Conjugated diene polymer, method for producing the same, and rubber composition

Abstract

To provide a conjugated diene polymer in which cold flow after molding into a bale is suppressed, which has superior processability in forming a vulcanizate, and which, upon vulcanization, exhibits excellent fracture properties and abrasion resistance, together with an excellent balance of low hysteresis loss characteristics and wet skid resistance.SOLUTION: A conjugated diene polymer has a Mooney viscosity measured at 100°C of 30 or more and 120 or less, a 1,2-vinyl bond content of 25 mol% or less, a 1,4-cis bond content of 40 mol% or less, and a degree of branching (Bn) measured by a GPC-light scattering method with a viscosity detector of 4 or more and 25 or less, and contains a nitrogen atom.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a conjugated diene polymer, a method for producing a conjugated diene polymer, and a rubber composition. do. [Background technology]

[0002] Demand for fuel-efficient automobiles has been increasing for some time now, and automobile tires, especially those that are used on roads, There is a need for improvements in the rubber materials used in the contacting tire tread.

[0003] In recent years, with the increasing demand for fuel economy regulations for automobiles, the required characteristics for tires have become There is a demand for tires that minimize energy loss, especially for tires that come into contact with the road. The rubber material used for the tread has low rolling resistance, i.e. low hysteresis loss. There is a need for a rubber material having the following properties.

[0004] In particular, the performance required for tires used on large vehicles such as trucks and buses that are subject to high loads In addition to the high strength and abrasion resistance required to support heavy loads, There is a demand for tires with improved fuel efficiency and low energy loss. The rubber material used for the ear tread has high breaking strength, excellent abrasion resistance, and low hysteresis. Rubber materials with excellent slip resistance and wet skid resistance are required from the perspective of safety. are.

[0005] As rubber materials that meet the above-mentioned requirements, for example, rubber-like polymers and carbon black are available. In particular, rubber compositions containing a reinforcing filler such as tack or silica are preferred. The rubber used in the red is natural rubber with good breaking strength and abrasion resistance, and conjugated diene polymer. The body is preferably used.

[0006] In addition, rubber polymers themselves have been improved, for example, by adding hydroxyl groups to the ends of the polymer chains. modified conjugated diene polymers having hydroxyl groups and compositions thereof, and After reacting the hydroxysilane compound with the hydroxysilane compound, A method for producing a conjugated diene polymer by reacting a specific compound such as a hydroxybenzoate with a conjugated diene polymer, and a composition thereof have been proposed. (See, for example, Patent Documents 1 and 2).

[0007] Furthermore, organolithium compounds are used as initiators, and the ends of polymer chains are capped with specific compounds. A method for producing a branched butadiene polymer by pulling has been proposed (for example, Patent Document See 3). [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2017-171806 [Patent Document 2] International Publication No. 03 / 046020 Brochure [Patent Document 3] Japanese Patent Application Laid-Open No. 2014-108977 Summary of the Invention [Problem to be solved by the invention]

[0009] Here, when a rubber composition containing silica is used, low hysteresis loss and wet skip resistance are achieved. In addition, the molecular terminals of the highly mobile rubber-like polymer are By introducing a functional group having affinity or reactivity with rubber, The dispersibility of the silica is improved, and furthermore, the molecular end of the rubber-like polymer is bonded to the silica particles. Reduces the mobility of the part, reduces hysteresis loss, and improves wear resistance and breaking strength. It is possible.

[0010] However, carbon black has a hydrophobic surface, whereas silica has a hydrophilic surface. Therefore, the affinity with the conjugated diene polymer is low, and However, compared to silicon black, it has the disadvantage of being less dispersible in the composition. The composition containing silica provides a bond between the silica and the conjugated diene polymer, improving dispersibility in the composition. To improve this, it is necessary to add a silane modifier or the like separately.

[0011] In addition, when a functional group highly reactive with silica is introduced into the molecular end of a conjugated diene polymer, This is due to the reaction with silica particles progressing during the kneading process, which increases the viscosity of the composition. This can make it difficult to knead, or can cause roughness when forming a sheet after kneading, or can make it difficult to cut the sheet. There is a tendency for workability to deteriorate, such as cracks becoming more likely to occur.

[0012] Furthermore, when such a composition is made into a vulcanizate, particularly a vulcanizate containing an inorganic filler such as silica, When used as a product, it has a balance between abrasion resistance, low hysteresis loss and wet skid resistance. Not enough lance.

[0013] In addition, the conjugated diene polymer, which is suitable for use in high load tire treads, is available in the form of a product. Some bales tend to flow (hereinafter referred to as cold flow), making them difficult to handle after storage. There is a problem.

[0014] Therefore, in the present invention, the cold flow property after molding into a bale is suppressed, and then the processing It has excellent processability when made into a vulcanized product, and excellent fracture properties and abrasion resistance when made into a vulcanized product. Conjugated diene polymer with an excellent balance of low hysteresis loss and wet skid resistance. The purpose is to provide a union. [Means for solving the problem]

[0015] As a result of extensive research and investigation into solving the above-mentioned problems of the prior art, the present inventors have The Mooney viscosity measured at 0°C is within a predetermined range, and the microstructure of the conjugated diene polymer is characterized. The degree of branching measured by GPC-light scattering with a viscosity detector is within a specific range. A conjugated diene copolymer containing nitrogen atoms in the polymer chain of the conjugated diene polymer is It also suppresses cold flow after molding, and has excellent processability when vulcanized. It has excellent fracture characteristics and abrasion resistance when used in wet skids, and has low hysteresis loss. The present inventors have found that this provides an excellent balance between the resistance to oxidation and the resistance to oxidation, and have completed the present invention.

[0016] That is, the present invention is as follows. [1] The Mooney viscosity measured at 100°C is 30 or more and 120 or less, The amount of 1,2 vinyl bonds is 25 mol% or less, and the amount of 1,4 cis bonds is 40 mol% or less and The branching degree (Bn) measured by GPC-light scattering method with a viscosity detector is 4 or more and 25 or less. and a nitrogen atom-containing conjugated diene polymer. [2] The branching degree (Bn) of the 1 / 2Hi polymer measured by GPC-light scattering measurement with a viscosity detector is 7 or greater, The branching degree (Bn) of the 1 / 2Hi polymer is determined by the peak top of the absolute molecular weight curve. Height (however, if there are multiple peak tops in the absolute molecular weight curve, The height of the peak top where the molecular weight is maximum (Hi) is used as the standard, and the height in the absolute molecular weight curve is The highest of at least two absolute molecular weights when the height is half the height of Hi (1 / 2Hi) The conjugated diene-based polymerization method according to [1], wherein the degree of branching (Bn) of the polymer at a high absolute molecular weight is body. [3] [1] or [2], where the modification rate measured by column adsorption GPC is 60% by mass or more. The conjugated diene polymer according to claim 1. [4] It has a moiety derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group, In the moiety derived from the vinyl monomer containing an alkoxysilyl group or a halosilyl group, The conjugated diene polymer according to any one of [1] to [3], which has a branched structure. [5] The moiety derived from the vinyl monomer containing an alkoxysilyl group or a halosilyl group is A monomer unit derived from a compound represented by formula (1) or (2): Branching of polymer chains by monomer units derived from compounds represented by the following formula (1) or (2): The conjugated diene polymer according to [4], having the above points. [ka] (In the formula, R 1 is a hydrogen atom or a group having 1 to 2 carbon atoms which may have a branched structure in part an alkyl group having 0 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 2 ~R 3 each independently represents a C1 to C20 alkyl group which may have a branched structure in part thereof or an aryl group having 6 to 20 carbon atoms, When there are a plurality of R1 to R3, they are independent of each other. X 1 indicates an independent halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 3, and l represents an integer of 0 to 3; (m+n+l) is 3.) [ka] (In the formula, R 2 ~R 5 each independently represents a group having 1 carbon atom, which may have a branched structure in part thereof R represents an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and when there are multiple R 2 ~ R 5 are independent of each other, X 2 ~X 3 each represents an independent halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 3, and l represents an integer of 0 to 3; (m+n+l) is 3, a represents an integer of 0 to 2, b represents an integer of 0 to 3, and c represents an integer of 0 to 3; (a+b+c) is 3.) [6] The compound has a monomer unit derived from the compound represented by formula (1), and in formula (1), R 1 but The conjugated diene polymer according to [5], wherein m represents a hydrogen atom and m represents 0. [7] The compound has a monomer unit derived from the compound represented by the formula (2), and in the formula (2), m is 0. and b is 0. [8] The compound has a monomer unit derived from the compound represented by formula (1), and in formula (1), R 1 but [5], wherein m represents a hydrogen atom, n represents 3, and l represents 0. Polyimide polymer. [9] The compound has a monomer unit derived from the compound represented by the formula (2), and in the formula (2), m is 0. n represents 3, l represents 0, a represents 0, b represents 0, and c represents 3, 5. The conjugated diene polymer according to [5].

[10] Using an organolithium compound as a polymerization initiator, a conjugated diene compound is polymerized while undergoing decomposition. a polymerization and branching step of adding a branching agent to obtain a conjugated diene-based polymer having a branched structure; [1] to [3], wherein the conjugated diene polymer is modified with a modifying agent. [9] A method for producing a conjugated diene polymer according to any one of [9].

[11] a rubber component and 5.0 parts by mass or more and 150 parts by mass or less per 100 parts by mass of the rubber component a filler; The rubber component is any one of [1] to

[10] with respect to 100% by mass of the total amount of the rubber component. A rubber composition comprising 10% by mass or more of the conjugated diene polymer described above. [Effects of the Invention]

[0017] The conjugated diene polymer according to the present invention suppresses cold flow after molding into a bale. In addition, it has excellent processability when vulcanized, and when vulcanized, it has excellent fracture properties and wear resistance. It has excellent wear resistance and a good balance between low hysteresis loss and wet skid resistance. [Brief explanation of the drawings]

[0018] [Figure 1] FIG. 1 is an image diagram showing an example of the relationship between the absolute molecular weight curve and the branching degree distribution measured by GPC-light scattering measurement method with a viscosity detector. DETAILED DESCRIPTION OF THE INVENTION

[0019] The following describes in detail an embodiment of the present invention (hereinafter referred to as "the present embodiment"). However, the present invention is not limited to this, and various modifications can be made without departing from the spirit of the present invention. Various modifications are possible.

[0020] [Conjugated diene polymer] The conjugated diene polymer of the present embodiment has a Mooney viscosity measured at 100°C of 30 or more. 120 or less, the amount of 1,2 vinyl bonds is 25 mol % or less, and the amount of 1,4 cis bonds is , 40 mol % or less, and the branching degree measured by GPC-light scattering method with a viscosity detector (hereinafter referred to as Also referred to as "Bn.") is 4 to 25 and contains a nitrogen atom.

[0021] As described above, the degree of branching (Bn) is set within a specific range, and the microcrystalline cellulose of the conjugated diene polymer is then A conjugated diene polymer with a specific structure and a specific range of Mooney viscosity measured at 100°C. The composite suppresses cold flow after bale molding and has excellent processability when vulcanized. When vulcanized, it has excellent fracture properties and abrasion resistance. The presence of nitrogen atoms provides low hysteresis loss and wet skid resistance when vulcanized. Excellent balance of resistance.

[0022] (Mooney viscosity) The conjugated diene polymer of this embodiment has a structure with a specific branching degree (Bn), as will be described later. Generally, polymers with a branched structure have a higher molecular weight than linear polymers with the same molecular weight. When polymers are mixed, the molecular size tends to become smaller. Gel permeation chromatography (hereinafter referred to as "GPC") is a method for comparing the samples with standard polystyrene samples. The molecular weight calculated as polystyrene by GPC is also known as "GPC." However, this tends to result in an underestimation of the molecular weight of the polymer.

[0023] The absolute molecular weight measured by GPC-light scattering method with a viscosity detector is The molecular weight is compared with that calculated using polystyrene standards by gel permeation chromatography (GPC). Then, the molecular size is directly observed by the light scattering method, and the molecular weight (absolute molecular weight) is measured. The branching of conjugated diene polymers is not affected by the polymer structure or interactions with the column packing material. It tends to be possible to accurately measure molecular weight without being affected by polymer structure, etc. However, the detection method of the light scattering detector is easily affected, and a relative comparison under specific measurement conditions is difficult. However, it is difficult to identify the true structure of the conjugated diene polymer.

[0024] On the other hand, Mooney viscosity is determined by the molecular weight, molecular weight distribution, branching degree, and softener content of the conjugated diene polymer. It is an index showing the overall characteristics of the conjugated diene polymer, including information on the content. The method for measuring knee viscosity is specified in ISO289, and the measurement error due to differences in equipment is small. This is extremely effective in controlling the performance of the conjugated diene polymer.

[0025] As mentioned above, viscosity is generally considered to be an alternative index to molecular weight. In the case of the conjugated diene system of this embodiment, it is difficult to accurately grasp the molecular weight. The Mooney viscosity was set as one of the requirements for the polymer. In diene polymers, the Mooney viscosity measured at 100°C (hereinafter simply referred to as "Mooney viscosity") The "ML" is between 30 and 120, but is usually in the lower limit range. The ML can be adjusted by simply lowering the molecular weight or by adding a softener (oil, etc.). If this is the case, the abrasion resistance and breaking strength of the vulcanized product tend to be impaired.

[0026] That is, in order to obtain a conjugated diene polymer that exhibits the desired performance, it is necessary to control the molecular weight or In addition to controlling the viscosity, the degree of branching is set to a specific value in order to increase the rigidity of the compound. By adjusting the range (adjusting the type and amount of branching agent and adjusting the type and amount of modifier) It is possible to control this by combining the above requirements and preventing the processability of the composition from being impaired. The abrasion resistance and puncture strength of the vulcanizate can be improved without any additives.

[0027] The conjugated diene polymer of the present embodiment has the following advantages: productivity of the conjugated diene polymer, and the ability to blend a filler or the like. The processability of the composition and the abrasion resistance and fracture resistance of the vulcanized composition were investigated. From the viewpoint of strength, the Mooney viscosity measured at 100°C is preferably 30 or more and 120 or less. It is preferably 35 or more and 100 or less, and more preferably 40 or more and 90 or less.

[0028] The Mooney viscosity measured at 100°C is 30 or more, which means that the durability of the material when vulcanized is high. The abrasion resistance and breaking strength are improved, and the Mooney viscosity measured at 100°C is 120 or less. This prevents any problems from occurring in the production of conjugated diene polymers, and allows for the addition of fillers and the like. This improves the processability when the resulting composition is mixed with the raw material.

[0029] The Mooney viscosity was measured using a sample of a conjugated diene polymer formed into a plate shape using a pressure press. After setting the sample in the instrument, preheat the sample at 100°C for 1 minute, then rotate the rotor at 2 rpm. After 4 minutes, measure the torque and use the measured value as the Mooney viscosity (ML(1+4)). More specifically, it can be measured by the method described in the Examples below. The Mooney viscosity of the ethylene-based polymer can be controlled by controlling the temperature and other conditions in the polymerization process. The degree of branching can be controlled within the above range by adjusting the degree of branching in the branching step. More specifically, the method for producing the modified conjugated diene polymer will be described later.

[0030] (microstructure) The conjugated diene polymer of the present embodiment has a microstructure in which the number of 1,2 vinyl bonds is 2. The amount of 1,4 cis bonds is specified to be 5 mol % or less, and the amount of 1,4 cis bonds is specified to be 40 mol % or less.

[0031] The microstructure of the conjugated diene polymer was measured using a Fourier transform infrared spectrophotometer as described below. It can be measured by the method described in the Examples.

[0032] The conjugated diene polymer of the present embodiment preferably has a 1,2 vinyl bond content of 25 mol % or less. It is preferably 23 mol % or less, more preferably 22 mol % or less, and even more preferably is 20 mol % or less. The lower limit of the 1,2-vinyl bond content is not particularly limited, but is preferably 7 mol % or more. It is more preferably 10 mol % or more, and even more preferably 12 mol % or more.

[0033] In order to set the amount of 1,2-vinyl bonds within the above specific range, the amount of polar substance added in the polymerization process is The amount of polar compound added can be controlled by the amount of the compound added. In addition to increasing the amount of vinyl bonds, it also has the effect of accelerating the polymerization reaction, but it also has the effect of reducing the amount of fillers, etc. When a composition containing polar substances is prepared, the breaking strength and abrasion resistance tend to deteriorate. It is necessary to adjust the amount of 1,2 vinyl bond to be controlled within a specific range. will be described in the Examples below.

[0034] The 1,4 cis bond content of the conjugated diene polymer of this embodiment is preferably 40 mol % or less. It is preferably 38 mol % or less, and more preferably 36 mol % or less.

[0035] In order to set the 1,4 cis bond amount within the above specific range, organic alkali metals, organic alkaline earth metals, etc. This is achieved by carrying out polymerization through a living anionic polymerization reaction using metalloids as polymerization initiators. This makes it possible to obtain a conjugated diene polymer having an active terminal. Then, in the branching step using a branching agent, which will be described later, the branched structure can be appropriately controlled. Furthermore, by adding a nitrogen-containing modifier, which will be described later, it is possible to achieve a high degree of modification of the conjugated diene polymerization. When a composition containing fillers is prepared, it tends to have low hysteresis. This tends to result in compositions that have a better balance of loss and wet skid resistance.

[0036] (Branching degree (Bn)) The conjugated diene polymer of the present embodiment has a viscosity of 10 ... The branching degree (Bn) measured by GPC-light scattering with a detector is 4 or more and 25 or less.

[0037] The degree of branching (Bn) being 4 or more means that the conjugated diene polymer of the present embodiment is substantially This means that the longest polymer main chain has four or more branched polymer chains.

[0038] The branching degree (Bn) of conjugated diene polymers was measured by GPC-light scattering method with a viscosity detector. Using the measured contraction factor (g'), g' = 6Bn / {(Bn+1)(Bn+2)} be defined.

[0039] In general, a polymer with branches has a higher molecular weight than a linear polymer of the same absolute molecular weight. In this case, the size of the molecule tends to be small.

[0040] The shrinkage factor (g') is the molecular occupancy for a linear polymer of assumed identical absolute molecular weight. In other words, the larger the degree of branching of the polymer, the larger the shrinkage factor ( g') tends to be smaller.

[0041] In this embodiment, the intrinsic viscosity is used as an index of the molecular size for this shrinkage factor. The intrinsic viscosity of the chain polymer is [η] = -3.883M 0.771 The relational expression is as follows: In the formula, M is the absolute molecular weight.

[0042] However, the shrinkage factor expresses the rate of decrease in molecular size and is not related to the branching of the polymer. It is not an accurate representation of the structure.

[0043] Therefore, using the value of the shrinkage factor (g') at each absolute molecular weight of the conjugated diene polymer, The branching degree (Bn) of the conjugated diene polymer is calculated from the above formula. For the longest main chain structure, the number of polymers directly or indirectly linked to each other is accurately expressed. It is what manifests itself.

[0044] The calculated branching degree (Bn) is an index that represents the branching structure of the conjugated diene polymer. For example, in the case of a typical four-branched star polymer (four polymer chains connected at the center), the longest Two polymer chain arms are connected to the highly branched main chain structure, and the branching degree (Bn) is evaluated as 2. can be.

[0045] In the case of a typical six-branched star polymer, the polymer chain has four arms for the longest highly branched main chain structure. It is bonded and the branching degree (Bn) is estimated to be 4.

[0046] The conjugated diene polymer of this embodiment has a branching degree (Bn) of 4 or more and 25 or less. In this case, the star polymer structure should have the same branches as the star polymer structure with 6 to 27 branches. It means that the modified conjugated diene polymer has the following structure:

[0047] Here, "branched" means that one polymer is directly or indirectly linked to another polymer. The "branching degree (Bn)" is the number of main chain structures that form the longest branching degree. is the number of polymers that are directly or indirectly bonded to each other.

[0048] The degree of branching (Bn) is 4 or more and 25 or less, so that the conjugated diene polymer of this embodiment The cold flow of the bale, which is the product form of the conjugated diene copolymer, is suppressed and then processed. It has excellent processability when vulcanized, and when vulcanized it has excellent abrasion resistance and breaking strength. .

[0049] Generally, as absolute molecular weight increases, processability tends to deteriorate. If the molecular weight is increased, the viscosity of the vulcanized product increases significantly, significantly worsening processability. do.

[0050] Therefore, many functional groups are introduced into the polymer to increase the affinity with the silica blended as a filler. Even if the silica is sufficiently dispersed in the polymer during the kneading process, it is difficult to improve the properties and / or reactivity of the polymer. As a result, the functions of the introduced functional groups are not exhibited, and the expected results are not achieved. The introduction of functional groups improves the balance between low hysteresis loss and wet skid resistance. This means that the desired effect will not be realized.

