Conjugated diene polymer, and method for producing conjugated diene polymer.

Description

1 / 124 Conjugated diene polymer, and method for producing conjugated diene polymer. Technical Field

[001] The present invention relates to a conjugated diene polymer, and a method for producing a conjugated diene polymer. Background of the technique

[002] One of the basic functions required of a vehicle's tire tread is its braking performance on the road. Due to climate change in recent years, the road surface may become wet due to sudden rain, or it may change to an icy or snowy surface due to a sudden snowstorm. In these environments, there is a demand for a tire with excellent braking performance not only on a dry road, but also on an icy or snowy road, or a wet road. Since a tire that meets this requirement does not need to be changed according to the seasons, consumer needs have been increasingly growing.

[003] The grip performance on wet surfaces, which is a necessary property for a tire tread to exhibit braking properties on a wet road in general, and winter performance, which is a necessary property for a tire to exhibit braking properties on icy and snowy roads, are contradictory properties. Specifically, improving one of these properties tends to cause the deterioration of the other. Therefore, a tire tread needs to have the contradiction between these properties resolved.

[004] Furthermore, in accordance with the growing demand for fuel efficiency regulations for vehicles, there is a demand Petition 870250088816, dated 09 / 30 / 2025, page 9 / 146 2 / 124 of the increase is due to the use of resins in vehicle parts and the reduction in tire thickness for the purpose of reducing vehicle weight. To reduce the thickness of a tire, it is necessary to reduce the thickness of a part of the tread that occupies a high proportion of the entire tire and comes into contact with the road, and therefore there is a demand for a rubber material that is even more excellent than ever in terms of abrasion resistance.

[005] On the other hand, from the point of view of tire durability, it is also necessary for a rubber material to have traction properties. When a plurality of rubber types is used to improve both wet grip performance and winter performance described above, if the affinity between the various rubber types is low, the mechanical strength of the resulting rubber material tends to deteriorate and, therefore, there is a demand for a rubber material capable of satisfying these properties.

[006] As a rubber material that satisfies the requirements described above to improve various properties, for example, a rubber composition containing a rubber-like polymer, and a reinforcing filler such as carbon black or silica is already known.

[007] In such a rubber composition, attempts have already been made to improve various properties such as abrasion resistance by improving the dispersibility of the filler in the rubber composition by introducing, in a portion of the molecular end of a rubber-like polymer with high motility, a functional group having affinity or reactivity with the filler.

[008] For example, Patent Documents 1 to 3 disclose rubber compositions each containing a modified conjugated diene polymer, which is obtained by reaction of an alkoxysilane. Petition 870250088816, dated 09 / 30 / 2025, page 10 / 146 Patent Document 3 / 124 having an amino group with an active end of a conjugated diene polymer, and silica. Patent Document 4 discloses a rubber composition containing a modified conjugated diene polymer with a low vinyl content. Patent Document 5 discloses a rubber composition containing a conjugated diene polymer composition containing a plurality of types of modified conjugated diene-based polymers. List of State of the Art Documents Patent Document Patent Document 1: Japanese Patent Open to Public Inspection No. 2005-290355 Patent Document 2: Japanese Patent Open to Public Inspection No. 11-189616 Patent Document 3: Japanese Patent Open to Public Inspection No. 2003-171418 Patent Document 4: Japanese Patent No. 6512240 Patent Document 5: Japanese Patent Open to Public Inspection No. 2021-143324 Summary of the Invention Problems to be solved by the invention

[009] Conventionally known rubber compositions, including the rubber compositions disclosed in Patent Documents 1 to 4, however, present a problem that still has room for improvement in physical properties. For example, a rubber composition containing a conventional conjugated diene polymer presents the problem that when wet grip performance is improved, winter performance deteriorates, as does performance on icy and snowy roads, making it difficult to excel in both. Furthermore, when such a rubber composition is vulnerabilities are applied, the rubber composition is vulnerabilities are not fully developed. Petition 870250088816, dated 09 / 30 / 2025, page 11 / 146 4 / 124 canized particularly to obtain a vulcanizate containing an inorganic filler such as silica, problems arise in that the dispersibility of the silica is reduced, the flexibility is reduced, the performance on a road with ice and snow is deteriorated, and the abrasion resistance is insufficient.

[0010] Furthermore, as a result of a detailed study of the rubber composition described in Patent Document 5, it was found that it was appropriate to design a tire that required grip performance on wet surfaces, such as a summer tire, but it was found that there was still room for improvement in winter performance for use in lower temperature environments as well as all-season use.

[0011] Therefore, an object of the present invention is to provide a conjugated diene polymer from which an excellent rubber composition can be obtained in terms of wet surface adhesion performance, winter performance, abrasion resistance, and tensile properties, and a method for producing a conjugated diene polymer. Ways to Solve the Problems

[0012] As a result of further studies conducted by the present inventors to solve the problems described above, the following was found: when an absolute value of a difference in the amount of conjugated diene monomer units linked and a difference in the amount of vinyl linkages between a plurality of polymer segments contained in a conjugated diene polymer are within the determined numerical ranges, and an estimated glass transition temperature based on the microstructure of the conjugated diene polymer (estimated Tg) is within a determined numerical range, a rubber composition that is excellent both in terms of adhesion performance Petition 870250088816, dated 09 / 30 / 2025, page 12 / 146 5 / 124 on wet surfaces when performing in winter, and it is also excellent in terms of abrasion resistance and tensile properties. Thus, the present invention has been realized.

[0013] Specifically, the present invention presents the following.

[0014] [1] A conjugated diene polymer containing two or more polymer segments, wherein an absolute value of a difference (|Xi - X2|) between the amount of linked aromatic vinyl monomer units Xi (% by mass) in a first polymer segment and the amount of linked aromatic vinyl monomer units X2 (% by mass) in a second polymer segment is 5% by mass or less, a difference (Y2 - Y1) between an amount of vinyl linkages Y1 (% by mol) in the linked conjugated diene of the first polymer segment and an amount of vinyl linkages Y2 (% by mol) in the linked conjugated diene of the second polymer segment is 15% by mol or more and 50% by mol or less, and an estimated glass transition temperature (estimated Tg) of the conjugated diene polymer is -72°C or more and -40°C or less.

[0015] [2] The diene conjugate polymer according to item [1], where the ratio Mw / Mn between a weight-average molecular weight Mw and a number-average molecular weight Mn is 1.7 or more.

[0016] [3] The conjugated diene polymer according to item [1] or [2], wherein the ratio (R = r1 / r2) of the mass ratio (n) of the first polymer segment to the mass ratio (r2) of the second polymer segment varies from 0.25 to 4.

[0017] [4] The diene polymer conjugated according to any one of items [1] to [3], having a weight average molecular weight Mw of 350,000 or more and 1,350,000 or less.

[0018] [5] The diene polymer conjugated according to any Petition 870250088816, dated 09 / 30 / 2025, page 13 / 146 6 / 124 one of items [1] to [4], having a modifying group containing nitrogen, and having a modification ratio of 60% or more.

[0019] [6] A method for producing the conjugated diene polymer according to any one of items [1] to [5], including: a polymerization step (P1) for forming the first polymer segment with two or more continuous reactors; and a polymerization step (P2) for forming the second polymer segment at one end of the first polymer segment obtained in step (P1), wherein a polar material is additionally added in polymerization step (P2).

[0020] [7] The method of producing the conjugated diene polymer according to item [6], wherein a conjugated diene compound is additionally added in the polymerization step (P2).

[0021] [8] The method for producing the conjugated diene polymer according to item [6] or [7], including, after the polymerization step (P2), a coupling step of reacting the conjugated diene polymer with a coupling agent having a group containing a nitrogen atom.

[0022] [9] The method of producing the conjugated diene polymer according to item [7] or [8], wherein an amount of conjugated diene compound added in the polymerization step (P2) is 15% by mass or more in relation to the total amount of conjugated diene compound added. Advantages of the Invention

[0023] The present invention may provide a conjugated diene polymer from which a rubber composition may be obtained exhibiting excellent abrasion resistance and tensile properties, and exhibiting excellent wet grip performance and winter performance. Method of Carrying Out the Invention Petition 870250088816, dated 09 / 30 / 2025, page 14 / 146 7 / 124

[0024] Now, one embodiment for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail.

[0025] It is noted that the present embodiment below is merely an example to describe the present invention, and is not intended to limit the present invention to the content that follows. The present invention can be implemented with various modifications made appropriately within the scope thereof. [Conjugated diene polymer]

[0026] A conjugated diene polymer of the present embodiment contains a conjugated diene monomer unit, and preferably contains a conjugated diene monomer unit and an aromatic vinyl monomer unit.

[0027] The conjugated diene polymer of the present embodiment is a conjugated diene polymer having two or more polymer segments, and an absolute value of a difference (|Xi - Xs|) between the amount of linked conjugated diene monomer units Xi (% by mass) in a first polymer segment and the amount of linked conjugated diene monomer units X2 (% by mass) of a second polymer segment is 5% by mass or less.

[0028] Furthermore, a difference (Y2 - Y1) between the amount of vinyl linkages Y1 (mol %) in the conjugated diene linked from the first polymer segment and the amount of vinyl linkages Y2 (mol %) in the conjugated diene linked from the second polymer segment is 15 mol % or more and 50 mol % or less.

[0029] Furthermore, it is a conjugated diene polymer having an estimated glass transition temperature (estimated Tg) calculated based on the conjugated diene polymer microstructure of -72°C or more and -40°C or less. Petition 870250088816, dated 09 / 30 / 2025, page 15 / 146 8 / 124

[0030] The configurations described above feature a conjugated diene polymer from which a rubber compound can be obtained exhibiting excellent abrasion resistance and tensile properties, and exhibiting excellent wet grip performance and winter performance. (Conjugated Diene Compound)

[0031] Examples of a conjugated diene compound forming the conjugated diene monomer unit include, but are not limited to, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, and 1,3-heptadiene. Among these, 1,3-butadiene and isoprene are preferred from the point of view of industrial availability. One of these may be used alone, or two or more of these may be used together.

[0032] The conjugated diene compound is preferably 1,3-butadiene or isoprene, and more preferably 1,3-butadiene from the point of view of availability and controllability of the structure in polymer synthesis. (Aromatic Vinyl Compound)

[0033] Examples of an aromatic vinyl compound that forms the aromatic vinyl monomer unit include, but are not limited to, styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and diphenylethylene. Among these, styrene is preferred from the point of view of industrial availability. One of these can be used alone, or two or more of these can be used together.

[0034] The preferred aromatic vinyl compound is styrene from the point of view of availability and controllability of structure in polymer synthesis. (Quantity of Units of X-linked conjugated diene monomer)

[0035] The quantity of X-linked conjugated diene monomer units (% by mass) in this application refers to a value of one Petition 870250088816, dated 09 / 30 / 2025, page 16 / 146 9 / 124 mass fraction (% by mass) of the aromatic vinyl monomer unit attached to the total mass of the conjugated diene polymer or of a polymer segment described below.

[0036] Here, the quantity of linked conjugated diene monomer units can be calculated by measuring the ultraviolet absorption of a phenyl group contained in a derived portion of an aromatic vinyl compound of the conjugated diene polymer (hereinafter referred to as the linked aromatic vinyl monomer unit). When the conjugated diene polymer contains both the linked aromatic vinyl monomer unit and a linked conjugated diene monomer unit, the quantity of linked conjugated diene monomer units can also be obtained based on the quantity of linked conjugated diene monomer units obtained in the manner described above. Specifically, the quantity can be measured by a method described in the examples below. (Number of vinyl Y bonds in the conjugated diene bond)

[0037] The amount of vinyl linkages Y (mol %) in the conjugated diene linked in this application refers to the value of a mole fraction (mol %) of a 1,2-linked unit in a conjugated diene-derived polymer unit contained in the conjugated diene polymer or polymer segment described below.

[0038] When the conjugated diene polymer of the present embodiment is a butadiene-styrene copolymer, the amount of vinyl linkages in the conjugated diene can be obtained by determining the amount of vinyl linkages (amount of 1,2-linked) in the butadiene linked by Hampton's method (RR Hampton, Analytical Chemistry, 21, 923 (1949)). Specifically, the amount can be measured by a method described in the examples below. (Microstructure)

[0039] Microstructure in this application refers to a composition Petition 870250088816, dated 09 / 30 / 2025, page 17 / 146 10 / 124 of a polymer, including the type of isomer, in the conjugated diene polymer containing the aromatic vinyl compound and the conjugated diene compound, or in the polymer segment described below.

[0040] In the conjugated diene polymer of the present embodiment, the mass of a copolymer consisting of styrene and butadiene is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more based on the mass of the total conjugated diene polymer. (Content of Blocks of Conjugated Diene Monomer Units)

[0041] The conjugated diene polymer of the present embodiment preferably contains some blocks or no blocks in which 4 or more linked conjugated diene monomer units are chain-linked (hereinafter sometimes referred to as the linked conjugated diene monomer unit block).

[0042] The conjugated diene polymer of the present embodiment contains some or no blocks of linked conjugated diene monomer units and, therefore, is unlikely to tend to have two or more glass transition temperatures (Tg).

[0043] The content of blocks of conjugated diene monomer units linked in the conjugated diene polymer can be measured, when the conjugated diene polymer is a butadiene styrene copolymer, by means of a known method in which the conjugated diene polymer is decomposed by the Kolthoff method (a method described by IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)) to analyze the amount of polystyrene insoluble in methanol. The content of blocks of conjugated diene monomer units linked measured by such method is preferably 1.0% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0% by mass based on the total amount of polymer of Petition 870250088816, dated 09 / 30 / 2025, page 18 / 146 11 / 124 Conjugated diene. When the linked conjugated diene monomer block is not contained within a conjugated diene copolymer, and in the polymer segment described below, the conjugated diene polymer tends to exhibit consecutive properties against temperature variation. As a result, a vulcanizate using the conjugated diene polymer changes consecutively over a wide temperature range and tends to have excellent tensile strength. (Method for Estimating the Glass Transition Temperature of the Polymer): Estimated Glass Transition Temperature (Estimated To)

[0044] The glass transition temperature of the conjugated diene polymer of the present embodiment can be estimated using the Gordon Taylor formula expanded for two or more component series of expression (1) as follows (Gordon, M., Taylor, JSJ, Appl. (Chem. 1952, 2, 493). This value is called the estimated glass transition temperature. Estimated Tg = y / ΔίΙ; UZjTgA = / · · (D2.11 Pi J

[0045] In expression (1), the subscript i of each variable indicates each component of the microstructure contained in the conjugated diene polymer, Δαί denotes a difference in the coefficient of thermal expansion of a homopolymer of component i caused through the glass transition, Wi denotes the mass ratio of component i in the conjugated diene polymer, Tg denotes the glass transition temperature of the homopolymer of component i, and pi denotes the density of the homopolymer of component i. A value known from the literature or a measured value can be used as these values. For example, when the conjugated diene polymer contains styrene, and one of the components i is a styrene component, Δαί can be 3.6 x 10-4K'1 based on the coe Petition 870250088816, dated 09 / 30 / 2025, page 19 / 146 12 / 124 thermal expansion coefficient of polystyrene (J. BRANDRUP et al., Polymer Handbook, 3rd edition, (USA), John Wiley & Sons, Inc., 1966, VI-75), Tg, can be 105.3°C based on the measured value of the glass transition temperature, and pi can be 1.02 g / cm3 based on the measured value of the density.

[0046] For example, when the conjugated diene polymer is a butadiene-styrene copolymer, the estimated glass transition temperature (estimated Tg) can be calculated according to the following expression (i) using the amount of linked conjugated diene monomer units Xaii (% by mass), the amount of vinyl linkages Yau (% by mol) in the linked conjugated diene, and the coefficient of thermal expansion (Aa,), the glass transition temperature (Tg,), and the density (pi) of each of polystyrene (PS), poly-1,2-butadiene (1,2-PBd), and poly-1,4-butadiene (1,4-PBd): PPP)4*Aio )41-^)^(1.1^)-^11.2 ph d) 41-^)4^)^7( 1.2 PHJ) λ=> Aa, _Ít / tXgMLJ. I Aa,,Λ •'ΟιΠΊ.,.Λ'αίΓιÚaSt Ί00 ί1ICO,'**1100 fíftQ t,1100 J \ICO / =(-5.38 / ) >XO36+(l-^)xí(l-^)xiO^6)+(^>(O.16)} _ -5750+945 XAr <T^+52.12X?;Jn-0 ( i )

[0047] The influence, in the denominator of expression (i), of a product of the amount of conjugated diene monomer units linked Xaii (% by mass) and the amount of vinyl linkages Yaii (% by mol) in the conjugated diene linked is very small and, thus, the expression can be approximated to expression (ii) below. Furthermore, the following (ii) can be approximated to expression (iii) below. -5750+94. 7 X Xall+52. (2XYall-0. 52l2XXallX Yall 56-0. 2X Chi,,ιι-0. IKY,,, Petition 870250088816, dated 09 / 30 / 2025, page 20 / 146 13 / 124 _ -5750+95 X Xall+52 X Yall-0. 52 X XallX YallTg ------------------------------------------------- · - - (in) 56-0. 2 X Xall-0. 1 X Ya]]

[0048] Specifically, when the conjugated diene polymer is a butadiene homopolymer, or a butadiene-styrene copolymer, the glass transition temperature (estimated Tg) of the conjugated diene polymer can be estimated according to expression (iii) based on values ​​normally used in the design.

[0049] As described above, the mass ratio between the microstructure components can be obtained based on the microstructure as the amount of linked conjugated diene monomer units Xaii (wt%) and the amount of vinyl linkages Yaii (mol%) in the linked conjugated diene in the conjugated diene polymer of the present embodiment, and the glass transition temperature (estimated Tg) of the conjugated diene polymer can be calculated according to expression (1). In other words, expression (1) is a standard indicating the variation of the glass transition temperature of the conjugated diene polymer against the variation of the amount of linked conjugated diene monomer units Xaii (wt%) and the amount of vinyl linkages Yaii (mol%) in the linked conjugated diene.

[0050] When the value of expression (1) is low, the glass transition temperature (Tg) of the conjugated diene polymer of the present embodiment is low, and when the value is high, the glass transition temperature (Tg) is high.

[0051] For example, when expression (1) is -70, the glass transition temperature of the conjugated diene polymer is estimated at 70°C, and when it is -40, the glass transition temperature is estimated at -40°C.

[0052] In this way, the value of expression (1) obtained based on the polymer microstructure is an index of the transition temperature. Petition 870250088816, dated 09 / 30 / 2025, page 21 / 146 14 / 124 of glass conjugated diene polymer in general. The present inventors, however, have found that when the relaxation of a conjugated diene polymer in the vicinity of a measured glass transition temperature occurs over a wide temperature range, the effective viscoelasticity of a vulcanizate thereof does not always agree with the viscoelasticity calculated based on the estimated glass transition temperature (estimated Tg) calculated by expression (1) based on the microstructure. Specifically, when the difference in the value of expression (1) between polymer segments described below is 33 or more, or the mass ratio of a polymer segment described below is within the numerical range of 0.67 to 1.5, the discrepancy between the estimated glass transition temperature based on expression (1) (estimated Tg) and the measured glass transition temperature (Tg) tends to be apparent.Therefore, it was discovered that, from the point of view of controlling the performance of a vulcanizate affected by the glass transition temperature, it is more effective to adjust the estimated glass transition temperature (estimated Tg) calculated by expression (1) based on the microstructure than to adjust the measured glass transition temperature of the conjugated diene polymer to a specific value. This appears to occur because small energy changes are detected in DSC (differential scanning calorimetry), and thus the entire glass transition temperature is affected by the onset of relaxation of a low Tg portion of the conjugated diene polymer, resulting in the measured glass transition temperature being lower than the estimated glass transition temperature.For example, it has already been experimentally confirmed that in conjugated diene-based polymers having the same overall microstructure, the glass transition temperature measured by DSC can differ by about 2 to 5°C depending on the difference in the microstructure of each polymer segment. Petition 870250088816, dated 09 / 30 / 2025, page 22 / 146 15 / 124

[0053] When the glass transition temperature of the conjugated diene polymer of the present embodiment estimated according to expression (1) (estimated Tg) is defined to satisfy the numerical range of -72°C or more and -40°C or less, the glass transition temperature obtained in the form of a vulcanizate tends to be ideal, and the balance between wet surface adhesion performance, winter performance, and abrasion resistance tends to be excellent.

[0054] In the conjugated diene polymer of the present embodiment, the lower limit of expression (1) is -72 or more, preferably -70 or more, and most preferably -68 or more.

[0055] When the lower limit of expression (1) is within this range, a vulcanizate of the conjugated diene polymer of the present embodiment can be improved in terms of adhesion performance on wet surfaces.

