), 7.0 mmol of 2,2-di(2-tetrahydrofuryl)propane, and 240 g of styrene were introduced into a nitrogen-substituted autoclave with a volume of 40 L. After adjusting the temperature of the reactor contents to 43°C, a cyclohexane solution containing 40.0 mmol of n-butyllithium was added to initiate polymerization, and polymerization was carried out under adiabatic conditions for 10 minutes. Subsequently, a hydrogenated conjugated diene polymer A2 was obtained in the same manner as in Example 1, except that 210 g of styrene and 2,550 g of 1,3-butadiene were additionally added and polymerization was carried out under adiabatic conditions.

[0341] (Comparative Example 2: Preparation of hydrogenated conjugated diene polymer A2')

[0342] 22,000 g of cyclohexane, 30 mmol of tetrahydrofuran (THF), 7.0 mmol of 2,2-di(2-tetrahydrofuryl)propane, and 360 g of styrene were introduced into a nitrogen-substituted autoclave with a volume of 40 L. After adjusting the temperature of the reactor contents to 43°C, a cyclohexane solution containing 40.0 mmol of n-butyllithium was added to initiate polymerization, and polymerization was carried out under adiabatic conditions for 10 minutes. Subsequently, a hydrogenated conjugated diene polymer A2' was obtained in the same manner as in Example 1, except that 90 g of styrene and 2,550 g of 1,3-butadiene were additionally added and polymerization was carried out under adiabatic conditions.

[0343] (Comparative Example 3: Preparation of hydrogenated conjugated diene polymer A3')

[0344] A hydrogenated conjugated diene polymer A3' was obtained in the same manner as Comparative Example 1, except that the reaction time of the hydrogenation process was set to 100 minutes.

[0345] (Comparative Example 4: Preparation of hydrogenated conjugated diene polymer A4')

[0346] A hydrogenated conjugated diene polymer A4' was obtained in the same manner as in Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 56 mmol, n-butyllithium was 320 mmol, 2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1,2-azacillidine was 64 mmol, and methanol was 64 mmol.

[0347] (Comparative Example 5: Preparation of hydrogenated conjugated diene polymer A5')

[0348] A hydrogenated conjugated diene polymer A5' was obtained in the same manner as in Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 1.2 mmol, n-butyllithium was 6.4 mmol, 2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1,2-azacillidine was 1.3 mmol, and methanol was 1.3 mmol.

[0349] (Example 3: Preparation of hydrogenated conjugated diene polymer A3)

[0350] Hydrogenated conjugated diene polymer A3 was obtained in the same manner as in Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 6.1 mmol, n-butyllithium was 35 mmol, and methanol was 35 mmol, and 2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1,2-azacillidine was not added.

[0351] (Comparative Example 6: Preparation of hydrogenated conjugated diene polymer A6')

[0352] A hydrogenated conjugated diene polymer A6' was obtained in the same manner as Comparative Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 6.1 mmol, n-butyllithium was 35 mmol, and methanol was 35 mmol, and 2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1,2-azacillidine was not added.

[0353] (Example 4: Preparation of hydrogenated conjugated diene polymer A4)

[0354] A hydrogenated conjugated diene polymer A4 was obtained in the same manner as in Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 6.1 mmol, n-butyllithium was 35 mmol, 1,3-dimethyl-2-imidazolidinone was 28 mmol, and methanol was 7.0 mmol.

[0355] (Comparative Example 7: Preparation of hydrogenated conjugated diene polymer A7')

[0356] A hydrogenated conjugated diene polymer A7' was obtained in the same manner as Comparative Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 6.1 mmol, n-butyllithium was 35 mmol, 1,3-dimethyl-2-imidazolidinone was 28 mmol, and methanol was 7.0 mmol.

[0357] (Example 5: Preparation of hydrogenated conjugated diene polymer B1)

[0358] Hydrogenated conjugated diene polymer B1 was obtained in the same manner as in Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 4.6 mmol, styrene was 120 g, and 1,3-butadiene was 2880 g.

[0359] (Comparative Example 8: Preparation of hydrogenated conjugated diene polymer B1')

[0360] Hydrogenated conjugated diene polymer B1' was obtained in the same manner as Comparative Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 4.6 mmol, styrene was 120 g, and 1,3-butadiene was 2880 g.

[0361] (Example 6: Preparation of hydrogenated conjugated diene polymer B2)

[0362] Hydrogenated conjugated diene polymer B2 was obtained in the same manner as in Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 11.6 mmol, styrene was 240 g, and 1,3-butadiene was 2760 g.