[0051] On the other hand, the conjugated diene polymer of the present embodiment has a branching degree (Bn) of 4 or more and 25 or less. By identifying the specific molecular weight, the increase in viscosity during vulcanization is significantly suppressed. Therefore, for example, it is thoroughly mixed with silica in the kneading process, and the conjugated diene As a result, for example, it is possible to disperse silica around the conjugated diene polymer. In polyethylene-based polymers, increasing the molecular weight makes it possible to improve abrasion resistance and breaking strength. Furthermore, by sufficiently kneading the silica is dispersed around the polymer, and the functional groups are activated and / or Or it becomes possible to react, so that it has practically sufficient low hysteresis loss and wet skin It is possible to make the material have high resistance.

[0052] The degree of branching (Bn) of the conjugated diene polymer of this embodiment is 4 or more and 25 or less, and preferably is 5 or more and 23 or less, more preferably 6 or more and 20 or less, and further preferably 7 or more The degree of branching (Bn) of the conjugated diene polymer is in this range and can be used as a vulcanizate. When vulcanized, they tend to have excellent abrasion resistance.

[0053] The degree of branching of the conjugated diene polymer is determined by the combination of the amount of branching agent and the amount of terminal modifier added. By this, the degree of branching can be controlled to be between 4 and 25. The number of functional groups of the branching agent, the amount of branching agent added, the timing of adding the branching agent, and the nitrogen atom-containing This can be controlled by the number of functions of the modifying agent and the amount of addition. More specifically, the conjugated A method for producing a diene polymer is described.

[0054] (Degree of branching in the polymer region (Bn)) The conjugated diene polymer of the present embodiment is characterized by an absolute viscosity of 1.03g as measured by GPC-light scattering measurement with a viscosity detector. The height of the peak top in the molecular weight curve (however, the height of the peak top in the above absolute molecular weight curve) When multiple peaks exist, the height of the peak top with the maximum absolute molecular weight (Hi) is used as the reference. The height of the absolute molecular weight curve is half the height of Hi (1 / 2Hi). The polymer with the highest absolute molecular weight of the two absolute molecular weights (hereinafter referred to as "1 / 2Hi polymer") It is preferable that the branching degree (Bn) of the 1 / 2Hi copolymer is 7 or more. The branching degree (Bn) of the polymer chain is 7 or more, which means that the average Conjugated dienes with a high branching degree in the high molecular weight region and a branching degree distribution relative to the branching degree (Bn) In the absolute molecular weight curve, 1 / 2Hi means that the polymer is a peak. There are at least two peaks on the low molecular weight side and the high molecular weight side from the peak top. The highest of at least two absolute molecular weights at half the height Hi (1 / 2Hi) For polymers with high absolute molecular weight, 1 / 2Hi is on the low molecular weight side and the high molecular weight side from the peak top. When there are two, it means a polymer with an absolute molecular weight of 1 / 2Hi on the higher molecular weight side. In addition, there are multiple peak tops, and there are also multiple 1 / 2Hi peaks on the higher molecular weight side than the peak tops. If present, it means the polymer with the highest absolute molecular weight, 1 / 2Hi. do.

[0055] Figure 1 shows the absolute molecular weight curve and branching distribution measured by GPC-light scattering measurement with a viscosity detector. FIG. 10 is an image diagram showing an example of a relationship. Generally, a coupling agent or a nitrogen atom is added to one of the active terminals of the conjugated diene polymer. A simple star-shaped conjugated diene undergoes a coupling reaction with a coupling agent containing a group. In the case of the polymer, as shown in Figure 1, a condensation reaction occurs due to some of the coupling agent residues. The molecular weight of the polymer is higher than that of the 1 / 2Hi polymer (hereinafter referred to as "high molecular weight region"). Although there are some changes in the degree of branching (Bn), the degree of branching (Bn) in the high molecular weight region is basically the same. tends to be constant depending on the functionality of the coupling agent. On the other hand, when the branching degree (Bn) of the 1 / 2Hi polymer is 7 or more, the conjugated dimer of the present embodiment As shown in Figure 1, the branching degree distribution of the main chain branched polymer of the ene-based polymer is It can be seen that the higher the molecular weight, the higher the branching. The introduction of a star structure can also increase the branching degree (Bn) in the high molecular weight region to some extent. However, when the branching degree (Bn) of the 1 / 2Hi polymer is 7 or more, the conjugated dimer of this embodiment is Ene-based polymers have a higher branching degree (Bn) in the high molecular weight region due to condensation of coupling agent residues. Compared to the method of controlling the polymerization, the condensation reaction tends to proceed uniformly, and the This is preferable in terms of quality control of the resulting conjugated diene polymer, since the viscosity is less likely to fluctuate.

[0056] The conjugated diene polymer of the present embodiment has a branching degree (Bn) of 1 / 2Hi polymer of 7 or more. Conjugated diene polymers having a preferred branching distribution, specifically, for example, star-shaped Each polymer chain constituting the structure is a conjugated diene polymer with a further branched structure. The conjugated diene polymer having such a preferable branching degree distribution is not particularly limited. However, it can be obtained, for example, by the following method: A branched structure is previously introduced into a part of the carbonyl group (preferably having a nitrogen atom-containing group). By using a coupling agent, the degree of branching (Bn) in the high molecular weight region is increased by the coupling reaction. The branching degree distribution is higher than the functionality of the branching agent and is higher than the peak top of the molecular weight distribution. Therefore, a conjugated diene polymer having a broad range of

[0057] Conjugated diene polymers with a high branching degree (Bn) in the high molecular weight region, for example, In the case of the polymer, the proportion of conjugated diene polymers with branched structures in the main chain is high, and the coupling agent This means that the coupling efficiency is high.

[0058] The branching degree (Bn) of the 1 / 2Hi polymer and the branching degree (Bn) of the polymer in the high molecular weight region are The number of functional groups of the branching agent, the amount of branching agent added, the timing of adding the branching agent, and coupling the functionality of the coupling agent or nitrogen atom-containing modifying agent, The viscosity of the conjugated diene polymer of the present embodiment can be controlled by adjusting the amount of the modifier added. The peak height (or height of the peak) in the absolute molecular weight curve measured by GPC-light scattering measurement with a detector However, when there are a plurality of peak tops in the absolute molecular weight curve, the absolute molecular weight is the highest. The height of the peak top (highest peak) Hi on the absolute molecular weight curve is taken as the standard. The highest absolute molecular weight of at least two absolute molecular weights at half height (1 / 2Hi) The degree of branching (Bn) of the molecular weight polymer is preferably 7 or more, more preferably 8 or more. More preferably, it is 10 or more, and even more preferably, it is 12 or more. In the case of the conjugated diene polymer, the upper limit of the branching degree (Bn) of the 1 / 2Hi polymer is, Although not limited thereto, for example, it is 50 or less.

[0059] In this embodiment, the branching degree (Bn) of the 1 / 2Hi polymer is as described in the examples below. It can be measured by the following method.

[0060] The branching degree (Bn) is 4 or more, and the branching degree (Bn) of the 1 / 2Hi polymer is 7 or more. Conjugated diene polymers with a preferred structure having a branching degree distribution above tend to have low melt viscosity. In the kneading process, which is under high temperature and high shear conditions, a compound containing silica etc. is obtained. Generally, polymers with many branches have a higher degree of branching than polymers with a linear structure. When comparing all the same molecular weights, the viscosity drops significantly in the high shear region, making it easier to knead (processability is improved). This is because even at high molecular weights, the molecular weight per chain of the base polymer is This is thought to be due to the small branching degree (Bn) of the 1 / 2Hi polymer. The effect of shortening each base polymer by increasing the branching degree in the high molecular weight region It can be said that the effect is more pronounced when the molecular weight is increased to improve abrasion resistance and breaking strength. However, the viscosity of the polymer is high and it becomes difficult to mix it with fillers, etc., when the molecular weight is increased. However, as mentioned above, the branching degree (Bn ) is 7 or more, and the high branching degree in the high molecular weight region provides good processability, resulting in a molecular In other words, the branching degree (Bn) of the 1 / 2Hi polymer is 7. As mentioned above, conjugated diene polymers with a high degree of branching in the high molecular weight region have good processability when obtaining blends. Because of its excellent properties, it is possible to design high molecular weight conjugated diene polymers, and when vulcanized, Therefore, a conjugated diene polymer having excellent abrasion resistance and fracture properties tends to be obtained.

[0061] (Nitrogen-containing conjugated diene polymer) The conjugated diene polymer of the present embodiment contains a nitrogen atom in the polymer chain. The conjugated diene polymer contained in the rubber provides a balance between low hysteresis loss and wet skid resistance. Such a conjugated diene polymer is, for example, a nitrogen atom-containing polymer described below. It can be obtained by carrying out a modification reaction using a modifying agent having a group.

[0062] In order to make the conjugated diene polymer obtained through the polymerization and branching steps more highly branched, The reaction agent has a nitrogen atom-containing group with two or more functional groups attached to the active terminal of the conjugated diene polymer. A compound having a nitrogen atom-containing group (hereinafter also referred to as a "modifying agent having a nitrogen atom-containing group") is more preferred.

[0063] In the modification step described below, a nitrogen atom is bonded to one of the active terminals of the conjugated diene polymer. The resulting polymer is modified with a modifying agent having a diol-containing group to obtain a conjugated diene polymer.

[0064] The modified conjugated diene polymer modified with a modifying agent having a nitrogen atom-containing group can be used as a filler, etc. When a composition containing the above is prepared, the dispersibility of silica is improved, and the composition containing a filler, etc. The processability is good, and when the composition is vulcanized, the abrasion resistance and breaking strength are good. The balance between low hysteresis loss and wet skid resistance is improving dramatically. More specifically, the method for producing a conjugated diene polymer will be described later.

[0065] The modifying agent having a nitrogen atom-containing group is not particularly limited, but examples thereof include isopropyl alcohol, Cyanate compounds, isothiocyanate compounds, isocyanuric acid derivatives, nitrogen-containing carboxylic acids Examples of the vinyl compound include hydroxyl compounds, nitrogen-containing vinyl compounds, and nitrogen-containing epoxy compounds.

[0066] The nitrogen atom-containing functional group of the modifying agent is preferably an amine compound having no active hydrogen. For example, tertiary amine compounds, protected amine compounds in which the active hydrogen is substituted with a protecting group, an imine compound represented by the general formula -N=C, and an alkyl group bonded to the nitrogen atom-containing group; More specifically, the conjugated diene polymer may be produced by the method for producing the conjugated diene polymer described below. Please write in.

[0067] The conjugated diene polymer of the present embodiment is subjected to gel electrolysis, which is a relative comparison method with a standard polystyrene sample. Polystyrene equivalent molecular weight measured by gel permeation chromatography (hereinafter referred to as "GPC") The number average molecular weight and weight average molecular weight (hereinafter simply referred to as "number average molecular weight" and "weight average molecular weight") are calculated as the amount of The number average molecular weight is 5.0 x 10 4 g / mol Over 100 x 10 4 g / mol or less, and preferably 10 × 10 4 g / mol or more5 0×10 4 g / mol or less is more preferable, and 20×10 4 g / mol or more 35× 10 4 It is more preferable that the weight average molecular weight is 10×10 g / mol or less. 4 g / m ol or more 200×10 4 g / mol or less is preferable, and 20×10 4 g / mol or more Upper 125×10 4 g / mol or less is more preferable, and 30×10 4 g / mol or more 75×10 4 It is more preferably g / mol or less.

[0068] The conjugated diene polymer of the present embodiment has a weight average molecular weight (Mn) relative to the number average molecular weight (Mn). The molecular weight distribution (Mw / Mn) expressed as the ratio of Mw to Mn is preferably 1.60 or more and 2.30 or less. The conjugated diene polymer with a molecular weight distribution in this range is a composition containing a filler, etc. When the product is vulcanized, it tends to have excellent abrasion resistance and breaking strength. , more preferably 1.65 or more and 2.20 or less, and even more preferably 1.70 or more and 2. 00 or less, and even more preferably 1.75 or more and 1.95 or less.

[0069] The number average molecular weight, weight average molecular weight, and molecular weight distribution of the conjugated diene polymer are determined by the experimental method described below. It can be measured by the method described in the Examples. The weight average molecular weight and molecular weight distribution can be determined by controlling conditions such as temperature conditions in the polymerization process. By adjusting the degree of branching in the branching process, it is possible to control the degree of branching within the above range. More specifically, the method for producing the modified conjugated diene polymer will be described later.

[0070] (denaturation rate) In this specification, the "modification rate" refers to the ratio of the nitrogen atom-containing functional group to the total amount of the conjugated diene polymer. represents the mass ratio of the conjugated diene polymer having

[0071] For example, when a nitrogen atom-containing modifying agent is reacted with the terminal end, the nitrogen atom-containing modifying agent The ratio of the conjugated diene polymer having a nitrogen atom-containing functional group to the total amount of the conjugated diene polymer The mass ratio is expressed as the modification rate.

[0072] On the other hand, when the polymer is branched using a branching agent containing a nitrogen atom, the resulting copolymer Since the diene polymer has a nitrogen atom-containing functional group, this branched polymer also This will be counted when calculating the denaturation rate.

[0073] That is, in this specification, a coupling polymer produced by a modifying agent having a nitrogen atom-containing functional group and / or a branched polymer using a branching agent having a nitrogen atom-containing functional group, The total mass ratio is the "modification ratio."

[0074] The conjugated diene polymer of the present embodiment has at least one end modified with a nitrogen atom-containing group. This improves the processability when the composition is compounded with fillers, etc., and the wear resistance when the composition is vulcanized. Low hysteresis loss and wet skid resistance while maintaining wear resistance and breaking strength. The balance tends to improve dramatically.

[0075] The conjugated diene polymer of the present embodiment has excellent processability, abrasion resistance, breaking strength, and low hysteresis. From the viewpoint of the balance between slip resistance and wet skid resistance, the total amount of conjugated diene polymers is The modification rate measured by column adsorption GPC (hereinafter also simply referred to as "modification rate") is preferably 60% by mass or more.

[0076] The modification rate is more preferably 65% ​​by mass or more, and even more preferably 70% by mass or more. More preferably, it is 75% by mass or more, and even more preferably, it is 80% by mass or more. The upper limit of the modification rate is not particularly limited, but is, for example, 98% by mass.

[0077] By making the modification rate 60% by mass or more, the processability when making a vulcanizate is excellent, and the vulcanizate When the tensile strength is increased, the abrasion resistance and low hysteresis loss performance tend to be superior.

[0078] The modification rate can be determined by chromatography, which can separate functional group-containing modified components from non-modified components. It can be measured as follows.

[0079] This method using chromatography involves the use of polar silica or other materials that adsorb specific functional groups. A column for gel permeation chromatography packed with the substance was used to measure the internal structure of the non-adsorbed components. Examples include a method of quantifying using a standard for comparison (column adsorption GPC method).

[0080] More specifically, the denaturation rate was determined by dissolving a sample solution containing a sample and a low-molecular-weight internal standard polystyrene. The chromatogram measured on a polystyrene gel column and the chromatogram measured on a silica column were The amount of adsorption onto the silica column can be determined by subtracting the amount of adsorption from the corresponding chromatogram.

[0081] More specifically, the modification rate can be measured by the method described in the Examples.

[0082] In the conjugated diene polymer of the present embodiment, the modification rate varies depending on the amount of the modifier added and the reaction method. This can be controlled to 60% by mass or more. do.

[0083] For example, the polymerization initiator may be an organic lysine having at least one nitrogen atom in the molecule, which will be described later. A method for polymerizing a monomer having at least one nitrogen atom in the molecule using a lithium compound. The copolymerization method and the method using a modifier of the structural formula described later are combined to control the polymerization conditions. By doing so, the above-mentioned modification rate can be achieved.

[0084] The conjugated diene polymer of the present embodiment has an alkoxysilyl group or a halogen atom in a part of the polymer chain. The alkoxysilyl group or the vinyl monomer containing the alkoxysilyl group is included. It is preferred that the moiety derived from the vinyl monomer containing a silyl group has a branched structure. stomach.

[0085] The branched structure is a moiety derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group. At branching points in the branching portion, there is one or more branching points, preferably three or more branching points, and four or more branching points. More preferably, it is equal to or greater than this.

[0086] In addition, the branching points that form the branched structure have at least one polymer chain. It is preferable that the polymer has two or more polymer chains that are not the main chain, and it is even more preferable that the polymer has two or more polymer chains that are not the main chain. has four or more polymer chains that are not the main chain.

[0087] In particular, in a branched structure consisting of a vinyl monomer containing an alkoxysilyl group or a halosilyl group, When signal detection was performed by 29Si-NMR, the range was -45 ppm to -65 ppm. Furthermore, peaks due to branched structures were detected in the range of -50 ppm to -60 ppm. can be.

[0088] In a preferred embodiment of the conjugated diene polymer of the present embodiment, the polymer chain has a terminal nitrogen atom. The polymer chain is modified with a modifying agent containing an alkoxysilyl group or It has a moiety derived from a vinyl monomer containing a halosilyl group, and the alkoxysilyl group or Modification having a further branched structure in the portion derived from the vinyl monomer containing a halosilyl group Regarding the method for obtaining conjugated diene polymerization, the number of functional groups of the nitrogen atom-containing modifier and the amount of addition are The branched structure can be formed by adjusting the number of functional groups of the branching agent, the amount of branching agent added, etc. can be controlled by adjusting the timing of the addition of the branching agent. In the present specification, the term "a portion derived from a vinyl monomer" refers to a vinyl monomer which is a branching agent described later. The alkoxy group and / or halogen of the alkyl monomer becomes a leaving group, and the polymerization active terminal is substituted. The polymer chain is bonded to the silicon of the vinylsilane, and the vinyl group of the vinylsilane is It represents the structure of an aromatic vinyl compound polymerized. It contains multiple alkoxy groups and / or halogens. When a vinyl monomer containing the above-mentioned compound is used as a branching agent, the resulting "portion derived from the vinyl monomer" In the vinylsilane, multiple polymer chains can be attached to the silicon of the vinylsilane.

[0089] The polymer chain is derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group. and the vinyl monomer containing the alkoxysilyl group or halosilyl group. In order to obtain a conjugated diene polymerization having a further branched structure in the resulting portion, for example, Polymerization is carried out using an organolithium compound as a polymerization initiator, and further special treatment is carried out during or after polymerization. A branching agent is added to give a specific branching point, and a modifier is added to give a specific branching rate after continuing polymerization. Examples of methods include a method of denaturing the polymer using

[0090] Such means for controlling the polymerization conditions will be described in the production method in the examples below.

[0091] The conjugated diene polymer of the present embodiment has the above-mentioned alkoxysilyl group or halosilyl group. The portion derived from the vinyl monomer containing the vinyl monomer is derived from a compound represented by the following formula (1) or (2): The monomer unit is derived from a compound represented by the following formula (1) or (2): It is preferable that the polymer chain has a branching point at the position, and the polymer chain is obtained by using a branching agent described later. It is more preferable that the polymer is a conjugated diene polymer, and at least one end of the conjugated diene polymer is It is more preferable that the polymer is a modified conjugated diene polymer modified with a nitrogen atom-containing group. . [ka] In the formula, R 1 is a hydrogen atom or a group having 1 to 2 carbon atoms which may have a branched structure in part an alkyl group having 0 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 2 ~R 3 each independently represents a C1 to C20 alkyl group which may have a branched structure in part thereof or an aryl group having 6 to 20 carbon atoms, When there are a plurality of R1 to R3, they are independent of each other. X 1 indicates an independent halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 3, and l represents an integer of 0 to 3; (m+n+l) is 3. [ka] In the formula, R 2 ~R 5 each independently represents a group having 1 carbon atom, which may have a branched structure in part thereof R represents an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and when there are multiple R 2 ~ R 5 are independent of each other, X 2 ~X 3 each represents an independent halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 3, and l represents an integer of 0 to 3; (m+n+l) is 3, a represents an integer of 0 to 2, b represents an integer of 0 to 3, and c represents an integer of 0 to 3; (a+b+c) is 3.

[0092] The conjugated diene polymer of the present embodiment is a polymer obtained by polymerizing a monomer derived from a compound represented by the above formula (1): In formula (1), R 1 Preferably, represents a hydrogen atom and m represents 0. This improves the number of branches and reduces the cold flow of veils, which are the product form of conjugated diene polymers. After suppressing this, the processability when vulcanized is extremely excellent, and when vulcanized, it has excellent abrasion resistance and This provides excellent effects in terms of fracture strength.