[0056] The upper bound of expression (1) is -40 or less, preferably -44 or less, and most preferably -50 or less.

[0057] When the upper limit of expression (1) is within this range, a vulcanizate of the conjugated diene polymer of the present embodiment can be improved in terms of winter performance and abrasion resistance.

[0058] Expression (1) can be controlled to be within the numerical range described above by adjusting the microstructure of the conjugated diene polymer. For example, when the conjugated diene polymer of the present embodiment is a butadiene-styrene-based polymer, the estimated Tg can be controlled to be within the numerical range described above by adjusting the amount of styrene bonded Xall (% by mass) of the conjugated diene polymer, and the amount of vinyl linkages Yall (% by mol) in the butadiene according to expression (iii). (Polymer segment) Petition 870250088816, dated 09 / 30 / 2025, page 23 / 146 16 / 124

[0059] The conjugated diene polymer of the present embodiment has two or more polymer segments.

[0060] Polymer segment refers to a portion of the conjugated diene polymer containing a conjugated diene monomer unit and an aromatic vinyl monomer unit, or containing a conjugated diene monomer unit. The polymer segment preferably contains a conjugated diene monomer unit and an aromatic vinyl monomer unit.

[0061] Furthermore, in the conjugated diene polymer of the present embodiment, the polymer segment preferably contains some blocks or no blocks in which 4 or more linked conjugated diene monomer units are chain-linked.

[0062] The plurality of polymer segments contained in the conjugated diene polymer of the present embodiment has mutually different microstructures. In the respective polymer segments, for example, the number of linked conjugated diene monomer units and the number of vinyl linkages in the linked conjugated diene may be different, and the respective polymer segments may be distinguished by a method described in the examples below.

[0063] The conjugated diene polymer of the present embodiment has two or more polymer segments. Because the polymer has two or more polymer segments, the glass transition is caused in a plurality of temperature regions in a conjugated diene polymer. When the microstructure of the conjugated diene polymer of the present embodiment is stipulated within an appropriate range, and the difference between the respective polymer segments, at the estimated glass transition temperature calculated by means of expression (1), the quantities of conjugated diene monomer units linked to the respective polymer segments (Xi and X2) and the quantities of vinyl linkages (Y1 and Y2) are controlled for this Petition 870250088816, dated 09 / 30 / 2025, page 24 / 146 17 / 124 rem within a specified range, a vulcanized product tends to exhibit excellent grip performance on wet surfaces and excellent winter performance.

[0064] Of the two or more polymer segments contained in the conjugated diene polymer of the present embodiment, a polymer segment having an estimated glass transition temperature calculated according to expression (1) lower by 5°C or more than an average estimated glass transition temperature of the conjugated diene polymer of the present embodiment is defined as a first polymer segment, and a polymer segment having an estimated glass transition temperature higher by 5°C or more is defined as a second polymer segment.

[0065] Each of the first polymer segment and the second polymer segment may contain a plurality of polymer segments, and from the manufacturability point of view, preferably contain one polymer segment. The ratio of the total mass of the first polymer segment and the second polymer segment to the mass of the entire conjugated diene polymer is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more from the point of view of the balance between wet surface adhesion performance and winter performance of a vulcanizate obtained using the conjugated diene polymer of the present embodiment.

[0066] A conventionally known continuously polymerized conjugated diene polymer contains a polymer segment having a uniform microstructure and pronounced glass transition behavior over a narrow temperature range. In general, when winter performance is considered more significant, a conjugated diene polymer having a low glass transition temperature is used to obtain sufficient flexibility. Petition 870250088816, dated 09 / 30 / 2025, page 25 / 146 18 / 124 is significantly high around -30 to -10°C, but the glass transition does not occur and little energy absorption occurs around 0°C, and thus, adhesion performance on wet surfaces tends to be inferior.

[0067] On the other hand, in the conjugated diene polymer of the present embodiment, the various polymer segments have, respectively, different glass transition temperatures and, thus, the glass transition behavior is smooth. Therefore, this polymer is sufficiently softened down to -30 to -10°C and, in this way, by exhibiting good performance in winter, the energy absorption around 0°C can be increased, and the polymer tends to be excellent also in terms of adhesion performance on wet surfaces.

[0068] In the two polymer segments contained in the conjugated diene polymer of the present embodiment, as the difference in glass transition temperature between the two polymer segments is greater, the glass transition behavior is smoother, and the trend described above becomes more noticeable, and thus both winter performance and wet surface adhesion performance tend to be excellent.

[0069] In the conjugated diene polymer of the present embodiment, to increase the difference in glass transition temperature between the polymer segments, it is preferable to increase the difference in the amount of aromatic vinyl monomer units and the difference in the amount of vinyl linkages in the conjugated diene linked between the first polymer segment and the second polymer segment.

[0070] On the other hand, when the difference in the number of aromatic vinyl monomer units between the two polymer segments is large, the compatibility between the two polymer segments is impaired, and the tensile strength obtained in the form of a vul Petition 870250088816, dated 09 / 30 / 2025, page 26 / 146 19 / 124 vulcanized material tends to deteriorate. From this point of view, to obtain a vulcanizate with excellent tensile strength, it is effective to stipulate the difference in the number of aromatic vinyl monomer units between the two polymer segments within a suitable range, and to increase the difference in the number of vinyl linkages in the conjugated diene bond.

[0071] The lower limit of the amount of aromatic vinyl monomer units Xi (% by mass) of the first polymer segment, and of the amount of aromatic vinyl monomer units X2 (% by mass) of the second polymer segment is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 9% by mass or more in each of the polymer segments. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 23% by mass or less in each of the polymer segments.

[0072] The lower limit of the amount of vinyl linkages Y1 (mol %) in the conjugated diene linked to the first polymer segment is preferably 14 mol % or more, more preferably 16 mol % or more, and even more preferably 17 mol % or more. The upper limit is preferably 40 mol % or less, more preferably 35 mol % or less, even more preferably 30 mol % or less, and even more preferably 23 mol % or less.

[0073] On the other hand, the lower limit of the amount of Y2 vinyl linkages (mol%) in the conjugated diene linked to the second polymer segment is preferably 40 mol% or more, more preferably 45 mol% or more, even more preferably 50 mol% or more, and even more preferably 55 mol% or more. The upper limit is preferably 65 mol% or Petition 870250088816, dated 09 / 30 / 2025, page 27 / 146 20 / 124 less, more preferably 62 mol or less, and even more preferably 61 mol or less.

[0074] Each of the amounts of vinyl linkages Yi and Y2 in the conjugated diene linked to the polymer segments may lie within a range obtained by the arbitrary combination of any of the upper and lower limits described above.

[0075] In the conjugated diene polymer of the present embodiment, a difference (Y2 - Y1) between the amount of vinyl linkages Y1 (mol %) in the conjugated diene linked to the first polymer segment and the amount of vinyl linkages Y2 (mol %) in the conjugated diene linked to the second polymer segment is 15 mol % or more and 50 mol % or less, preferably 20 mol % or more and 45 mol % or less, and more preferably 25 mol % or more and 45 mol % or less.

[0076] When (Y2 - Y1) is 15 mol% or more, a vulcanizate thereof tends to be excellent in terms of the balance between wet surface adhesion performance and winter performance. On the other hand, when (Y2 - Y1) is 50 mol% or less, phase separation of the conjugated diene polymer is eliminated, and a vulcanizate thereof tends to be excellent in terms of tensile strength.

[0077] The value of (Y2 - Y1) can be measured by a method described in the examples below, and can be controlled to stay within the numerical range described above by adjusting the amount of a polar material to be added in the polymerization steps (P1 and P2) described below.

[0078] The absolute value of the difference (|Xi - X2|) between the quantity of conjugated diene monomer units linked X1 (% by mass) in the first polymer segment and the quantity of conjugated diene monomer units linked X2 (% by mass) in the second Petition 870250088816, dated 09 / 30 / 2025, page 28 / 146 21 / 124 The polymer segment of the conjugated diene polymer of the present embodiment is 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less.

[0079] When (|Xi - Xs|) is 5% by mass or less, the distribution of aromatic vinyl monomer units becomes uniform, the separation of microphases of the conjugated diene polymer is eliminated, and a vulcanizate thereof tends to have better tensile properties.

[0080] The absolute value of the difference in the amounts of vinyl aromatic monomers linked between the polymer segments can be measured by a method described in the examples below, and can be controlled to be within the numerical range described above by adjusting the amount of a vinyl aromatic monomer to be added in the polymerization steps for the respective polymer segments.

[0081] In the conjugated diene polymer of the present embodiment, in order for the second polymer segment to have an estimated glass transition temperature 5°C or more higher than the average estimated glass transition temperature of the conjugated diene polymer, it is a basic design concept that the amount of vinyl linkages Y2 (mol %) of the second polymer segment is stipulated to be higher than the amount of vinyl linkages Y1 (mol %) of the first polymer segment, and that there is no difference in the amount of linked aromatic vinyl monomer between the polymer segments.

[0082] In the present embodiment, the absolute value of the difference in the amount of aromatic vinyl monomer bonded between the segments is 5% by mass or less in order to allow for a production error. As the content of aromatic vinyl monomer units is also a factor affecting the glass transition temperature, Petition 870250088816, dated 09 / 30 / 2025, page 29 / 146 22 / 124 Made, the polymer segments can be designed to have a difference in the amount of linked aromatic vinyl monomer units, but when the difference in linked conjugated diene monomer units between the polymer segments is reduced, the distribution of aromatic vinyl monomer units can also become uniform as described above, and thus, the advantage of eliminating microphase separation can be expected.

[0083] The estimated glass transition temperature of each polymer segment can be estimated using expression (1) in the same way as that of the conjugated diene polymer.

[0084] A conjugated diene monomer unit can be added to the conjugated diene polymer of the present embodiment, before the coupling step, to increase the reactivity between the conjugated diene polymer and a coupling agent.

[0085] In the conjugated diene polymer of the present embodiment, the polymer segments can be directly coupled to each other, or they can be coupled through a coupling agent. (Ratio R of the mass ratio of the first polymer segment / Mass ratio of the second polymer segment)

[0086] In the conjugated diene polymer of the present embodiment, the first and second polymer segments preferably have a determined mass ratio.

[0087] Mass ratio of each polymer segment refers to the mass ratio (r) of the polymer segment to the entire conjugated diene polymer.

[0088] The mass ratio of each of the first and second polymer segments of the conjugated diene polymer of the present embodiment is defined as the mass ratio to the total mass of the conjugated diene polymer, of a polymer segment obtained in each of the polymerization steps P1 and P2 which are polymerization steps. Petition 870250088816, dated 09 / 30 / 2025, page 30 / 146 23 / 124 suitability for these polymer segments.

[0089] The ratio (R = ri / rs) between the mass ratio of a first polymer segment (ri) and the mass ratio of a second polymer segment (rs) preferably ranges from 0.25 to 4, more preferably from 0.33 to 3, and even more preferably from 0.4 to 2.4. When the lower limit of R is 0.25 or more, the low fuel consumption performance obtained in vulcanization tends to be excellent. When the upper limit of R is 4 or less, the processability obtained in the form of a vulcanizate tends to be excellent.

[0090] AR can be measured by a method described in the examples below, and can be controlled to be within the numerical range described above by adjusting, in the production process of the conjugated diene polymer of the present embodiment, conditions such as polymerization time, polymerization temperature, amount of a monomer to be added, and amount of vinyl linkages in the polymerization steps for the respective polymer segments.

[0091] A method for introducing a plurality of polymer segments into a conjugated diene polymer molecule can be carried out by adding, using a continuous solution polymerization method with a plurality of reactors arranged in series, a conjugated diene compound, an aromatic vinyl compound, a polar material, and a solvent successively to the respective reactors as described below. The substances to be added successively may be the same or different between the reactors. (Glass Transition Temperature)

[0092] The glass transition temperature (Tg) of the conjugated diene polymer of the present embodiment is preferably 72°C or higher, and more preferably -67°C or lower. The temperature Petition 870250088816, dated 09 / 30 / 2025, page 31 / 146 The glass transition temperature of the conjugated diene polymer of the present embodiment is -40°C or less, and more preferably -45°C or less. When the glass transition temperature is within this range, the low fuel consumption performance of a vulcanizate of the conjugated diene polymer of the present embodiment tends to be even more excellent.

[0093] Furthermore, the conjugated diene polymer of the present embodiment having the estimated Tg from expression (1) that satisfies the numerical range of -72°C or more and -40°C or less basically has a glass transition temperature (Tg) measured within this range.

[0094] The glass transition temperature (Tg) may be within a range obtained by the arbitrary combination of any of the upper and lower limits described above. The glass transition temperature of the conjugated diene polymer can be measured according to ISO 22768:2006. More specifically, a differential scanning calorimetry (DSC) curve is recorded by measuring the DSC with increasing temperature within a determined temperature range, and an inflection point of the DSC curve is defined as the glass transition temperature. Specifically, it can be measured by a method described in the examples below.

[0095] The conjugated diene polymer of the present embodiment may contain a plastic component such as a resin or a process oil described below, and it is necessary to exclude such component in the DSC measurement to obtain the glass transition temperature of the conjugated diene copolymer of the present embodiment.

[0096] The glass transition temperature of the conjugated diene polymer varies depending on the amount of conjugated diene monomer units attached to the conjugated diene polymer, and the amount of vinyl linkages in the attached conjugated diene. Specifi Petition 870250088816, dated 09 / 30 / 2025, page 32 / 146 25 / 124 Specifically, the glass transition temperature is increased by increasing the amount of conjugated diene monomer units attached and the amount of vinyl linkages in the conjugated diene attached, and the glass transition temperature is reduced by decreasing the amount of conjugated diene monomer units attached and the amount of vinyl linkages in the conjugated diene attached.

[0097] In the conjugated diene polymer of the present embodiment, the measured glass transition temperature can be stipulated to be within a preferable range by stipulating the estimated Tg calculated by expression (1) at -72°C or more and -40°C or less. (Weight-Average Molecular Weight)

[0098] The weight-average molecular weight (Mw) of the conjugated diene polymer of the present embodiment measured by a GPC measurement method is preferably 35 χ 10⁴ or more, more preferably 40 χ 10⁴ or more, and even more preferably 45 χ 10⁴ or more. When the lower limit of the weight-average molecular weight measured by the GPC measurement method satisfies the range described above, a vulcanizate thereof tends to be excellent in terms of abrasion resistance. The weight-average molecular weight is preferably 135 χ 10⁴ or less, more preferably 95 χ 10⁴ or less, and even more preferably 75 χ 10⁴ or less. When the upper limit of the weight-average molecular weight is within the range described above, a vulcanizate thereof tends to be excellent in terms of filler dispersibility and excellent in terms of processability.

[0099] The weight-average molecular weight may lie within a range obtained by arbitrarily combining any of the upper and any of the lower limits described above.

[00100] The weight-average molecular weight of the conjugated diene polymer can be measured by a GPC measurement method, and Petition 870250088816, dated 09 / 30 / 2025, page 33 / 146 26 / 124 can be specifically measured by a method described in the examples below. (Number Average Molecular Weight)

[00101] The number average molecular weight of the conjugated diene polymer of the present embodiment measured by a GPC measurement method is preferably 10 χ 10⁴ or more, more preferably 15 χ 10⁴ or more, and even more preferably 20 χ 10⁴ or more. When the lower limit of the number average molecular weight measured by the GPC measurement method satisfies the range described above, a vulcanizate thereof tends to be excellent in terms of abrasion resistance. The number average molecular weight is preferably 100 χ 10⁴ or less, more preferably 70 χ 10⁴ or less, and even more preferably 50 χ 10⁴ or less. When the upper limit of the number average molecular weight satisfies the range described above, the vulcanizate thereof tends to be better in terms of filler dispersibility and excellent in terms of processability.The number-average molecular weight can be within a range obtained by arbitrarily combining any of the upper and any of the lower limits described above. The number-average molecular weight of the conjugated diene polymer can be measured by a GPC measurement method, and can be measured by a method described in the examples below.

[00102] The weight-average molecular weight and the number-average molecular weight of the conjugated diene polymer can be controlled to be within the ranges described above by adjusting the ratio between the amount of a polymerization initiator to be used and the amount of monomer to be used, and the type and amount of a coupling agent to be used. (Molecular Weight Distribution)

[00103] The molecular weight distribution of the diene polymer Petition 870250088816, dated 09 / 30 / 2025, page 34 / 146 27 / 124 The molecular weight distribution of the present embodiment is represented by the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn). The molecular weight distribution of the conjugated diene polymer of the present embodiment is preferably 1.7 or more. A conjugated diene polymer having a molecular weight distribution within this range tends to be better in terms of processability for obtaining a vulcanizate.

[00104] The molecular weight distribution of the conjugated diene polymer of the present embodiment is more preferably 1.75 or more, and even more preferably 1.8 or more. The molecular weight distribution is more preferably 2.4 or less, and even more preferably 2.2 or less. (Reason for modification)

[00105] The conjugated diene polymer of the present embodiment preferably has a nitrogen-containing modifying group.

[00106] In this application, the term modification ratio refers to, when a mixture of a modified conjugated diene polymer and an unmodified conjugated diene polymer can be obtained by modifying a conjugated diene polymer with a modifier having a nitrogen atom, a mass content, expressed as a percentage (%) of a component modified conjugated diene polymer having, in a polymer molecule, a specific functional group having affinity or binding reactivity with a charge, for the total amount of the mixture of conjugated diene-based polymers. Thus, when the specific functional group has a nitrogen atom, the modification ratio indicates the mass ratio (%) of a modified conjugated diene polymer containing a nitrogen atom for the total amount of the mixture of conjugated diene-based polymers.

[00107] In this application, the term modified conjugated diene polymer means a modified conjugated diene polymer, and a Petition 870250088816, dated 09 / 30 / 2025, page 35 / 146 28 / 124 mixture of a modified conjugated diene polymer and an unmodified conjugated diene polymer.

[00108] For example, when a conjugated diene polymer containing a modified conjugated diene polymer is obtained, modified by reacting a terminal end of the conjugated diene polymer with a modifier containing a nitrogen atom, the mass ratio of the modified conjugated diene polymer having a functional group containing a nitrogen atom derived from the modifier containing a nitrogen atom to the total amount of the modified conjugated diene polymer corresponds to the modification ratio.

[00109] The modification ratio can be measured by chromatography capable of separating a modified component containing functional groups and an unmodified component.

[00110] An example of a method employing chromatography includes a method in which a gel permeation chromatography column using, as a feedstock, a polar material that adsorbs a specific functional group, such as silica, is used to perform quantitative determination using an internal standard of a non-adsorbed component for comparison.

[00111] More specifically, the modification ratio can be obtained by measuring an amount of adsorption on a silica column based on the difference between a chromatogram measured on a sample solution containing a sample and low molecular weight internal standard polystyrene using a polystyrene-based gel column and a chromatogram measured using a silica-based column. More specifically, the modification ratio can be measured by a method described in the examples.

[00112] In the conjugated diene polymer of the present embodiment, the modification ratio can be controlled by adjusting the amount of modifier to be added, and a reaction method. Petition 870250088816, dated 09 / 30 / 2025, page 36 / 146 29 / 124

[00113] For example, when a method in which polymerization is carried out using, as a polymerization initiator, an organic lithium compound having at least one nitrogen atom in a molecule described below, a method in which a monomer having at least one nitrogen atom in a molecule is copolymerized, and a method in which a modifier having a structural formula described below is used are combined, and the polymerization conditions are controlled, and thus, a modification ratio described above can be obtained.

[00114] In the conjugated diene polymer of the present embodiment, from the point of view of low fuel consumption performance of a vulcanizate thereof, the modification ratio is preferably 60% or more, more preferably 65% ​​or more, and even more preferably 70% or more. [Method for Producing Conjugated Diene Polymer]

[00115] The method for producing a conjugated diene polymer of the present embodiment includes: a polymerization step (P1) forming the first polymer segment with two or more continuous reactors; and a polymerization step (P2) forming the second polymer segment at one end of the first polymer segment obtained in polymerization step (P1), and a polar material is additionally added in polymerization step (P2). (Polymerization Initiator)

[00116] In the polymerization step (P1), a polymerization initiator is preferably used.

[00117] In the polymerization step (P2), it is preferable that a polymerization initiator not be used.

[00118] As the polymerization initiator, at least one Competition 870250088816, dated 09 / 30 / 2025, page 37 / 146 30 / 124 organic monolithic compound can be used.

[00119] Examples of organic monolithin compounds include, but are not limited to, organic monolithin compounds of a low molecular weight compound, and a soluble oligomer.

[00120] Examples of organic monolithin compounds also include, in terms of the mode of bonding between an organic group and lithium in the same, a compound having a carbon-lithium bond, a compound having a nitrogen-lithium bond, and a compound having a tin-lithium bond.