[0363] (Comparative Example 9: Preparation of hydrogenated conjugated diene polymer B2')

[0364] Hydrogenated conjugated diene polymer B2' was obtained in the same manner as Comparative Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 11.6 mmol, styrene was 240 g, and 1,3-butadiene was 2760 g.

[0365] (Example 7: Preparation of hydrogenated conjugated diene polymer B3)

[0366] Hydrogenated conjugated diene polymer B3 was obtained in the same manner as in Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 19.5 mmol, styrene was 780 g, and 1,3-butadiene was 2220 g.

[0367] (Comparative Example 10: Preparation of hydrogenated conjugated diene polymer B3')

[0368] Polymer B3' was obtained in the same manner as Comparative Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 19.5 mmol, styrene was 780 g, and 1,3-butadiene was 2220 g.

[0369] (Example 8: Preparation of hydrogenated conjugated diene polymer B4)

[0370] Hydrogenated conjugated diene polymer B4 was obtained in the same manner as in Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 11.6 mmol, styrene was 1200 g, and 1,3-butadiene was 1800 g.

[0371] (Comparative Example 11: Preparation of hydrogenated conjugated diene polymer B4')

[0372] Hydrogenated conjugated diene polymer B4' was obtained in the same manner as Comparative Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 11.6 mmol, styrene was 1200 g, and 1,3-butadiene was 1800 g.

[0373] (Example 9: Preparation of hydrogenated conjugated diene polymer B5)

[0374] Hydrogenated conjugated diene polymer B5 was obtained in the same manner as in Example 1, except that styrene was not added and 1,3-butadiene was used at 3000g.

[0375] (Comparative Example 12: Preparation of hydrogenated conjugated diene polymer B5')

[0376] A hydrogenated conjugated diene polymer B5' was obtained in the same manner as Comparative Example 1, except that styrene was not added and 1,3-butadiene was used at 3000g.

[0377] (Example 10: Preparation of hydrogenated conjugated diene polymer C1)

[0378] Hydrogenated conjugated diene polymer C1 was obtained in the same manner as in Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 11.6 mmol, styrene was 240 g, and 1,3-butadiene was 2760 g.

[0379] (Example 11: Preparation of hydrogenated conjugated diene polymer C2)

[0380] Hydrogenated conjugated diene polymer C2 was obtained in the same manner as in Example 1, except that 11.6 mmol of 2,2-di(2-tetrahydrofuryl)propane, 240 g of styrene, 2760 g of 1,3-butadiene, and a polymer feed rate of 1.5 kg / h were used in the hydrogenation reaction process.

[0381] (Example 12: Preparation of hydrogenated conjugated diene polymer C3)

[0382] Hydrogenated conjugated diene polymer C3 was obtained in the same manner as in Example 1, except that 11.6 mmol of 2,2-di(2-tetrahydrofuryl)propane, 240 g of styrene, 2760 g of 1,3-butadiene, and a polymer feed rate of 1.2 kg / h in the hydrogenation reaction process were used.

[0383] (Example 13: Preparation of hydrogenated conjugated diene polymer C4)

[0384] Hydrogenated conjugated diene polymer C4 was obtained in the same manner as in Example 1, except that 11.6 mmol of 2,2-di(2-tetrahydrofuryl)propane, 240 g of styrene, 2760 g of 1,3-butadiene, and a polymer feed rate of 2.7 kg / h in the hydrogenation reaction process were used.

[0385] (Example 14: Preparation of hydrogenated conjugated diene polymer C5)

[0386] Hydrogenated conjugated diene polymer C5 was obtained in the same manner as in Example 1, except that 11.6 mmol of 2,2-di(2-tetrahydrofuryl)propane, 240 g of styrene, 2760 g of 1,3-butadiene, and a polymer feed rate of 3.3 kg / h in the hydrogenation reaction process were used.

[0387] (Comparative Example 13: Preparation of hydrogenated conjugated diene polymer C1')

[0388] A hydrogenated conjugated diene polymer C1' was obtained in the same manner as Comparative Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 11.6 mmol, styrene was 240 g, and 1,3-butadiene was 2760 g.