[0093] The conjugated diene polymer of the present embodiment is a polymer obtained by polymerizing a monomer derived from a compound represented by the above formula (2): In the formula (2), it is preferable that m represents 0 and b represents 0. The effect of improving wear resistance and processability is obtained.

[0094] The conjugated diene polymer of the present embodiment is a polymer obtained by polymerizing a monomer derived from a compound represented by the above formula (2): In formula (2), m represents 0, n represents 3, l represents 0, and a represents 0, It is preferable that b represents 0 and c represents 3. This allows the product form of the conjugated diene polymer to be This suppresses the cold flow of the veil, which is a state of the veil, and improves its wear resistance and processability. can be.

[0095] The conjugated diene polymer of the present embodiment is a polymer obtained by polymerizing a monomer derived from a compound represented by the above formula (1): In formula (1), R 1 represents a hydrogen atom, m represents 0, n represents 3, and l represents 0 This improves the modification rate and the branching degree, and the conjugated diene polymer It suppresses the cold flow of the veil, which is the product form of the combined product, and has fuel-saving performance and abrasion resistance. The effect of improving processability is also obtained.

[0096] [Method for producing conjugated diene polymer] The method for producing a conjugated diene polymer according to the present embodiment is a method for producing a conjugated diene polymer. The method comprises the steps of: While polymerizing the above, a branching agent is added to obtain a conjugated diene polymer having a branched structure. and a modification step of modifying the conjugated diene polymer with a modifying agent.

[0097] (Polymerization and branching process) The polymerization and branching steps (hereinafter simply referred to as "the steps") in the production method of the conjugated diene polymer of this embodiment The polymerization and branching step is, for example, carried out using an organic monolithium compound as a polymerization initiator. At least one type of conjugated diene compound is polymerized, and a branching agent is added to form a branched structure. The polymerization reaction in the polymerization and branching step is as follows: When explaining the reaction with a branching agent, it is called the "polymerization process." It is also called.

[0098] In the polymerization step, polymerization is carried out by a propagation reaction due to a living anionic polymerization reaction. This makes it possible to obtain a conjugated diene-based polymerization having an active terminal. After that, the main chain branching can be appropriately controlled in the branching process using a branching agent, and a high modification rate can be achieved. Therefore, a conjugated diene polymer having the above structure tends to be obtained.

[0099] Conjugated diene polymers are homopolymers obtained using a single conjugated diene compound as a monomer. , a polymer obtained by using different types of conjugated diene compounds as monomers, i.e., a copolymer It may be the body.

[0100] Specific examples of the conjugated diene compound include, but are not limited to, 1,3-butadiene. ethylene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3- Examples include methyl-1,3-pentadiene, 1,3-hexadiene, and 1,3-heptadiene. Among these, 1,3-butadiene and Isoprene is preferred. These may be used alone or in combination of two or more. .

[0101] In the conjugated diene polymer of the present embodiment, the Mooney viscosity and the degree of branching depend on the addition of a polymerization initiator. the type (functional number) and amount of branching agent added, the type (functional number) and amount of modifier having a nitrogen atom-containing group The effect of the microstructure is relatively small. Therefore, it can be appropriately designed within the range of a general microstructure. However, the amount of 1,4 cis bonds, The amount of 1,2 vinyl bonds affects the Tg of conjugated diene polymers, and therefore affects fuel economy and brake performance. It is preferable to set the value within the above range from the viewpoint of performance.

[0102] The microstructure of the conjugated diene polymer of this embodiment is as follows: and the bond amount of each of the above is within the above range, and further, the glass transition temperature of the conjugated diene polymer is -110 To obtain a vulcanizate with excellent breaking strength and abrasion resistance when the temperature is in the range of ℃ or higher and -80℃ or lower. The glass transition temperature is determined in accordance with ISO 22768:2006. The DSC curve was recorded while the temperature was raised within a predetermined temperature range, and the peak top of the DSC differential curve ( The glass transition temperature is the inflection point.

[0103] <Polymerization initiator> As the polymerization initiator, at least an organic monolithium compound can be used. The organic monolithium compound is not particularly limited, but examples thereof include low molecular weight compounds, soluble Examples of suitable organomonolithium compounds include organolithium compounds of substituted oligomers. In addition, as for the organic monolithium compound, the organic group and the bonding mode of the lithium are For example, compounds having a carbon-lithium bond, compounds having a nitrogen-lithium bond, and compounds having a tin-lithium bond. The amount of the organic monolithium compound used as a polymerization initiator is determined based on the target conjugated diene polymerization. It is preferable to determine the molecular weight of the substance. The amount of monomers such as conjugated diene compounds used relative to the amount of polymerization initiator used is related to the degree of polymerization. That is, it tends to be related to the number average molecular weight and / or the weight average molecular weight. Therefore, in order to increase the molecular weight, it is necessary to adjust the amount of polymerization initiator used to a smaller amount. To lower the molecular weight, it is advisable to increase the amount of polymerization initiator used. good.

[0104] Organomonolithium compounds are used as a method for introducing nitrogen atoms into conjugated diene polymers. From the viewpoint of being able to be used, preferred are alkyllithium compounds having a substituted amino group, Or dialkylaminolithium.

[0105] In this case, a conjugated diene polymer having a nitrogen atom consisting of an amino group at the polymerization initiation terminal is Obtained.

[0106] A substituted amino group is an amino group that does not have active hydrogen or has a structure in which the active hydrogen is protected. be.

[0107] The alkyllithium compound having an amino group without active hydrogen is not particularly limited. However, for example, 3-dimethylaminopropyl lithium, 3-diethylaminopropyl lithium lithium, 4-(methylpropylamino)butyllithium, and 4-hexamethyleneimino butyllithium.

[0108] The alkyllithium compounds having an amino group with a structure in which active hydrogen is protected are not particularly limited. Examples include, but are not limited to, 3-bistrimethylsilylaminopropyllithium and 4-trimethylsilylaminopropyllithium. trimethylsilylmethylaminobutyllithium.

[0109] The dialkylaminolithium is not particularly limited, but examples thereof include lithium dimethyl Amides, lithium diethylamide, lithium dipropylamide, lithium dibutylamide , lithium di-n-hexylamide, lithium diheptylamide, lithium diisopropylamide Lithium dioctylamide, Lithium di-2-ethylhexylamide, Lithium Lithium didecylamide, Lithium ethylpropylamide, Lithium ethylbutylamide, Li Lithium ethylbenzylamide, Lithium methylphenethylamide, Lithium hexamethylene Lithium imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, Lithium morpholide, 1-lithioazacyclooctane, 6-lithio-1,3,3-trimethyl 1-Lithium-6-azabicyclo[3.2.1]octane, and 1-Lithium-1,2,3,6-tetramethyl- tetrahydropyridine is an example.

[0110] These organomonolithium compounds having substituted amino groups can be used as polymerizable monomers, e.g. , 1,3-butadiene, isoprene, styrene, etc., are reacted with a small amount of monomers to solubilize Oligomeric organomonolithium compounds can also be used.

[0111] As for organomonolithium compounds, they are industrially readily available and have good control over the polymerization reaction. From the viewpoint of ease of use, alkyllithium compounds are preferred. A conjugated diene polymer having alkyl groups at its ends is obtained.

[0112] The alkyllithium compound is not particularly limited, but for example, n-butyllithium , sec-butyllithium, tert-butyllithium, n-hexyllithium, benzoyllithium Examples include lithium, phenyllithium, and stilbenelithium.

[0113] As for alkyllithium compounds, they are industrially readily available and have good control over the polymerization reaction. From the standpoint of ease, n-butyllithium and sec-butyllithium are preferred.

[0114] These organic monolithium compounds may be used alone or in combination of two or more. It may also be used in combination with other organometallic compounds.

[0115] Other organometallic compounds include, for example, alkaline earth metal compounds, other alkali metal compounds, compounds and other organometallic compounds.

[0116] The alkaline earth metal compound is not particularly limited, but for example, an organomagnesium compound Organic compounds, organic calcium compounds, and organic strontium compounds. Potassium earth metal alkoxides, sulfonates, carbonates, and amide compounds are also available. Examples include:

[0117] Examples of the organomagnesium compound include dibutylmagnesium and ethylbutylmagnesium. Other organometallic compounds include organoaluminum compounds. Compounds include:

[0118] In the polymerization step, the polymerization reaction mode is not particularly limited, but for example, a batch system (" Examples of polymerization reaction modes include batch polymerization and continuous polymerization.

[0119] In a continuous system, one or more connected reactors can be used. The reactor used in the continuous process is, for example, a tank type or a tubular type equipped with an agitator. Preferably, the monomer, the inert solvent, and the polymerization initiator are continuously fed into the reactor; A polymer solution containing a polymer is obtained in the reactor, and the polymer solution is continuously discharged.

[0120] As the batch reactor, for example, a tank-type reactor equipped with a stirrer is used. Preferably, a monomer, an inert solvent, and a polymerization initiator are fed, and if necessary, the monomer is added continuously or intermittently during polymerization, and a polymer solution containing the polymer is obtained in the reactor. After the polymerization is completed, the polymer solution is discharged.

[0121] In the method for producing a conjugated diene polymer of the present embodiment, To obtain a diene polymer, the polymer is continuously discharged and subjected to the next reaction in a short time. A continuous system is preferred, which allows

[0122] The polymerization step for the conjugated diene polymer is preferably carried out in an inert solvent. The solvent is not particularly limited, but examples thereof include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specific hydrocarbon solvents include, but are not limited to, butane, aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane alicyclic hydrocarbons such as methylcyclopentane and methylcyclohexane; benzene, toluene Examples of the hydrocarbons include aromatic hydrocarbons such as benzene and xylene, and hydrocarbons consisting of mixtures thereof.

[0123] Before the polymerization reaction, the impurities, allenes and acetylenes, are removed with an organometallic compound. By performing the treatment, a conjugated diene polymer having a high concentration of active terminals tends to be obtained, This is preferred because it tends to give a modified conjugated diene polymer with a high modification rate.

[0124] In the polymerization step, a polar compound may be added. It is also likely to be used as a vinylating agent to control the amount of vinyl bonds. It also tends to be effective in promoting polymerization reactions.

[0125] The polar compound is not particularly limited, but examples thereof include tetrahydrofuran, diethyl ether, ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dhibutyl Diethylene glycol dimethyl ether, diethylene glycol dibutyl ether Ethers such as ether, dimethoxybenzene, and 2,2-bis(2-oxolanyl)propane Tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylenediamine Tertiary amine compounds such as tertiary amines, pyridines, and quinuclidines; potassium tert-amines tert-butylate, potassium tert-butylate, sodium tert-butylate, sodium Alkali metal alkoxide compounds such as umamirate; phosphine and other phosphazenes Fin compounds and the like can be used. These polar compounds may be used alone or in combination of two or more.

[0126] The amount of the polar compound to be used is not particularly limited and can be selected depending on the purpose, etc. The amount is preferably 0.01 moles or more and 100 moles or less per mole of the polymerization initiator. Such polar compounds (vinylating agents) are useful as modifiers of the microstructure of conjugated diene polymers. An appropriate amount can be used depending on the desired amount of 1,2 vinyl bonds.

[0127] The polymerization temperature in the polymerization step is preferably a temperature at which living anionic polymerization proceeds. From the viewpoint of productivity, the temperature is preferably 0°C or higher, and 120°C or lower. By being in such a range, it is possible to prevent the active terminals from being modified by the modifier after the polymerization is completed. It is more preferable to use a temperature of 50°C or higher. It is below 00℃.

[0128] (branching agent) In the conjugated diene polymer of the present embodiment, when a branched structure is constructed, For this purpose, a branching agent represented by the following formula (1) or formula (2) is used. [ka] In the formula, R 1 is a hydrogen atom or a group having 1 to 2 carbon atoms which may have a branched structure in part an alkyl group having 0 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 2 ~R 3each independently represents a C1 to C20 alkyl group which may have a branched structure in part thereof or an aryl group having 6 to 20 carbon atoms, When there are a plurality of R1 to R3, they are independent of each other. X 1 indicates an independent halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 3, and l represents an integer of 0 to 3; (m+n+l) is 3. [ka] In the formula, R 2 ~R 5 each independently represents a group having 1 carbon atom, which may have a branched structure in part thereof R represents an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and when there are multiple R 2 ~ R 5 are independent of each other, X 2 ~X 3 each represents an independent halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 3, and l represents an integer of 0 to 3; (m+n+l) is 3, a represents an integer of 0 to 2, b represents an integer of 0 to 3, and c represents an integer of 0 to 3; (a+b+c) is 3.

[0129] The branching agent represented by formula (1) is not particularly limited, but for example, trimethoxy ( (4-vinylphenyl)silane, triethoxy(4-vinylphenyl)silane, tripropon Tributoxy(4-vinylphenyl)silane, Tributoxy(4-vinylphenyl)silane, Tributoxy(4-vinylphenyl)silane Isopropoxy(4-vinylphenyl)silane, trimethoxy(3-vinylphenyl)silane Silane, triethoxy(3-vinylphenyl)silane, tripropoxy(3-vinylphenyl)silane Tributoxy(3-vinylphenyl)silane, Tributoxy(3-vinylphenyl)silane, Triisopropoxy(3-vinylphenyl)silane (2-vinylphenyl)silane, trimethoxy(2-vinylphenyl)silane, triethoxy(2 -vinylphenyl)silane, tripropoxy(2-vinylphenyl)silane, tributoxy silane, triisopropoxy(2-vinylphenyl)silane, Dimethoxymethyl(4-vinylphenyl)silane, diethoxymethyl(4-vinylphenyl) dipropoxymethyl(4-vinylphenyl)silane, dibutoxymethyl(4 -vinylphenyl)silane, diisopropoxymethyl(4-vinylphenyl)silane, di Methoxymethyl(3-vinylphenyl)silane, diethoxymethyl(3-vinylphenyl)silane ) silane, dipropoxymethyl(3-vinylphenyl)silane, dibutoxymethyl(3- (vinylphenyl)silane, diisopropoxymethyl (3-vinylphenyl)silane, dimethicone Diethoxymethyl(2-vinylphenyl)silane, diethoxymethyl(2-vinylphenyl)silane Silane, Dipropoxymethyl(2-vinylphenyl)silane, Dibutoxymethyl(2-vinylphenyl)silane (2-vinylphenyl)silane, diisopropoxymethyl(2-vinylphenyl)silane, dimethic dimethylethoxy(4-vinylphenyl)silane, dimethylethoxy(4-vinylphenyl)silane silane, dimethylpropoxy(4-vinylphenyl)silane, dimethylbutoxy(4-vinyl dimethylisopropoxy(4-vinylphenyl)silane, dimethyl Methoxy(3-vinylphenyl)silane, dimethylethoxy(3-vinylphenyl)silane silane, dimethylpropoxy(3-vinylphenyl)silane, dimethylbutoxy(3-vinyl phenyl)silane, dimethylisopropoxy(3-vinylphenyl)silane, dimethylmethyl ethoxy(2-vinylphenyl)silane, dimethylethoxy(2-vinylphenyl)silane , dimethylpropoxy(2-vinylphenyl)silane, dimethylbutoxy(2-vinylphenyl)silane dimethylisopropoxy(2-vinylphenyl)silane, trimethoxy (4-isopropenylphenyl)silane, triethoxy(4-isopropenylphenyl) Silane, tripropoxy(4-isopropenylphenyl)silane, tributoxy(4-isopropenylphenyl)silane Triisopropoxy(4-isopropenylphenyl)silane, triisopropoxy(4-isopropenylphenyl)silane Silane, trimethoxy(3-isopropenylphenyl)silane, triethoxy(3-isopropenylphenyl)silane tripropoxy(3-isopropenylphenyl)silane, ... Triisopropoxy(3-isopropenylphenyl)silane, Triisopropoxy(3-isopropenylphenyl)silane (2-isopropenylphenyl)silane, trimethoxy(2-isopropenylphenyl)silane, triethoxy(2-isopropenylphenyl)silane Tripropoxy(2-isopropenylphenyl)silane, tripropoxy(2-isopropenylphenyl)silane phenyl)silane, tributoxy(2-isopropenylphenyl)silane, triisopropanol Dimethoxy(2-isopropenylphenyl)silane, Dimethoxymethyl(4-isopropenylphenyl)silane (phenyl)silane, diethoxymethyl(4-isopropenylphenyl)silane, dipropoxy Dimethyl(4-isopropenylphenyl)silane, Dibutoxymethyl(4-isopropenylphenyl)silane diisopropoxymethyl(4-isopropenylphenyl)silane, diisopropoxymethyl(4-isopropenylphenyl)silane, Dimethoxymethyl(3-isopropenylphenyl)silane, diethoxymethyl(3-isopropenylphenyl)silane (3-isopropenylphenyl)silane, dipropoxymethyl (3-isopropenylphenyl)silane Dibutoxymethyl(3-isopropenylphenyl)silane, Diisopropoxymethyl (3-isopropenylphenyl)silane, dimethoxymethyl(2-isopropenylphenyl) (2-isopropenylphenyl)silane, diethoxymethyl(2-isopropenylphenyl)silane, dipropoxymethyl Dibutoxymethyl(2-isopropenylphenyl)silane, Dibutoxymethyl(2-isopropenylphenyl)silane (2-isopropenylphenyl)silane, diisopropoxymethyl (2-isopropenylphenyl)silane, dimethicone Dimethylmethoxy(4-isopropenylphenyl)silane, Dimethylethoxy(4-isopropenylphenyl)silane dimethylpropoxy(4-isopropenylphenyl)silane, dimethylpropoxy(4-isopropenylphenyl)silane, Dimethylbutoxy(4-isopropenylphenyl)silane, Dimethylisopropoxy(4 -isopropenylphenyl)silane, dimethylmethoxy(3-isopropenylphenyl) Silane, dimethylethoxy(3-isopropenylphenyl)silane, dimethylpropoxy (3-isopropenylphenyl)silane, dimethylbutoxy(3-isopropenylphenyl) Dimethylisopropoxy(3-isopropenylphenyl)silane, Dimethyl Methoxy(2-isopropenylphenyl)silane, dimethylethoxy(2-isopropenylphenyl)silane dimethylpropoxy(2-isopropenylphenyl)silane, dimethylpropoxy(2-isopropenylphenyl)silane, Dimethylbutoxy(2-isopropenylphenyl)silane, Dimethylisopropoxy(2-isopropenylphenyl)silane (isopropenylphenyl)silane, trichloro(4-vinylphenyl)silane, trichloro (3-vinylphenyl)silane, trichloro(2-vinylphenyl)silane, tribromo (4-vinylphenyl)silane, tribromo(3-vinylphenyl)silane, tribromo (2-vinylphenyl)silane, dichloromethyl(4-vinylphenyl)silane, dichloro Dichloromethyl(3-vinylphenyl)silane, Dichloromethyl(2-vinylphenyl)silane , dibromomethyl(4-vinylphenyl)silane, dibromomethyl(3-vinylphenyl)silane )silane, dibromomethyl(2-vinylphenyl)silane, dimethylchloro(4-vinyl phenyl)silane, dimethylchloro(3-vinylphenyl)silane, dimethylchloro(2 -vinylphenyl)silane, dimethylbromo(4-vinylphenyl)silane, dimethylbromo(4-vinylphenyl)silane, Bromo(3-vinylphenyl)silane and dimethylbromo(2-vinylphenyl)silane Examples include:

[0130] Among these, trimethoxy(4-vinylphenyl)silane, triethoxy(4-vinylphenyl)silane, (4-vinylphenyl)silane, tripropoxy(4-vinylphenyl)silane, tributoxy( (4-vinylphenyl)silane Triisopropoxy(4-vinylphenyl)silane, Trimethylsilane Triethoxy(3-vinylphenyl)silane, triethoxy(3-vinylphenyl)silane, triethoxy(3-vinylphenyl)silane, triethoxy(3-vinylphenyl)silane Tripropoxy(3-vinylphenyl)silane, Tributoxy(3-vinylphenyl)silane silane, triisopropoxy(3-vinylphenyl)silane, and trichloro(4-vinylphenyl)silane Preferred are trimethoxy(4-vinylphenyl)silane and triethoxy(4-vinylphenyl)silane. (4-vinylphenyl)silane, tripropoxy(4-vinylphenyl)silane, and tripropoxy(4-vinylphenyl)silane Butoxy(4-vinylphenyl)silane Triisopropoxy(4-vinylphenyl)silane Orchids are more preferable.