[00121] The amount of organic monolithin compound to be used as the polymerization initiator is preferably determined depending on the molecular weight of a conjugated diene polymer or the modified conjugated diene polymer to be obtained.

[00122] The amount of a monomer, such as a conjugated diene compound, to be used in relation to the amount of polymerization initiator to be used refers to the degree of polymerization. Specifically, the amount of a monomer to be used in relation to the amount of polymerization initiator to be used refers specifically to the number average molecular weight and the weight average molecular weight.

[00123] Thus, to increase the molecular weight of a conjugated diene polymer, the amount of polymerization initiator to be used can be adjusted to be reduced, and to decrease the molecular weight, the amount of polymerization initiator to be used can be adjusted to be increased.

[00124] When a nitrogen atom is to be introduced into the conjugated diene polymer using the polymerization initiator, the organic monolithin compound is preferably an alkyl-lithium compound having a substituted amino group, or dialkylaminolithium, from the point of view that the compound is used in one of the methods of in Petition 870250088816, dated 09 / 30 / 2025, page 38 / 146 31 / 124 Introduction of a nitrogen atom into a conjugated diene polymer.

[00125] In this case, a conjugated diene polymer having a nitrogen atom from an amino group is obtained at the end of the polymerization.

[00126] A substituted amino group refers to an amino group that does not have an active hydrogen, or has a structure that includes a protected active hydrogen.

[00127] Examples of alkyl-lithium compounds containing amino groups without active hydrogen include, but are not limited to, 3-dimethylaminopropyl-lithium, 3-diethylaminopropyl-lithium, 4-(methylpropylamino)butyl-lithium and 4-hexamethyleneiminobutyl-lithium.

[00128] Examples of alkyl-lithium compounds containing amino groups having a structure that includes protected active hydrogen include, but are not limited to, 3-bistrimethylsilylaminopropyl-lithium and 4-trimethylsilylmethylaminobutyl-lithium.

[00129] Examples of dialkylaminolithium include, but are not limited to, lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium dibutylamide, lithium di-n-hexylamide, lithium diheptylamide, lithium diisopropylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium ethylpropylamide, lithium ethylbutylamide, lithium ethylbenzylamide, lithium methylphenethylamide, lithium hexamethyleneimide, lithium pyrrolide, lithium piperide, lithium heptamethyleneimide, lithium morpholide, 1-lithioazacyclooctane, 6-lithium-1,3,3-trimethyl-6-azabicyclo[3,2,1]octane, and 1-lithium-1,2,3,6-tetrahydropyridine.

[00130] Such an organic monolithin compound having a substituted amino group can be reacted with a small amount of a polymerizable monomer, such as 1,3-butadiene, isoprene or styrene, to also be used as an organic monolithin compound of a soluble oligomer. Petition 870250088816, dated 09 / 30 / 2025, p. 39 / 146 32 / 124

[00131] Alternatively, the polymerization initiator may be an initiator produced by reaction of a vinyl aromatic compound having a substituted amino group and / or a diene compound conjugated with an organic monolithinated compound, and may be an initiator in which a functional group may be introduced at one end of a polymer chain.

[00132] The organic monolithin compound is preferably an alkyl-lithium compound from the point of view of industrial application and controllability of the polymerization reaction. In this case, a conjugated diene polymer having an alkyl group is obtained at the end of the polymerization.

[00133] Examples of alkyl-lithium compounds include, but are not limited to, n-butyl-lithium, sec-butyl-lithium, tert-butyl-lithium, n-hexyl-lithium, benzyllithium, phenyllithium, and stilbene-lithium.

[00134] As with the alkyl-lithium compound, from the point of view of industrial availability and controllability of a polymerization reaction, n-butyl-lithium and sec-butyl-lithium are preferred.

[00135] One of these organic monolithin compounds may be used alone, or two or more of these may be used together. Alternatively, another organometallic compound may be used together with it.

[00136] Examples of other organometallic compounds include alkaline earth metal compounds, other alkali metal compounds, and other organometallic compounds.

[00137] Examples of alkaline earth metal compounds include, but are not limited to, organomagnesium compounds, organocalcium compounds, and organostrontium compounds. Other examples include alkoxide, sulfonate, carbonate, and amide compounds of alkaline earth metals.

[00138] Examples of organomagnesium compounds include dibutyl Petition 870250088816, dated 09 / 30 / 2025, page 40 / 146 33 / 124 magnesium and ethyl butyl magnesium. Examples of other organometallic compounds include organoaluminum compounds.

[00139] In the production method of a conjugated diene polymer of the present embodiment, a coupling step described below can be performed after the polymerization step described above. The weight-average molecular weight of the conjugated diene polymer before the coupling step is controlled according to the amount of polymerization initiator used relative to the conjugated diene compound and relative to the vinyl aromatic compound, and as the amount of polymerization initiator to be used is reduced, the weight-average molecular weight of the conjugated diene polymer tends to decrease. The amount of polymerization initiator to be used is preferably 0.15 mol or more and 1.5 mol or less, assuming that the total mass of the conjugated diene compound and the vinyl aromatic compound to be used is 100 kg. (Polar Material)

[00140] In the present embodiment of a conjugated diene polymer production method, a polar material is added in the polymerization step (P2) of forming the second polymer segment.

[00141] The polar material can leave the aromatic vinyl compound copolymerized randomly with the conjugated diene compound, and tends to be useful as a vinylizing agent to control the microstructure of a portion of the conjugated diene. In addition, it also tends to have an effect on accelerating the polymerization reaction or similar.

[00142] Examples of polar material include, but are not limited to, ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, and Petition 870250088816, dated 09 / 30 / 2025, page 41 / 146 34 / 124 2,2-bis(2-oxolanyl)propane; tertiary amine compounds such as tetramethylethylenediamine, dipiperidineethane, trimethylamine, triethylamine, pyridine, and quinuclidine; alkali metal alkoxide compounds such as potassium tert-amylate, potassium tert-butylate, sodium tert-butylate, and sodium amylate; and phosphine compounds such as triphenylphosphine.

[00143] One of these polar materials can be used alone, or two or more of these can be used together.

[00144] The amount of polar material to be used is not particularly limited, and may be selected according to the purpose, and is preferably 0.01 mol or more and 100 mol or less per mole of polymerization initiator used in the polymerization step.

[00145] Such a polar material (vinylizing agent) can be used as an adjuster for the microstructure of the conjugated diene portion of the conjugated diene polymer, in an appropriate amount according to a desired amount of vinyl linkage. Many polar materials exhibit an effective randomization effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound simultaneously, and tend to be able to adjust the randomness of one aromatic vinyl monomer unit and one conjugated diene monomer unit in each polymer segment.

[00146] As a method of randomizing a conjugated diene monomer unit and an aromatic vinyl monomer unit, for example, as described in Japanese Patent Open to Public Inspection No. 59-140211, a method in which a copolymerization reaction is initiated using the total amount of styrene and a portion of 1,3-butadiene, with the remainder of the 1,3-butadiene added intermittently during the copolymerization reaction, may be employed. The 1,3-butadiene added here is added to adjust the randomness, and does not always need to form a polymer segment. Petition 870250088816, dated 09 / 30 / 2025, page 42 / 146 35 / 124 (Polymerization Stage)

[00147] In the present embodiment of a conjugated diene polymer production method, the polymerization step is carried out in a continuous reactor in which two or more reactors are connected in series, and the polymerization step (P1) to obtain the first polymer segment, and the polymerization step (P2) to obtain the second polymer segment are carried out.

[00148] Each of the polymerization steps (P1) and (P2) can be carried out using one reactor, or two or more connected reactors. The reactor format can be a tank reactor or a tubular reactor equipped with a stirrer, or similar.

[00149] It is not essential to assign the polymerization steps (P1) and (P2) to the respective reactors and, for example, the polymerization step (P2) can be configured to start on the downstream side of a first reactor. The respective reactors may have a temperature control function. (Solids Content)

[00150] In the present embodiment of the method for producing a conjugated diene polymer, a conjugated diene polymer of interest can be collected at a determined solids content.

[00151] Solids content in this application refers to the mass of the conjugated diene polymer collected per unit time at a measurement point.

[00152] Note that the mass of the conjugated diene polymer includes the mass of only one polymer formed through a reaction with the polymerization initiator, and does not include the masses of an unreacted conjugated diene compound or an unreacted vinyl aromatic compound, a solvent, among others. (Conversion Rate)

[00153] In the production method of a conjugated diene polymer Petition 870250088816, dated 09 / 30 / 2025, page 43 / 146 36 / 124 of the present embodiment, the term conversion rate is defined as the mass of a conjugated diene polymer obtained at the end of the reaction at a given instant of measurement in relation to the total mass of the conjugated diene compound and the vinyl aromatic compound.

[00154] Specifically, the conversion rate can be obtained according to expression (2) below using the solids content. wordoailidü [ktfhl conwsio [%]------------------------C-- -- _________________________X100 -Jqjanldado dac-mpceoCTi-Sanocoriundo [ktfhl + qjartdadQdac-npoao [kQiTi]

[00155] Furthermore, the conversion rates of the conjugated diene compound and the vinyl aromatic compound can be obtained according to expressions (3) and (4) below using, respectively, the amount of conjugated diene monomer units linked and the amount of conjugated diene monomer units linked from the solids content obtained by the solids content measurement described above. then d c-znei Fg'Hi μ οπκ5Λ·ϊα( to .rd Co-wk twraeof sy, jgjted d morcrner jmt [Sij _ os'! jgcted de'e tcfci cmcu-t ofco-i jgctedde^eammjrdlJigfhj so dco-te-t Mh] h jnojrt de bou^d Co-resiyaeaf__3>πι3Ρ Mnylmo^ne'nrt|Sii____________d l. □tniacwnyl Mafomourtof yrniic vnylctndou*d ptgfh]

[00156] Note that the denominator in the conversion rate calculation corresponds to the mass of all monomers added throughout the polymerization step (P1 and P2). Therefore, the conversion rate obtained at the end of P1 is not 100% even though all monomers supplied up to that point have all reacted.

[00157] From the point of view of controlling the physical properties of the conjugated diene polymer of the present embodiment, the conversion rate is preferably 95% or more until the end of the polymerization step. Specifically, the conversion rate can be controlled to be 95% or more at the end of the polymerization step (P2), and can be lower than this at the polymerization step (P1).

[00158] When the conversion rate is in this range, the Petition 870250088816, dated 09 / 30 / 2025, page 44 / 146 37 / 124 The quantity of conjugated diene monomer units linked to the Xaii conjugated diene polymer can be controlled according to the ratio between the total quantity of conjugated diene compound and the total quantity of vinyl aromatic compound added during the polymerization step, and thus, structural control is facilitated.

[00159] In the production method of a conjugated diene polymer of the present embodiment, the first polymer segment is obtained in the polymerization step (P1), and in this polymerization step (P1), the reactor preferably has a raw material supply section for continuous supply, from one end of the reactor, of the conjugated diene compound, the vinyl aromatic compound, the inert solvent, the polymerization initiator, and the polar material, and has, at the opposite end from the raw material supply section, a discharge section for continuous distribution of the polymer solution.

[00160] The conjugated diene polymer solution resulting from the polymerization step (P1) flows continuously out of the reactor to be fed into the next step. The feed destination is, for example, preferably the polymerization step (P2) for the second polymer segment described below.

[00161] In the polymerization step (P2) to obtain the second polymer segment, a reactor, or two or more connected reactors, are used in the same way as in the polymerization step (P1). At this point, the conjugated diene compound, the vinyl aromatic compound, the inert solvent, the polar material, among others, have recently been added halfway to the reactor, or to a tube connecting the previous step to this step, and thus, a second polymer segment having a greater number of vinyl linkages in the attached conjugated diene than that synthesized in the previous polymerization step is introduced at one end of the first segment. Petition 870250088816, dated 09 / 30 / 2025, page 45 / 146 38 / 124 polymer. In this way, the second polymer segment, having a higher Tg than the first polymer segment, can be formed.

[00162] The second polymer segment has a higher amount of Y2 vinyl linkages (mol %) than the first polymer segment and, therefore, in the polymerization step (P2) of forming the second polymer segment, the conditions are set so that the amount of vinyl linkages in the polymer can be higher.

[00163] In the polymerization step (P2), one, two or more polar materials are additionally added. As polar material is added, the amount of vinyl linkages in the conjugated diene linked to the second polymer segment is higher than that of the first polymer segment, resulting in an increase in the difference in the amount of vinyl linkages in the diene linked between the first polymer segment and the second polymer segment.

[00164] The amount of polar material to be added in the polymerization step is, in terms of the total amount of polar material to be added in the polymerization step (P1) and in the polymerization step (P2), preferably 0.01 mol or more and 100 mol or less per mole of polymerization initiator. The amount of each polar material to be added can be selected within the range described above to control the difference in the amount of vinyl linkages in the conjugated diene linked between the first polymer segment and the second polymer segment.The destination of the polar material to be added in the polymerization steps (P1) and (P2) varies depending on several factors such as the type of polar material, the polymerization temperature, and the shape of the reactor and, therefore, is not particularly limited and, for example, the concentration of the polar material in the polymerization step (P2) is preferably 3 or more times and 20 or less times that in the polymerization step (P1). Petition 870250088816, dated 09 / 30 / 2025, page 46 / 146 39 / 124

[00165] The conjugated diene polymer solution resulting from the polymerization step (P2) flows continuously out of the reactor to be fed into the next step. The destination of the feed is, for example, the coupling step described below.

[00166] In the conjugated diene polymer of the present embodiment, to stipulate at 5% by mass or less, the absolute value of the difference (Xi - X2) in the amount of conjugated diene monomer units linked between the first polymer segment and the second polymer segment, it is necessary to react the conjugated diene compound and the vinyl aromatic compound added in the polymerization step in similar proportions in the polymerization step (P1) and in the polymerization step (P2). For this purpose, the difference in the conversion rate between the conjugated diene compound and the vinyl aromatic compound is preferably reduced in the polymerization step (P1).For example, when the conversion rate of the vinyl aromatic compound is lower than the conversion rate of the conjugated diene compound, the amount of conjugated diene monomer units linked to the first polymer segment is reduced, and conversely, a large amount of the vinyl aromatic compound flows into the polymerization step (P2), resulting in an increase in the difference in the amount of conjugated diene monomer units linked between the first polymer segment and the second polymer segment. On the other hand, when the absolute value of the difference in conversion rate between them is small in the polymerization step (P1), both the first polymer segment and the second polymer segment contain the vinyl aromatic monomer unit in the same ratio, and thus the difference in the amount of conjugated diene monomer units linked is reduced.The difference in conversion rate between the conjugated diene compound and the vinyl aromatic compound is preferably less than 10% by mass, more preferably. Petition 870250088816, dated 09 / 30 / 2025, p. 47 / 146 40 / 124 less than 8% by mass, and even more preferably less than 6% by mass.

[00167] Since an effect of increasing the reaction rate of the vinyl aromatic compound can be expected with the addition of polar material, the difference in conversion rate between the conjugated diene compound and the vinyl aromatic compound can also be reduced by increasing the amount of polar material added. On the other hand, the polar material also acts as a vinylizing agent in general, and thus the number of vinyl linkages in the segment to be formed tends to increase when the amount of it to be added is increased. Therefore, the amount of polar material is a variable for controlling the conversion rate, but it is difficult to select the design to control the number of vinyl linkages.It is preferable that the amount of monomers to be supplied to each segment be adjusted by determining the amount of polar material to be added and the polymerization temperature, rather than controlling the conversion rate according to the amount of polar material to be added.

[00168] To reduce the difference in conversion rate between the conjugated diene compound and the vinyl aromatic compound, it is effective to add the conjugated diene compound and the vinyl aromatic compound to be added in the polymerization step fractionally in polymerization step (P1) and polymerization step (P2). When the amount to be added of either monomer having a high reaction rate constant is reduced in polymerization step (P1), the reduction in reaction rate is induced by raw material depletion, and thus, the conversion rates can be adjusted to be substantially the same at the end of polymerization step (P1).

[00169] Due to the fractional addition of monomers for control Petition 870250088816, dated 09 / 30 / 2025, page 48 / 146 41 / 124 of the conversion rate, if the amount of a compound added in the polymerization step (P1) is low compared to the total amount to be essentially added, the shortage is added in the polymerization step (P2). Since the conversion rate at the end of the polymerization step is preferably 95% or more, as described above, the amount of linked conjugated diene monomer units Xall in the naturally conjugated diene polymer is substantially equal to the ratio between (the vinyl aromatic compound) and (the conjugated diene polymer + the vinyl aromatic compound). This value is substantially equal to the amount of linked conjugated diene monomer units Xi of the first polymer segment synthesized in the polymerization step (P1).

[00170] For example, when a generic copolymerization reaction is carried out with normal hexane as a solvent and with 1,3-butadiene and styrene, respectively, as the conjugated diene compound and as the vinyl aromatic compound that are polymerization monomers, the polymerization reaction rate of the conjugated diene compound is higher than that of the vinyl aromatic compound. Therefore, the conversion rate of the conjugated diene compound tends to be higher than the conversion rate of the vinyl aromatic compound.

[00171] Here, to reduce the difference in conversion rate between these compounds, assuming that the conversion rates of the conjugated diene compound and the vinyl aromatic compound estimated when polymerization is completed individually through step P1 are, respectively, A and B, the difference in conversion rate between the conjugated diene compound and the vinyl aromatic compound can be reduced by adding the conjugated diene compound in a ratio obtained by dividing B by A in step P1, and the remainder is additionally added in step P2. Petition 870250088816, dated 09 / 30 / 2025, page 49 / 146 42 / 124

[00172] The amount of conjugated diene compound to be additionally added in the polymerization step (P2) is preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more of the total amount of conjugated diene compound to be added.When the amount to be added in the polymerization step (P2) is 15% by mass or more of the total amount of conjugated diene compound to be added, it tends to easily satisfy the conditions that the absolute value of the difference (Xi - X2) between the amount of conjugated diene monomer units linked X1 (% by mass) in the first polymer segment and the amount of conjugated diene monomer units linked X2 (% by mass) in the second polymer segment is 5% by mass or less, and that the ratio (R = n / r2) of the mass ratio of the first polymer segment (n) to the mass ratio of the second polymer segment (r2) is in the numerical range of 0.25 to 4.00.

[00173] In the conjugated diene polymer of the present embodiment, the ratio (R = n / r2) between the mass ratio of the first polymer segment (n) and the mass ratio of the second polymer segment (r2) can be controlled according to the ratio between the conjugated diene compound and the vinyl aromatic compound to be added in the polymerization step (P2).

[00174] When the ratio between the conjugated diene compound and the vinyl aromatic compound to be added in the polymerization step (P2) is reduced, the conversion rate of the respective components in the polymerization step (P1) increases and, therefore, R increases. At this point, the difference between the conversion rate of the conjugated diene compound and the conversion rate of the vinyl aromatic compound is preferably controlled to be small.

[00175] From the point of view of reaction controllability, the rate of Petition 870250088816, dated 09 / 30 / 2025, p. 50 / 146 43 / 124 conversion is preferably high in each polymerization step, and R can be controlled by supplying, to the next step, a portion of the conjugated diene compound and / or the vinyl aromatic compound that did not react in the previous polymerization step.

[00176] The production of a conjugated diene polymer of the present embodiment may include the steps determined, respectively, before and after the first polymerization step (P1) and before and after the second polymerization step (P2). For example, a polymerization step synthesizing a polymer different from the first polymer segment and the second polymer segment may be included.

[00177] The polymerization temperature employed in the polymerization step for the conjugated diene polymer of the present embodiment is preferably a temperature at which the polymerization of living anions occurs, and from the point of view of productivity, it is more preferably 0°C or higher, and even more preferably 120°C or lower. When the temperature is within this range, there is a tendency for a sufficient amount of modifier to be reacted at the active end after the polymerization is complete. The temperature is even more preferably 50°C or higher and 100°C or lower.

[00178] In the production of the conjugated diene polymer of the present embodiment, to obtain a high molecular weight distribution, the height (L) / diameter (D) of a tank reactor can be reduced. When L / D is reduced, the residence time distribution in the reactor is increased, and thus, the variation in reaction time between the polymerization initiator molecules is increased, resulting in an increase in the molecular weight distribution. (Coupling Stage) Petition 870250088816, dated 09 / 30 / 2025, page 51 / 146 44 / 124

[00179] In the present embodiment of the method for producing a conjugated diene polymer, a coupling step can be performed at an active end of the conjugated diene polymer obtained through the polymerization steps of the polymer segments described above with a coupling agent, such as a trifunctional or higher functionality reactive compound, and / or a modification step at the active end with a modifier having a group containing a nitrogen atom (preferably, a coupling agent having a group containing a nitrogen atom).