[0389] (Comparative Example 14: Preparation of hydrogenated conjugated diene polymer C2')

[0390] Hydrogenated conjugated diene polymer C2' was obtained in the same manner as Comparative Example 1, except that 11.6 mmol of 2,2-di(2-tetrahydrofuryl)propane, 240 g of styrene, and 2760 g of 1,3-butadiene were used and no hydrogenation reaction process was performed.

[0391] (Comparative Example 15: Preparation of hydrogenated conjugated diene polymer C3')

[0392] Hydrogenated conjugated diene polymer C3' was obtained in the same manner as Comparative Example 1, except that 11.6 mmol of 2,2-di(2-tetrahydrofuryl)propane, 240 g of styrene, 2760 g of 1,3-butadiene, and a reaction time of 35 minutes for the hydrogenation process were used.

[0393] (Comparative Example 16: Preparation of hydrogenated conjugated diene polymer C4')

[0394] A hydrogenated conjugated diene polymer C4' was obtained in the same manner as Comparative Example 1, except that 11.6 mmol of 2,2-di(2-tetrahydrofuryl)propane, 240 g of styrene, 2760 g of 1,3-butadiene, and a reaction time of 20 minutes for the hydrogenation process were used.

[0395] (Example 15: Preparation of hydrogenated conjugated diene polymer D1)

[0396] Hydrogenated conjugated diene polymer D1 was obtained in the same manner as in Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 11.6 mmol, styrene was 240 g, and 1,3-butadiene was 2760 g.

[0397] (Example 16: Preparation of hydrogenated conjugated diene polymer D2)

[0398] Three types of hydrogenated conjugated diene polymers with different hydrogenation rates were obtained in the same manner as in Example 1, except that 11.6 mmol of 2,2-di(2-tetrahydrofuryl)propane, 240 g of styrene, and 2760 g of 1,3-butadiene were used, and the reaction times of the hydrogenation process were set to 81 minutes, 70 minutes, and 55 minutes, with 1 / 3 of the contents being extracted at each time. Subsequently, hydrogenated conjugated diene polymer D2 was obtained by mixing equal amounts of the obtained hydrogenated conjugated diene polymers. At this time, the value of the hydrogenation rate distribution HWD was 1.01.

[0399] (Example 17: Preparation of hydrogenated conjugated diene polymer D3)

[0400] Five types of hydrogenated conjugated diene polymers with different hydrogenation rates were obtained in the same manner as in Example 1, except that 11.6 mmol of 2,2-di(2-tetrahydrofuryl)propane, 240 g of styrene, and 2760 g of 1,3-butadiene were used, and the reaction times of the hydrogenation process were set to 105 min, 81 min, 70 min, 55 min, and 42 min, and 1 / 5 of the content was extracted at each time. Then, hydrogenated conjugated diene polymer D3 was obtained by mixing the five types of obtained hydrogenated conjugated diene polymers so that their content was equal. At this time, the value of the hydrogenation rate distribution HWD was 1.04.

[0401] (Example 18: Preparation of hydrogenated conjugated diene polymer D4)

[0402] Hydrogenated conjugated diene polymer D4 was obtained in the same manner as in Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 11.6 mmol, styrene was 240 g, and 1,3-butadiene was 2760 g, and in the hydrogenation process, the polymer solution was supplied from nozzle F at the bottom of the reactor and discharged from nozzle B at the top of the reactor. At this time, the value of the number of complete mixing tanks N by the impulse response method was 2.3.

[0403] (Example 19: Preparation of hydrogenated conjugated diene polymer D5)

[0404] Hydrogenated conjugated diene polymer D5 was obtained in the same manner as in Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 11.6 mmol, styrene was 240 g, and 1,3-butadiene was 2760 g, and the rotation speed in the hydrogenation process was 70 rpm. At this time, the value of the number of complete mixing tanks N by the impulse response method was 1.3.

[0405] (Example 20: Preparation of hydrogenated conjugated diene polymer D6)

[0406] Hydrogenated conjugated diene polymer D6 was obtained in the same manner as in Example 19, except that 2,2-di(2-tetrahydrofuryl)propane was 11.6 mmol, styrene was 240 g, and 1,3-butadiene was 2760 g, and 20% of the polymer solution supplied from nozzle A at the top of the reactor during the hydrogenation process was supplied from nozzle G at the middle side of the reactor, thereby changing the number of complete mixing tanks N to 1.2. At this time, the value of the number of complete mixing tanks N by the impulse response method was 1.2.