[0131] The branching agent represented by formula (2) is not particularly limited, but for example, 1,1-bis( 4-trimethoxysilylphenyl)ethylene, 1,1-bis(4-triethoxysilylphenyl)ethylene phenyl)ethylene, 1,1-bis(4-tripropoxysilylphenyl)ethylene, 1 ,1-bis(4-tripentoxysilylphenyl)ethylene, 1,1-bis(4-triyl) 1,1-bis(3-trimethoxysilylphenyl)ethylene, 1,1-bis(3-trimethoxysilylphenyl)ethylene 1,1-bis(3-triethoxysilylphenyl)ethylene, 1,1-bis(3-triethoxysilylphenyl)ethylene, bis(3-tripentoxysilylphenyl)ethylene, 1,1-bis(3-tripentoxysilylphenyl)ethylene 1,1-bis(3-triisopropoxysilylphenyl)ethylene, 1,1-bis(3-triisopropoxysilylphenyl) Ethylene, 1,1-bis(2-trimethoxysilylphenyl)ethylene, 1,1-bis( 2-triethoxysilylphenyl)ethylene, 1,1-bis(3-tripropoxysilyl) 1,1-bis(2-tripentoxysilylphenyl)ethylene, 1,1-bis(2-tripentoxysilylphenyl)ethylene, 1,1-bis(2-triisopropoxysilylphenyl)ethylene, 1,1-bis(4- (dimethylmethoxysilyl)phenyl)ethylene, 1,1-bis(4-(diethylmethoxysilyl)phenyl)ethylene 1,1-bis(4-(dipropylmethoxysilyl)phenyl)ethylene, 1,1-bis(4-(dipropylmethoxysilyl)phenyl)ethylene 1,1-bis(4-(dimethylethoxysilyl)phenyl)ethylene, 1,1-bis(4-(diethylethoxysilyl)phenyl)ethylene, and 1,1-bis (4-(dipropylethoxysilyl)phenyl)ethylene.

[0132] Among these, 1,1-bis(4-trimethoxysilylphenyl)ethylene, 1,1 -Bis(4-triethoxysilylphenyl)ethylene, 1,1-bis(4-tripropoxy) 1,1-bis(4-tripentoxysilylphenyl)ethylene, 1,1-bis(4-tripentoxysilylphenyl)ethylene ethylene, and 1,1-bis(4-triisopropoxysilylphenyl)ethylene are preferred. Of these, 1,1-bis(4-trimethoxysilylphenyl)ethylene is more preferred.

[0133] In the method for producing a conjugated diene polymer according to the present embodiment, the branching step for forming a branched structure The amount of the branching agent to be added is not particularly limited and can be selected depending on the purpose, etc. The amount is preferably 0.03 mol or more and 0.5 mol or less per mol of the initiator, and more preferably 0.0 It is more preferably 5 mol or more and 0.4 mol or less, and more preferably 0.01 mol or more and 0.25 mol or less. It's even better if it's below.

[0134] The branching agent acts as a branching point of the branched structure of the conjugated diene portion of the conjugated diene polymer, and An appropriate amount can be used depending on the number of branch points.

[0135] In the branching step, the timing of adding the branching agent is not particularly limited, and may be determined depending on the purpose, etc. However, it is possible to select the conjugated diene polymer by increasing the absolute molecular weight and the modification rate. From this viewpoint, the timing when the raw material conversion rate is 20% or more after adding the polymerization initiator is preferable, and 40 % or more is more preferable, 50% or more is even more preferable, and 65% or more is even more preferable. It is even more preferable that the ratio is 75% or more, and even more preferable that the ratio is 75% or more. In addition, after adding the branching agent, the desired raw material is further added, and the polymerization process is continued after branching. The above description may be repeated.

[0136] The monomer to be added is not particularly limited, but from the viewpoint of improving the modification rate of the conjugated diene polymer, The total amount of conjugated diene monomers used in the polymerization process, for example, the total amount of butadiene, is 5% or more. It is preferable that the ratio is 10% or more, more preferable that the ratio is 15% or more. It is preferably 20% or more, and even more preferably 25% or more and 30% or less. is even more preferred.

[0137] If the amount of added monomer is within the above range, the branching points by the branching agent and the branching points by the modifier are The molecular weight between branch points becomes longer and the molecule tends to have a highly linear molecular structure. By adopting this molecular structure, the molecular chains of the conjugated diene polymer are entangled when vulcanized. By increasing the amount of bale, cold flow is suppressed, and abrasion resistance, handling stability and breaking strength are improved. An excellent rubber composition tends to be easily obtained.

[0138] The conjugated diene polymer of the present embodiment is not particularly limited, and may be a polymer obtained by polymerizing a conjugated diene monomer and a branching agent. It may be a polymer of a conjugated diene monomer, a branching agent and a monomer other than these. For example, the conjugated diene monomer may be butadiene or isoprene. When this is polymerized with a branching agent containing a vinyl aromatic moiety, the polymer chain becomes what is called a poly Butadiene or polyisoprene, polymers containing a vinyl aromatic structure in the branched portion This structure improves the linearity of each polymer chain and This has the effect of improving the crosslink density after vulcanization, thereby improving the abrasion resistance. Conjugated diene polymers in this form are used in tires, resin modification, automobile interior and exterior parts, vibration-proof rubber, It is suitable for use in footwear and the like.

[0139] When the conjugated diene polymer is used for the tread of a tire with high load, the conjugated diene monomer Copolymers of the copolymer with a branching agent are preferred.

[0140] (Denaturation process) In the method for producing a conjugated diene polymer of this embodiment, the above-mentioned polymerization and branching steps are a modification step of modifying the conjugated diene polymer obtained through the above process with a modifying agent having a nitrogen-containing group. (hereinafter, also referred to simply as "modification step").

[0141] In the modification step, a nitrogen-containing group is attached to one of the active terminals of the conjugated diene polymer. A conjugated diene polymer is obtained by a modification reaction using a modifying agent.

[0142] The reaction temperature in the modification step is preferably the same as the polymerization temperature of the conjugated diene polymer. It is more preferable that the temperature is 0°C or higher and 120°C or lower, and more preferably 50°C or higher and 1 It is below 00℃.

[0143] The reaction time in the modification step is preferably 10 seconds or more, more preferably 30 seconds or more. The applicant shall be required to comply with the requirements.

[0144] The mixing in the modification process can be carried out by mechanical stirring or by a static mixer. That's fine too.

[0145] When the polymerization step is continuous, it is preferred that the modification step is also continuous.

[0146] The reactor used in the modification step may be, for example, a tank type or a tubular type equipped with a stirrer. The modifier may be diluted with an inert solvent and continuously fed to the reactor. In the case of a separate polymerization system, the modifier may be directly added to the polymerization reactor, or may be transferred to a separate reactor. The modification step may be carried out in this manner.

[0147] The time from the polymerization step to the modification step is preferably short, preferably within 10 minutes, more preferably In this case, a conjugated diene polymer with high modification efficiency tends to be obtained. .

[0148] The time from the polymerization step to the modification step is, for example, the time from the peak of polymerization when the polymerization step is a batch process. This indicates the time from when the temperature is reached to when the modifier is added. If the polymerization process is continuous, This refers to the time it takes for the modifier to be added to the solution containing the conjugated diene polymer that has left the reactor. .

[0149] <Denaturant> The nitrogen atom-containing modifier is not particularly limited, but examples thereof include isocyanates. isocyanate compounds, isocyanuric acid derivatives, nitrogen atom group-containing compounds Examples of the compounds include carbonyl compounds, nitrogen atom group-containing vinyl compounds, and nitrogen atom group-containing epoxy compounds. It can be obtained.

[0150] The isocyanate compound, which is a modifying agent having a nitrogen atom-containing group, is particularly limited. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, cyanate, diphenylmethane diisocyanate, polymeric type diphenylmethane Diisocyanate (C-MDI), Phenylisocyanate, Isophoronediisocyanate hexamethylene diisocyanate, butyl isocyanate, and 1,3,5-benzophenone Examples include diisocyanate.

[0151] The isothiocyanate compound, which is a modifying agent having a nitrogen atom-containing group, is not particularly limited. However, for example, butyl isothiocyanate, cyclohexyl isothiocyanate, ester, phenyl isothiocyanate, 2-chlorophenyl isothiocyanate, benzyl isothiocyanate, 2,6-diisopropylphenyl isothiocyanate, and 1,4 -phenylene diisothiocyanate.

[0152] The isocyanuric acid derivative, which is a modifying agent having a nitrogen atom-containing group, is particularly limited. However, for example, 1,3,5-tris(3-trimethoxysilylpropyl)iso Cyanurate, 1,3,5-tris(3-triethoxysilylpropyl) isocyanurate 1,3,5-tri(oxiran-2-yl)-1,3,5-triazinane-2,4, 6-trione, 1,3,5-tris(isocyanatomethyl)-1,3,5-triazinane -2,4,6-trione, and 1,3,5-trivinyl-1,3,5-triazinane-2 ,4,6-trione.

[0153] As the nitrogen atom-containing carbonyl compound, which is a modifying agent having a nitrogen atom-containing group, particularly Examples include, but are not limited to, 1,3-dimethyl-2-imidazolidinone, 1-methyl-2-imidazolidinone, 1-methyl-3-(2-methoxyethyl)-2-imidazolidinone 2-Imidazolidinone, N-Methyl-2-pyrrolidone, N-Methyl-2-piperidone, N -methyl-2-quinolone, 4,4'-bis(diethylamino)benzophenone, 4,4' -Bis(dimethylamino)benzophenone, methyl-2-pyridyl ketone, methyl-4- Pyridyl ketone, propyl-2-pyridyl ketone, di-4-pyridyl ketone, 2-benzo Ilpyridine, N,N,N',N'-tetramethylurea, N,N-dimethyl-N',N' -Diphenylurea, N,N-diethylcarbamate methyl, N,N-diethylacetamide N,N-dimethyl-N',N'-dimethylaminoacetamide, N,N-dimethylpi Examples include choline acid amide and N,N-dimethylisonicotinamide.

[0154] The vinyl compound as a modifying agent having a nitrogen atom-containing group is not particularly limited. However, for example, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide , N-methylmaleimide, N-methylphthalimide, N,N-bistrimethylsilyl acrylate acrylamide, morpholinoacrylamide, 3-(2-dimethylaminoethyl)styrene, (Dimethylamino)dimethyl-4-vinylphenylsilane, 4,4'-vinylidenebis( N,N-dimethylaniline), 4,4'-vinylidenebis(N,N-diethylaniline) , 1,1-bis(4-morpholinophenyl)ethylene, 1-phenyl-1-(4-N,N -dimethylaminophenyl)ethylene and the like.

[0155] The epoxy compound that is a modifier having a nitrogen atom-containing group is not particularly limited. Although there are no particular examples, examples thereof include hydrocarbon compounds containing an epoxy group bonded to an amino group. The epoxy compound may have an epoxy group bonded to an ether group. Although not limited to the following, for example, an epoxy compound represented by general formula (i) Examples include:

[0156] [ka] In the formula, R is a hydrocarbon group having two or more valences, or an oxygen-containing group such as ether, epoxy, or ketone. polar groups containing sulfur, such as thioethers and thioketones, and tertiary amino groups, a divalent or higher valent group having at least one polar group selected from nitrogen-containing polar groups such as an amino group; Indicates an organic group.

[0157] The divalent or higher hydrocarbon group may be saturated or unsaturated, linear, branched or cyclic. It is a hydrogen group, and includes an alkylene group, an alkenylene group, a phenylene group, etc. Preferably, It is a hydrocarbon group with a prime number of 1 to 20. For example, methylene, ethylene, butylene, cyclohexane, etc. Xylene, 1,3-bis(methylene)-cyclohexane, 1,3-bis(ethylene)-cyclohexane Cyclohexane, o-, m-, p-phenylene, m-, p-xylene, bis(phenylene) -Methane, etc.

[0158] In formula (i), R 1 and R 4 each represents a hydrocarbon group having 1 to 10 carbon atoms, and R 1 and R 4 may be the same or different from each other.

[0159] In formula (i), R 2 and R 5 each represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R 5 may be the same or different from each other.

[0160] In formula (i), R 3 represents a hydrocarbon group having 1 to 10 carbon atoms, or a structure of the following formula (ii):

[0161] R 1 , R 2 , and R 3 may be bonded to each other to form a cyclic structure.

[0162] Also, R 3 When R represents a hydrocarbon group, it may be bonded to R to form a cyclic structure. In the case of the cyclic structure shown above, R 3 The N bonded to R may be directly bonded to the N bonded to R. stomach.

[0163] In formula (i), n represents an integer of 1 or more, and m represents 0 or an integer of 1 or more. [ka]

[0164] In formula (ii), R 1 and R 2 is R in formula (i). 1 and R 2 is defined similarly to R 1 and R 2 teeth They may be the same or different from each other.

[0165] The epoxy compound, which is a modifying agent having a nitrogen atom-containing group, includes epoxy group-containing hydrocarbons. Those having a hydrocarbon group containing a glycidyl group are preferred, and those having a hydrocarbon group containing a glycidyl group are more preferred. is.

[0166] The epoxy group-containing hydrocarbon group bonded to an amino group or an ether group is not particularly limited. Examples of the alkyl group include, but are not limited to, a glycidylamino group, a diglycidylamino group, and a glycidoxy group. More preferred molecular structures include a glycidylamino group or a diglycidylamino group, and glycidoxy groups, and the epoxy group-containing compound is represented by the following general formula (ii i) is a compound represented by the formula:

[0167] [ka] In formula (iii), R is defined as R in formula (i) above, and R 6 has 1 to 10 carbon atoms or a structure of the following formula (iv):

[0168] R 6 When represents a hydrocarbon group, it may be bonded to R to form a cyclic structure. is R 6 The N bonded to R may be directly bonded to the N bonded to R. In formula (iii), n represents an integer of 1 or more, and m represents 0 or an integer of 1 or more.

[0169] [ka]

[0170] As the epoxy compound which is a modifying agent having a nitrogen atom-containing group, particularly preferred is a compound having a nitrogen atom-containing group in the molecule It is a compound having one or more diglycidylamino groups and one or more glycidoxy groups.

[0171] Specific examples of epoxy compounds used as modifiers having a nitrogen atom-containing group include N,N -Diglycidyl-4-glycidoxyaniline, 1-N,N-diglycidylaminomethyl- 4-Glycidoxy-cyclohexane, 4-(4-glycidoxyphenyl)-(N,N-di Glycidyl)aniline, 4-(4-glycidoxyphenoxy)-(N,N-diglycidyl ) aniline, 4-(4-glycidoxybenzyl)-(N,N-diglycidyl)aniline, 4-(N,N'-diglycidyl-2-piperazinyl)-glycidoxybenzene, 1,3- Bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetramethyl Diglycidyl-m-xylenediamine, 4,4-methylene-bis(N,N-diglycidyl aniline), 1,4-bis(N,N-diglycidylamino)cyclohexane, N,N,N ',N'-Tetraglycidyl-p-phenylenediamine, 4,4'-bis(diglycidyl Amino)benzophenone, 4-(4-glycidylpiperazinyl)-(N,N-diglycidyl 2-[2-(N,N-diglycidylamino)ethyl]-1-glycidylpyridine Roridin, N,N-diglycidylaniline, 4,4'-diglycidyl-dibenzylmethyl amines, N,N-diglycidylaniline, N,N-diglycidylorthotoluidine, and Among these, N,N-diglycidylaminomethylcyclohexane is preferred. Examples include N,N-diglycidyl-4-glycidoxyaniline, 1,3-bis(N ,N-diglycidylaminomethyl)cyclohexane.

[0172] The modifier having a nitrogen atom-containing group is also preferably an amine compound having no active hydrogen. For example, tertiary amine compounds, protected amine compounds in which the active hydrogen is substituted with a protecting group, an imine compound represented by the general formula -N=C (a compound represented by the general formula (D) described later); and alkoxysilane compounds bonded to a nitrogen atom-containing group.

[0173] Modifiers with nitrogen-containing groups that can form primary or secondary amines. As a compound having an unsaturated bond and a protected amine in the molecule, there is no particular limitation. Although it is not intended to be used as a polymer, for example, 4,4'-vinylidenebis[N,N-bis(trimethylsilyl) 4,4'-vinylidenebis[N,N-bis(triethylsilyl)aniline], 4,4'-vinylidenebis[N,N-bis(t-butyldimethylsilyl)aniline ], 4,4'-vinylidenebis〔N-methyl-N-(trimethylsilyl)aniline〕, 4, 4'-Vinylidenebis[N-ethyl-N-(trimethylsilyl)aniline], 4,4'- Vinylidenebis[N-methyl-N-(triethylsilyl)aniline], 4,4'-vinylidene Denbis[N-ethyl-N-(triethylsilyl)aniline], 4,4'-vinylidene bis[N-methyl-N-(t-butyldimethylsilyl)aniline], 4,4'-vinylidene Bis[N-ethyl-N-(t-butyldimethylsilyl)aniline], 1-[4-N,N- bis(trimethylsilyl)aminophenyl)-1-[4-N-methyl-N-(trimethyl silyl)aminophenyl]ethylene, and 1-[4-N,N-bis(trimethylsilyl) [4-N,N-dimethylaminophenyl]ethylene .

[0174] Modifiers with nitrogen-containing groups that can form primary or secondary amines. As a compound having an alkoxysilane and a protected amine in the molecule, there is no particular limitation. Although not limited thereto, for example, N,N-bis(trimethylsilyl)aminopropyl Trimethoxysilane, N,N-bis(trimethylsilyl)aminopropylmethyldimethoxy Silane, N,N-bis(trimethylsilyl)aminopropyltriethoxysilane, N,N -Bis(trimethylsilyl)aminopropylmethyldiethoxysilane, N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane (trimethylsilyl)aminoethyltrimethoxysilane, N,N-bis(trimethylsilyl) Aminoethylmethyldiethoxysilane, N,N-bis(triethylsilyl)aminopropyl Dimethyldiethoxysilane, 3-(4-trimethylsilyl-1-piperazino)propyl Iethoxysilane, 3-(3-triethylsilyl-1-imidazolidinyl)propylmethyl Diethoxysilane, 3-(3-trimethylsilyl-1-hexahydropyrimidinyl)propanol Propyltrimethoxysilane, 2,2-dimethoxy-1-(3-trimethoxysilylpropyl) 2,2-diethoxy-1-(3-triethoxy)-1-aza-2-silacyclopentane, silylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-( 4-trimethoxysilylbutyl)-1-aza-2-silacyclohexane, 2,2-dimeth 1-(3-dimethoxymethylsilylpropyl)-1-aza-2-silacyclopentasilane 2,2-dimethoxy-1-phenyl-1-aza-2-silacyclopentane, 2,2- Diethoxy-1-butyl-1-aza-2-silacyclopentane, and 2,2-dimethoxy -1-methyl-1-aza-2-silacyclopentane.

[0175] Modifiers with nitrogen atom-containing groups, as alkoxysilane compounds with tertiary amines is not particularly limited, but for example, 3-dimethylaminopropyltrimethoxy Silane, 3-dimethylaminopropylmethyldimethoxysilane, 3-diethylaminopropyl Pyrithoxysilane, 3-morpholinopropyltrimethoxysilane, 3-piperidino Propyltriethoxysilane, 3-hexamethyleneiminopropylmethyldiethoxysilane silane, 3-(4-methyl-1-piperazino)propyltriethoxysilane, 1-[3-(triethoxysilane) 3-(4-(tri-(2 ... Methylsilyl-1-piperazino)propyltriethoxysilane, 3-(3-triethylsilane (3-(3-trimethyl)-1-imidazolidinyl)propylmethyldiethoxysilane Silyl-1-hexahydropyrimidinyl)propyltrimethoxysilane, 3-dimethyl 2-(dimethylaminomethyl)propyltrimethoxysilane, bis(3-dimethylaminomethyl)propyltrimethoxysilane Bis(3-trimethoxysilylpropyl)-N-methylamine )-N-methylamine, bis(3-triethoxysilylpropyl)methylamine, tris (Trimethoxysilyl)amine, Tris(3-trimethoxysilylpropyl)amine, N ,N,N',N'-tetra(3-trimethoxysilylpropyl)ethylenediamine, 3- Isocyanatopropyltrimethoxysilane, 3-cyanopropyltrimethoxysilane, 2 ,2-Dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silicic 2,2-diethoxy-1-(3-triethoxysilylpropyl)-1-aza -2-Silacyclopentane, 2,2-dimethoxy-1-(4-trimethoxysilylbutyl )-1-Aza-2-silacyclohexane, 2,2-dimethoxy-1-(3-dimethoxymethyl (silylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1- Phenyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-butyl-1- Aza-2-silacyclopentane, 2,2-dimethoxy-1-methyl-1-aza-2-sila Cyclopentane, 2,2-dimethoxy-8-(4-methylpiperazinyl)methyl-1,6 -Dioxa-2-silacyclooctane, 2,2-dimethoxy-8-(N,N-diethyl) and (amino)methyl-1,6-dioxa-2-silacyclooctane.