[00180] Hereafter, the coupling implementation step and / or the modification step will be referred to as the coupling step.

[00181] In the coupling step, one end of the active end of the conjugated diene polymer is subjected to a modification reaction with a coupling agent or with a modifier having a nitrogen atom, and thus, a modified conjugated diene polymer is obtained. <Agente de Acoplamento>

[00182] In the present embodiment of a conjugated diene polymer production method, the coupling agent used in the coupling step can have any structure provided it is a trifunctional or higher functionality reactive compound, and is preferably a trifunctional or higher functionality reactive compound having a silicon atom.

[00183] Examples of the trifunctional or higher functionality reactive compound having a silicon atom include, but are not limited to, a halogenated silane compound, an epoxidized silane compound, a vinylized silane compound, an alkoxysilane compound, and an alkoxysilane compound containing nitrogen-containing groups. Petition 870250088816, dated 09 / 30 / 2025, page 52 / 146 45 / 124

[00184] Examples of halogenated silane compounds used as coupling agents include, but are not limited to, methyltrichlorosilane, tetrachlorosilane, tris(trimethylsiloxy)chlorosilane, tris(dimethylamino)chlorosilane, hexachlorodisilane, bis(trichlorosilyl)methane, 1,2-bis(trichlorosilyl)ethane, 1,2-bis(methyldichlorosilyl)ethane, 1,4-bis(trichlorosilyl)butane, and 1,4-bis(methyldichlorosilyl)butane.

[00185] Examples of epoxidized silane compounds used as coupling agents include, but are not limited to, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and epoxy-modified silicone. <Modificador Tendo um Grupo Contendo um Átomo de Nitrogênio>

[00186] Examples of the modifier having a group containing a nitrogen atom include, but are not limited to, an isocyanate compound, an isothiocyanate compound, an isocyanuric acid derivative, a carbonyl compound containing a nitrogen atom, a vinyl compound containing a nitrogen atom, and an epoxy compound containing a nitrogen atom.

[00187] The modifier having a group containing a nitrogen atom is preferably an amine compound without active hydrogen, and examples include a tertiary amine compound, a protected amine compound in which the active hydrogen is replaced by a protecting group, an imine compound represented by a general formula, -N=C, and an alkoxysilane compound attached to the group containing a nitrogen atom.

[00188] Examples of the isocyanate compound used as the modifier having a group containing a nitrogen atom include, but are not limited to, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate (CMDI), phenyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate. Petition 870250088816, dated 09 / 30 / 2025, page 53 / 146 46 / 124 isocyanate, butyl isocyanate, and 1,3,5-benzene triisocyanate.

[00189] Examples of isocyanuric acid derivatives used as modifiers having a group containing a nitrogen atom include, but are not limited to, 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate, 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.

[00190] Examples of the carbonyl compound used as the modifier having a group containing a nitrogen atom include, but are not limited to, 1,3-dimethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-(2-methoxyethyl)-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-benzoylpyridine, N,N,N',N'-tetramethylurea, N,N-dimethyl-N',N'-diphenylurea, Methyl N,N-diethylcarbamate, N,N-diethylacetamide, N,N-dimethyl-N',N'-dimethylaminoacetamide, N,N-dimethylpicolinic acid amide, and N,N-dimethylisonicotinic acid amide.

[00191] Examples of the vinyl compound used as the modifier having a group containing a nitrogen atom include, but are not limited to, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methylmaleimide, N-methylphthalimide, N,N-bistrimethylsylacrylamide, morpholinoacrylamide, 3-(2-dimethylaminoethyl)styrene, (dimethylamino)dimethyl-4-vinylphenylsilane, 4,4'-vinylidene bis(N,N-dimethylaniline), 4,4'-vinylidene bis(N,N-dimethylaniline), 1,1-bis(4-morpholinophenyl)ethylene, and 1-phenyl-1-(4N,N-dimethylaminophenyl)ethylene.

[00192] An example of an epoxy compound used as the modifier having a group containing a nitrogen atom includes, but is not limited to, a hydrocarbon compound containing epoxy groups bonded to an amino group, which may further have an epoxy group bonded to Petition 870250088816, dated 09 / 30 / 2025, page 54 / 146 47 / 124 an ether group.

[00193] An example of such an epoxy compound includes, but is not limited to, an epoxy compound represented by the following general formula (a): (Ra—CH—CH—R1—N )nR- tO~R*-CH-CH-RB)m OR3O (a)

[00194] In formula (a), R represents a divalent or higher valence hydrocarbon group, or a divalent or higher valence organic group having at least one polar group selected from an oxygen-bearing group such as an ether, epoxy or ketone, a sulfur-bearing polar group such as a thioether or thioketone, and a nitrogen-bearing polar group such as a tertiary amino group or an imino group.

[00195] The divalent or higher valence hydrocarbon group is a linear, branched or cyclic hydrocarbon group, optionally saturated or unsaturated, and includes an alkylene group, an alkenylene group, a phenylene group, among others. A hydrocarbon group having 1 to 20 carbon atoms is preferred. Examples of the same include groups such as methylene, ethylene, butylene, cyclohexylene, 1,3-bis(methylene)-cyclohexane, 1,3-bis(ethylene)-cyclohexane, o-, m-, or p-phenylene, m-, or p-xylene, and bis(phenylene)-methane.

[00196] In formula (a), R1 and R4 are a hydrocarbon group having from 1 to 10 carbon atoms, and R1 and R4 are optionally the same or different.

[00197] In formula (a), R2 and R5 are hydrogen, or a hydrocarbon group having from 1 to 10 carbon atoms, and R2 and R5 are optionally the same or different.

[00198] In formula (a), R3 is a hydrocarbon group having from 1 to 10 carbon atoms, or a structure represented by formula (a1) a Petition 870250088816, dated 09 / 30 / 2025, p. 55 / 146 48 / 124 next.

[00199] R1, R2, and R3 may be mutually linked cyclic structures.

[00200] When R3 is a hydrogen group, R3 can be a cyclic structure mutually bonded to R. In the cyclic structure, the N bonded to R3 can be directly bonded to R.

[00201] In formula (a), n is an integer of 1 or more, in is 0, or an integer of 1 or more. r2-ch-ch-r'° (a1)

[00202] In formula (a1), R1 and R2 are defined in the same way as R1 and R2 in formula (a), and R1 and R2 are optionally equal or different.

[00203] The epoxy compound used as the modifier having a group containing a nitrogen atom preferably has an epoxy-containing hydrocarbon group, and more preferably has a glycidyl-containing hydrocarbon group.

[00204] A hydrocarbon group containing epoxy groups linked to an amino group or an ether group is not particularly limited, and examples thereof include a glycidylamino group, a diglycidylamino group, or a glycidoxy group. More preferred molecular structures are compounds containing epoxy groups containing, respectively, a glycidylamino group or a diglycidylamino group, and a glycidoxy group, and an example thereof includes a compound represented by the following general formula (a2): (CH2-CH—CHj-N )n- R — (O-CHs-CH-CH2)tti X / I XX °0(a2)

[00205] In formula (a2), R is defined in the same way as R in formula (a), and R6 is a hydrocarbon group having from 1 to 10 atoms of Petition 870250088816, dated 09 / 30 / 2025, p. 56 / 146 49 / 124 carbon, or a structure represented by the following formula (a3).

[00206] When R6 is a hydrocarbon group, R6 can be a cyclic structure mutually bonded to R, and in this case, the N bonded to R6 can be directly bonded to R.

[00207] In formula (a2), n is an integer of 1 or more, in is 0, or an integer of 1 or more. CH2”CH-CH20 Ía3)

[00208] The epoxy compound used as the modifier having a group containing a nitrogen atom is particularly preferably a compound having one or more diglycidylamino groups, and one or more glycidoxy groups in one molecule.

[00209] Examples of epoxy compounds using a nitrogen-containing group as the modifier include, but are not limited to, N,N-diglycidyl-4-glycidoxyaniline, 1-N,N-diglycidylaminomethyl-4-glycidoxycyclohexane, 4-(4-glycidoxyphenyl)-(N,N-diglycidyl)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'-tetraglycidyl-m-xylenediamine, 4,4-methylene-bis(N,N-diglycidylaniline), 1,4-bis(N,N-diglycidylamino)cyclohexane, Ν,Ν,Ν',Ν'tetraglycidyl-p-phenylenediamine, 4,4'-bis(diglycidylamino)benzophenone, 4(4-glycidylpiperazinyl)-(N,N-diglycidyl)aniline, 2-[2-(N,Ndiglycidylamino)ethyl]-1-glycidylpyrrolidine, N,N-diglycidylaniline, 4,4'diglycidyl-dibenzylmethylamine, N,N-diglycidylaniline, Ν,Ν-diglycidyl orthotoluidine, and Ν,Ν-diglycidylaminomethylcyclohexane.Among these, N,N-diglycidyl-4-glycidoxyaniline and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane are particularly preferred. Petition 870250088816, dated 09 / 30 / 2025, page 57 / 146 50 / 124

[00210] From the point of view that the effects of the present embodiment are effectively and definitively presented, the modifier is preferably an alkoxysilane compound having a group containing a nitrogen atom. Examples of such a modifier include, but are not limited to, 3-dimethylaminopropyltrimethoxysilane, 3-dimethylaminopropylmethyldimethoxysilane, 3-diethylaminopropyltriethoxysilane, 3-morpholinopropyltrimethoxysilane, 3-piperidinopropyltriethoxysilane, 3-hexamethyleneiminopropylmethyldiethoxysilane, 3-(4-methyl-1-piperazino)propyltriethoxysilane, 1-[3-(triethoxysilyl)-propyl]-3-methylhexahydropyrimidine, 3-(4-trimethylsilyl-1-piperazino)propyltriethoxysilane, 3-(3-triethylsilyl-1-imidazolidinyl)propylmethyldiethoxysilane, 3-(3-trimethylsilyl-1-hexahydropyrimidine)propyltrimethoxysilane, 3-dimethylamino-2(dimethylaminomethyl)propyltrimethoxysilane, bis(3-dimethoxymethylsilylpropyl)N-methylamine, bis(3-trimethoxysilylpropyl)-N-methylamine, bis(3triethoxysilylpropyl)methylamine,tris(trimethoxysilyl)amine, tris(3trimethoxysilylpropyl)amine, N,N,N',N'-tetra(3trimethoxysilylpropyl)ethylenediamine, 3-isocyanatopropyltrimethoxysilane, 3-cyanopropyltrimethoxysilane, 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1aza-2-silacyclopentane, 2,2-diethoxy-1-(3-triethoxysilylpropyl)-1-aza-2silacyclopentane, 2-2-dimethoxy-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclohexane, 2,2-dimethoxy-1-(3-dimethoxymethylsilylpropyl)-1-aza-2silacyclopentane, and 2,2-dimethoxy-8-(N,N-diethylamino)methyl-1,6-dioxa-2sylacecloctane.,

[00211] Particularly preferred examples of the alkoxysilane compound having a group containing a nitrogen atom include the following: Petition 870250088816, dated 09 / 30 / 2025, page 58 / 146 51 / 124

[00212] Specific examples include tris(3trimethoxysilylpropyl)amina, tris(3-triethoxysilylpropyl)amina, tris(3tripropoxysilylpropyl)amina, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimetóxi-1aza-2-silaciclopentano)propyl]amina, tetrakis(3-trimethoxysilylpropyl)-1,3propanodiamine (também denominated N,N,N',N'-tetrakis(3trimethoxysilylpropyl)-1,3-propanodiamina), tris(3-trimethoxysilylpropyl)-[3(1-metóxi-2-trimetilsilil-1-sila-2-azaciclopentano)propyl]-1,3propanodiamina, tris(3-trimethoxysilylpropyl)-[3-(1-metóxi-2-metil-1-sila2-azaciclopentano)propyl]-1,3-propanodiamine, bis(3-triethoxysilylpropyl)[3-(2,2-diethoxy-1-aza-2-silacyclopentano)propyl]-[3-(1-ethoxy-2-trimethylsilyl1 -sila-2-azacyclopentano)propyl]-1,3-propanediamine, tetrakis(3trimethoxysilylpropyl)-1,3-bisaminomethylcyclo-hexane, tris(3trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentano)propyl]1,3-bisaminomethylcyclo-hexane, tetrakis(3trimethoxysilylpropyl)-1,6hexamethylenediamine,pentakis(3-trimethoxysilylpropyl)-diethylenetriamine, tris(3-trimethoxysilylpropyl)-methyl-1,3-propanediamine, tetrakis[3-(2,2dimethoxy-1-aza-2-silacyclopentane)propyl]silane, bis(3trimethoxysilylpropyl)-bis[3-(2,2-dimethoxy-1-aza-2silacyclopentane)propyl]silane, tris[3-(2,2-dimethoxy-1-aza-2silacyclopentane)propyl]-(3-trimethoxysilylpropyl)silane, tris[3-(2,2dimethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-methoxy-1-trimethylsilyl-1syl-2-azacyclopentane)propyl]silane, 3-tris[2-(2,2-dimethoxy-1-aza-2sylacyclopentane)ethoxy]silyl-1-trimethoxysilylpropane, 1-[3-(1-methoxy-2trimethylsilyl-1-sila-2-azacyclopentane)propyl]-3,4,5-tris(3trimethoxysilylpropyl)-cyclohexane, 1 -[3-(2,2-dimethoxy-1-aza-2silacyclopentane)propyl]-3,4,5-tris(3-trimethoxysilylpropyl)-cyclohexane, 3,4,5-tris(3-trimethoxysilylpropyl)-cyclohexyl-[3-(2,2-dimethoxy-1-aza-2silacyclopentane)propyl ether], and (3-trimethoxysilylpropyl) phosphate.,

[00213] Other examples include bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]phosphate, bis ... 52 / 124 aza-2-silacyclopentano)propyl]-(3-trimethoxysilylpropyl)phosphate, tris[3-(2,2dimethoxy-1-aza-2-silacyclopentano)propyl]phosphate, N-(1,3dimethylbutylidene)-3-(triethoxysilyl)-1-propanamina, N-(1,3dimethylbutylidene)-3-(trimethoxysilyl)-1-propanamina, N-benzylidene-3-(triethoxysilyl)propan-1-amina, N-benzylidene-3-(trimethoxysilyl)propan-1amina, 1,1-(1,4-phenylene)bis(N-(3-(triethoxysilyl)propyl)methanamina), 1,1(1,4-phenylene)bis(N-(3(trimethoxysilyl)propyl)methanamina), 2-methoxy-2methyl-1-(benzylideneaminoethyl)-1-aza-2-silacyclopentano, and 2-methoxy-2methyl-1-(4-methoxybenzylideneaminoethyl)-1-aza-2-silacyclopentano.

[00214] Still other examples include 1-methyl-4-[3(trimethoxysilyl)propyl]piperazine, 1-methyl-4-[3(triethoxysilyl)propyl]piperazine, 1-methyl-4-[3(methyldimethoxysilyl)propyl]piperazine, 3,3'-(1, 1,3,3tetramethoxydisiloxano-1,3-di-yl) bis(N,N-dimethylpropan-1-amine), 3,3'(1,1,3,3-tetraethoxydisiloxano-1,3-di-yl) bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxano-1,3-di-yl) bis(N,N-dimethylpropan-1-amine), 3,3'-(1, 1,3,3-tetramethoxydisiloxano-1,3-di-yl) bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydissiloxane-1,3-di-yl) bis(N,N-dipropylpropan-1-amina), 3,3-(1,1,3,3tetraethoxydissiloxane-1,3-di-yl) bis(N,N-diethylpropan-1-amina), 3,3'(1,1,3,3-tetrapropoxydissiloxane-1,3-di-yl) bis(N,N-diethylpropan-1-amina), and 3,3'-(1,1,3,3-tetraethoxydissiloxane-1,3-di-yl) bis(N,N-dipropylpropan-1-amina).

[00215] Still other examples include 3,3'-(1,1,3,3tetrapropoxysiloxano-1,3-di-yla) bis(N,N-dipropylpropane-1-amine), 3,3'-(1,1,3,3-tetramethoxidissiloxano-1,3-di-ylamine)(N,1-methyl), 3,3'-(1,1,3,3-tetraethoxysiloxano-1,3-di-amine) bis(N,Ndiethylmethane-1-amine), 3,3'-(1,1,3,3-tetrapropoxysiloxano-1,3-di-amine) bis(N,N-diethylmethane-1-amine), 3,3'-(1,1,3,3-tetramethoxysisiloxano-1,3di-yl) bis(N,N-dimethylmethane-1-amine), 3,3'-(1,1,3,3 Petition 870250088816, of 30 / 09 / 2025, p. 60 / 146 53 / 124 tetramethoxysiloxano-1,3-di-yla) bis(N,N-dipropylmethane-1-amine), 3,3'(1,1,3,3-tetrapropoxysiloxano-1,3-di-yla) bis(N,N-dimethylmethane-1amine), 3,3'-(1,1,3,3-tetrapropoxysiloxano-1,3-di-yla) bis(N,N dipropylmethane-1-amine), 3,3'-(1, 1,3,3-tetraethoxysiloxano-1,3-di-yla) bis(N,N-dimethylmethane-1-amine), 3,3'-(1,1,3,3-tetraethoxysiloxano-1,3di-yl) yl)propyl) yl)propyl)bis(N,N-dipropylmethane-1-amine), 1,1,3,3-tetramethoxysiloxane, 1,1,3,3-tetraethoxydisiloxane, and 1,3-bis(3-(1H-imidazol-11,3-bis(3-(1H-imidazol-11,3-bis(3-(1H-imidazol-1yl)propyl) 1,1,3,3-tetrapropoxydisiloxane.

[00216] In coupling modifiers having a group containing a nitrogen atom, an example of a protected amine-type compound in which the active hydrogen is replaced by a protecting group includes a compound having alkoxysilane and a protected amine in the molecule.

[00217] Examples of such a compound include, but are not limited to, N,N-bis(trimethylsilyl)aminopropyltrimethoxysilane, bis(trimethylsilyl)aminopropylmethyldimethoxysilane, bis(trimethylsilyl)aminopropyltriethoxysilane, bis(trimethylsilyl)aminopropylmethyldiethoxysilane, bis(trimethylsilyl)aminoethyltrimethoxysilane, bis(trimethylsilyl)aminoethylmethyldiethoxysilane, bis(triethylsilyl)aminopropylmethyldiethoxysilane, bis(triethylsilyl)aminopropylmethyldiethoxysilane, piperazino)propyltriethoxysilane, imidazolidinyl)propylmethyldiethoxysilane, hydropyrimidinyl)propyltrimethoxysilane, trimethoxysilylpropyl)-1-aza-2-silacyclopentane, triethoxysilylpropyl)-1-aza-2-silacyclopentane, trimethoxysilylbutyl)-1-aza-2-silacyclo-hexane, N,NN,NN,NN,NN,NN,N3-(4-trimethylsilyl-13-(3-triethylsilyl-13-(3-trimethylsilyl-1-hexa2,2-dimethoxy-1-(32,2-diethoxy-1-(32,2-dimethoxy-1-(42,2-dimethoxy-1-(3dimethoxymethylsilylpropyl)-1-aza-2-silacyclopentano, 2,2-dimethoxy-1-phenyl-1aza-2-silacyclopentano, 2,2-diethoxy-1-butyl-1-aza-2-silacyclopentano, and Petition 870250088816, de 30 / 09 / 2025, pág. 61 / 146 54 / 124 2,2-dimethoxy-1-methyl-1-aza-2-silacyclopentano.

[00218] Other examples include N-(1,3-dimethylbutylidene)-3methyl(dimethoxysilyl)-1-propanamine, N-(1,3-dimethylbutylidene)-3methyl(diethoxysilyl)-1-propanamine, N-(1-methylethylidene)-3-(triethoxysilyl)-1propanamine, N-(1-methylethylidene)-3-(trimethoxysilyl)-1-propanamine, N-(1-methylethylidene)-3-methyl(dimethoxysilyl)-1-propanamine, N-(1methylethylidene)-3-methyl(diethoxysilyl)-1-propanamine, N-ethylidene-3-(triethoxysilyl)-1propanamine, N-ethylidene-3-(trimethoxysilyl)-1propanamine, N-ethylidene-3-(trimethoxysilyl)-1propanamine, Netilideno-3-metil(diethoxysilyl)-1-propanamina, N-(1-metilpropilideno)-3(triethoxysilyl)-1-propanamina, N-(1-metilpropilideno)-3-(trimethoxysilyl)-1propanamina, N-(1-metilpropilideno)-3-metil(dimethoxysilyl)-1propanamina, N-(1-metilpropilideno)-3-metil(diethoxysilyl)-1propanamina, N-benzylidene-3-metil(dimethoxysilyl)propan-1-amina, Nbenzylidene-3-metil(diethoxysilyl)propan-1-amina, N-4-metilbenzylideno3-(triethoxysilyl)propan-1-amina,N-4-methylbenzylidene-3(trimethoxysilyl)propan-1-amine, N-4-methylbenzylidene-3methyl(dimethoxysilyl)propan-1-amine, N-4-methylbenzylidene-3methyl(diethoxysilyl)propan-1-amine, N-naphthylidene-3-(triethoxysilyl)propan1-amine, N-naphthylidene-3-(trimethoxysilyl)propan-1-amine, N-naphthylidene3-methyl(dimethoxysilyl)propan-1-amine, 1,1-(1,4-phenylene)bis(N(3methyl(dimethoxysilyl)propyl)methanamine), 1,1-(1,4-phenylene)bis(N(3methyl(diethoxysilyl)propyl)methanamine), 2-ethoxy-2-methyl-1-(benzylideneaminoethyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(methylisobutylideneaminoethyl)-1-aza-2-silacyclopentane, 1-trimethylsilyl-4-[3-(trimethoxysilyl)propyl]piperazine, and 1-trimethylsilyl-4-[3(triethoxysilyl)propyl]piperazine.