[0407] (Example 21: Preparation of hydrogenated conjugated diene polymer D7)

[0408] Hydrogenated conjugated diene polymer D7 was obtained in the same manner as in Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 11.6 mmol, styrene was 240 g, and 1,3-butadiene was 2760 g, and in the hydrogenation process, the rotational speed was 20 rpm, the polymer feed amount was 2.3 kg / h, and the liquid level in the reactor was 80%. At this time, H / D (H: height of the liquid level, D: diameter of the reactor) was 1.8, and the value of the number of complete mixing tanks N by the impulse response method was 2.2.

[0409] (Comparative Example 17: Preparation of hydrogenated conjugated diene polymer D1')

[0410] A hydrogenated conjugated diene polymer D1' was obtained in the same manner as Comparative Example 1, except that 2,2-di(2-tetrahydrofuryl)propane was 11.6 mmol, styrene was 240 g, and 1,3-butadiene was 2760 g.

[0411] (Example 22: Preparation of hydrogenated conjugated diene polymer D8)

[0412] Four types of hydrogenated conjugated diene polymers with different hydrogenation rates were obtained in the same manner as in Example 1, except that 4.6 mmol of 2,2-di(2-tetrahydrofuryl)propane, 120 g of styrene, 2880 g of 1,3-butadiene, and the reaction time of the hydrogenation process was changed to four levels of 90 min, 80 min, 30 min, and 20 min (1 / 4 of the content volume was extracted at each time). Subsequently, hydrogenated conjugated diene polymer D8 was obtained by mixing the four types of hydrogenated conjugated diene polymers obtained and, additionally, hydrogenated conjugated diene polymer B1 obtained in Example 5, in equal amounts, for a total of five types of hydrogenated conjugated diene polymers.

[0413] [Evaluation of rubber compositions comprising hydrogenated conjugated diene polymers A1 to D1']

[0414] A rubber composition was obtained by mixing each component according to the formulation shown in Table 2 below using the method described below.

[0415] In addition, the amount of each compounding agent added in Table 2 is expressed as the number of parts by mass per 100 parts by mass of a rubber component that does not contain a rubber softener, namely a hydrogenated conjugated diene polymer.

[0416] (Mixing method)

[0417] Using a sealed mixer (capacity 0.5L) equipped with a temperature control device, materials other than sulfur and vulcanization accelerators were mixed as a first stage of mixing under conditions of a filling rate of 65% and a rotor rotation speed of 50 to 90 rpm. At this time, the temperature of the sealed mixer was controlled, and a mixture was obtained at a discharge temperature of 150 to 160℃.

[0418] Next, as a second stage of mixing, the mixture obtained above was cooled to room temperature and then mixed again to improve the dispersion of the filler, namely carbon black. In this case as well, the discharge temperature of the mixture was adjusted to 150 to 160°C by controlling the temperature of the mixer.

[0419] After cooling, as a third stage of mixing, a vulcanization accelerator and sulfur were added and mixed using an open roll set to 70°C to obtain an unvulcanized rubber composition.

[0420] After that, the mixture was molded and vulcanized by a vulcanizing press at 160°C for a predetermined vulcanization time to obtain a vulcanized rubber composition. The vulcanization time was set to the value obtained by adding 5 minutes to the 90% vulcanization time of the unvulcanized rubber composition.

[0421] The rubber composition after vulcanization was evaluated by the following method.

[0422] [Evaluation Items and Test Methods]

[0423] The following evaluations were performed on the obtained unvulcanized rubber composition and vulcanized rubber composition. The results are shown in Tables 3 to 6 below.

[0424] ((1) Processability (Moonie viscosity (Mixture ML)))

[0425] Using the unvulcanized rubber composition obtained above as a sample, a Mooney viscometer (product name “VR1132”) manufactured by Uejima Seisakusho Co., Ltd. was used, and in accordance with ISO 289, the viscosity was measured after preheating at 130°C for 1 minute and then rotating the rotor at 2 revolutions per minute for 4 minutes.

[0426] The measurement results of the unvulcanized rubber composition of the hydrogenated conjugated diene polymer, which serves as the standard for comparison, were indexed to 100 and evaluated using the following indicators.

[0427] The standard hydrogenated conjugated diene polymers are shown in Table 1 below.

[0428] ◎: Index less than 80

[0429] ○: Index is 80 or higher and less than 90

[0430] △: Index is 90 or higher and less than 110

[0431] ×: Exponent is 110 or higher

[0432] ((2) Tensile properties)

[0433] The vulcanized rubber composition obtained above was used as a sample, and tensile properties were measured in accordance with the tensile test method of JIS K6251.