[0176] Particularly preferred modifiers having a nitrogen atom-containing group include alkoxysilanes having a tertiary amine. The amine compounds include tris(3-trimethoxysilylpropyl)amine, tris(3-trimethoxysilylpropyl)amine, Tris(3-tripropoxysilylpropyl)amine, Tris(3-tripropoxysilylpropyl)amine bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-azabicyclo[2,3-dimethyl-2,4-dioxo-1,4-dione] -2-silacyclopentane)propyl]amine, tetrakis(3-trimethoxysilylpropyl)amine propyl)-1,3-propanediamine, tris(3-trimethoxysilylpropyl)-[ 3-(1-Methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propanol Pyr]-1,3-propanediamine, tris(3-trimethoxysilylpropyl)-[3 -(1-methoxy-2-methyl-1-sila-2-azacyclopentane)propyl]-1, 3-Propanediamine, bis(3-triethoxysilylpropyl)-[3-(2,2-di Ethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-ethoxy-2 -trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-propane Diamine, tetrakis(3-trimethoxysilylpropyl)-1,3-bisaminomethyl cyclohexane, tris(3-trimethoxysilylpropyl)-[3-(2,2-dimethylsilyl)propyl]- [1-(2-(silacyclopentane)propyl]-1,3-bisaminomethylsilyl] Cyclohexane, tetrakis(3-trimethoxysilylpropyl)-1,6-hexamethylene diamine, pentakis(3-trimethoxysilylpropyl)-diethylenetriamine, Tris(3-trimethoxysilylpropyl)-methyl-1,3-propanediamine, tetramethyl Rachis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane Ran, bis(3-trimethoxysilylpropyl)-bis[3-(2,2-dimethoxy-1 -aza-2-silacyclopentane)propyl]silane, tris[3-(2,2-dimethox [3-(1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl silane, tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane Propyl]-[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopropyl pentane)propyl]silane, 3-tris[2-(2,2-dimethoxy-1-aza-2- Silacyclopentane)ethoxy]silyl-1-trimethoxysilylpropane, 1-[3- (1-Methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl ]-3,4,5-tris(3-trimethoxysilylpropyl)-cyclohexane, 1-[ 3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-3,4, 5-Tris(3-trimethoxysilylpropyl)-cyclohexane, 3,4,5-tris (3-trimethoxysilylpropyl)-cyclohexyl-[3-(2,2-dimethoxy- 1-Aza-2-silacyclopentane)propyl]ether, (3-trimethoxysilylpropyl) propyl) phosphate, bis(3-trimethoxysilylpropyl)-[3-(2,2-di methoxy-1-aza-2-silacyclopentane)propyl]phosphate, bis[3-( 2,2-Dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimetho hydroxysilylpropyl) phosphate, and tris[3-(2,2-dimethoxy-1-azabicyclo ... -2-silacyclopentane)propyl]phosphate.

[0177] (Preferred Structure of Conjugated Diene Polymer) The conjugated diene polymer of the present embodiment is represented by the following general formula (i) or any one of (A) to (E): It is preferable that the compound contains a structure derived from a compound having a nitrogen atom-containing group, as represented by the following formula: The general formula (i) below is the same as that of the epoxy compound represented by the general formula (i) above. The same applies to the general formula (i) and the general formula (ii). The compound having a nitrogen atom-containing group is used to produce a conjugated diene polymer having a desired degree of branching. From the viewpoint of obtaining a desired nitrogen atom, one type may be used alone, or two or more types of compounds having a nitrogen atom-containing group may be used. The substances may be used in combination.

[0178] [ka] In the formula, R 1 ~R 4 are each independently an alkyl group having 1 to 20 carbon atoms or a group having 6 to 20 carbon atoms. R 5 represents an alkylene group having 1 to 10 carbon atoms, and R 6 is a compound with 1 to 10 carbon atoms. 20 alkylene groups. m represents an integer of 1 or 2, n represents an integer of 2 or 3, and (m+n) represents an integer of 4 or more. Indicates an integer. R when there are multiple integers 1 ~R 4 are each independent of each other.

[0179] [ka] In the formula, R 1 ~R 6 are each independently an alkyl group having 1 to 20 carbon atoms or a represents an aryl group, and R 7 ~R 9 are each independently an alkylene group having 1 to 20 carbon atoms. m, n, and l each independently represent an integer of 1 to 3, and (m+n+l) is 4 or more. Indicates an integer. R when there are multiple integers 1 ~R 6 are each independent of each other.

[0180] [ka] In the formula, R 12 ~R 14 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, R 15 ~R 18 and R20 each independently represent an alkyl group having 1 to 20 carbon atoms; R 19 and R 22 each independently represents an alkylene group having 1 to 20 carbon atoms; R 21 is a compound with 1 to 20 carbon atoms It represents an alkyl group or a trialkylsilyl group. m represents an integer of 1 to 3; p represents 1 or 2; R when there are multiple of each 12 ~R 22 , m, and p are each independent and the same. may be different. i represents an integer from 0 to 6, j represents an integer from 0 to 6, and k represents an integer from 0 to 6; (i+j+k) is an integer between 4 and 10. A is a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen atom, a nitrogen atom, a silicon atom, or a sulfur atom. and phosphorus atoms, and has no active hydrogen. or represents any of the general formulae (II) to (V) described below.

[0181] [ka] R in the formula 1 and R 4 each independently represents an alkylene group having 1 to 20 carbon atoms or a 0 alkyl group, and R 2 and R 5 are each independently an alkyl group having 1 to 20 carbon atoms, or represents an aryl group having 6 to 20 carbon atoms, and R 3 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms. vinegar. n represents an integer of 1 to 3. When a plurality of R 1 ~R 5 are each independent of each other.

[0182] [ka] R in the formula 1 ~R 4 are each independently an alkyl group having 1 to 20 carbon atoms or a represents an aryl group, and R 5 ~R 7 each independently represents an alkylene group having 1 to 20 carbon atoms. m and n each represent an integer of 1 to 3 and may be the same or different. 1 ~R 7 are each independent of each other.

[0183] The modifying agent having a nitrogen atom-containing group represented by formula (A) is not particularly limited, but examples thereof include: For example, 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-trimethoxysilyl) (butyl)-1-aza-2-silacyclohexane, 2,2-dimethoxy-1-(5-trimethylbutyl)-1-aza-2-silacyclohexane, Methoxysilylpentyl)-1-aza-2-silacycloheptane, 2,2-dimethoxy- 1-(3-dimethoxymethylsilylpropyl)-1-aza-2-silacyclopentane, 2 ,2-diethoxy-1-(3-diethoxyethylsilylpropyl)-1-aza-2-sila Cyclopentane, 2-methoxy, 2-methyl-1-(3-trimethoxysilylpropyl) -1-Aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-1-(3-triethoxy) (xysilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy, 2-methyl -1-(3-dimethoxymethylsilylpropyl)-1-aza-2-silacyclopentane, and 2-ethoxy, 2-ethyl-1-(3-diethoxyethylsilylpropyl)-1-a Examples include 2-silacyclopentane.

[0184] Among these, the functional group of the modifier having a nitrogen atom-containing group and the inorganic filler such as silica are preferred. From the viewpoints of reactivity and interactivity, as well as processability, it is preferable that m is 2 and n is 3. Specifically, 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)- 1-Aza-2-silacyclopentane and 2,2-diethoxy-1-(3-triethoxy) Silylpropyl)-1-aza-2-silacyclopentane is preferred.

[0185] When a modifying agent having a nitrogen atom-containing group represented by formula (A) is reacted with an active polymerization terminal, The reaction temperature, reaction time, etc. are not particularly limited, but are preferably from 0°C to 120°C, It is preferable to react for 0 seconds or more.

[0186] The alkyl group bonded to the silyl group in the modifying compound having the nitrogen atom-containing group represented by formula (A) The total number of moles of alkoxy groups is determined by the amount of the alkali metal compound and / or alkaline earth metal compound of the polymerization initiator. The amount of the metal compound added is preferably in the range of 0.6 to 3.0 times the molar number of the metal compound added. A range of 0.8 to 2.5 times is more preferable, and a range of 0.8 to 2.0 times is more preferable. It is more preferable that the range is such that the obtained conjugated diene polymer has a sufficient degree of modification and From the viewpoint of obtaining a good molecular weight and branched structure, it is preferable to set the ratio at 0.6 times or more. Therefore, it is preferable to couple the polymer ends together to obtain a branched polymer component. Additionally, from the viewpoint of the cost of the modifier, it is preferable to set the ratio to 3.0 times or less.

[0187] More specifically, the number of moles of the polymerization initiator is preferably 3.0 times the number of moles of the modifying agent. The molar ratio is preferably 4.0 times or more, more preferably 4.0 times or more.

[0188] The modifying agent having a nitrogen atom-containing group represented by formula (B) is not particularly limited, but examples thereof include For example, tris(3-trimethoxysilylpropyl)amine, tris(3-methyldimethoxy Tris(3-triethoxysilylpropyl)amine, Tris(3-triethoxysilylpropyl)amine, Tris (3-Methyldiethoxysilylpropyl)amine, Tris(trimethoxysilylmethyl) Amine, tris(2-trimethoxysilylethyl)amine, and tris(4-trimethoxysilyl)amine and silylbutylamine.

[0189] Among these, the reactivity and interaction between the functional groups of the modifier and inorganic fillers such as silica are important. From the viewpoint of the polymerizable composition and the processability, it is preferable that n, m, and l all represent 3. Preferred examples include tris(3-trimethoxysilylpropyl)amine, and Tris(3-triethoxysilylpropyl)amine is an example.

[0190] When a modifying agent having a nitrogen atom-containing group represented by formula (B) is reacted with a polymerization active terminal, The reaction temperature, reaction time, etc. are not particularly limited, but are preferably from 0°C to 120°C, It is preferable to react for 0 seconds or more.

[0191] The total number of moles of alkoxy groups bonded to silyl groups in the modifying compound represented by formula (B) is 0.6 to 3.0 times the number of moles of lithium constituting the polymerization initiator. It is preferable that the ratio is in the range of 0.8 times or more and 2.5 times or less. The range is preferably 0.8 times or more and more preferably 2.0 times or less. In order to obtain a sufficient modification rate, molecular weight and branched structure in the polymer, the ratio is set to 0.6 times or more. It is preferable to couple the polymer ends together to form a branched polymer for improved processability. In addition to the fact that it is preferable to obtain the desired component, from the viewpoint of the cost of the denaturant, it is preferable to keep the ratio at 3.0 times or less. It is preferable that:

[0192] More specifically, the number of moles of the polymerization initiator is preferably 4.0 times the number of moles of the modifying agent. The molar ratio is preferably 5.0 times or more, more preferably 5.0 times or more.

[0193] In formula (C), A is preferably represented by any one of the following general formulae (II) to (V): do. [ka] In the formula, B 1 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and a is an integer of 1 to 10. If there are multiple B 1 are each independent of each other.

[0194] [ka] In formula (III), B 2 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, B 3 is carbon represents an alkyl group having a number of 1 to 20, and a represents an integer of 1 to 10. B in combination 2 and B 3 are each independent of each other.

[0195] [ka] In formula (IV), B 4 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and a represents 1 to 1 Indicates an integer of 0. If there are multiple B 4 are each independent of each other.

[0196] [ka] In formula (V), B 5 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and a represents 1 to 10 If there are multiple integers, B 5 are each independent of each other.

[0197] In formula (C), a modifying agent having a nitrogen atom-containing group when A is represented by formula (II) Examples of the silyl group include, but are not limited to, tris(3-trimethoxysilylpropyl)amine. bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-azabicyclo[2,3-dimethyl-2,4-dioxo-1,4-dione] -2-silacyclopentane)propyl]amine, bis[3-(2,2-dimethoxy-1- aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)amine Tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl ]amine, tris(3-ethoxysilylpropyl)amine, bis(3-triethoxysilyl) (2,2-diethoxy-1-aza-2-silacyclopentane)propyl bis[3-(2,2-diethoxy-1-aza-2-silacyclopentane) Propyl]-(3-triethoxysilylpropyl)amine, tris[3-(2,2-diene thoxy-1-aza-2-silacyclopentane)propyl]amine, tetrakis(3-tri methoxysilylpropyl)-1,3-propanediamine, tris(3-trimethoxysilylpropyl)-1,3-propanediamine (2,2-dimethoxy-1-aza-2-silacyclopentane)propyl propyl]-1,3-propanediamine, bis(3-trimethoxysilylpropyl)-bis[ 3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3- Propanediamine, tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentasilane] [3-(3-methyl-2-methylpropyl)-1,3-propanediamine]-(3-trimethoxysilylpropyl)-1,3-propanediamine, Tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl] ]-1,3-propanediamine, tris(3-trimethoxysilylpropyl)-[3-( 1-Methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl] -1,3-propanediamine, bis(3-trimethoxysilylpropyl)-[3-(2, 2-dimethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-methoxy 2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3- Propanediamine, bis[3-(2,2-dimethoxy-1-aza-2-silacyclopenta[ -(3-trimethoxysilylpropyl)-[3-(1-methoxy-2-methylpropyl)- Trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-propanedi Amine, tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propane] pyryl]-[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopenta[3-(1-methoxy-2-trimethylsilyl) ... Tetrakis(3-triethoxysilyl)propyl]-1,3-propanediamine propyl)-1,3-propanediamine, tris(3-triethoxysilylpropyl)-[ 3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-1,3- Propanediamine, bis(3-triethoxysilylpropyl)-bis[3-(2,2-di Ethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine , tris[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl] -(3-triethoxysilylpropyl)-1,3-propanediamine, tetrakis[3- (2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-1,3-pro Pandiamine, tris(3-triethoxysilylpropyl)-[3-(1-ethoxy-2 -trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-propane Diamine, bis(3-triethoxysilylpropyl)-[3-(2,2-diethoxy- 1-Aza-2-silacyclopentane)propyl]-[3-(1-ethoxy-2-trimethyl [(1-sila-2-azacyclopentane)propyl]-1,3-propanediamine , bis[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]- (3-triethoxysilylpropyl)-[3-(1-ethoxy-2-trimethylsilyl- 1-Sila-2-azacyclopentane)propyl]-1,3-propanediamine, tris[ 3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-[3-( 1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl] -1,3-Propanediamine, Tetrakis(3-trimethoxysilylpropyl)-1,3 -bisaminomethylcyclohexane, tris(3-trimethoxysilylpropyl)-[3 -(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-bi bis(3-trimethoxysilylpropyl)-bis[3- (2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-bis Aminomethylcyclohexane, tris[3-(2,2-dimethoxy-1-aza-2-sila] Cyclopentane)propyl]-(3-trimethoxysilylpropyl)-1,3-bis(amino) Monomethylcyclohexane, tetrakis[3-(2,2-dimethoxy-1-aza-2-sila] cyclopentane)propyl]-1,3-propanediamine, tris(3-trimethoxysilane) (3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyl)- cyclohexane, bis(3-trimethylcyclohexane)propyl]-1,3-bisaminomethylcyclohexane methoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentasilane methylsilyl)-[3-(1-methoxy-2-trimethylsilyl-1-sila-2-yl]- cyclopentane)propyl]-1,3-bisaminomethylcyclohexane, bis[3- (2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethyl (3-(1-methoxy-2-trimethylsilylpropyl)-[3-(1-methoxy-2-trimethylsilyl-1-sila-2 -azacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, tris [3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-[3- (1-Methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl ]-1,3-bisaminomethylcyclohexane, tetrakis(3-triethoxysilylpropionate) propyl)-1,3-propanediamine, tris(3-triethoxysilylpropyl)-[ 3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-1,3- Bisaminomethylcyclohexane, bis(3-triethoxysilylpropyl)-bis[3 -(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-1,3-bi bisaminomethylcyclohexane, tris[3-(2,2-diethoxy-1-aza-2-cyclohexane [cyclopentane)propyl]-(3-triethoxysilylpropyl)-1,3-propane diamine, tetrakis[3-(2,2-diethoxy-1-aza-2-silacyclopenta[ Tris(3-triethoxysilylpropyl)-1,3-propanediamine )-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane )propyl]-1,3-bisaminomethylcyclohexane, bis(3-triethoxysilyl) (3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl)-[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl] pyryl]-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopenta[3-(1-ethoxy-2-trimethylsilyl) ... bis[3-(2,2-diaminomethylcyclohexane, 2,2-dimethyl-2,2-dimethyl-1,3 ... Ethoxy-1-aza-2-silacyclopentane)propyl]-(3-triethoxysilyl Propyl)-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopropyl pentane)propyl]-1,3-bisaminomethylcyclohexane, tris[3-(2, 2-diethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-ethoxy 2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3- Bisaminomethylcyclohexane, tetrakis(3-trimethoxysilylpropyl)-1 , 6-hexamethylenediamine, and pentakis(3-trimethoxysilylpropyl)- Diethylenetriamine is an example.

[0198] In the formula (C), a modifying agent having a nitrogen atom-containing group when A is represented by the formula (III) Although not particularly limited, examples thereof include tris(3-trimethoxysilylpropyl)- Methyl-1,3-propanediamine, bis(2-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-methyl-1, 3-Propanediamine, bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentadiene] [3-(trimethoxysilylpropyl)-methyl-1,3-propane] Diamine, tris(3-triethoxysilylpropyl)-methyl-1,3-propanedia amine, bis(2-triethoxysilylpropyl)-[3-(2,2-diethoxy-1- The-2-silacyclopentane)propyl]-methyl-1,3-propanediamine, bis[ 3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-(3- N-(ethoxysilylpropyl)-methyl-1,3-propanediamine 1 ,N 1 '-(professional Pan-1,3-diyl)bis(N 1 -methyl-N 3 ,N 3 -bis(3-(trimethoxysilyl) (N-propyl)-1,3-propanediamine), and N 1 -(3-(bis(3-(trimmed (N-(2-hydroxysilyl)propyl)amino)propyl)-N 1 -methyl-N 3 -(3-(methyl(3 -(trimethoxysilyl)propyl)amino)propyl)-N 3 -(3-(trimethoxy Silyl)propyl)-1,3-propanediamine.

[0199] In formula (C), a modifying agent having a nitrogen atom-containing group when A is represented by formula (IV) Examples of suitable amines include, but are not limited to, tetrakis[3-(2,2-dimethoxy-1-azabicyclo[2,2-diyl]methyl] and tetrakis[3-(2,2-dimethoxy-1-azabicyclo[2,2-diyl]methyl]methyl]. thia-2-silacyclopentane)propyl]silane, tris[3-(2,2-dimethoxy- 1-Aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl) Silane, tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)pro pyryl]-[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopenta[3-(1-methoxy-2-trimethylsilyl) ... bis(3-trimethoxysilylpropyl)-bis[3-(2, 2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane, (3-trimethylsilane 3-(1-methoxy-2-trimethylsilyl)-[3-(1-methoxy-2-trimethylsilyl)-1-sila-2-azacyl cyclopentane)-bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane )propyl]silane, bis[3-(1-methoxy-2-trimethylsilyl-1-sila-2 -azacyclopentane)-bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane] pentane)propyl]silane, tris(3-trimethoxysilylpropyl)-[3-(2 ,2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane, bis(3- Trimethoxysilylpropyl)-[3-(1-methoxy-2-trimethylsilyl-1-silyl 1-(2,2-dimethoxy-1-aza-2-cyclopentane)propyl]-[3-(2,2-dimethoxy-1-aza-2-cyclopentane)propyl]- -silacyclopentane)propyl]silane, bis[3-(1-methoxy-2-trimethyl Silyl-1-sila-2-azacyclopentane)propyl]-bis(3-trimethoxysilyl silane, and bis(3-trimethoxysilylpropyl)-bis[3-(1- Examples include methoxy-2-methyl-1-sila-2-azacyclopentanepropyl]silane. can be.