[00219] In the production step of a conjugated diene polymer of the present embodiment, when the coupling step is carried out, it is even preferable that a modifier having a group containing a, Petition 870250088816, dated 09 / 30 / 2025, page 62 / 146 55 / 124 nitrogen atom represented by any of the following formulas (A) to (D) is used in the coupling step. One of these may be used alone or two or more of these may be used in combination. R8 R7— N / \R9,· p<3-a) N—R10—Si— (ORn)a(A)

[00220] Here, R10 and R11 are hydrocarbon groups having 1 to 12 carbon atoms, optionally having an unsaturated bond, and are optionally the same or different. R12 is a hydrocarbon group having 1 to 20 carbon atoms.

[00221] R8 and R9 are an aliphatic hydrocarbon group having 1 to 6 carbon atoms, optionally having an unsaturated bond, and are optionally the same or different.

[00222] R7 is a hydrocarbon group having 1 to 20 carbon atoms optionally substituted with an organic group containing Si, O, or N, and having no active hydrogen, and optionally having an unsaturated bond.

[00223] a is an integer from 1 to 3. Fl16·™ Ris—Si—(0Ri^h

[00224] In formula (B), A represents a hydrocarbon group. Petition 870250088816, dated 09 / 30 / 2025, page 63 / 146 56 / 124 of 1 to 20 carbon atoms, or an organic group that has at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom, and phosphorus atoms, and has no active hydrogen.

[00225] R13, R14, and R15, each independently, represent a single bond, or an alkylene group having 1 to 20 carbon atoms.

[00226] R16, R17, R18, R19, and R21, each independently, represent an alkyl group having 1 to 20 carbon atoms.

[00227] R20 and R22, each independently, represent an alkylene group having 1 to 20 carbon atoms.

[00228] Each R23 independently represents an alkyl group having from 1 to 20 carbon atoms, or a trialkylsilyl group.

[00229] Each b independently represents an integer from 1 to 3, each c independently represents 1 or 2, i represents an integer from 0 to 6, j represents an integer from 0 to 6, k represents an integer from 0 to 6, and the sum of i, j, and k is an integer from 4 to 10. ^(3-s) ípS-t) (RMO)S—Si— R; / - N— R31--Si— (OR25)t (C) R32 Si — R29C3-> (R26O)U

[00230] In formula (C), R24, R25, R26, R27, R28, and R29 each independently represent an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[00231] R30, R31, and R32, each independently, represent an alkylene group having from 1 to 20 carbon atoms.

[00232] s, t, i, each independently, represent an integer from 1 to 3, and the sum of s, t, i is an integer of 4 Petition 870250088816, dated 09 / 30 / 2025, p. 64 / 146 57 / 124 or more. L- OR33OR35Ls N B1— Si 0— Si — B-—1% L2' | EU \ |_4 OR34OR36(D)

[00233] In formula (D), B1 and B2, each independently, represent a divalent hydrocarbon group having from 1 to 20 carbon atoms containing or not containing an oxygen atom.

[00234] R33a R36, each independently, represent a monovalent hydrocarbon group having from 1 to 20 carbon atoms. L1a L4, each independently, represent a divalent, trivalent, or tetravalent alkylsilyl group substituted with an alkyl group having from 1 to 10 carbon atoms, or a monovalent hydrocarbon group having from 1 to 20 carbon atoms, or L1 and L2, and L3 and L4 are optionally mutually linked to form a ring having from 1 to 5 carbon atoms, and when L1 and L2, and L3 and L4 are mutually linked to form a ring, the ring thus formed optionally contains from 1 to 3 heteroatoms of one or more selected from the group consisting of N, O, and S.

[00235] Specifically, in formula (D), B1 and B2 are each independently an alkylene group having 1 to 10 carbon atoms, R33 and R36 are each independently an alkyl group having 1 to 10 carbon atoms, L1 and L4 are each independently a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, or L1 and L2, and L3 and L4 are optionally mutually linked to form a ring having 1 to 3 carbon atoms, and when L1 and L2, and L3 and L4 are mutually linked to form a ring, the ring thus formed optionally contains 1 to 3 heteroatoms of one or more Petition 870250088816, dated 09 / 30 / 2025, p. 65 / 146 58 / 124 selected from the group consisting of N, O, and S.

[00236] Examples of the coupling modifier represented by formula (A) include, but are not limited to, 1-methyl-4-[3(trimethoxysilyl)propyl]piperazine, 1-methyl-4-[3(triethoxysilyl)propyl]piperazine, 1-propyl-4-[3(trimethoxysilyl)propyl]piperazine, 1-propyl-4-[3(triethoxysilyl)propyl]piperazine, 1-trimethylsilyl-4-[3(trimethoxysilyl)propyl]piperazine, and 1-trimethylsilyl-4-[3(triethoxysilyl)propyl]piperazine.

[00237] Among these, a modifier represented by formula (A) wherein a is 3 is preferred from the point of view of increasing the reactivity and interaction between the conjugated diene polymer of the present embodiment and an inorganic filler such as silica, and from the point of view of increasing processability.

[00238] A reaction temperature and reaction time in the coupling step using the coupling modifier represented by formula (A) are not particularly limited, and the reaction is preferably carried out at 0°C or more and 120°C or less, and preferably for 30 seconds or more.

[00239] The amount of coupling modifier represented by formula (A) to be added corresponds to the total number of moles of an alkoxy group attached to a silyl group of the compound represented by formula (A) preferably 0.2 or more times and 2.0 or less times, more preferably 0.3 or more times and 1.5 or less times, and even more preferably 0.4 or more times and 1.0 or less times the number of moles of polymerization initiator to be added. From the point of view that the modified diene conjugate polymer thus obtained has a molecular weight within a more preferred range, the amount is preferably 0.2 or more times, and from the point of view of stability to storage in arms Petition 870250088816, dated 09 / 30 / 2025, p. 66 / 146 59 / 124 prolonged storage, the quantity is preferably 2.0 or less times.

[00240] More specifically, the amounts of polymerization initiator and coupling modifier represented by formula (A) to be added can be adjusted so that the number of moles of coupling modifier represented by formula (A) can preferably be 0.1 or more times and 1.0 or less times the number of moles of polymerization initiator.

[00241] In formula (B), A is preferably represented by any of the following formulas (I) to (IV). 4N-DU (Formula I)

[00242] In formula (I), D1 represents a single bond, or a divalent hydrocarbon group having from 1 to 20 carbon atoms, h represents an integer from 1 to 10. D1, if present multiple times, is respectively independent. D3 -4N— D2— N4h (Formula II)

[00243] In formula (II), D2 represents a single bond, or a divalent hydrocarbon group having from 1 to 20 carbon atoms. D3 represents an alkyl group having from 1 to 20 carbon atoms, and e represents an integer from 1 to 10. Each of D2 and D3, if present multiple times, is respectively independent. Formula (III) Petition 870250088816, dated 09 / 30 / 2025, p. 67 / 146 60 / 124

[00244] In formula (III), D4 represents a single bond, or a divalent hydrocarbon group having from 1 to 20 carbon atoms. h represents an integer from 1 to 10. D4, if present multiple times, is respectively independent. THE I (Formula IV)

[00245] In formula (IV), D5 represents a single bond, or a divalent hydrocarbon group having from 1 to 20 carbon atoms. h represents an integer from 1 to 10. D5, if present multiple times, is respectively independent.

[00246] In formula (B), examples of the coupling modifier in which A is represented by formula (I) include, but are not limited to, tris(3-trimethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]amine, bis[3-(2,2-dimethoxy-1aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)amine, tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]amine, tris(3ethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]amine, bis[3-(2,2-diethoxy-1 -aza-2silacyclopentane)propyl]-(3-triethoxysilylpropyl)amine, tris[3-(2,2-diethoxy-1aza-2-silacyclopentane)propyl]amine, tetrakis(3-trimethoxysilylpropyl)-1,3propanediamine, tris(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2silacyclopentane)propyl]-1,3-propanediamine, bis(3-trimethoxysilylpropyl)bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3propanedimane, and tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl](3-trimethoxysilylpropyl)1,3-propanediamine.

[00247] Other examples include tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tris(3-trimethoxysilylpropyl) Petition 870250088816, dated 09 / 30 / 2025, page 68 / 146 61 / 124 [3-(1-methoxy-2-trimethylsilyl-1-sila-azacyclopentane)propyl]-1,3propanediamine, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2silacyclopentane)propyl]-[3-(1-methoxy-2-trimethylsilyl-1-sila-2azacyclopentane)propyl]-1,3-propanediamine, bis[3-(2,2-dimethoxy-1-aza2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)-[3-(1-methoxy-2trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-propanediamine, tris[3(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-methoxy-2-trimethylsilyl1-syl-2-azacyclopentane)propyl]-1,3-propanediamine, tetrakis(3triethoxysilylpropyl)-1,3-propanediamine, and tris(3-triethoxysilylpropyl)-[3(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine.

[00248] Still other examples include bis(3-triethoxysilylpropyl)bis[3-(2,2-diethoxy-1-aza-2-silacyclopentano)propyl]-1,3-propanediamine, tris[3-(2,2-diethoxy-1-aza-2-silacyclopentano)propyl]-(3-triethoxysilylpropyl)1,3-propanediamine, tetrakis[3-(2,2-diethoxy-1-aza-2silacyclopentano)propyl]-1,3-propanediamine, tris(3-triethoxysilylpropyl)[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentano)propyl]-1,3-propanediamine, bis(3-triethoxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2silacyclopentano)propyl]-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2azacyclopentano)propyl]-1,3-propanediamine, bis[3-(2,2-diethoxy-1-aza-2silacyclopentano)propyl]-(3-triethoxysilylpropyl)-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2azacyclopentano)propyl]-1,3-propanediamine, tris[3-(2,2-diethoxy-1aza-2-silacyclopentano)propyl]-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2azacyclopentano)propyl]-1,3-propanediamine, and tetrakis(3trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane.

[00249] Still other examples include tris(3-trimethoxysilylpropyl)-[3(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, bis(3-trimethoxysilylpropyl)-bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane, tetrakis[3-(2,2-dimethoxy-1-aza-2. Petition 870250088816, dated 09 / 30 / 2025, page 69 / 146 62 / 124 silacyclopentane)propyl]-1,3-propanediamine, tris(3-trimethoxysilylpropyl)[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3bisaminomethylcyclohexane, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy1 -aza-2-silacyclopentane)propyl]-[3-(1-methoxy-2-trimethylsilyl-1-sila-2azacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, and bis[3-(2,2dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)-[3-(1methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3bisaminomethylcyclohexane.

[00250] Still other examples include tris[3-(2,2-dimethoxy-1-aza-2cyclopentano)propyl]-[3-(1-methoxy-2-trimethylsilyl-1-sila-2azacyclopentano)propyl]-1,3-bisaminomethylcyclohexane, tetrakis(3triethoxysilylpropyl)-1,3-propanediamine, tris(3-triethoxysilylpropyl)-[3-(2,2diethoxy-1-aza-2-silacyclopentano)propyl]-1,3-bisaminomethylcyclohexane, bis(3-trimethoxysilylpropyl)-bis[3-(2,2-diethoxy-1-aza-2-silacyclopentano)propyl]-1,3-bisaminomethylcyclohexane, tris[3-(2,2diethoxy-1-aza-2-silacyclopentano)propyl]-(3-triethoxysilylpropyl)-1,3-propanediamine, tetrakis[3-(2,2-diethoxy-1-aza-2-silacyclopentano)propyl]-1,3-propanediamina, tris(3-triethoxysilylpropyl)[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentano)propyl]-1,3bisaminomethylcyclo-hexane, bis(3-triethoxysilylpropyl)-[3-(2,2-diethoxy-1aza-2-silacyclopentano)propyl]-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2azacyclopentano)propyl]-1,3bisaminomethylcyclo-hexane, bis[3-(2,2diethoxy-1-aza-2-silacyclopentane)propyl]-(3-triethoxysilylpropyl)-[3-(1-ethoxy2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, tris[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-ethoxy-2trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, tetrakis(3-trimethoxysilylpropyl)-1,6-hexamethylenediamine, and pentakis(3-trimethoxysilylpropyl)-diethylenetriamine.,

[00251] In formula (B), examples of a coupling modifier in which A is represented by formula (II) include, but without Petition 870250088816, dated 09 / 30 / 2025, page 70 / 146 63 / 124 limitation, tris(3-trimethoxysilylpropyl)-methyl-1,3-propanediamine, bis(2trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]methyl-1,3-propanediamine, bis[3-(2,2-dimethoxy-1-aza-2silacyclopentane)propyl]-(3-trimethoxysilylpropyl)-methyl-1,3propanediamine, tris(3-triethoxysilylpropyl)-methyl-1,3-propanediamine, bis(2-triethoxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]methyl-1,3-propanediamine, bis[3-(2,2-diethoxy-1-aza-2-sylcyclopentane)propyl]-(3-triethoxysilylpropyl)-methyl-1,3-propanediamine, N1,N1'-(propane-1,3-di-yl)bis(N1-methyl-N3,N3-bis(3(trimethoxysilyl)propyl)-1,3-propanediamine), and N1-(3-(bis(3(trimethoxysilyl)propyl)amino)propyl)-N1-methyl-N3-(3-(methyl(3(trimethoxysilyl)propyl)amino)propyl)-N3-(3-(trimethoxysilyl)propyl)-1,3propanediamine.

[00252] In formula (B), examples of a coupling modifier in which A is represented by formula (III) include, but are not limited to, tetrakis[3-(2,2-dimethoxy-1-aza-2sylacyclopentane)propyl]silane, tris[3-(2,2-dimethoxy-1-aza-2sylacyclopentane)propyl]-(3-trimethoxysilylpropyl)silane, tris[3-(2,2dimethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-methoxy-2-trimethylsilyl-1syl-2-azacyclopentane)propyl]silane, bis(3-trimethoxysilylpropyl)-bis[3(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane, (3-trimethoxysilyl)[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)-bis[3-(2,2-dimethoxy1 -aza-2-silacyclopentane)propyl]silane, bis[3-(1-methoxy-2-trimethylsilyl-1syl-2-azacyclopentane)-bis[3-(2,2-dimethoxy-1-aza-2sylacyclopentane)propyl]silane, tris(3-trimethoxysilylpropyl)-[3-(2,2dimethoxy-1-aza-2-silacyclopentane)propyl]silane, bis(3trimethoxysilylpropyl)-[3-(1-methoxy-2-trimethylsilyl-1-sila-2azacyclopentane)propyl]-[3-(2,2-dimethoxy-1-aza-2sylacyclopentane)propyl]silane, bis[3-(1-methoxy-2-trimethylsilyl-1-sila-2azacyclopentane)propyl]-bis(3-trimethoxysilylpropyl)silane, and bis(3, Petition 870250088816, dated 09 / 30 / 2025, page 71 / 146 64 / 124 trimethoxysilylpropyl)-bis[3-(1-methoxy-2-methyl-1-sila-2azacyclopentane)propyl]silane.

[00253] In formula (B), examples of the coupling modifier in which A is represented by formula (IV) include, but are not limited to, 3-tris[2-(2,2-dimethoxy-1-aza-2-silacyclopentane)ethoxy]silyl-1-(2,2-dimethoxy-1-aza-2-silacyclopentane)propane, and 3-tris[2-(2,2-dimethoxy-1aza-2-silacyclopentane)ethoxy]silyl-1-trimethoxysilylpropane.

[00254] The amount of modifier represented by formula (B) to be added is preferably determined based on the ratio between the number of moles of polymerization initiator to be added and the number of moles of modifier represented by formula (B) to be added. Thus, the conjugated diene polymer and the modifier can be adjusted to react with each other in a desired stoichiometric ratio.

[00255] More specifically, the amounts of the polymerization initiator and the coupling modifier represented by formula (B) to be added can be adjusted so that the number of moles of the coupling modifier represented by formula (B) can preferably be 0.012 or more times and 1.0 or less times, and more preferably 0.02 or more times and 0.5 or less times the number of moles of the polymerization initiator. In this case, the number of functional groups of the modifier in formula (B) (for example, when iej are 2 or more, each of wex is present several times, and several fs and gs are respectively equal, fxi + (g + 1) xj + k) is preferably an integer from 5 to 10, and more preferably an integer from 6 to 10. From the point of view of stipulating the molecular weight of a modified conjugated diene polymer to be obtained in a preferred range, the number of moles of the modifier is preferably 0.012 or more times.Furthermore, from a stability standpoint, storage is more efficient in pro storage. Petition 870250088816, dated 09 / 30 / 2025, page 72 / 146 65 / 124 elongated, the number of moles is preferably 0.2 or less times.

[00256] Among these, from the point of view of increasing the reactivity and interaction between the modified conjugated diene polymer and an inorganic filler such as silica, and from the point of view of increasing processability, i, j, and k in formula (B) are all preferably 3.

[00257] Examples of the coupling modifier represented by formula (C) include, but are not limited to, tris(3-trimethoxysilylpropyl)amine, tris(3-methyldimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl)amine, tris(3-methyldiethoxysilylpropyl)amine, tris(trimethoxysilylmethyl)amine, tris(2-trimethoxysilylethyl)amine, and tris(4-trimethoxysilylbutyl)amine.

[00258] The reaction temperature and reaction time in the coupling step using the coupling modifier represented by formula (C), although not limited to the following values, the reaction is preferably carried out at 0°C or more and 120°C or less preferably for 30 seconds or more.

[00259] The amount of coupling modifier represented by formula (C) to be added corresponds to a total number of moles of alkoxy groups linked to silyl groups of the compound represented by formula (C) preferably 0.1 or more times and 2.0 or less times, more preferably 0.2 or more times and 1.0 or less times, and even more preferably 0.3 or more times and 0.5 or less times the number of moles of polymerization initiator to be added. From the point of view of the molecular weight of a modified diene conjugate polymer to be obtained, the number of moles is preferably 0.1 or more times. From the point of view of stability to long-term storage, the number of moles is preferably 2.0 or less times.

[00260] Examples of the coupling modifier represented in Petition 870250088816, dated 09 / 30 / 2025, page 73 / 146 66 / 124 formula (D) includes 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-di-yl) bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-di-yl) bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-di-yl) bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-di-yl) bis(N,N-dipropylpropan-1-amine), and 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-di-yl)bis(N,N-diethylpropan-1-amine).

[00261] The reaction temperature and reaction time in the coupling step using the coupling modifier represented by formula (D) are not particularly limited, and the reaction is preferably carried out at 0°C or more and 120°C or less, and preferably for 30 seconds or more.

[00262] The amount of coupling modifier represented by formula (D) to be added corresponds to the total number of moles of alkoxy groups linked to silyl groups of the compound represented by formula (D), preferably 0.25 or more times and 2.0 or less times, more preferably 0.3 or more times and 1 or less times, and even more preferably 0.35 or more times and 0.5 or less times the number of moles of polymerization initiator to be added. From the point of view of the molecular weight of a modified diene conjugate polymer to be obtained, and from the point of view of stability to prolonged storage, the number of moles is preferably 2.0 or less times.

[00263] The method for producing a conjugated diene polymer of the present embodiment may include, after the coupling step and / or before the coupling step, a condensation reaction step to cause a condensation reaction by adding a condensation accelerator.

[00264] In the production method of a conjugated diene polymer Petition 870250088816, dated 09 / 30 / 2025, page 74 / 146 67 / 124 of the present embodiment, after the coupling step, a deactivator and / or a neutralizer or similar may be added, if necessary, to the resulting polymer solution.

[00265] Examples of the deactivator include, but are not limited to, water, and alcohols such as methanol, ethanol, and isopropanol.