[0434] The measurement results of the vulcanized rubber composition of the hydrogenated conjugated diene polymer, which serves as the standard for comparison, were indexed to 100 and evaluated using the following indicators.

[0435] The standard hydrogenated conjugated diene polymers are shown in Table 1 below.

[0436] Tensile Strength (TB)

[0437] ◎: Index is 120 or higher

[0438] ○: Index is 110 or higher and less than 120

[0439] △: Index is 90 or higher and less than 110

[0440] ×: Exponent less than 90

[0441] Tensile Elongation (EB)

[0442] ◎: Index is 120 or higher

[0443] ○: Index is 110 or higher and less than 120

[0444] △: Index is 90 or higher and less than 110

[0445] ×: Exponent less than 90

[0446] ((3) Ozone resistance)

[0447] From the vulcanized rubber composition obtained above, a strip-shaped sample (length 6 cm × width 1 cm × thickness 2.0 mm) was punched, placed in an ozone bath (40°C, 50 ppm), and left to stand for 96 hours under a 20% elongation state. Afterward, the strip-shaped sample (vulcanized rubber sheet) was observed, and the number of cracks with a length of 1 mm or more present on the surface was counted. Then, the number of cracks in the vulcanized rubber sheet of a hydrogenated conjugated diene polymer, which serves as a reference for comparison, was indexed to 100 and evaluated using the following indicators.

[0448] The standard hydrogenated conjugated diene polymers are shown in Table 1 below.

[0449] ◎: Index less than 60, or no cracks in the vulcanized rubber sheet

[0450] ○: Index is 60 or higher and less than 80

[0451] △: Index is 80 or higher and less than 120

[0452] ×: Index is 120 or higher, or vulcanized rubber sheet breaks

[0453] ((4) Low fuel consumption performance)

[0454] Using the "ARES" viscoelasticity tester manufactured by Rheometrics Scientific, tanδ measured in torsional mode at 50°C with a frequency of 10 Hz and a deformation of 3% was used as an indicator of low fuel consumption. Then, the measurement results of the vulcanized rubber composition of a hydrogenated conjugated diene polymer, which serves as a standard for comparison, were set to 100 and indexed, and evaluated using the following indicators.

[0455] The standard hydrogenated conjugated diene polymers are shown in Table 1 below.

[0456] ◎: Index less than 80

[0457] ○: Index is 80 or higher and less than 90

[0458] △: Index is 90 or higher and less than 110

[0459] ×: Exponent is 110 or higher

[0460] For each component in Table 2 below, the product names used are as follows.

[0461] · Hydrogenated conjugated diene polymers: A1 to D1'

[0462] · Natural Rubber: RSS No.3 (Producer: UNIMAC RUBBER CO.,LTD. (Thailand), Supplier: Marubeni Techno Rubber)

[0463] · Carbon Black: Tokai Carbon's cyst SO(FEF) (nitrogen adsorption specific surface area 42 m² / g)

[0464] · Softener: JXTG Energy Process Oil PF30 (SRAE Oil)

[0465] · Zinc oxide: Zinc oxide of Sakai Kagaku High School teachers

[0466] · Stearic acid: Kaosaze's Lunarc S-90V

[0467] · Wax: Ouchi Shinko Kagakusa's San-nok

[0468] · Anti-aging agent: Knocklock 6C manufactured by Ouchi Shinko Kagaku Co., Ltd.

[0469] · Sulfur: Powdered Sulfur Sulfax 200S manufactured by Tsurumi Kagaku High School Co., Ltd.

[0470] · Vulcanization accelerator: TBBS Sanseller NS-G (N-tert-butylbenzothiazole-2-sulfenamide) manufactured by Sanshin Kagaku

[0471]

[0472]

[0473]

[0474]

[0475]

[0476]

[0477] From Tables 3 to 6, it was confirmed that the polymers of Examples 1 to 22 each have excellent processability and cold flow resistance compared to the "standard hydrogenated conjugated diene polymer" listed in Table 1, and have excellent ozone resistance and fracture properties when used as a rubber composition.

[0478] As described above, according to the present invention, it has become clear that it is possible to provide a hydrogenated conjugated diene polymer that ensures processability and cold flow resistance of the hydrogenated conjugated diene polymer and the rubber composition using it, while also having excellent ozone resistance, breakage properties, and low hysteresis loss when used as a rubber composition.