[0200] In the formula (C), when A is represented by the formula (V), the modifying agent having a nitrogen atom-containing group is Examples of suitable amines include, but are not limited to, 3-tris[2-(2,2-dimethoxy-1-azabicyclo ... -2-silacyclopentane)ethoxy]silyl-1-(2,2-dimethoxy-1-aza- 2-silacyclopentane)propane, and 3-tris[2-(2,2-dimethoxy-1- Aza-2-silacyclopentane)ethoxy]silyl-1-trimethoxysilylpropane Examples include:

[0201] In formula (C), A is preferably represented by formula (II) or formula (III), and k is 0. Shows.

[0202] Modifiers having such nitrogen atom-containing groups tend to be readily available and are also easy to use. When a diene polymer is vulcanized, it has good abrasion resistance and low hysteresis loss. The modifiers having such a nitrogen atom-containing group are particularly For example, but not limited to, bis(3-trimethoxysilylpropyl)-[3-(2,2 -dimethoxy-1-aza-2-silacyclopentane)propyl]amine, tris(3- Tris(3-triethoxysilylpropyl)amine, Tris(3-triethoxysilylpropyl)amine , tris(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-azabicyclo[2,3-dimethyl-2,4-dioxo-1,4-diyl]propyl] -2-silacyclopentane)propyl]-1,3-propanediamine, tetrakis[3- (2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-pro Panediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine amine, tetrakis(3-trimethoxysilylpropyl)-1,3-bisaminomethylsilane hexane, tris(3-trimethoxysilylpropyl)-methyl-1,3-propanediol Amines, and bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propane] propyl]-(3-trismethoxysilylpropyl)-methyl-1,3-propanediamine Examples include:

[0203] In formula (C), A is more preferably represented by formula (II) or formula (III), and k is , 0, and in formula (II) or formula (III), a represents an integer of 2 to 10.

[0204] This results in better abrasion resistance and low hysteresis loss when vulcanized. It tends to become something.

[0205] The modifier having such a nitrogen atom-containing group is not particularly limited, but examples thereof include the following: Trachys[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl] -1,3-Propanediamine, Tetrakis(3-trimethoxysilylpropyl)-1,3 -Propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-bis(a) Aminomethylcyclohexane, and N 1 -(3-(bis(3-(trimethoxysilyl)propion) Phenyl)amino)propyl)-N 1 -methyl-N 3 -(3-(methyl(3-(trimethoxysilyl) (aryl)propyl)amino)propyl)-N 3 -(3-(trimethoxysilyl)propyl) -1,3-propanediamine.

[0206] The amount of the compound represented by formula (C) added as a modifying agent having a nitrogen atom-containing group is The moles of ene polymer to the moles of modifier are adjusted to react in the desired stoichiometric ratio. This tends to achieve the desired star-shaped highly branched structure.

[0207] Specifically, the number of moles of the polymerization initiator is preferably 5.0 times or more the number of moles of the modifying agent. The molar ratio is preferably 6.0 times or more, and more preferably 6.0 times or more. In this case, in formula (C), the number of functional groups of the modifying agent ((m-1)×i+p×j+k) is An integer of 5 to 10 is preferred, and an integer of 6 to 10 is more preferred.

[0208] The modifying agent having a nitrogen atom-containing group represented by formula (D) is not particularly limited, but examples thereof include: For example, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propane N-(1,3-dimethylbutylidene)-3-(trimethoxysilyl)-1-propanol Propanamine, N-(1,3-dimethylbutylidene)-3-methyl(dimethoxysilyl) -1-Propanamine, N-(1,3-dimethylbutylidene)-3-methyl(diethoxy) N-(1-methylethylidene)-3-(triethoxysilyl)-1-propanamine N-(1-methylethylidene)-3-(trimethoxysilyl)-1-propanamine N-(1-methylethylidene)-3-methyl(dimethoxysilane) N-(1-methylethylidene)-3-methyl(diethoxy)-1-propanamine N-ethylidene-3-(triethoxysilyl)-1-propanamine propanamine, N-ethylidene-3-(trimethoxysilyl)-1-propanamine, N -Ethylidene-3-methyl(dimethoxysilyl)-1-propanamine, N-Ethylidene -3-methyl(diethoxysilyl)-1-propanamine, N-(1-methylpropylidene N-(1-methylpropylidene)-3-(triethoxysilyl)-1-propanamine N-(1-methylpropylidene)-3-(trimethoxysilyl)-1-propanamine N-(1-methylpropionyl)-3-methyl(dimethoxysilyl)-1-propanamine N-benzylidene)-3-methyl(diethoxysilyl)-1-propanamine 3-(triethoxysilyl)propan-1-amine, N-benzylidene-3-(trimethysilyl)propan-1-amine N-Benzylidene-3-methyl(dimethoxysilyl)propan-1-amine ) Propane-1-amine, N-benzylidene-3-methyl(diethoxysilyl)propane -1-amine, N-4-methylbenzylidene-3-(triethoxysilyl)propane-1 -amine, N-4-methylbenzylidene-3-(trimethoxysilyl)propane-1-amine amine, N-4-methylbenzylidene-3-methyl(dimethoxysilyl)propane-1-amine amine, N-4-methylbenzylidene-3-methyl(diethoxysilyl)propane-1-amine N-naphthylidene-3-(triethoxysilyl)propan-1-amine, N-naphthylidene-3-(triethoxysilyl)propan-1-amine N-naphthylidene-3-(trimethoxysilyl)propan-1-amine Methyl(dimethoxysilyl)propan-1-amine, 1,1-(1,4-phenylene)biphenyl N-(3(triethoxysilyl)propyl)methanamine), 1,1-(1,4- phenylene)bis(N-(3(trimethoxysilyl)propyl)methanamine), 1,1- (1,4-phenylene)bis(N-(3-methyl(dimethoxysilyl)propyl)methanamine) amine), 1,1-(1,4-phenylene)bis(N-(3-methyl(diethoxysilyl)propion) (propyl)methanamine), 2-methoxy-2-methyl-1-(benzylideneaminoethyl )-1-Aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(p-methoxy) (benzylideneaminoethyl)-1-aza-2-silacyclopentane, 2-ethoxy-2 -methyl-1-(benzylideneaminoethyl)-1-aza-2-silacyclopentane, and and 2-methoxy-2-methyl-1-(methylisobutylideneaminoethyl)-1-aza- 2-Silacyclopentane is an example.

[0209] When a modifying agent having a nitrogen atom-containing group represented by formula (D) is reacted with a polymerization active terminal, The reaction temperature, reaction time, etc. are not particularly limited, but are preferably from 0°C to 120°C, It is preferable to react for 0 seconds or more.

[0210] The total number of moles of alkoxy groups bonded to silyl groups in the modifying compound represented by formula (D) is 0.2 to 2.0 times the number of moles of lithium constituting the polymerization initiator. It is preferable that the ratio is in the range of 0.3 times or more and 1.5 times or less. In order to obtain a sufficient modification rate and molecular weight in the conjugated diene polymer, it is preferable to use a copolymer of 0.3 times or more. From the viewpoint of the cost of the modifier, it is preferable to set it to 2.0 times or less. .

[0211] The modifying agent having a nitrogen atom-containing group represented by formula (E) is not particularly limited, but examples thereof include For example, N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilane) aryl)-N-(3-(triethoxysilyl)propyl)propan-1-amine, N-(3 -(1H-imidazol-1-yl)propyl)-3-(trimethoxysilyl)-N-( 3-(trimethoxysilyl)propyl)propan-1-amine, N-(3-(1H-imino) N-(3-(ethoxypropyl)-3-(ethyldiethoxysilyl)-N-(3-(ethoxypropyl)-1-azol-1-yl) ... N-(3-(1H-imidazoline)-2-methyl-2-propan-1-amine N-(3-(methyl-1-yl)propyl)-3-(methyldimethoxysilyl)-N-(3-(methyl-1-yl)propyl)- N-(3-(1H-imidazoline)propyl)propan-1-amine, (3-(diethyl-1-yl)propyl)-3-(diethylethoxysilyl)-N-( ... N-(3-(1H-imidazolinone)ethoxysilyl)propyl)propan-1-amine, and N-(3-(1H-imidazolinone)propyl)propan-1-amine N-(3-(dimethylphenyl)-1-yl)propyl)-3-(dimethylmethoxysilyl)-N ...phenyl)-1-yl and (methylmethoxysilyl)propyl)propan-1-amine.

[0212] When a modifying agent having a nitrogen atom-containing group represented by formula (E) is reacted with a polymerization active terminal, The reaction temperature, reaction time, etc. are not particularly limited, but are preferably from 0°C to 120°C, It is preferable to react for 0 seconds or more.

[0213] The total number of moles of alkoxy groups bonded to silyl groups in the modifying compound represented by formula (E) is 0.2 to 2.0 times the number of moles of lithium constituting the polymerization initiator. It is preferable that the ratio is in the range of 0.3 times or more and 1.5 times or less. In order to obtain a sufficient modification rate and molecular weight in the conjugated diene polymer, it is preferable to use a copolymer of 0.3 times or more. From the viewpoint of the cost of the modifier, it is preferable to set it to 2.0 times or less. .

[0214] In this embodiment, after the modification step, a condensation reaction step in which a condensation reaction is carried out in the presence of a condensation promoter is carried out. Further steps may be carried out.

[0215] The conjugated diene polymer of the present embodiment is a polymer in which the conjugated diene portion in the conjugated diene polymer chain is substituted with water. It may be elementalized.

[0216] The method for hydrogenating the conjugated diene portion of the conjugated diene polymer is not particularly limited, and may be any known method. is available.

[0217] A suitable hydrogenation method is to blow gaseous hydrogen into a polymer solution in the presence of a catalyst. The catalyst is not particularly limited, but examples thereof include a method of hydrogenating the olefin using a noble metal. Heterogeneous catalysts such as catalysts supported on porous inorganic materials; solubilizing salts of nickel, cobalt, etc. catalysts using organoaluminum, etc., and catalysts using metallocenes such as titanocene, etc. Among these, the use of a single catalyst is preferred from the viewpoint of being able to select mild hydrogenation conditions. The hydrogenation of aromatic groups can be carried out by using a supported noble metal catalyst. Therefore, it can be done.

[0218] The hydrogenation catalyst is not particularly limited, but examples thereof include: (1) Ni, Pt, Pd, Ru, etc. Supported heterogeneous hydrogenation catalysts in which the metals are supported on carbon, silica, alumina, diatomaceous earth, etc. (2) transition metal salts such as organic acid salts or acetylacetonates of Ni, Co, Fe, Cr, etc. and a reducing agent such as organoaluminum, so-called Ziegler-type hydrogenation catalysts, (3) Ti Also included are so-called organometallic complexes such as organometallic compounds of Ru, Rh, Zr, etc. The hydrogenation catalyst is not particularly limited, but examples thereof include those described in Japanese Patent Publication No. 42-8704, Publication No. 43-6636, Publication No. 4841 of 1983, Publication of Special Publication No. 1-37970 , Japanese Patent Publication No. 1-53851, Japanese Patent Publication No. 2-9041, Japanese Patent Application Publication No. 8-109219 The hydrogenation catalyst may also be a known hydrogenation catalyst described in the publication. Examples of suitable catalysts include a reaction mixture of a Sen compound and a reducing organometallic compound.

[0219] In the method for producing a conjugated diene polymer of this embodiment, after the modification step, If necessary, a deactivator, a neutralizer, etc. may be added.

[0220] The quenching agent is not particularly limited, but examples thereof include water; methanol, ethanol, isopropyl alcohol, and the like. Examples include alcohols such as propanol.

[0221] The neutralizing agent is not particularly limited, but examples thereof include stearic acid, oleic acid, and versatility. carboxylic acids (a mixture of highly branched carboxylic acids with 9 to 11 carbon atoms, mainly 10 carbon atoms), etc. Examples include carboxylic acids, aqueous solutions of inorganic acids, and carbon dioxide gas.

[0222] In the method for producing a conjugated diene polymer of this embodiment, gel formation after polymerization is prevented. From the viewpoint of improving the stability during processing, it is preferable to add a rubber stabilizer. stomach.

[0223] The rubber stabilizer is not limited to the following, and known stabilizers can be used. For example, 2,6-di-tert-butyl-4-hydroxytoluene (hereinafter referred to as "BHT") ), n-octadecyl-3-(4'-hydroxy-3',5'-di-tert- Butylphenol)propionate, 2-methyl-4,6-bis[(octylthio)methyl ] Antioxidants such as phenol are preferred.

[0224] The productivity of the conjugated diene polymer of the present embodiment, the processing time when the polymer is made into a composition containing a filler, etc. In order to further improve the processability, a rubber softener may be added as needed.

[0225] The rubber softener is not particularly limited, but examples thereof include extender oil, liquid rubber, and resin. It can be obtained.

[0226] The method for adding the rubber softener to the conjugated diene polymer is not particularly limited. The rubber softener is added to the conjugated diene polymer solution and mixed to obtain a polymer solution containing the rubber softener. A method of removing the solvent from the resulting solution is preferred.

[0227] Preferred extender oils include, for example, aromatic oils, naphthenic oils, and paraffin oils. Among these, environmental safety, prevention of oil bleeding and wet grip are the most important. From the viewpoint of performance, the polycyclic aromatic (PCA) content according to the IP346 method is 3% by mass or less. Aroma substitute oils are preferred. TDAE (Trea) shown in unststoffe 52(12)799(1999) ted Distillate Aromatic Extracts), MES(Mi In addition to RAE (Residual Extraction Solvate), romatic Extracts).

[0228] Preferred liquid rubbers are not particularly limited, but include, for example, liquid polybutadiene, liquid , styrene-butadiene rubber, etc.

[0229] As an effect of adding liquid rubber, a composition containing a conjugated diene polymer and a filler, etc. In addition to improving processability when made into a product, the glass transition temperature of the composition is shifted to the lower side. This allows for excellent abrasion resistance, low hysteresis loss, and low-temperature properties when vulcanized. There is a tendency to improve the quality.

[0230] Preferred resins are not particularly limited, but include, for example, aromatic petroleum resins, coumarone, Indene resin, terpene resin, rosin derivatives (including tung oil resin), tall oil derivatives, rosin ester resins, natural and synthetic terpene resins, aliphatic hydrocarbon resins, aromatic Aromatic hydrocarbon resin, mixed aliphatic-aromatic hydrocarbon resin, coumarin-indene resin, pheno resin, p-tert-butylphenol-acetylene resin, phenol-formal Dehyde resin, xylene-formaldehyde resin, monoolefin oligomer, diolefin Oligomers of vinyl ethers, aromatic hydrocarbon resins, aromatic petroleum resins, hydrogenated aromatic hydrocarbon resins , cycloaliphatic hydrocarbon resin, hydrogenated hydrocarbon resin, hydrocarbon resin, hydrogenated tung oil resin, hydrogen Examples of the ester include hydrogenated oil resins and esters of hydrogenated oil resins with monofunctional or polyfunctional alcohols. These resins may be used alone or in combination of two or more. The saturated groups may be entirely hydrogenated or some may remain.

[0231] As an effect of adding a resin, a composition containing a conjugated diene polymer and a filler, etc. In addition to improving the processability when cured, it also improves the breaking strength when vulcanized. The glass transition temperature of the composition can be shifted to the higher temperature side, which makes it possible to improve wet skin This tends to improve thrombus resistance.

[0232] The amount of extender oil, liquid rubber, resin, or the like added as a rubber softener is not particularly limited. and preferably 1 part by mass or more to 6 parts by mass of the modified conjugated diene polymer of the present embodiment. 0 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, and even more preferably 10 parts by mass or less The content is not less than 37.5 parts by mass and not more than 37.5 parts by mass.

[0233] When the rubber softener is added within the above range, the conjugated diene polymer and the filler are blended. The composition has good processability, and the vulcanizate has high breaking strength and abrasion resistance. Sex tends to be better.

[0234] (Desolvation process) In the method for producing a conjugated diene polymer of this embodiment, the obtained conjugated diene polymer is As a method for obtaining the polymer from the polymer solution, a known method can be used. The method is not particularly limited, but for example, the solvent is separated by steam stripping or the like, and then the resulting mixture is subjected to polymerization. The polymer is obtained by filtering the coalescence, dehydrating and drying it, and Concentration in a gas purifier and then devolatilization in a vent extruder, etc., or direct devolatilization in a drum dryer, etc. One method is to

[0235] (Rubber composition) The rubber composition of the present embodiment comprises a rubber component and 5.0 parts by mass of a rubber component per 100 parts by mass of the rubber component. and 150 parts by mass or more of a filler. In addition, the rubber component is preferably a rubber component having a high viscosity and a high viscosity, from the viewpoint of improving fuel economy, processability, and abrasion resistance. The above-mentioned conjugated diene polymer or the above-mentioned conjugated diene polymer, based on the total amount (100% by mass) of the above-mentioned The composition contains 10% by mass or more of a vinyl polymer composition.

[0236] The filler preferably contains a silica-based inorganic filler. By including silica-based inorganic fillers, the processability when vulcanized tends to be better, When used as a product, it has excellent abrasion resistance, breaking strength, low hysteresis loss and wet skid resistance. It tends to have a better balance with resistance to oxidation.

[0237] The rubber composition of this embodiment is suitable for use in vulcanized rubber applications such as tires, automobile parts such as vibration-proof rubber, and shoes. When used, it is preferable to include a silica-based inorganic filler.

[0238] The rubber composition of this embodiment is a rubbery polymer other than the above-mentioned conjugated diene-based polymer (hereinafter referred to as a simple polymer). (hereinafter referred to as "rubber-like polymer") can be used in combination with the above-mentioned conjugated diene polymer. .

[0239] Such rubber-like polymers are not particularly limited, but include, for example, conjugated diene polymers. or hydrogenated products thereof, random copolymers of conjugated diene compounds and vinyl aromatic compounds, or hydrogenated products thereof, block copolymers of conjugated diene compounds and vinyl aromatic compounds, or Examples include hydrogenated products thereof, non-diene polymers, and natural rubber.

[0240] Specific examples of rubbery polymers include, but are not limited to, butadiene rubber or the like. hydrogenated isoprene rubber or its hydrogenated derivatives, styrene-butadiene rubber or its hydrogenated derivatives Hydrogenated products, styrene-butadiene block copolymers or their hydrogenated products, styrene-iso styrene-based elastomers such as styrene block copolymers or their hydrogenated products, acrylonitrile Examples thereof include tolyl-butadiene rubber and hydrogenated products thereof.

[0241] The non-diene polymer is not particularly limited, but for example, ethylene-propylene rubber , ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene Olefin elastomers such as ethylene rubber, ethylene-hexene rubber, and ethylene-octene rubber -, butyl rubber, brominated butyl rubber, acrylic rubber, fluororubber, silicone rubber, chlorine Polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic acid ethylene Examples include ster-conjugated diene copolymer rubber, urethane rubber, and polysulfide rubber.

[0242] The natural rubber is not particularly limited, but for example, smoked sheet RSS3~ No. 5, SMR, and epoxidized natural rubber.

[0243] The various rubber-like polymers mentioned above are modified by adding polar functional groups such as hydroxyl groups and amino groups. When used for tires, butadiene rubber, isoprene rubber, styrene rubber, Preferably used are ethylene-butadiene rubber, natural rubber, and butyl rubber.

[0244] The weight average molecular weight of the rubber polymer is 2000 from the viewpoint of the balance between performance and processing characteristics. It is preferably 5,000 or more and 1,500,000 or less, more preferably 5,000 or more and 1,500,000 or less. It is more preferable to use a low molecular weight rubber polymer, so-called liquid rubber. These rubber polymers may be used alone or in combination of two or more. stomach.

[0245] The rubber composition of the present embodiment is a rubber composition containing the above-mentioned conjugated diene polymer and a rubber-like polymer. When the product is made into a rubber-like polymer, the content ratio of the above-mentioned conjugated diene polymer to the rubber-like polymer (quality) The ratio of the conjugated diene polymer to the rubbery polymer is 10 / 90 or more and 100 / 100 or less. 20 / 80 or more and 90 / 10 or less are preferable, and 50 / 50 or more and 80 / 10 or less are more preferable. 0 / 20 or less is even more preferable.

[0246] Therefore, the rubber component contains the above-mentioned conjugated diolefin copolymer with respect to the total amount (100 parts by mass) of the rubber component. The ethylene polymer is preferably contained in an amount of 10 parts by mass or more and 100 parts by mass or less, more preferably 20 parts by mass or less. The content is preferably from 50 parts by mass to 80 parts by mass, more preferably from 50 parts by mass to 80 parts by mass.

[0247] When the content ratio (of the above-mentioned conjugated diene polymer / rubber-like polymer) is within the above range, the vulcanizate It has excellent abrasion resistance and breaking strength when used in combination with other materials, and also has low hysteresis loss and wet skid resistance. The balance with resistance is also satisfactory.