[00266] Examples of neutralizers include, but are not limited to, carboxylic acids such as stearic acid, oleic acid, and versatic acid (a mixture of highly branched carboxylic acids having 9 to 11 carbon atoms, and containing, as a major component, a carboxylic acid having 10 carbon atoms), an aqueous solution of an inorganic acid, and carbon dioxide gas.

[00267] From the point of view of preventing gel formation after polymerization, and from the point of view of improving stability in processing, a rubber stabilizer is preferably added to the conjugated diene polymer of the present embodiment.

[00268] Although the rubber stabilizer is not limited to the following, any of the known stabilizers may be used, and preferred examples include antioxidants such as 2,6-di-tert-4-hydroxytoluene (BHT), n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol)propionate, and 2-methyl-4,6-bis[(octylthio)methyl]phenol. (Polymer Solution Preparation Step)

[00269] The method for producing a conjugated diene polymer of the present embodiment may include a step for obtaining the resulting conjugated diene polymer from the polymer solution. As a method for obtaining the conjugated diene polymer from the polymer solution, any of the known methods may be employed and, for example, the following methods may be employed. Examples of the method include a method in which the conjugated diene polymer is filtered after separation from the solvent by extra Petition 870250088816, dated 09 / 30 / 2025, page 75 / 146 68 / 124 steam treatment or similar, and the resulting product is dehydrated and dried to obtain the conjugated diene polymer, a method in which the solution is concentrated in a washing tank, and the resulting product is devolatilized by means of a curved extruder or similar to obtain the conjugated diene polymer, and a method in which the solution is directly devolatilized by means of a drum dryer or similar to obtain the conjugated diene polymer. (Extended Conjugated Diene Polymer Production Step)

[00270] In the production method of a conjugated diene polymer of the present embodiment, at least one polymer selected from the group consisting of an extender oil, a liquid rubber and a resin may be added to the conjugated diene polymer produced to obtain an extended conjugated diene polymer.

[00271] It is observed that the extended conjugated diene polymer encompasses not only an extended conjugated diene polymer with an oil containing an oil, but also a polymer containing a liquid polybutadiene or any of several resins except for an oil.

[00272] Therefore, the processability of the conjugated diene polymer can be improved even further.

[00273] As a method of adding an extender oil to the conjugated diene polymer, although not limited to the following, a method is preferred in which an extender oil is added to the conjugated diene polymer solution to be mixed, and the extended polymer solution thus obtained is desolvated.

[00274] Examples of extender oils include an aromatic oil, a naphthenic oil, a paraffinic oil, and a vegetable oil. Vegetable oil can be prepared from an oil selected from the group consisting of linseed oil, safflower oil, soybean oil, corn oil, cottonseed oil, castor oil, tung oil, etc. Petition 870250088816, dated 09 / 30 / 2025, p. 76 / 146 69 / 124 pine, sunflower oil, palm oil, olive oil, coconut oil, peanut oil, and grapeseed oil. Among these, from the point of view of environmental safety, and from the point of view of preventing oil leakage and the property of adhesion to wet surfaces, an alternative aromatic oil containing 3% by mass or less of a polycyclic aromatic compound (PCA) according to IP 346 is preferred.

[00275] Examples of alternative aromatic oils include TDAE (Treated Distillate Aromatic Extracts), and MES (Mild Extraction Solvate) mentioned in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999), and RAE (Residual Aromatic Extracts).

[00276] Examples of liquid rubber include, but are not limited to, liquid polybutadiene and liquid styrene-butadiene rubber.

[00277] Examples of resin include, but are not limited to, an aromatic petroleum resin, a coumarone-indene resin, a terpene-based resin, and a rosin derivative (including a manioc oil resin), tallow oil, a tallow oil derivative, a rosin ester resin, a natural or synthetic terpene resin, an aliphatic hydrocarbon resin, an aromatic hydrocarbon resin, a mixed aliphatic / aromatic hydrocarbon resin, a coumarin-indene resin, a phenol resin, a p-tert-butylphenol-acetylene resin, a phenol-formaldehyde resin, a xylene-formaldehyde resin, a monoolefin oligomer, a diolefin oligomer, a hydrogenated aromatic hydrocarbon resin, a cyclic aliphatic hydrocarbon resin, a hydrogenated hydrocarbon resin, a wood oil resin hydrogenated, a hydrogenated oil resin, and an ester of a hydrogenated oil resin and a monofunctional or polyfunctional alcohol. Petition 870250088816, dated 09 / 30 / 2025, page 77 / 146 70 / 124

[00278] One of these resins can be used alone or two or more of them can be used together.

[00279] When such resin is hydrogenated, all unsaturated groups may be hydrogenated, or some of them may be left unhydrogenated.

[00280] The amount to be added of at least one component selected from the group consisting of an extender oil, a liquid rubber, and a resin is not particularly limited, and preferably varies from 1 to 60 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 15 to 37.5 parts by mass based on 100 parts by mass of the conjugated diene polymer of the present embodiment. [Rubber Composition]

[00281] The conjugated diene polymer of the present embodiment can be transformed into a rubber composition (hereinafter sometimes referred to as the rubber composition of the present embodiment) by adding a filler thereto.

[00282] The rubber composition of the present embodiment contains a rubber component containing the conjugated diene polymer of the present embodiment, and 5.0 parts by mass or more and 150 parts by mass or less of a filler based on 100 parts by mass of the rubber component, and the rubber component preferably contains 10 parts by mass or more of the conjugated diene polymer of the present embodiment based on 100 parts by mass of the total quantity of the rubber component. When the filler is dispersed in the rubber component containing the conjugated diene polymer of the present embodiment, a rubber composition is further improved in terms of processability in vulcanization, and further improved in terms of the low hysteresis loss property, fracture performance, and abrasion resistance of a vulcanized product. Petition 870250088816, dated 09 / 30 / 2025, page 78 / 146 71 / 124 obtained from it can be obtained. When the rubber component contains the conjugated diene polymer of the present embodiment in a determined ratio, the processability and abrasion resistance are further improved.

[00283] Examples of fillers include, but are not limited to, an inorganic silica-based filler, carbon black, a metal oxide, and a metal hydroxide. Among these, an inorganic silica-based filler is preferred. In particular, when the rubber composition is used in vehicle components such as a tire, and an anti-vibration rubber, or in the application to a vulcanized rubber for footwear, among others, it is particularly preferable that an inorganic silica-based filler be contained. One of these fillers may be used alone, or two or more of these may be used together.

[00284] The silica-based inorganic filler is not particularly limited; any of the known fillers may be used. A solid particle containing SiOs or SisAl as a constituent unit is preferred, and a solid particle containing SiOs or SisAl as a major component of a constituent unit is more preferred. Herein, major component refers to a component contained in the silica-based inorganic filler in an amount of more than 50% by mass, preferably 70% by mass or more, and most preferably 80% by mass or more.

[00285] Examples of silica-based inorganic fillers include, but are not limited to, silica, clay, talc, mica, diatomite, wollastonite, montmorillonite, zeolite, and fibrous inorganic substances such as fiberglass. Alternatively, a silica-based inorganic filler having a hydrophobized surface may be used, and a mixture of a silica-based inorganic filler and an inorganic filler other than silica may be used. Among these, from the point of view of improvement Petition 870250088816, dated 09 / 30 / 2025, p. 79 / 146 72 / 124 To further improve the mechanical strength and abrasion resistance of the rubber composition of the present embodiment, silica or fiberglass is preferred, and silica is more preferred. Silica is not particularly limited, and examples include dry silica, wet silica, and synthetic silicate. Among these silicas, wet silica is preferred from the point of view of further improving the fracture resistance of the resulting rubber composition.

[00286] From the point of view of obtaining a more definitive rubber compound having practically good abrasion resistance and fracture resistance, the specific surface area for nitrogen adsorption, obtained by the BET adsorption method, of the silica-based inorganic filler is preferably 100 m² / g or more and 300 m² / g or less, and more preferably 170 m² / g or more and 250 m² / g or less. Furthermore, a silica-based inorganic filler having a comparatively small specific surface area (e.g., a specific surface area less than 200 m² / g) and a silica-based inorganic filler having a comparatively large specific surface area (e.g., 200 m² / g or more) can be used in combination, if necessary.Particularly when an inorganic silica-based filler having a comparatively large specific surface area (e.g., 200 m² / g or more) is used, the rubber composition of the present embodiment is further improved in terms of silica dispersibility. As a result, a rubber composition having even better abrasion resistance, fracture resistance, and low hysteresis loss properties tends to be obtained.

[00287] Examples of carbon black include, but are not limited to, carbon black of the SRF, FEF, HAF, ISAF and SAF classes. Among these, a carbon black having a specific surface area for nitrogen adsorption of 50 m² / g or more and oil absorption of di Petition 870250088816, dated 09 / 30 / 2025, page 80 / 146 73 / 124 butyl phthalate (DBP) at 80 mL / 100 g or less is preferred.

[00288] Metal oxide is not particularly limited as long as it is a solid particle containing a major component of a constituent unit represented by the chemical formula MxOy (where M represents a metal atom, x and y each independently represent an integer from 1 to 6), and examples include alumina, titanium oxide, magnesium oxide, and zinc oxide.

[00289] Metal hydroxide is not particularly limited, and examples include aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.

[00290] The filler content in the rubber composition of the present embodiment is preferably 5.0 parts by mass or more and 150 parts by mass or less, more preferably 20 parts by mass or more and 100 parts by mass or less, and even more preferably 30 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the rubber component. When the filler content satisfies this range, the rubber composition tends to be even better in terms of processability in vulcanization, and even better in terms of the low hysteresis loss property, fracture performance, and abrasion resistance of a vulcanizate thereof.

[00291] From the point of view of definitively conferring the necessary performance in use as a tire or similar, such as grip performance on dry surfaces and conductivity, the rubber composition of the present embodiment preferably contains 0.5 parts by mass or more and 100 parts by mass or less of carbon black based on 100 parts by mass of the rubber component containing the conjugated diene polymer of the present embodiment. From a similar point of view, the rubber composition contains carbon black in a more preferred quantity. Petition 870250088816, dated 09 / 30 / 2025, page 81 / 146 74 / 124 preferably 3.0 parts by mass or more and 100 parts by mass or less, and even more preferably 5.0 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the rubber component containing the conjugated diene polymer of the present embodiment.

[00292] The rubber composition of the present embodiment may also contain a silane-type coupling agent. When the rubber composition contains a silane-type coupling agent, the interaction between the rubber component and the filler may be further improved.

[00293] Examples of silane-type coupling agents are, but are not limited to, preferably a compound containing, in one molecule, a sulfur linking moiety and an alkoxysilyl group moiety or a silanol group moiety. Examples of such a compound include, but are not limited to, bis-[3-(triethoxysilyl)-propyl]-tetrasulfide, bis-[3-(triethoxysilyl)-propyl]-disulfide and bis-[2-(triethoxysilyl)-ethyl]tetrasulfide.

[00294] In the rubber composition of the present embodiment, the content of the silane-type coupling agent is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, and even more preferably 1.0 part by mass or more and 15 parts by mass or less based on 100 parts by mass of the filler. When the content of the silane-type coupling agent is within the range described above, there is a tendency for the interaction between the rubber component and the filler to be further improved.

[00295] The rubber composition of the present embodiment may contain, as the rubber component, a rubber-like polymer other than the conjugated diene polymer of the present embodiment. Petition 870250088816, dated 09 / 30 / 2025, page 82 / 146 75 / 124 (hereinafter simply referred to as rubber-like polymer).

[00296] Examples of rubber-like polymers include, but are not limited to, a conjugated diene polymer and a hydrogenated product thereof, a random copolymer of a conjugated diene-based compound and a vinyl aromatic compound, and a hydrogenated product thereof, a block copolymer of a conjugated diene-based compound and a vinyl aromatic compound, and a hydrogenated product thereof, and a non-diene-based polymer and a natural rubber.

[00297] Examples of rubber-like polymers include, but are not limited to, butadiene rubber and a hydrogenated product thereof, isoprene rubber and a hydrogenated product thereof, styrene-based elastomers such as styrene-butadiene rubber and a hydrogenated product thereof, styrene-butadiene block copolymer and a hydrogenated product thereof, and styrene-isoprene block copolymer and a hydrogenated product thereof, and acrylonitrile-butadiene rubber and a hydrogenated product thereof.

[00298] Examples of non-diene-based polymers include, but are not limited to, olefin-based elastomers such as ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber and ethylene-octene rubber, butyl rubber, brominated butyl rubber, acrylic rubber, fluorine rubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, nitrile α,β-unsaturated-acrylic acid ester-diene copolymer rubber, urethane rubber and polysulfide rubber. Petition 870250088816, dated 09 / 30 / 2025, page 83 / 146 76 / 124

[00299] Examples of natural rubber include, but are not limited to, smoked sheets of RSS No. 3 to 5, SMR and epoxidized natural rubber.

[00300] The rubber-like polymer may be in the form of a modified rubber having a functional group having polarity such as a hydroxyl group or an amino group. When the rubber composition of the present invention is used in a tire, the rubber-like polymer is preferably one or more polymers selected from the group consisting of butadiene rubber, isoprene rubber, styrene-butadiene rubber, natural rubber and butyl rubber.

[00301] The number average molecular weight of the rubber-like polymer is preferably 2,000 or more and 2,000,000 or less, and more preferably 5,000 or more and 1,500,000 or less from the point of view of abrasion resistance and fracture resistance, and the balance between the low hysteresis loss property and the processability of the rubber composition.Like rubber-like polymers, a low molecular weight rubber-like polymer, that is, one that is called liquid rubber, can be used. One of these rubber-like polymers can be used alone, or two or more of them can be used together.

[00302] When the rubber composition of the present embodiment contains the rubber-like polymer in addition to the conjugated diene polymer of the present embodiment, the ratio (in a mass ratio) of the conjugated diene polymer to the rubber-like polymer is, in terms of (conjugated diene polymer / rubber-like polymer), preferably 10 / 90 or more and 100 / 0 or less, more preferably 20 / 80 or more and 90 / 10 or less, and even more preferably 30 / 70 or more and 80 / 20 or less. In other words, the rubber component contains, based on 100 Petition 870250088816, dated 09 / 30 / 2025, p. 84 / 146 77 / 124 parts by mass of the total quantity of the rubber component, preferably 10 parts by mass or more and 100 parts by mass or less, more preferably 20 parts by mass or more and 90 parts by mass or less, and even more preferably 30 parts by mass or more and 80 parts by mass or less of the conjugated diene polymer of the present embodiment. When the ratio of the conjugated diene polymer of the present embodiment contained in the rubber component is within the range described above, a vulcanizate of the rubber composition tends to be even better in terms of abrasion resistance and low hysteresis loss property.

[00303] A rubber softener may be added to the rubber composition of the present embodiment in addition to the rubber component from the point of view of further improving processability.

[00304] As with the rubber softener, the same softeners as those described as examples to be contained in the conjugated diene polymer described above can be used, and a mineral oil, or a liquid or synthetic softener of low molecular weight is suitable.

[00305] A mineral oil-based rubber softener, which is used to soften, expand, and improve the processability of a rubber component and is designated as a process oil or extender oil, is a mixture of an aromatic ring, a naphthenic ring, and a paraffin chain. In particular, a softener in which the number of carbon atoms in the paraffin chain is 50% or more is designated as a paraffin-based softener, a softener in which the number of carbon atoms in the naphthenic ring is 30% or more and 45% or less is designated as a naphthene-based softener, and a softener in which the number of carbon atoms belonging to aromatic carbons exceeds 30% of the number of all carbon atoms is designated as a naphthene-based softener. Petition 870250088816, dated 09 / 30 / 2025, p. 85 / 146 78 / 124 aromatic. The rubber composition of the present embodiment preferably contains, as a rubber softener, a softener having a suitable aromatic content. When such a rubber softener is included, the compatibility with the conjugated diene polymer is further improved.

[00306] The rubber softener content in the rubber composition of the present embodiment is expressed as the sum of the amount of rubber softener previously added to the conjugated diene polymer or rubber-like polymer, and the amount of rubber softener added during the formation of the rubber composition.

[00307] In the rubber composition of the present embodiment, the content of the rubber softener is preferably 0 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 90 parts by mass or less, and even more preferably 30 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the rubber component. When the content of the rubber softener is 100 parts by mass or less based on 100 parts by mass of the rubber component, leakage can be suppressed, and the stickiness of the surface of the rubber composition can be further suppressed.

[00308] Rubber compositions can be produced by mixing conjugated diene polymer, rubber-like polymer, filler, silane-type coupling agent, rubber softener, among others. The mixing method is not particularly limited, and examples include a melt kneading method using a generic mixer, such as an open roll, a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, or a multi-screw extruder. Petition 870250088816, dated 09 / 30 / 2025, page 86 / 146 79 / 124 screws, and a method in which the respective components are melted and mixed and then the solvent is removed by heating. Among these methods, the melt kneading method using a roller, a Banbury mixer, a kneader or an extruder is preferred from the point of view of productivity and high kneading capacity. In addition, the rubber component, the filler, the silane-type coupling agent, and the additive can be kneaded all together, or they can be mixed separately several times.

[00309] The rubber composition of the present embodiment may be in the form of a vulcanizate obtained by vulcanization with a vulcanizing agent. The vulcanizing agent is not particularly limited; examples include radical generators such as organic peroxides and azo compounds, oxime-type compounds, nitroso compounds, polyamine-type compounds, sulfur, and sulfur compounds. Sulfur compounds include sulfur monochloride, sulfur dichloride, disulfide-type compounds, high molecular weight polysulfide-type compounds, among others.

[00310] In the rubber composition of the present embodiment, the content of the vulcanizing agent is 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 and 15 parts by mass or less based on 100 parts by mass of the rubber component. As a vulcanization method, any of the conventionally known methods may be employed. The vulcanization temperature is preferably 120°C or more and 200°C or less, and more preferably 140°C or more and 180°C or less.

[00311] For the vulcanization of the rubber composition, a vulcanization accelerator and / or a vulcanization aid may be used, if necessary. As a vulcanization accelerator, either Petition 870250088816, dated 09 / 30 / 2025, p. 87 / 146 80 / 124 of conventionally known materials can be used, and examples include, but are not limited to, sulfenamide-based, guanidine-based, thiuram-based, aldehyde-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, thiourea-based and dithiocarbamate-based vulcanization accelerators.

[00312] In addition, examples of vulcanizing aids include, but are not limited to, zinc oxide and stearic acid.

[00313] The vulcanization accelerator content and the vulcanization auxiliary content are, respectively, 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 and 15 parts by mass or less based on 100 parts by mass of the rubber component.

[00314] In the rubber composition of the present embodiment, provided that the effects of the present embodiment are not impaired, various additives such as another softener, and filler excluding those described above, a heat resistance stabilizer, an antistatic agent, a weathering stabilizer, an anti-aging agent, a colorant and a lubricant may be used. As the softener, any of the known softeners may be used. Examples of filler excluding those described above include, but are not limited to, calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate. As the heat resistance stabilizer, the antistatic agent, the weathering stabilizer, the anti-aging agent, the colorant and the lubricant, any of the known materials may be used respectively.

[00315] The rubber compound of the present embodiment is suitably used as a rubber compound for a tire. The rubber compound of the present embodiment can be suitably used, but without limitation, in various tires such as a low fuel consumption tire, an all-purpose tire Petition 870250088816, dated 09 / 30 / 2025, p. 88 / 146 81 / 124 treads, a high-performance tire and a tire without treads; and various tire parts such as the tread, the carcass; the sidewall and the bead.

[00316] Note that each numerical range described above as a preferred or similar range may be a numerical range obtained by arbitrary combination of any of the values ​​described as upper limits and any of the values ​​described as lower limits even when not specifically indicated. Examples

[00317] The present embodiment will now be described in detail with regard to specific examples and comparative examples, and it is noted that the present invention is in no way limited to the following examples and comparative examples.

[00318] Several physical properties of the examples and comparative examples were measured by the following methods. ((Physical Property 1) Polymer Segment Ratio)<Teor de Sólidos>

[00319] The solids content in a conjugated diene polymer solution was obtained based on the amount of a non-volatile component in the conjugated diene polymer solution flowing through a measuring point in a unit of time. The total amount of conjugated diene polymer solution flowing through a measuring point was collected for 3 minutes, and immediately after this, a polymerization terminator was added. Then, the collected solution was transferred to a heat-resistant dish, and the mass (M) of the remaining solid after drying the resulting product in an oven at 140°C for 30 minutes or more was measured.