[0479] This application is based on Japanese patent application (patent application 2024-069920) filed with the Japan Patent Office on April 23, 2024, the contents of which are incorporated herein by reference. Industrial applicability

[0480] The present invention has industrial applicability as a casing such as a tire tread or sidewall, packing or gasket, sealing material, anti-vibration rubber, vibration isolation rubber, vibration damping material, conveyor belt, shoe outsole or shoe midsole, weatherstrip for automobile, glass run, trunk lid, component for railway vehicle, component for aircraft, waterproof sheet, engine mount, air spring, rubber glove, medical hygiene product, hose for industrial and various uses, battery case, adhesive, wire insulation, window frame rubber, rubber roller for OA equipment or spinning, keypad, keyboard cover, underwater goggles, swimming cap, container bag, marine-related part, indoor flooring material, artificial muscle material, material for various industrial products, etc.

Claims

Claim 1 A hydrogenated conjugated diene polymer satisfying the following conditions (i) to (iii). <Condition (i)> It contains conjugated diene monomer units and may also contain aromatic vinyl monomer units; if it contains aromatic vinyl monomer units, it is a random polymer, and the content of aromatic vinyl monomer blocks is less than 10 mass% of the hydrogenated conjugated diene polymer. <Condition (ii)> Its weight average molecular weight is 10×10 4 More than 200×10 4 The following applies: <Condition (iii)> The full width at half maximum temperature of the elution amount peak measured by temperature gradient interaction chromatography is in the range of 20 to 80°C. Claim 2 A hydrogenated conjugated diene polymer according to claim 1, wherein the hydrogenation rate is 97 mol% or less. Claim 3 A hydrogenated conjugated diene polymer according to claim 1, wherein the hydrogenation rate is 50 mol% or more. Claim 4 A hydrogenated conjugated diene polymer according to claim 1, having an ethylene structure, wherein the ethylene structure is 1 mass% or more. Claim 5 A hydrogenated conjugated diene polymer containing aromatic vinyl monomer units, according to claim 1. Claim 6 A method for manufacturing a hydrogenated conjugated diene polymer as described in any one of claims 1 to 5, wherein the weight average molecular weight is 10×10 4 More than 200×10 4 A method for producing a hydrogenated conjugated diene polymer, comprising: a polymerization process for obtaining a conjugated diene polymer having an aromatic vinyl monomer block content of less than 10 mass% and less than or equal to the following; a hydrogenation process for obtaining multiple types of hydrogenated conjugated diene polymers with different hydrogenation rates; and a mixing process for mixing the multiple types of hydrogenated conjugated diene polymers to obtain a hydrogenation rate distribution HWD represented by the following formula (1) of 1.005 or more. (In Equation (1), n ​​represents the total number of components of hydrogenated conjugated diene polymers having different hydrogenation rates, and w i is a specific hydrogenation rate H among them i It represents the mass fraction of the hydrogenated conjugated diene polymer having [the component] in the total hydrogenated conjugated diene polymer. Claim 7 A method for manufacturing a hydrogenated conjugated diene polymer as described in any one of claims 1 to 5, wherein the weight average molecular weight is 10×10 4 More than 200×10 4 A method for producing a hydrogenated conjugated diene polymer, comprising a polymerization process for obtaining a conjugated diene polymer having an aromatic vinyl monomer block content of less than 10 mass% and a hydrogenation process for adding hydrogen to the conjugated diene polymer, wherein the hydrogenation process is a continuous process and the number N of the complete mixing heat is 1.0 to 2.5 when the residence time distribution in the reactor is fitted by the impulse response method to a complete mixing heat model. Claim 8 A method for producing a hydrogenated conjugated diene polymer according to claim 7, wherein hydrogen and the conjugated diene polymer are supplied to the reactor of the hydrogenation process from opposite directions, or hydrogen and / or the conjugated diene polymer are supplied from multiple locations, respectively. Claim 9 A method for producing a hydrogenated conjugated diene polymer according to claim 7, wherein, in the above continuous process, a stirred tank reactor is used to supply the conjugated diene polymer and a hydrogenation catalyst from the upper part of the tank of the stirred tank reactor, stirring while supplying hydrogen from the bottom part of the tank of the stirred tank reactor, and extruding the hydrogenated conjugated diene polymer from the bottom part of the tank of the stirred tank reactor.

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