[0248] The filler contained in the rubber composition of the present embodiment is not particularly limited, but may be, for example, Examples include silica-based inorganic fillers, carbon black, metal oxides, and metal hydroxides. Among these, silica-based inorganic fillers are preferred. The fillers may be used alone or in combination of two or more.

[0249] The content of the filler in the rubber composition of the present embodiment is the same as that of the rubber containing the conjugated diene polymer. 5.0 parts by mass or more and 150 parts by mass or more, and 20 parts by mass or more and 10 parts by mass or more, based on 100 parts by mass of the component The amount is preferably 0 parts by mass or less, and more preferably 30 parts by mass or more and 90 parts by mass or less.

[0250] In the rubber composition of the present embodiment, the content of the filler is determined from the viewpoint of exhibiting the effect of adding the filler. From this viewpoint, the amount is 5.0 parts by mass or more per 100 parts by mass of the rubber component, and the filler is sufficiently dispersed. From the viewpoint of making the processability and mechanical strength of the composition practically sufficient, 0 parts by mass, it is 150 parts by mass or less.

[0251] The silica-based inorganic filler is not particularly limited, and known fillers can be used. Solid particles containing SiO2 or Si3Al as a constituent unit are preferred, and SiO2 or Si3 Solid particles containing Al as the main component of the structural unit are more preferred. The inorganic filler contains 50% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more. This refers to ingredients contained in an amount of % or more.

[0252] Specific silica-based inorganic fillers are not particularly limited, but include, for example, silica, clay, , talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, glass Inorganic fibrous materials such as silica-based inorganic fillers with hydrophobic surfaces, silica-based inorganic fillers with hydrophobic surfaces, and silica-based inorganic fillers with hydrophobic surfaces are also suitable. Also included are mixtures of silica-based inorganic fillers and inorganic fillers other than silica-based fillers. From the viewpoints of strength and abrasion resistance, silica and glass fiber are preferred, and silica is more preferred. Examples of silica include dry silica, wet silica, and synthetic silicate silica. Among these silicas, the silica that has the effect of improving fracture strength and varying wet skid resistance is From the viewpoint of excellent performance, wet silica is preferred.

[0253] From the viewpoint of obtaining practically good abrasion resistance and breaking strength of the rubber composition, silica-based inorganic filler The nitrogen adsorption specific surface area determined by the BET adsorption method is 100m 2 / g or more 300m 2 / g or less It is preferable that the 2 / g or more 250m 2 / g or less is more preferable. If necessary, a relatively small specific surface area (for example, a specific surface area of ​​200 m 2 / g or less silica-based inorganic fillers and those with a relatively large specific surface area (e.g., 200 m 2 / g or more) In this embodiment, the silica-based inorganic filler can be used in combination with the silica-based inorganic filler. Relatively large specific surface area (e.g., 200 m 2 / g or more) silica-based inorganic filler In this case, the composition containing the conjugated diene polymer improves the dispersibility of silica, and in particular, Effective in improving wear resistance, with a high level of balance between good fracture strength and low hysteresis loss There is a tendency to be able to do this.

[0254] The content of the silica-based inorganic filler in the rubber composition is 1.0% by weight of the rubber component containing the conjugated diene polymer. 00 parts by mass, the amount is preferably 5.0 parts by mass or more and 150 parts by mass, and more preferably 20 parts by mass or more and 100 parts by mass or more. In the rubber composition of the present embodiment, the content of the silica-based inorganic filler is more preferably 100 parts by mass or less. The content is 5 parts by mass per 100 parts by mass of the rubber component from the viewpoint of exhibiting the effect of adding the inorganic filler. 0.0 parts by mass or more, which disperses the inorganic filler sufficiently and achieves the processability and mechanical strength of the composition. From the viewpoint of practically sufficient use, the amount is 150 parts by mass or less per 100 parts by mass of the rubber component. be.

[0255] The carbon black is not particularly limited, but examples thereof include SRF, FEF, HAF, Examples of carbon black include ISAF, SAF, and other classes of carbon black. Adsorption specific surface area is 50m 2 / g or more, and dibutyl phthalate (DBP) oil absorption is 80m Carbon black of L / 100g or less is preferred.

[0256] In the rubber composition of the present embodiment, the content of carbon black is Preferably, the amount is 0.5 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the rubber component containing More preferably, the amount is 3.0 parts by mass or more and 100 parts by mass or less, and 5.0 parts by mass or more and 50 parts by mass or less. In the rubber composition of the present embodiment, the content of carbon black is From the viewpoint of realizing the performance required for applications such as tires, such as grip performance and conductivity, It is preferable to use 0.5 parts by mass or more per 100 parts by mass of the component, and from the viewpoint of dispersibility The amount is preferably 100 parts by mass or less per 100 parts by mass of the rubber component.

[0257] Metal oxides are compounds having the chemical formula MxOy (where M represents a metal atom, and x and y each independently represent a , which represents an integer of 1 to 6.) as the main component of the structural unit.

[0258] The metal oxide is not particularly limited, but examples thereof include alumina, titanium oxide, and magnesium oxide. Examples include cadmium, zinc oxide, and zinc oxide.

[0259] The metal hydroxide is not particularly limited, but examples thereof include aluminum hydroxide, magnesium hydroxide, and the like. Examples include magnesium and zirconium hydroxide.

[0260] The rubber composition of the present embodiment may contain a silane coupling agent. The blocking agent has the function of strengthening the interaction between the rubber component and the inorganic filler. and silica-based inorganic fillers, and has an affinity or bonding group for each of them. A compound having a moiety and an alkoxysilyl group or a silanol group moiety in one molecule is preferred. Such compounds are not particularly limited, but examples thereof include bis-[3-(triethoxy)methyl]-2-benzothiazolinone, bis-[3-(triethoxysilyl)-propyl]-tetrasulfide, bis-[3-(triethoxysilyl)-propyl]-tetrasulfide propyl]-disulfide, bis-[2-(triethoxysilyl)-ethyl]-tetrasulfide Fido is one example.

[0261] In the rubber composition of the present embodiment, the content of the silane coupling agent is Preferably, the amount is 0.1 parts by mass or more and 30 parts by mass or less, and 0.5 parts by mass or less, relative to 100 parts by mass of the filler. More preferably from 1.0 part by mass to 15 parts by mass, and even more preferably from 1.0 part by mass to 15 parts by mass. When the content of the silane coupling agent is within the above range, the above-mentioned effect of the silane coupling agent can be achieved. The effect of addition tends to be more pronounced.

[0262] The rubber composition of the present embodiment contains a rubber softener from the viewpoint of improving its processability. Good too.

[0263] The amount of the rubber softener added is 100 parts by mass of the rubber component containing the conjugated diene polymer. The rubber softener, which is previously contained in the above-mentioned conjugated diene polymer or other rubber-like polymer, The total amount is expressed as the total amount of the rubber softener added when preparing the rubber composition.

[0264] As the rubber softener, mineral oil or a liquid or low molecular weight synthetic softener is suitable. do.

[0265] Process oils used to soften rubber, increase its volume, and improve its processability Mineral oil-based rubber softeners, known as extender oils, contain aromatic rings, naphthenic rings, and A mixture of paraffin chains, with the number of carbon atoms in the paraffin chains accounting for 50% or more of the total carbon are called paraffinic, and the number of naphthenic ring carbon atoms accounts for 30% to 45% of the total carbon. Those with aromatic carbon atoms accounting for more than 30% of the total carbon are called aromatics. The conjugated diene polymer of the present embodiment is a polymer obtained by polymerizing a conjugated diene compound and a vinyl aromatic compound. In the case of a copolymer, the rubber softener used should have a moderate aromatic content. This is preferred because it tends to have good compatibility with polymers.

[0266] In the rubber composition of the present embodiment, the content of the rubber softener is On the other hand, the amount is preferably 0 parts by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass or more and 90 parts by mass or less. The content of the rubber softener is more preferably 30 parts by mass or more and 90 parts by mass or less. By using 100 parts by mass or less of the rubber component, bleeding out is suppressed. This tends to suppress stickiness on the surface of the rubber composition.

[0267] Conjugated diene polymers and other rubbery polymers, silica-based inorganic fillers, carbon black Regarding the method of mixing other additives such as fillers, silane coupling agents, rubber softeners, etc. The mixing method is not particularly limited, but examples thereof include an open roll, a Banbury mixer, a kneader, General mixers such as single screw extruders, twin screw extruders, and multi-screw extruders and a method of melt-kneading using a Japanese machine, and a method of dissolving and mixing each component and then removing the solvent by heating. Among these, the melt kneading method using rolls, Banbury mixers, kneaders, and extruders has been developed. It is preferable from the viewpoint of productivity and good kneading properties. The method of mixing the binder and additives at once or the method of mixing them in several batches is also applicable.

[0268] The rubber composition of the present embodiment may be a vulcanized composition that has been subjected to vulcanization treatment with a vulcanizing agent. The vulcanizing agent is not particularly limited, but examples thereof include radicals such as organic peroxides and azo compounds. These include chlorine generators, oxime compounds, nitroso compounds, polyamine compounds, sulfur, and sulfur compounds. Sulfur compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, and polymeric polysulfides. In the rubber composition of the present embodiment, the content of the vulcanizing agent is 1:1:1. 00 parts by mass, preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.1 parts by mass or more As the vulcanization method, a conventionally known method can be applied, and the vulcanization temperature is The temperature is preferably 120°C or higher and 200°C or lower, more preferably 140°C or higher and 180°C or lower. is.

[0269] In vulcanization, a vulcanization accelerator may be used as needed. Known materials can be used, and are not particularly limited. For example, sulfenamide-based, Anidine, thiuram, aldehyde-amine, aldehyde-ammonia, thiazo Examples of vulcanization accelerators include urea-based, thiourea-based, and dithiocarbamate-based vulcanization accelerators. Examples of the vulcanization accelerator include, but are not limited to, zinc oxide and stearic acid. The content of the rubber component is preferably 0.01 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the rubber component. The amount is preferably 0.1 parts by mass or more and 15 parts by mass or less.

[0270] The rubber composition of the present embodiment may contain other components than those described above within the scope of the present invention. Other softeners and fillers, heat stabilizers, antistatic agents, weather stabilizers, anti-aging agents, colorants, Various additives such as lubricants may be used. As other softeners, known softeners may be used. The other fillers are not particularly limited, but examples thereof include carbonate Examples of the above include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate. Heat stabilizers, antistatic agents, weather stabilizers, antioxidants, colorants, and lubricants are Known materials can be used.

[0271] The rubber composition of the present embodiment is suitably used as a rubber composition for tires. The tire of the present embodiment contains the rubber composition of the present embodiment.

[0272] The rubber composition for tires is not particularly limited, but may be used for, for example, fuel-saving tires, all-cylinder tires, Various tires such as heavy-duty tires, high-performance tires, studless tires, and tires for heavy-duty vehicles : Can be used in various tire parts such as tread, carcass, sidewall, and bead. In particular, the rubber composition for tires has excellent abrasion resistance, breaking strength, and low heat resistance when vulcanized. It has an excellent balance between sterility loss and wet skid resistance, making it a fuel-efficient tire. The present invention is suitable for use in treads of tires, high performance tires, and tires for vehicles with high loads. [Example]

[0273] Hereinafter, the present embodiment will be described in more detail with reference to specific examples and comparative examples. The embodiments are not limited in any way by the following examples and comparative examples. Various physical properties in the examples and comparative examples were measured by the methods shown below.

[0274] (Physical Property 1) Mooney Viscosity Conjugated diene polymers or conjugated diene polymers modified with nitrogen atom-containing modifiers (hereinafter The term "modified conjugated diene polymer" is used collectively with the term "(modified) conjugated diene polymer." The viscometer was a Mooney viscometer (manufactured by Ueshima Seisakusho Co., Ltd.) VR1132) and Mooney viscosity measured in accordance with ISO 289 using an L-shaped rotor. was measured. The measurement temperature was 110°C when the sample was a conjugated diene polymer, and 110°C when the sample was a modified conjugated diene. When a polymer was used as a sample, the temperature was set at 100°C. First, the sample was preheated at the test temperature for 1 minute, then the rotor was rotated at 2 rpm. After 4 minutes, The torque was measured and used as the Mooney viscosity (ML (Physical Property 1)).

[0275] (Physical Property 2) Microstructure of Conjugated Diene Polymers Using a (modified) conjugated diene polymer as a sample, 50 mg of the sample was dissolved in 10 mL of carbon disulfide. The sample was dissolved and used for measurement. The infrared spectrum was recorded from 600 to 1000 using a solution cell. The absorbance at a given wavenumber was measured in the range of cm-1 and analyzed by the method of Morero (D. Morero, A. Santambrogio, L. Porri, F. Clampelli: Chim. e Ind., 41, 758 (1959) According to the calculation formula of the 1,4 cis bond content (mol%) of the conjugated diene polymer, 1,2 vinyl The amount of bond (mol %) was determined. (Measuring device: Fourier transform infrared spectrophotometer manufactured by JASCO Corporation.) FT-IR230

[0276] (Physical Property 3) Branching Degree (Bn) The branching degree (Bn) of the (modified) conjugated diene polymer was measured by GPC-light scattering method with a viscosity detector. The measurement was carried out by the standard method as follows. Gel permeation chromatography (GPC) using three columns packed with polyethylene gel. Using a measuring device (Malvern's product name "GPCmax VE-2001") , a light scattering detector, an RI detector, a viscosity detector (trade name "TDA305" manufactured by Malvern) ") measured using three detectors connected in sequence and based on a polystyrene standard Absolute molecular weight from the results of the light scattering detector and RI detector, and absolute molecular weight from the results of the RI detector and viscosity detector The intrinsic viscosity was determined. The linear polymer has an intrinsic viscosity [η] = -3.883M 0.771 It is used as a guideline for each section. The shrinkage factor (g') was calculated as the ratio of the intrinsic viscosity to the molecular weight. It represents the molecular weight. Then, using the obtained contraction factor (g'), g' = 6Bn / [(Bn+1)(Bn+2)] The defined branching degree (Bn) was calculated. The eluent was tetrahydrofuran containing 5 mmol / L triethylamine (hereinafter referred to as "THF"). (also referred to as "(1)") was used. The columns were manufactured by Tosoh Corporation under the trade names "TSKgel G4000HXL" and "TSKgel The "TSKgel G5000HXL" and "TSKgel G6000HXL" were connected and used. 20 mg of the sample to be measured was dissolved in 10 mL of THF to prepare a measurement solution. L was injected into the GPC measurement device and measured under the conditions of an oven temperature of 40°C and a THF flow rate of 1 mL / min. It was determined.

[0277] (Property 3) Branching degree (Bn) of 1 / 2Hi polymer The measurement conditions for the degree of branching (Bn) were the same as those described above, and the GPC-light scattering method with a viscosity detector was used. Absolute molecular weight chromatograms were obtained based on solution viscosity and light scattering using standard methods. The height of the peak top in the absolute molecular weight chromatogram (absolute molecular weight curve) (where When there are multiple peak tops in the absolute molecular weight curve, the absolute molecular weight is the maximum. The height of a peak (Hi) on the absolute molecular weight curve is 1 / Hi The highest absolute molecular weight among at least two absolute molecular weights at height 2 (1 / 2Hi) The branching degree of the polymer (branching degree (Bn) of the 1 / 2Hi polymer) was calculated by the above-mentioned branching degree (Bn) The calculation was carried out according to the measurement method.

[0278] (Physical property 4) Molecular weight Measurement condition 1: (modified) conjugated diene polymer as sample, polystyrene gel as filler A GPC measuring device (HLC-8320G manufactured by Tosoh Corporation) with three columns connected together was used. Using a PC, a RI detector (Tosoh Corporation, product name "HLC8020") was used. The chromatogram was measured, and the weight average was calculated based on the calibration curve obtained using standard polystyrene. The average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined. The eluent used was tetrahydrofuran (THF) containing 5 mmol / L triethylamine. The column was manufactured by Tosoh Corporation under the trade name "TSKgel SuperMultiporeH Three "TSKgu" (Those manufactured by Tosoh Corporation) are connected to the same pipe. It was used with the "Hardcolumn SuperMP(HZ)-H" connected. Dissolve 10 mg of the sample to be measured in 10 mL of THF to prepare a measurement solution. was injected into the GPC measurement device, and the oven temperature was 40°C and the THF flow rate was 0.35 mL / min. was measured. Among the various samples measured under the above measurement condition 1, the molecular weight distribution (Mw / Mn) was 1.6 Samples that were less than 100% were measured again under the following measurement condition 2. For samples whose molecular weight distribution was 1.6 or more, measurement was performed under measurement condition 1. Measurement condition 2: A conjugated diene polymer or a coupled conjugated diene polymer is used as a sample. Using a GPC measurement device with three columns packed with polystyrene gel, The chromatogram was measured and the weight average molecular weight ( The molecular weight (Mw) and number average molecular weight (Mn) were determined. The eluent was THF containing 5 mmol / L triethylamine. Column: Tosoh Corporation's product name "TSKguardcolumn SuperH-H" Ram: Tosoh Corporation's product names "TSKgel SuperH5000" and "TSKgel "SuperH6000" and "TSKgel SuperH7000" were used. The oven temperature was 40°C, the THF flow rate was 0.6 mL / min, and an RI detector (Tosoh Corporation) was used. A 10 mg sample was dissolved in 20 mL of THF. The resulting solution was used as a measurement solution, and 20 μL of the measurement solution was injected into a GPC measurement device and measured. For samples measured under measurement condition 1 and whose molecular weight distribution value was less than 1.6, Measurement was performed under condition 2.

[0279] (Physical Property 5) Modification rate The modification rate of (modified) conjugated diene polymers was measured using the column adsorption GPC method as follows: The coupling conjugated diene polymer was used as a sample, and the GP with silica gel as a filler was The measurement was performed by applying the adsorption characteristics of modified basic polymer components to the C column. . A sample solution containing a sample and a low molecular weight internal standard polystyrene is measured on a polystyrene column. The difference between the chromatogram measured on the silica column and the chromatogram measured on the silica column was used to determine the The amount of adsorption onto the phosphate column was measured, and the modification rate was calculated. Specifically, the results are as follows. Also, the measurement was performed under the measurement condition 1 of (Property 4) above. For samples whose molecular weight distribution value is 1.6 or more, the following measurement conditions 3 are used: For samples with a distribution value of less than 1.6, measurement was performed under measurement condition 4 below. Preparation of sample solution: Dissolve 10 mg of sample and 5 mg of standard polystyrene in 20 mL of THF. This was used to prepare a sample solution. Measurement condition 3: GPC measurement conditions using a polystyrene column: Tosoh Corporation's HLC-8320GPC product was used to obtain a 5mmol / L triethylenediamine THF containing ethylamine was used as the eluent, and 10 μL of the sample solution was injected into the device. Chromatography was performed using an RI detector under the conditions of an oven temperature of 40°C and a THF flow rate of 0.35 mL / min. The column was a product of Tosoh Corporation called "TSKgel SuperMultip Three Tosoh HZ-H columns were connected, and a guard column, Tosoh's "T It was used with the SKguardcolumn SuperMP(HZ)-H connected. Measurement condition 4: THF containing 5 mmol / L triethylamine was used as the eluent, and the sample 20 μL of the solution was injected into the device and measured. The column was a guard column manufactured by Tosoh Corporation. "TSKguardcolumn SuperH-H", column: product name of Tosoh Corporation TSKgel SuperH5000", "TSKgel SuperH6000", " The column oven temperature was 40°C, and THF Measurement was performed using an RI detector (Tosoh HLC8020) at a flow rate of 0.6 mL / min. A chromatogram was obtained. GPC measurement conditions using a silica column: Tosoh Corporation's product name "HLC-8320GP Using "C", 50 μL of the sample solution was injected into the device using THF as the eluent, and the column Chromatography was performed using an RI detector under the conditions of an oven temperature of 40°C and a THF flow rate of 0.5 ml / min. The columns were Zorbax PSM-1000S and PSM-3 00S" and "PSM-60S" are connected and used, and a guard column (product name: It was used with a "DIOL 4.6 x 12.5mm 5micron" connected. Calculation method for denaturation rate: Total peak area of ​​chromatogram using polystyrene column The peak area of ​​the sample is P1, the peak area of ​​the standard polystyrene is P2, and the peak area of ​​the styrene is P3. The total peak area of ​​the chromatogram using the kaolin column is set to 100, and the peak area of ​​the sample is Using the product of the two peaks as P3 and the peak area of ​​the standard polystyrene as P4, calculate the modification rate (%) using the following formula: Ta. Denaturation rate (%) = [1-(P2 x P3) / (P1 x P4)] x 100 (However, P1+P2=P3+P4=100)

[0280] (Example 1) Modified conjugated diene polymer (sample 1) The internal volume is 10 L, and the ratio of the internal height (L) to the diameter (D) (L / D) is 4.0. The reactor has an inlet at the bottom and an outlet at the top, and is a tank-type reactor equipped with an agitator and a temperature control jar. Two tank-type pressure vessels with a tank-type reactor were connected together as polymerization reactors. The water content was previously removed, and the 1,3-butadiene was 30.8 g / min and the n-hexane was 189.3 g / min. The mixed solution was mixed at a rate of 1000 g / min. In the static mixer, 0.07g of n-butyllithium was added to inactivate the remaining impurities. After adding and mixing at a rate of 2 mmol / min, the polar substance was continuously fed to the bottom of the reactor. 2,2-bis(2-oxolanyl)propane at a rate of 0.012 mmol / min. As a polymerization initiator, n-butyllithium was added at a rate of 0.279 mmol / min. and stirred vigorously with a stirrer. The mixture was fed to the bottom of the first reactor where it was thoroughly mixed, and the temperature inside the reactor was maintained at 73°C.