[00320] Here, the solids content (m) was obtained according to the following expression (I): Solid content m [g / min\ = mass M of the solid [g / 3 m] ^ 3 ... (I) Petition 870250088816, dated 09 / 30 / 2025, page 89 / 146 82 / 124

[00321] Furthermore, the measurement point was changed to a discharge part of a polymerization step (P1) synthesizing a first polymer segment, and to a discharge part of a polymerization step (P2) forming a second polymer segment, and the solids contents obtained in these parts were defined as m1 and m2, respectively. <Mass Ratios ne r2 of the First Polymer Segment and the Second Polymer Segment>

[00322] The mass ratios r of the first polymer segment and the second polymer segment were obtained according to expressions (II) and (III) below as ratios of the solids contents m1 and m2 obtained in the discharge parts of the polymerization step (P1) of synthesis of the first polymer segment and of the polymerization step (P2) of formation of the second polymer segment to the sum of the mass (U) of the conjugated diene compound and the mass (V) of the vinyl aromatic compound added per unit time in the entire polymerization step.

[00323] In this example, U refers to the total amount of 1,3-butadiene added to a first reactor and 1,3-butadiene added to a second reactor per unit time, and V refers to the total amount of styrene added to the first reactor and styrene added to the second reactor per unit time. Ratio of the first segment of the first n [%] = [(mú(U + V)) x 100 (II) Ratio of the first segment of the first r2 [%] = [(m2 - m1) / (U + V) x 100 (III)<Razão de Proporções dos Segmentos de Polímero: R>

[00324] The ratio R (= n / r2) of the mass ratio of the first polymer segment to the mass ratio of the second polymer segment was obtained according to the following expression (IV): Petition 870250088816, dated 09 / 30 / 2025, pp. 90 / 146 83 / 124 Ratio R between mass ratios of polymer segments = r1 / r2 (IV) ((Physical Property 2) Amount of conjugated diene monomer units linked (Amount of Styrene Linked))<Quantidade de Estireno Ligado Xall do Polímero de dieno Conjugado>

[00325] A conjugated diene polymer not containing a rubber softener, and collected from the discharge portion of the polymerization step (P2) of the second polymer segment formation was used as a sample, and 100 mg of the sample were diluted to 100 mL with chloroform and dissolved to obtain a measurement sample.

[00326] The amount of styrene bonded (% by mass) in 100% by mass of a coupling conjugated diene polymer used as the sample was measured by measuring the amount of absorption at an ultraviolet absorption wavelength (around 254 nm) by a phenyl group of styrene (measuring instrument: UV-2450 spectrophotometer produced by Shimadzu Corporation). <Quantidade de Estireno Ligado Xi no Primeiro Segmento de Polímero>

[00327] The sample was replaced from the conjugated diene polymer with a solids content of the polymer solution obtained from the discharge portion of the polymerization step (P1) of the synthesis of the first polymer segment. Except for this, the same conditions as those employed in the method for the amount of styrene bound in a segment of the conjugated diene polymer were employed to calculate the amount of styrene bound. <Quantidade de Estireno Ligado X2 no Segundo Segmento de Polímero>

[00328] Based on the solids contents m1 and m2 respectively of the polymerization step (P1) of the synthesis of the first segment of Petition 870250088816, dated 09 / 30 / 2025, page 91 / 146 84 / 124 polymer and the polymerization step (P2) of forming the second polymer segment, and in the amounts of styrene bonded Xi and Xaii, the amount of styrene bonded (X2) in the second polymer segment was calculated according to the following expression (VIII): lOOXaH-rjXjA2-------(VI II ) <Diferença ΙΔΧΙ na Quantidade de Estireno Ligado entre 0 Primeiro Segmento de Polímero e 0 Segundo Segmento de Polímero>

[00329] A difference |ΔΧ| in the amount of styrene bonded between the first polymer segment and the second polymer segment was obtained according to the following expression (IX): ((Physical Property 3) Number of Vinyl Bonds in the Linked Conjugated Diene (Number of 1,2-vinyl Bonds in the Linked Butadiene))<Quantidade de Ligações vinílicas Yaii no Polímero de dieno Conjugado>

[00330] A conjugated diene polymer not containing a rubber softener, and collected from the discharge portion of the polymerization step (P2) of the second polymer segment formation was used as a sample, and 50 mg of the sample were dissolved in 10 mL of carbon disulfide to obtain a measurement sample.

[00331] An infrared spectrum of each sample was measured in a range of 600 to 1,000 οητ1 with a Fourier transform infrared spectrophotometer (trade name FT-IR230 produced by JASCO Corporation). Petition 870250088816, dated 09 / 30 / 2025, page 92 / 146 85 / 124

[00332] According to Hampton's method (method described by RR Hampton, Analytical Chemistry 21, 923 (1949)), an amount of 1,2-vinyl bonding (mol%) in the bonded butadiene was obtained based on the absorbance at a determined wavelength. <Quantidade de Ligações vinílicas Yi no Primeiro Segmento de Polímerc»

[00333] The sample was replaced from the conjugated diene polymer with the solids content of the polymer solution obtained in the discharge portion of the polymerization step (P1) of the synthesis of the first polymer segment. Except for this, the same conditions as those employed in the method for the amount of vinyl linkages in the conjugated diene polymer were employed to calculate the amount of vinyl linkages. <Quantidade de Ligações vinílicas Y2 no Segundo Segmento de Polímerc»

[00334] Based on the solids contents rm and m2 respectively of the polymerization step (P1) of synthesis of the first polymer segment and the polymerization step (P2) of formation of the second polymer segment, and on the amounts of vinyl linkages Y1 and Yaii in the conjugated diene bonded, the amount of vinyl linkages in the second polymer segment was calculated according to the following expression (X): _ 100(100-Χβι)ΥΒιι-π(100-Χι)Υι (100-Χί)η <Diferença AY na Quantidade de ligações vinílicas entre 0 Primeiro Segmento de Polímero e 0 Segundo Segmento de Polímero>

[00335] A difference AY in the number of vinyl linkages in the conjugated diene bonded between the first polymer segment and the second polymer segment was obtained according to the expression Petition 870250088816, dated 09 / 30 / 2025, page 93 / 146 86 / 124 (XI) next: ΔΥ = Y2- Υι (XI) ((Physical Property 4) Conversion Rate, and Difference in Polymerization Conversion Rate)

[00336] The conversion rate Cbd of the conjugated diene compound and the conversion rate cst d of the vinyl aromatic compound in the polymerization step (P1) of the synthesis of the first polymer segment were obtained respectively according to expressions (V) and (VI) below: fcs s oon version of the «smpcsto de d eno conjugado em PI Crf [%] = m 1xH ~ 0.01XI) χ | yo lata de conversão do composts vini Tomatkoem P1 ç.jipX,] _ miXÜ.OlXi xiqq - (V]}

[00337] Furthermore, a difference between the conversion rate of the conjugated diene compound and the conversion rate of the vinyl aromatic compound, that is, a Cdif difference in the polymerization conversion rate, was obtained according to the following expression (VII): Cdif [%] = | cbd[%] - Cst [%] | (VII) ((Physical Property 5) Estimated Glass Transition Temperature)

[00338] The estimated glass transition temperature of a conjugated diene polymer was obtained through (iii). ((Physical Property 6) Molecular Weight)

[00339] A conjugated diene polymer from each of the Examples and Comparative Examples was used as a sample to measure a chromatogram using a GPC measuring instrument (trade name HLC-8320GPC produced by Tosoh Corporation) including a series of three columns using a polystyrene-based gel as feedstock, and an RI detector (trade name HLC8020 produced by Tosoh Corporation). Based on the calibration curve obtained using standard polystyrene, a weight-average molecular weight (Mw), a number-average molecular weight (Mn), and a molecular weight distribution (Mw / Mn) were obtained. Petition 870250088816, dated 09 / 30 / 2025, pp. 94 / 146 87 / 124

[00340] As eluent, 5 mmol / L triethylamine containing THF (tetrahydrofuran) was used. As columns, trade name TSKguardcolumn Super MP(HZ)-H produced by Tosoh Corporation were connected, as a guard column in an earlier stage, to a series of three columns trade name TSKgel Super Multipore HZ-H produced by Tosoh Corporation were used.

[00341] Ten (10) mg of a sample for measurement were dissolved in 10 mL of THF to obtain a measurement solution, and 10 pL of the measurement solution were injected into the GPC measuring apparatus to perform the measurement under conditions of a furnace temperature of 40°C and a THF flow rate of 0.35 mL / min. ((Physical Property 7) Mooney Viscosity of the Polymer)

[00342] A conjugated diene polymer from each of the Examples and Comparative Examples was used as a sample to measure Mooney viscosity using a Mooney viscometer (trade name VR1132 produced by Ueshima Seisakusho Co., Ltd.) according to ISO 289 with an L-type rotor used, and with a measurement temperature stipulated at 100°C.

[00343] After the sample was preheated to the test temperature for 1 minute, the rotor was rotated at 2 rpm, and a torque was measured 4 minutes later to measure the Mooney viscosity (ML(1+4)). ((Physical Property 8) Glass Transition Temperature (Tg))

[00344] When a conjugated diene polymer from each of the Examples and Comparative Examples was an oil-extended product, the conjugated diene polymer after extraction of the extender oil was used as a sample, and according to ISO 22768:2006, a DSC curve was recorded with a DSC 3200S differential scanning calorimeter produced by Mac Science with the temperature increased from -120°C to 40°C at 10°C / min under a flow of 50 mL / min of helium, and then, an inflection point of the curve Petition 870250088816, dated 09 / 30 / 2025, pp. 95 / 146 88 / 124 va of DSC observed in a section between -100°C and 20°C was determined as the glass transition temperature.

[00345] An extrapolated initial temperature was determined using the temperature at an intersection point between a straight line drawn extending, on the high-temperature side, the baseline on the low-temperature side and a tangent line drawn at a point corresponding to the maximum gradient of a curve of a gradually changing part of the glass transition.

[00346] An extrapolated final temperature was determined as the temperature at a point between a straight line drawn extending, on the low-temperature side, the baseline on the high-temperature side and the tangent line drawn at the point corresponding to the maximum gradient of the curve of a gradually changing part of the glass transition. ((Physical Property 9) Modification Rate)

[00347] The modification ratio of a conjugated diene polymer from each of the Examples and Comparative Examples was measured by GPC adsorption on the column as follows.

[00348] A conjugated diene polymer was used as a sample to perform the measurement using the characteristic that a basic polymer component is adsorbed onto a GPC column using a silica-based gel as a feedstock.

[00349] Based on the difference between a chromatogram obtained by measurement with a polystyrene-based column and a chromatogram obtained by measurement with a silica-based column, which were obtained from a sample solution containing the sample and the low molecular weight internal standard polystyrene, the amount of absorption on the silica-based column was measured to obtain a modification ratio. <Preparação da Solução de Amostra> : Petition 870250088816, dated 09 / 30 / 2025, pp. 96 / 146 89 / 124

[00350] 10 mg of the sample and 5 mg of the standard polystyrene were dissolved in 20 mL of THF (tetrahydrofuran) to obtain the sample solution. <Condições de Medição por GPC Usando uma Coluna à base de Poliestirenos

[00351] Using an instrument with the commercial name HLC8320GPC manufactured by Tosoh Corporation, and with 5 mmol / L of THF containing triethylamine used as eluent, 10 qL of the sample solution were injected into the instrument to obtain a chromatogram with an RI detector under conditions of a column oven temperature of 40°C, and a THF flow rate of 0.35 mL / min.

[00352] As columns, a series of TSKgel Super Multipore HZ-H commercial name columns produced by Tosoh Corporation were connected with a TSKguardcolumn SuperMP(HZ)-H commercial name column produced by Tosoh Corporation connected as a guard column in an earlier stage were used. <Condições de medição por GPC usando uma coluna à base de sílica>

[00353] The GPC measurement was performed using a device with the commercial name HLC-8320GPC manufactured by Tosoh Corporation and an RI detector (commercial name HLC8020 manufactured by Tosoh Corporation).

[00354] THF was used as eluent, and 50 qL of a sample solution were injected into the GPC apparatus to obtain a chromatogram under conditions of a column oven temperature of 40°C and a THF flow rate of 0.5 mL / min.

[00355] A series of columns with the trade names Zorbax PSM1000S, PSM-300S and PSM-60S produced by Agilent Technologies Japan Ltd., and a guard column with the trade name DIOL 4.6 x 12.5 mm 5 micron connected in a previous stage were used. Petition 870250088816, dated 09 / 30 / 2025, page 97 / 146 90 / 124 < Calculation Method for the Modification Ratio >:

[00356] In the chromatogram obtained using the polystyrene-based column, it was assumed that the total peak area was equal to 100, that a sample peak area was p1, that a standard polystyrene peak area was p2, and in the chromatogram using the silica-based column, it was assumed that the total peak area was equal to 100, that a sample peak area was p3, and that a standard polystyrene peak area was p4, and thus, a modification ratio (%) was obtained based on the following expression: Change rate (%) = [1 - (p2 x p3) / (p1 x p4)] x 100 where p1 + p2 = p3 + p4 = 100. [Production of Conjugated Diene Polymer] (Example 1)

[00357] Two tank pressure vessels, each being a tank reactor fitted with a stirrer having an internal volume of 10 L and an internal height (L) to diameter (D) ratio of 4.0, having an inlet at the bottom and an outlet at the top, and fitted with a stirrer and a temperature control jacket, were connected to each other as the polymerization reactor.

[00358] A first polymerization reactor was used to carry out the polymerization step (P1) of the synthesis of the first polymer segment. 1,3-butadiene, styrene, and normal hexane, from which the water content had been previously removed, were mixed under conditions of 20.3 g / min, 4.31 g / min, and 173 g / min, respectively. N-butyllithium for the inactivation of residual impurities was further added at 0.104 mmol / min in a static mixer placed in the middle of a tube to supply this mixed solution to the reactor inlet, and the resulting product was mixed and then continuously fed to the bottom of the reactor. In addition, 2,2-bis(2-oxolanyl)propane was used as a polar material and n-butyllithium was used as a poly initiator. Petition 870250088816, dated 09 / 30 / 2025, pp. 98 / 146 91 / 124 polymerization molecules were supplied at rates of 0.0235 mmol / min and 0.239 mmol / min, respectively, to the bottom of the first reactor where these substances were vigorously stirred with the stirrer, and the internal temperature of the reactor was maintained at 78°C. After that, when the polymerization reaction was stabilized, the total amount of a conjugated diene polymer was removed from the top of the reactor, and an antioxidant (BHT) was added to obtain an amount of 0.2 g per 100 g of conjugated diene polymer, and then the solvent was removed. After that, the amount of linked conjugated diene monomer units (Xi), the amount of vinyl linkages (Yi) in the linked conjugated diene, and the solids content concentration (m1) in the first polymer segment were measured.

[00359] Next, a second polymerization reactor was used to carry out step (P2) of forming the second polymer segment.

[00360] The conjugated diene polymer solution was continuously fed from the top of the first reactor to the bottom of the second reactor, and for the second reactor, 1,3-butadiene, normal hexane, and 2,2-bis(2-oxolanyl)propane used as the polar material were stirred respectively at rates of 8.71 g / min, 32.1 g / min, and 0.450 mmol / min, and the reaction continued at 78°C.

[00361] Next, to the conjugated diene polymer solution flowing from the top of the second reactor, tetrakis(3-trimethoxysilylpropyl)-1,3propanediamine (shown as Coupling Agent A in the Tables) and 1-methyl-4-[3-(trimethoxysilyl)propyl]piperazine (shown as Coupling Agent B in the Tables) were continuously added as the coupling agent at rates of 0.0103 mmol / min and 0.0965 mmol / min respectively, and the resulting product was mixed with the static mixer to cause a coupling reaction. Here, the time until the addition of the coupling agent to the solution Petition 870250088816, dated 09 / 30 / 2025, p. 99 / 146 92 / 124 The polymer flow rate through the reactor outlet was 4.8 min, and the temperature was 68°C.

[00362] The total amount of conjugated diene polymer solution after the coupling reaction was removed, an antioxidant (BHT) was added to it to obtain an amount of 0.2 g per 100 g of polymer, and then the solvent was removed, and the various molecular weights, the amount of vinyl aromatic bonded (Xall), the amount of vinyl linkages (Yall) in the conjugated diene bonded, the concentration of the solids content (m2), and the glass transition temperature were measured.

[00363] Next, to the conjugated diene polymer solution after the coupling reaction, an antioxidant (BHT) was continuously added at 0.055 g / min (in the form of an n-hexane solution) to obtain an amount of 0.2 g per 100 g of polymer, and thus, the coupling reaction was completed.

[00364] Simultaneously with the antioxidant, an SRAE oil (JOMO Process NC 140, produced by JX Nippon Oil & Energy Corporation) was continuously added as the rubber softener to obtain a quantity of 5.0 g per 100 g of polymer, and the resulting product was mixed with the static mixer. The solvent was removed by steam extraction, and thus, a modified diene conjugate polymer of Example 1 was obtained. (Example 2)

[00365] A modified conjugated diene polymer of Example 2 was obtained in the same manner as in Example 1 except that the rates of 1,3-butadiene and styrene supplied to the first reactor were changed to 18.7 g / min and 6.67 g / min, respectively, and that the rate of 1,3-butadiene added to the second reactor was changed to 8.00 g / min. (Example 3) Petition 870250088816, dated 09 / 30 / 2025, pp. 100 / 146 93 / 124

[00366] A modified conjugated diene polymer of Example 3 was obtained in the same manner as in Example 1 except that the rates of 1,3-butadiene and styrene supplied to the first reactor were changed to 17.3 g / min and 8.67 g / min, respectively, and that the rate of 1,3-butadiene added to the second reactor was changed to 7.40 g / min. (Example 4)

[00367] A modified conjugated diene polymer of Example 4 was obtained in the same manner as in Example 1 except that the rates of 1,3-butadiene and styrene supplied to the first reactor were changed to 21.0 g / min and 3.33 g / min, respectively, and that the rate of 1,3-butadiene added to the second reactor was changed to 9.00 g / min. (Example 5)

[00368] A modified conjugated diene polymer of Example 5 was obtained in the same manner as in Example 1 except that the rates of 1,3-butadiene and styrene supplied to the first reactor were changed to 21.9 g / min and 2.00 g / min, respectively, and that the rate of 1,3-butadiene added to the second reactor was changed to 9.40 g / min. (Example 6)

[00369] A modified conjugated diene polymer of Example 6 was obtained in the same manner as in Example 1 except that the L / D of the first reactor was changed to 6.0, that the rates of styrene, 2,2-bis(2-oxolanyl)propane used as the polar material, and n-butyllithium used as the polymerization initiator supplied to the first reactor were changed, respectively, to 3.88 g / min, 0.0208 mmol / min, and 0.208 mmol / min, that the rate of 2,2-bis(2-oxolanyl)propane supplied to the second reactor was changed to 0.396 mmol / min, that the rates of coupling agent A and coupling agent B added Petition 870250088816, dated 09 / 30 / 2025, pp. 101 / 146 94 / 124 of those in the modification step were respectively changed to 0.00917 mmol / min and 0.0856 mmol / min, and styrene was newly added to the second reactor at 0.43 g / min. (Example 7)

[00370] A modified conjugated diene polymer of Example 7 was obtained in the same manner as in Example 1 except that the rates of 1,3-butadiene and styrene supplied to the first reactor were changed to 24.9 g / min and 4.35 g / min, respectively, and that the rate of 1,3-butadiene added to the second reactor was changed to 4.35 g / min. (Example 8)

[00371] A modified conjugated diene polymer of Example 8 was obtained in the same manner as in Example 1 except that the rates of 1,3-butadiene and styrene supplied to the first reactor were changed to 4.64 g / min and 0.46 g / min, respectively, that the internal temperature of the first reactor was changed to 80°C, that the rate of 1,3-butadiene added to the second reactor was changed to 26.3 g / min, that the temperature of the second polymerization reactor was changed to 82°C, and that styrene was newly added to the second reactor at 1.98 g / min. (Example 9)

[00372] A modified conjugated diene polymer of Example 9 was obtained in the same manner as in Example 1 except that the rates of 1,3-butadiene and styrene fed to the first reactor were changed to 19.5 g / min and 2.66 g / min, respectively, that the rates of 1,3-butadiene and 2,2-bis(2-oxolanyl)propane used as the polar material added to the second reactor were changed to 10.5 g / min and 0.0177 mmol / min, respectively, and that styrene was newly added to the second reactor at 0.67 g / min. (Example 10) Petition 870250088816, dated 09 / 30 / 2025, pp. 102 / 146 95 / 124

[00373] A modified conjugated diene polymer of Example 10 was obtained in the same manner as in Example 1 except that the rates of 2,2-bis(2-oxolanyl)propane and n-butyllithium used as the polymerization initiator supplied to the first reactor were changed to 0.0408 mmol / min and 0.442 mmol / min, respectively, that the rate of 2,2-bis(2-oxolanyl)propane added to the second reactor was changed to 0.776 mmol / min, and that the rates of coupling agent A and coupling agent B added in the modification step were changed to 0.018 mmol / min and 0.168 mmol / min, respectively. (Example 11)