[0281] The polymer solution was continuously extracted from the top of the first reactor and continuously poured into the bottom of the second reactor. The reaction was continued at 73°C, and the mixture was further fed to the static mixer from the top of the second mixer. When the polymerization is sufficiently stable, the second reactive group is polymerized while 1,3-butadiene is polymerized. From the bottom, trimethoxy(4-vinylphenyl)silane (in the table, "BS- 1) was added at a rate of 0.027 mmol / min to obtain a branched conjugated diene. The polymerization reaction and branching reaction to obtain a polymer were carried out. At this point, a small amount of the conjugated diene polymer solution before the addition of the modifier was extracted, and the antioxidant (BHT ) was added to 100 g of polymer so that the amount was 0.2 g, and then the solvent was removed to obtain a conjugated diene. The Mooney viscosity of the polymer was measured, and the measurement results are shown in Table 1. Next, the polymer solution flowing out from the outlet of the reactor was treated with 1,3-bis(N,N -diglycidylaminomethyl)cyclohexane (abbreviated as "B" in the table) to 0.050 ml The solution was added continuously at a rate of 1000 mol / min and mixed using a static mixer to carry out the modification reaction. At this time, the time until the modifier was added to the polymer solution flowing out from the outlet of the reactor was The time was 4.8 minutes and the temperature was 71°C. The temperature difference was 2°C. After the modification reaction, a small amount of the conjugated diene polymer solution was extracted and After adding 0.2 g of a blocking agent (BHT) per 100 g of polymer, the solvent was removed. Ta.

[0282] Next, the modified polymer solution was added with an antioxidant (BHT) at a ratio of 0.01 per 100g of polymer. The modification reaction was continued by adding 0.055 g / min (n-hexane solution) to the mixture until the total weight reached 2 g. After that, the solvent was removed by steam stripping, and the following formula was added to a part of the main chain. (1) A branching agent (hereinafter also referred to as "branching agent structure") derived from a compound represented by the formula (1) Modified conjugated diene polymer ( Sample 1) was obtained. Various physical properties of the sample were measured. The measurement results are shown in Table 1.

[0283] Polymer before addition of branching agent, polymer before modification after addition of branching agent, and each step after addition of modifier The molecular weight of the polymer in the above was measured by GPC and the branching was measured by GPC with a viscometer. The structure of the modified conjugated diene polymer was identified by comparing with the tensile strength. The structure was identified.

[0284] [ka] (In the formula, R 1is a hydrogen atom or a group having 1 to 2 carbon atoms which may have a branched structure in part an alkyl group having 0 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 2 ~R 3 each independently represents a C1 to C20 alkyl group which may have a branched structure in part thereof or an aryl group having 6 to 20 carbon atoms, When there are a plurality of R1 to R3, they are independent of each other. X 1 indicates an independent halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 3, and l represents an integer of 0 to 3; (m+n+l) is 3.)

[0285] (Examples 2 to 29) Modified conjugated diene polymers (samples 2 to 29) The manufacturing conditions of Examples 2 to 29 shown in Tables 1 to 4 were changed from those of Example 1. Modified conjugated diene polymers (samples 2 to 29) were obtained in the same manner as in Example 1. Various physical properties were measured. The measurement results are shown in Tables 1 to 4. The branching agents and modifiers shown in the tables are "BS-2" to "BS-5" and "A", "C" to "G", and "J" are the following compounds, respectively. (The same applies to Table 5.) "BS-2": dimethylmethoxy(4-vinylphenyl)silane "BS-3": 1,1-bis(4-(dimethylmethoxysilyl)phenyl)ethylene (bottom A compound represented by the formula (2) "BS-4": 1,1-bis(4-trimethoxysilylphenyl)ethylene "BS-5": Trichloro(4-vinylphenyl)silane "A": 1,3-dimethylimidazolidinone "C": 1-[3-(trimethoxysilyl)-propyl]-4-methylpiperazine "D": N-benzylidene-3-(triethoxysilyl)propan-1-amine "E": 2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silyl Cyclopentane "F": Tris(3-trimethoxysilylpropyl)amine "G": tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine "J": N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxy Silyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine [ka] (In the formula, R 2 ~R 5 each independently represents a group having 1 carbon atom, which may have a branched structure in part thereof R represents an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and when there are multiple R 2 ~ R 5 are independent of each other, X 2 ~X 3 each represents an independent halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 3, and l represents an integer of 0 to 3; (m+n+l) is 3, a represents an integer of 0 to 2, b represents an integer of 0 to 3, and c represents an integer of 0 to 3; (a+b+c) is 3.)

[0286] (Comparative Example 1) Modified conjugated diene polymer (Sample 30) The internal volume is 10 L, and the ratio of the internal height (L) to the diameter (D) (L / D) is 4.0. The reactor has an inlet at the bottom and an outlet at the top, and is a tank-type reactor equipped with an agitator and a temperature control jar. Two tank-type pressure vessels with a tank-type reactor were connected together as polymerization reactors. The water content was previously removed, and the 1,3-butadiene was 30.8 g / min and the n-hexane was 189.3 g / min. The mixed solution was mixed at a rate of 1000 mg / min. In the static mixer, 0.07g of n-butyllithium was added to inactivate the remaining impurities. After adding and mixing at a rate of 2 mmol / min, the polar substance was continuously fed to the bottom of the reactor. 2,2-bis(2-oxolanyl)propane at a rate of 0.012 mmol / min. As a polymerization initiator, n-butyllithium was added at a rate of 0.279 mmol / min. and stirred vigorously with a stirrer. The mixture was fed to the bottom of the first reactor where it was thoroughly mixed, and the temperature inside the reactor was maintained at 73°C.

[0287] The polymer solution was continuously extracted from the top of the first reactor and continuously poured into the bottom of the second reactor. The reaction was continued at 73°C, and the mixture was further fed to the static mixer from the top of the second mixer. When the polymerization reaction is sufficiently stabilized, a small amount of the conjugated diene polymer solution before the addition of the modifier is extracted. After adding 0.2g of antioxidant (BHT) per 100g of polymer, The solvent was removed, and the Mooney viscosity of the conjugated diene polymer was measured. The measurement results are shown in Table 4.

[0288] Next, the polymer solution flowing out from the outlet of the reactor was treated with 1,3-bis(N,N -diglycidylaminomethyl)cyclohexane (abbreviated as "B" in the table) at 0.073 ml The solution was added continuously at a rate of 1000 mol / min and mixed using a static mixer to carry out the modification reaction. At this time, the time until the modifier was added to the polymer solution flowing out from the outlet of the reactor was The time was 4.8 minutes and the temperature was 71°C. The temperature difference was 2°C. After the modification reaction, a small amount of the conjugated diene polymer solution was extracted and After adding 0.2 g of a blocking agent (BHT) per 100 g of polymer, the solvent was removed. The microstructure of the butadiene part (1,2 vinyl bond amount, 1,4 cis bond amount: physical property 2) was measured. The measurement results are shown in Table 4.

[0289] Next, the modified polymer solution was added with an antioxidant (BHT) at a ratio of 0.01 per 100g of polymer. The modification reaction was continued by adding 0.055 g / min (n-hexane solution) to the mixture until the total weight reached 2 g. After that, the solvent was removed by steam stripping to obtain the modified conjugated diene polymer. The obtained coalescence (sample 30) was subjected to measurement of various physical properties. The measurement results are shown in Table 4.

[0290] (Comparative Examples 2 to 4) Modified conjugated diene polymers (Samples 31 to 33) The manufacturing conditions of Comparative Examples 2 to 12 shown in Table 4 were changed from those of Comparative Example 1. In the same manner as in Comparative Example 1, modified conjugated diene polymers (samples 31 to 33) were obtained and various physical properties were measured. The measurement results are shown in Table 4.

[0291] (Comparative Example 5) Conjugated diene polymer (Sample 34) The production conditions of Comparative Example 1 were changed to those of Comparative Example 5 shown in Table 5, and the polymerization reaction was sufficiently Once the mixture has stabilized, a branching agent is added to carry out polymerization to obtain a conjugated diene polymer having a branched structure. The reaction and branching reaction were then carried out in the same manner as in Comparative Example 1, except that no modifier was added. Similarly, a conjugated diene polymer (sample 34) was obtained and various physical properties were measured. Shown in Table 5.

[0292] (Comparative Examples 6 and 7) Conjugated diene polymers (Samples 35 and 36) The manufacturing conditions of Comparative Example 5 were changed to those of Comparative Examples 7 and 8 shown in Table 5. Conjugated diene polymers (samples 35 and 36) were obtained in the same manner as in Comparative Example 6, and various physical properties were measured. The measurement results are shown in Table 5.

[0293] (Comparative Example 8) Modified conjugated diene polymer (Sample 37) The production conditions of Comparative Example 1 were changed to those of Comparative Example 9 shown in Table 5, and the polymerization reaction was sufficiently Once the mixture has stabilized, a branching agent is added to carry out polymerization to obtain a conjugated diene polymer having a branched structure. After the polymerization and branching reactions were stabilized, A modified conjugated diene polymer (sample 3) was prepared in the same manner as in Comparative Example 1, except that a modifier was added. 7) was obtained and various physical properties were measured. The measurement results are shown in Table 5. " indicates the following compound. "H": Tetraethoxysilane

[0294] (Comparative Examples 9 to 13) Modified conjugated diene polymers (Samples 38 to 42) The manufacturing conditions of Comparative Examples 9 to 13 shown in Table 5 were changed from those of Comparative Example 8. In the same manner as in Comparative Example 8, modified conjugated diene polymers (samples 38 to 42) were obtained and various physical properties were measured. The measurement results are shown in Table 5. In the table, "I" shown as a modifier indicates the following compound. "I": 1,2-bis(triethoxysilyl)ethane

[0295] (Comparative Example 15) Conjugated diene polymer (Sample 43) ARLANXEO's product name "Buna CB24" (Nd-based high-cis BR ML Viscosity (100°C) 45) was prepared as sample 43.

[0296] [Table 1]

[0297] [Table 2]

[0298] [Table 3]

[0299] [Table 4]

[0300] [Table 5]

[0301] (Examples 30 to 58 and Comparative Examples 15 to 28) Samples 1 to 43 shown in Tables 1 to 5 were used as raw rubbers, and the following compositions were used: A rubber composition containing the raw rubber was obtained.

[0302] (rubber component) (Modified) conjugated diene polymers (samples 1-43) :50 parts by mass Natural rubber RSS#3 :50 parts by mass

[0303] (Combination conditions) The amount of each compounding ingredient added is shown in parts by mass per 100 parts by mass of the rubber component. Silica (product name "Ultrasil 7000GR" manufactured by Evonik Degussa) Nitrogen adsorption specific surface area 170m2 / g): 50.0 parts by mass Carbon black (product name "Seat KH (N339)" manufactured by Tokai Carbon Co., Ltd.) :5.0 parts by mass Silane coupling agent (product name "Si75" manufactured by Evonik Degussa), bis(tri Ethoxysilylpropyl disulfide): 4.5 parts by mass SRAE oil (product name "Process NC140" manufactured by JX Nippon Oil & Energy Corporation) :30.0 parts by mass ·Zinc white: 2.5 parts by mass Stearic acid: 1.0 parts by weight Antioxidant (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine) Amine): 2.0 parts by mass ·Sulfur: 2.2 parts by mass Vulcanization accelerator 1 (N-cyclohexyl-2-benzothiazylsulfinamide) :1.7 parts by mass Vulcanization accelerator 2 (diphenyl guanidine): 2.0 parts by mass ·Total: 200.9 parts by mass

[0304] (Kneading method) The above materials were kneaded by the following method to obtain a rubber composition. A kneader (capacity 0.3 L) was used, and the first stage of mixing was carried out at a filling rate of 65% with the rotor rotating. Under the condition of several 30-50 rpm, raw rubber (samples 1-43), filler (silica, carbon black) lac), silane coupling agent, SRAE oil, zinc oxide and stearic acid are mixed At this time, the temperature of the internal mixer is controlled, and the discharge temperature is 155 to 160°C. A compound was obtained. Next, in the second stage of kneading, the mixture obtained above is cooled to room temperature, and then an antioxidant is added. The mixture was mixed again to improve the dispersion of the silica. The discharge temperature of the mixture was adjusted to 155-160°C. After cooling, the mixture was mixed at 70°C for the third stage. Sulfur and vulcanization accelerators 1 and 2 were added and kneaded using an open roll. Then, molding was performed. The rubber composition was then vulcanized at 160°C for 20 minutes in a vulcanization press. The rubber compositions were evaluated. Specifically, they were evaluated by the following methods. The results are shown in Tables 6 to 8. Shown below.

[0305] (Rating 1) Cold flow property Samples 1 to 43 were taken from the bale, and the sample size was L x W x H = 40 mm x 40 mm x 50 mm. A 1 kg load was placed on the sample and the sample was left to stand for 24 hours at 40°C. The height (H) of the sample was measured, and the average retention rate of two test points was calculated. The index was set to 100. The larger the index, the better the cold flow properties.

[0306] (Evaluation 2) Compound Mooney Viscosity The compound obtained above after the second stage of mixing and before the third stage of mixing was used as a sample and measured using a Mooney viscosity tester. Using a thermometer, the product was preheated to 130°C for 1 minute in accordance with ISO 289. The viscosity was measured after rotating the rotor at 2 revolutions per minute for 4 minutes. The smaller the index, the better the workability.

[0307] (Evaluation 3) Tensile strength and tensile elongation The tensile strength and tensile elongation were measured in accordance with the tensile test method of JIS K6251. The result of 5 was indexed with 100. The larger the index, the greater the tensile strength and tensile elongation (breaking strength ) indicates that the

[0308] (Rating 4) Abrasion resistance Using an Acron abrasion tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.), conforming to JIS K6264-2 The amount of wear was measured at a load of 44.4 N and 1000 revolutions, and the result of Comparative Example 15 was set to 100. The larger the index, the better the abrasion resistance.

[0309] (Evaluation 5) Viscoelastic parameters Using the Rheometrics Scientific viscoelasticity testing machine "ARES", The viscoelastic parameters were measured in a torsion mode. The results for were indexed with 100. The tan δ measured at 0°C, a frequency of 10 Hz, and a strain of 1% was used to evaluate the wet grip properties. The larger the index, the better the wet grip performance. In addition, tan δ measured at 50°C, a frequency of 10 Hz, and a strain of 3% was used as an index of fuel economy. The higher the index, the better the fuel economy.

[0310] [Table 6]

[0311] [Table 7]

[0312] [Table 8]

[0313] As shown in Tables 6 to 8, Examples 30 to 58 were vulcanized compared with Comparative Examples 15 to 28. The compound has a low Mooney viscosity when vulcanized, which makes it easy to process. It was confirmed that the product had an excellent balance between steric loss and wet skid resistance. [Industrial Applicability]

[0314] The conjugated diene polymer according to the present invention is useful for tire treads, interior and exterior parts of automobiles, vibration dampers, and the like. It has industrial applicability in the fields of rubber, belts, footwear, foam, and various industrial goods. be. [Explanation of symbols]

[0315] A: Branching degree of 1 / 2Hi polymer, B: Branching degree distribution of main chain branched polymer (Po C: Branching degree distribution of simple star-shaped branching) Image of a fabric (basically a constant distribution depending on the functional number of the modifier).

Claims

1. The Mooney viscosity measured at 100°C is 30 or more and 120 or less, The amount of 1,2 vinyl bonds is 25 mol % or less, and the amount of 1,4 cis bonds is 40 mol % or less and The branching degree (Bn) measured by GPC-light scattering method with a viscosity detector is 4 or more and 25 or less. and a nitrogen atom-containing conjugated diene polymer.

2. The branching degree (Bn) of the polymer at 1 / 2Hi measured by GPC-light scattering measurement with a viscosity detector is 7 or greater, The branching degree (Bn) of the 1 / 2Hi polymer is the value at the peak top of the absolute molecular weight curve. Height (however, if there are multiple peak tops in the absolute molecular weight curve, The height of the peak top where the molecular weight is maximum (Hi) is used as the standard, and the height in the absolute molecular weight curve is The highest of at least two absolute molecular weights when the height is 1 / 2 of Hi (1 / 2Hi) The conjugated diene system according to claim 1, wherein the branching degree (Bn) of the polymer is at a high absolute molecular weight. Polymer.

3. 3. The method according to claim 1 or 2, wherein the modification rate measured by column adsorption GPC is 60% by mass or more. The conjugated diene polymer described above.

4. It has a moiety derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group, In the moiety derived from the vinyl monomer containing an alkoxysilyl group or a halosilyl group, The conjugated diene polymer according to any one of claims 1 to 3, which has a branched structure.

5. The moiety derived from the vinyl monomer containing an alkoxysilyl group or a halosilyl group is A monomer unit derived from a compound represented by formula (1) or (2): Branching of polymer chains by monomer units derived from compounds represented by the following formula (1) or (2): The conjugated diene-based polymer according to claim 4, wherein 【Chemistry 1】 (In the formula, R 1 is a hydrogen atom or a C1-2 alkyl group which may have a branched structure in part an alkyl group having 0 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 2 ~R 3 each independently represents a C1 to C20 alkyl group which may have a branched structure in part thereof or an aryl group having 6 to 20 carbon atoms, When there are a plurality of R1 to R3, they are independent of each other. X 1 indicates an independent halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 3, and l represents an integer of 0 to 3; (m+n+l) is 3. 【Chemistry 2】 (In the formula, R 2 ~R 5 each independently represents a C1 alkyl group which may have a branched structure in part thereof R represents an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and when a plurality of R 2 ~ R 5 are independent of each other, X 2 ~X 3 each represents an independent halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 3, and l represents an integer of 0 to 3; (m+n+l) is 3, a represents an integer of 0 to 2, b represents an integer of 0 to 3, and c represents an integer of 0 to 3. (a + b + c) is 3.

6. The compound has a monomer unit derived from the compound represented by formula (1), and in formula (1), R 1 but The conjugated diene polymer according to claim 5 , wherein m represents a hydrogen atom and m represents 0.

7. The compound has a monomer unit derived from the compound represented by the formula (2), and in the formula (2), m is 0. The conjugated diene polymer according to claim 5 , wherein b is 0.

8. The compound has a monomer unit derived from the compound represented by formula (1), and in formula (1), R 1 but 6. The conjugated diamine according to claim 5, wherein m represents a hydrogen atom, n represents 3, and l represents 0. Ene-based polymers.

9. The compound has a monomer unit derived from the compound represented by the formula (2), and in the formula (2), m is 0. wherein n represents 3, l represents 0, a represents 0, b represents 0, and c represents 3; 6. The conjugated diene polymer according to claim 5.

10. Using an organolithium compound as a polymerization initiator, a conjugated diene compound is polymerized while undergoing decomposition. a polymerization and branching step of adding a branching agent to obtain a conjugated diene-based polymer having a branched structure; and a modification step of modifying the conjugated diene-based polymer with a modifying agent.

10. A method for producing the conjugated diene polymer according to any one of claims 1 to 9.

11. a rubber component, and 5.0 parts by mass or more and 150 parts by mass or less per 100 parts by mass of the rubber component a filler; The rubber component is a rubber composition according to any one of claims 1 to 10, based on 100% by mass of the total amount of the rubber component. A rubber composition comprising 10% by mass or more of the conjugated diene polymer according to any one of the preceding claims.

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