[00374] A modified conjugated diene polymer of Example 11 was obtained in the same manner as in Example 1 except that the rates of 2,2-bis(2-oxolanyl)propane and n-butyllithium used as the polymerization initiator supplied to the first reactor were changed to 0.0271 mmol / min and 0.297 mmol / min, respectively, that the rate of 2,2-bis(2-oxolanyl)propane added to the second reactor was changed to 0.461 mmol / min, and that the rates of coupling agent A and coupling agent B added in the modification step were changed to 0.0125 mmol / min and 0.117 mmol / min, respectively. (Example 12)

[00375] A modified conjugated diene polymer of Example 12 was obtained in the same manner as in Example 1 except that the rates of 2,2-bis(2-oxolanyl)propane and n-butyllithium used as the polymerization initiator supplied to the first reactor were changed to 0.0190 mmol / min and 0.187 mmol / min, respectively, that the rate of 2,2-bis(2-oxolanyl)propane added to the second reactor was changed to 0.362 mmol / min, and that the rates of coupling agent A and coupling agent B added in the modification step were Petition 870250088816, dated 09 / 30 / 2025, pp. 103 / 146 96 / 124 ram changed, respectively, to 0.0084 mmol / min and 0.0783 mmol / min. (Example 13)

[00376] A modified conjugated diene polymer of Example 13 was obtained in the same manner as in Example 1 except that the rates of 2,2-bis(2-oxolanyl)propane and n-butyllithium used as the polymerization initiator supplied to the first reactor were changed to 0.0084 mmol / min and 0.065 mmol / min, respectively, that the rate of 2,2-bis(2-oxolanyl)propane added to the second reactor was changed to 0.168 mmol / min, that the rate of coupling agent A added in the modification step was changed to 0.0130 mmol / min, that coupling agent B was not added, and that the amount of SRAE oil was changed to 25 g per 100 g of polymer. (Example 14)

[00377] A modified conjugated diene polymer of Example 14 was obtained in the same manner as in Example 1 except that the rates of coupling agent A and coupling agent B added in the modification step were changed to 0.0067 mmol / min and 0.0627 mmol / min, respectively. (Example 15)

[00378] A modified conjugated diene polymer of Example 15 was obtained in the same manner as in Example 1 except that the coupling agent added in the modification step was changed from coupling agents A and B to 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (coupling agent C) added at 0.0895 mmol / min. (Example 16)

[00379] A conjugated diene polymer of Example 16 was obtained in the same manner as in Example 1 except that the amounts of 2,2bis(2-oxolanyl)propane and n-butyllithium used as the polymer initiator were reduced. Petition 870250088816, dated 09 / 30 / 2025, pp. 104 / 146 97 / 124 The rates of coupling agent A supplied to the first reactor were changed to 0.0200 mmol / min and 0.198 mmol / min, respectively, that the rate of 2,2-bis(2-oxolanyl)propane added to the second reactor was changed to 0.379 mmol / min, and that the rates of coupling agent A and coupling agent B added in the modification step were both changed to 0. (Example 17)

[00380] A modified conjugated diene polymer of Example 17 was obtained in the same manner as in Example 1 except that the rates of 2,2-bis(2-oxolanyl)propane and n-butyllithium used as the polymerization initiator supplied to the first reactor were changed to 0.013 mmol / min and 0.12 mmol / min, respectively, that the rate of 2,2-bis(2-oxolanyl)propane added to the second reactor was changed to 0.253 mmol / min, and that the rates of coupling agent A and coupling agent B added in the modification step were changed to 0.0059 mmol / min and 0.0546 mmol / min, respectively. (Example 18)

[00381] A modified conjugated diene polymer of Example 18 was obtained in the same manner as in Example 1 except that the rates of 2,2-bis(2-oxolanyl)propane and n-butyllithium used as the polymerization initiator supplied to the first reactor were changed to 0.012 mmol / min and 0.213 mmol / min, respectively, that the rate of 2,2-bis(2-oxolanyl)propane added to the second reactor was changed to 0.405 mmol / min, and that the rate of coupling agent A added in the modification step was changed to 0.0312 mmol / min, that coupling agent B was not added, and that the amount of SRAE oil added was changed to 25 g per 100 g of polymer. (Example 19) Petition 870250088816, dated 09 / 30 / 2025, pp. 105 / 146 98 / 124

[00382] A modified conjugated diene polymer of Example 19 was obtained in the same manner as in Example 1 except that the rates of 2,2-bis(2-oxolanyl)propane, n-butyllithium used as the polymerization initiator, n-butyllithium for inactivation of residual impurities, 1,3-butadiene, styrene, and normal hexane supplied to the first reactor were changed, respectively, to 0.0209 mmol / min, 0.208 mmol / min, 0.114 mmol / min, 21.6 g / min, 4.57 g / min, and 153 g / min, and that the rates of 2,2-bis(2-oxolanyl)propane, normal hexane, and 1,3-butadiene added to the second reactor were changed, respectively, to 0.396 mmol / min, 35.5 g / min, and 7.16 g / min, and that the rates of coupling agent A and coupling agent B added in the modification step were changed to 0.00917 mmol / min and 0.0856 mmol / min, respectively. (Example of Reference 1)

[00383] A modified conjugated diene polymer from Reference Example 1 was obtained in the same manner as in Example 1 except that the rate of 2,2-bis(2-oxolanyl)propane supplied to the first reactor was changed to 0.136 mmol / min, that 2,2-bis(2-oxolanyl)propane was not added to the second reactor, and also that the temperatures of the first and second reactors were changed to 68°C and 73°C, respectively. (Comparative Example 1)

[00384] A modified conjugated diene polymer from Comparative Example 1 was obtained in the same manner as in Example 1 except that the rates of 1,3-butadiene and styrene supplied to the first reactor, and of 1,3-butadiene added to the second reactor were changed to 16.8 g / min, 9.33 g / min, and 7.20 g / min, respectively. (Comparative Example 2)

[00385] A modified conjugated diene polymer from Comparative Example 2 was obtained in the same way as in Example 1 except Petition 870250088816, dated 09 / 30 / 2025, pp. 106 / 146 99 / 124 that the rates of 1,3-butadiene and styrene supplied to the first reactor, and of 1,3-butadiene added to the second reactor were changed, respectively, to 23.3 g / min, 1.00 g / min, and 9.70 g / min. (Comparative Example 3)

[00386] A modified conjugated diene polymer from Comparative Example 3 was obtained in the same manner as in Example 1 except that the rates of 2,2-bis(2-oxolanyl)propane and n-butyllithium used as the polymerization initiator supplied to the first reactor were changed to 0.168 mmol / min and 0.297 mmol / min, respectively, that 2,2-bis(2-oxolanyl)propane was not added to the second reactor, and that the rates of coupling agent A and coupling agent B added in the modification step were changed to 0.0125 mmol / min and 0.117 mmol / min, respectively. (Comparative Example 4)

[00387] A modified conjugated diene polymer from Comparative Example 4 was obtained in the same manner as in Example 1 except that the rates of 2,2-bis(2-oxolanyl)propane and n-butyllithium used as the polymerization initiator supplied to the first reactor were changed to 0.106 mmol / min and 0.187 mmol / min, respectively, that 2,2-bis(2-oxolanyl)propane was not added to the second reactor, and that the rates of coupling agent A and coupling agent B added in the modification step were changed to 0.0084 mmol / min and 0.0783 mmol / min, respectively. (Comparative Example 5)

[00388] A conjugated diene polymer of Comparative Example 5 was obtained in the same manner as in Example 1 except that the rates of 2,2-bis(2-oxolanyl)propane and n-butyllithium used as the polymerization initiator supplied to the first reactor were changed to 0.115 mmol / min and 0.198 mmol / min, respectively, that 2,2-bis(2-oxolanyl)propane was not added to the second reactor, and further, that the Petition 870250088816, dated 09 / 30 / 2025, pp. 107 / 146 100 / 124 temperatures of the first and second reactors were changed to 68°C and 73°C, respectively, and the rates of coupling agent A and coupling agent B added in the modification step were both changed to 0. (Comparative Example 6)

[00389] A modified conjugated diene polymer of Comparative Example 6 was obtained in the same manner as in Example 1 except that the rates of 2,2-bis(2-oxolanyl)propane, n-butyllithium used as the polymerization initiator, 1,3-butadiene, styrene, and hexane supplied to the first reactor were changed, respectively, to 0.145 mmol / min, 0.239 mmol / min, 21.0 g / min, 2.01 g / min, and 172 g / min, that the rates of 1,3-butadiene, styrene, and normal hexane added to the second reactor were changed, respectively, to 8.99 g / min, 2.01 g / min, and 32.9 g / min, and that 2,2-bis(2-oxolanyl)propane was not added to the second reactor. (Comparative Example 7)

[00390] Four tank pressure vessels, each of them being a tank reactor fitted with a stirrer having an internal volume of 10 L and the ratio (L / D) of internal height (L) to diameter (D) of 4.0, having an inlet at the bottom and an outlet at the top, and fitted with a stirrer and a temperature control jacket, were connected to each other as a polymerization reactor.

[00391] The first through third polymerization reactors were used to carry out the polymerization step (P1) of the synthesis of the first polymer segment. 1,3-butadiene, styrene, and normal hexane, from which the water content had been previously removed, were mixed under conditions of 21.3 g / min, 6.70 g / min, and 205 g / min, respectively. N-butyllithium for inactivation of residual impurities was added at 0.104 mmol / min in a static mixer placed in the middle of a tube to supply this mixed solution to the inlet. Petition 870250088816, dated 09 / 30 / 2025, pp. 108 / 146101 / 124 of the reactor, and the resulting product was mixed and then continuously fed to the bottom of the reactor. Additionally, 2,2-bis(2-oxolanyl)propane, used as the polar material, and n-butyllithium, used as the polymerization initiator, were fed at rates of 0.120 mmol / min and 0.205 mmol / min, respectively, to the bottom of the first reactor where these substances were vigorously stirred with the stirrer, and the internal temperature of the three reactors was maintained between 45 and 55°C. After that, when the polymerization reaction was stabilized, all of the conjugated diene polymer was removed from the top of the reactor, and an antioxidant (BHT) was added to obtain a quantity of 0.2 g per 100 g of conjugated diene polymer, and then the solvent was removed.After that, the amount of linked conjugated diene monomer units (Xi), and the amount of vinyl linkages (Yi) in the linked conjugated diene, and the concentration of the solids content (m1) of the first polymer segment were measured.

[00392] Next, the fourth polymerization reactor was used to carry out step (P2) of forming the second polymer segment.

[00393] The conjugated diene polymer solution was continuously fed from the top of the first reactor to the bottom of the second reactor, and 1,3-butadiene, normal hexane, and 2,2-bis(2-oxolanyl)propane used as the polar material were added to the second reactor, respectively, at rates of 5.30 g / min, 36.0 g / min, and 2.230 mmol / min with stirring, and the reaction continued at 60°C.

[00394] After the modification step, the process was carried out in the same manner as in Example 1 except that coupling agent B was added at a rate of 0.1200 mmol / min, and thus a conjugated diene polymer of Comparative Example 7 was obtained. Petition 870250088816, dated 09 / 30 / 2025, pp. 109 / 146 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8 Sample 9 Polymerization conditions n-Butyllithium for treatment (mmol / min) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 Polymerization initiator n-Butyllithium (mmol / min) 0.239 0.239 0.239 0.239 0.239 0.208 0.239 0.239 0.239 Butadiene added in P1 (g / min) 20.3 18.7 17.3 21 21.9 20.3 24.9 4.64 19.5 Styrene added at P1 (g / min) 4.31 6.67 8.67 3.33 2.00 3.88 4.35 0.46 2.66 Normal hexane added at P1 (g / min) 173 173 173 173 173 173 173 173 173 Polar material added at P1 (mmol / min) 0.0235 0.0235 0.0235 0.0235 0.0235 0.0208 0.0271 0.0235 0.0398 Polymerization temperature at P1 (°C) 78 78 78 78 78 78 80 78 78 Butadiene added at P2 (g / min) 8.71 8.00 7.40 9.00 9.40 8.71 4.35 26.3 10.5 Styrene added in P2 (g / min) 0 0 0 0 0 0.43 0 1.98 0.67 Normal Hexane added in P2 (g / min) 32.1 32,1 32.1 32.1 32.1 32.1 32.1 32.1 32.1 Polar Material added in P2 (mmol / min) 0.450 0.450 0.450 0.450 0.450 0.396 0.450 0.450 0.177 Polymerization Temperature in P2 (°C) 78 78 78 78 78 78 78 82 78 102 / 124 Petition 870250088816, dated 09 / 30 / 2025, pp. 110 / 146 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8 Sample 9 Coupling Agent A (mmol / min) 0.0103 0.0103 0.0103 0.0103 0.0103 0.00917 0.0103 0.0103 0.0103 Coupling Agent B (mmol / min) 0.0965 0.0965 0.0965 0.0965 0.0965 0.0856 0.0965 0.0965 0.0965 Coupling Agent C (mmol / min) 0 0 0 0 0 0 0 0 0 First Polymer Segment (Physical Property 1) Mass Ratio of Polymer Segments r1 62 62 62 62 62 62 85 15 60 (Physical Property 2) Amount of Styrene Bonded X1 (mass%) 12 19 25 9 7 12 12 8 10 (Physical Property 3) Amount of Vinyl Bonds Y1 (mol%) 20 20 20 20 20 20 20 20 25 Second Polymer Segment (Physical Property 1) Mass Ratio of Polymer Segments r2 38 38 38 38 38 38 15 85 40 (Physical Property 2) 2) Amount of Styrene Bonded X2 (mass%) 14 22 27 10 6 14 14 7 10 (Physical Property 3) Amount of vinyl bonds Y2 (mol%) 58 58 58 58 58 58 58 58 45, 103 / 124 Petition 870250088816, dated 09 / 30 / 2025, pp. 111 / 146 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8 Sample 9 Conjugated Diene Polymer (Physical Property 1) Mass Ratio of Polymer Segments R=r1 / r2 1.63 1.63 1.63 1.63 1.63 1.63 5.67 0.18 1.50 (Physical Property 2) Amount of Styrene Bonded Xall (mass%) 13 20 26 10 6 13 13 7 10 (Physical Property 3) Amount of Vinyl Bonds Yall (mol%) 34 32 31 34 34 34 29 52 37 (Physical Property 2) Difference in the Amount of Styrene Bonded |AX| (mass%) 2 3 2 1 1 2 2 1 0 (Physical Property 3) Difference in the number of vinyl bonds AY (mol%) 38 38 38 38 38 38 38 38 20 (Physical Property 4) Difference in Polymerization Conversion Rate (%) 4.2 4.4 4.2 3.8 4.0 3.0 7.3 2.7 2.7 104 / 124 Petition 870250088816, dated 09 / 30 / 2025, pp. 112 / 146 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8 Sample 9 (Physical Property 5) Estimated Glass Transition Temperature (°C) -60 -52 -44 -63 -68 -60 -63 -52 -61 (Physical Property 6) Weight-Average Molecular Weight Mw (10⁴ g / mol) 51 51 51 51 51 51 51 51 51 (Physical Property 6) Number-Average Molecular Weight Mn (10⁴ g / mol) 27 27 27 27 27 31 27 27 27 (Physical Property 6) Molecular Weight Distribution Mw / Mn 1.89 1.89 1.89 1.89 1.89 1.65 1.89 1.89 1.89 (Physical Property 7) Mooney Viscosity of the Polymer 63.0 63.0 63.0 63.0 63.0 63.0 63.0 63.0 63.0 (Physical Property 8) Extrapolated Initial Glass Transition Temperature (°C) -67.9 -59.3 -50.0 -71.4 -76.5 -68.0 -70.0 -59.5 -66.5 (Physical Property 8) Glass Transition Temperature (°C) -60.8 -52.0 -43.0 -63.0 -68.0 -60.8 -64.0 -52.8 -61.0 105 / 124 Petition 870250088816, dated 09 / 30 / 2025, pp. 113 / 146 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8 Sample 9 (Physical Property 8) Extrapolated Final Glass Transition Temperature (°C) -54.4 -46.9 -37.8 -57.6 -62.2 -54.3 -58.7 -48.7 -56.5 (Physical Property 8) Extrapolated Final-Initial Glass Transition Temperature (°C) 13.5 12.4 12.2 13.8 14.3 13.7 11.3 10.8 10.0 (Physical Property 9) Modification Ratio (%) 77 75 74 83 85 77 78 77 79 106 / 124 Petition 870250088816, dated 09 / 30 / 2025, pp. 114 / 146 [Table 2] Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Sample 10 Sample 11 Sample 12 Sample 13 Sample 14 Sample 15 Sample 16 Sample 17 Sample 18 Sample 19 n-Butyllithium Polymerization Conditions for Treatment (mmol / min) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.114 n-Butyllithium Polymerization Initiator (mmol / min) 0.442 0.297 0.187 0.065 0.239 0.239 0.198 0.12 0.213 0.208 Butadiene added in P1 (g / min) 20.3 20.3 20.3 20.3 20.3 20.3 20.3 20.3 21.6 Styrene added at P1 (g / min) 4.31 4.31 4.31 4.31 4.31 4.31 4.31 4.31 4.31 4.57 Normal Hexane added at P1 (g / min) 173 173 173 173 173 173 173 173 173 153 Polar Material added at P1 (mmol / min) 0.0408 0.0271 0.019 0.0084 0.0235 0.0235 0.02 0.013 0.012 0.0209 Polymerization temperature in reactor P1 (°C) 78 78 78 78 78 78 78 78 78 78 Butadiene added in P2 (g / min) 8.71 8.71 8.71 8.71 8.71 8.71 8.71 8.71 8.71 7.16 Styrene added at P2 (g / min) 0 0 0 0 0 0 0 0 0 0 Normal Hexane added at P2 (g / min) 32.1 32.1 32.1 32.1 32.1 32.1 32.1 32.1 32.1 35.5 Polar Material added at P2 (mmol / min) 0.776 0.461 0.362 0.168 0.45 0.45 0.379 0.253 0.405 0.396 107 / 124 Petition 870250088816, dated 09 / 30 / 2025, pp. 115 / 146 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Sample 10 Sample 11 Sample 12 Sample 13 Sample 14 Sample 15 Sample 16 Sample 17 Sample 18 Sample 19 Polymerization Temperature in reactor P2 (°C) 78 78 78 78 78 78 78 78 78 78 Coupling Agent A (mmol / min) 0.018 0.0125 0.0084 0.013 0.0067 0 0 0.0059 0.0312 0.00917 Coupling Agent B (mmol / min) 0.168 0.117 0.0783 0 0.0627 0 0 0.0546 0 0.0856 Coupling Agent C (mmol / min) 0 0 0 0 0 0,0895 0 0 0 0 First Polymer Segment (Physical Property 1) Mass Ratio of Polymer Segments r1 62 62 62 62 62 62 62 62 62 66 (Physical Property 2) Amount of Styrene Bonded X1 (mass%) 12 12 12 12 12 12 12 12 12 12 (Physical Property 3) Amount of Vinyl Bonds Y1 (mol%) 19 19 19 19 19 19 19 19 19 21 Second Polymer Segment (Physical Property 1) Mass Ratio of Polymer Segments r2 38 38 38 38 38 38 38 38 38 34 (Physical Property 2) Amount of Styrene Bonded X2 (mass%) 14 14 14 14 14 14 14 14 14 17, 108 / 124 Petition 870250088816, dated 09 / 30 / 2025, pp. 116 / 146 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Sample 10 Sample 11 Sample 12 Sample 13 Sample 14 Sample 15 Sample 16 Sample 17 Sample 18 Sample 19 (Physical Property 3) Amount of Vinyl Bonds Y2 (mol%) 58 58 58 58 58 58 58 58 58 58 Conjugated Diene Polymer (Physical Property 1) Mass Ratio of Polymer Segments R=r1 / r2 1.63 1.63 1.63 1.63 1.63 1.63 1.63 1.63 1.63 1.94 (Physical Property 2) Amount of Bonded Styrene Xall (mass%) 13 13 13 13 13 13 13 13 13 14 (Physical Property 3) Amount of Vinyl Bonds Yall (mol%) 34 34 34 34 34 34 34 34 34 29 (Physical Property 2) Difference in the Amount of Styrene Bonded |AX| (mass%) 2 2 2 2 2 2 2 2 2 5 (Physical Property 3) Difference in the Amount of Vinyl Bonds AY (mol%) 39 39 39 39 39 39 39 39 39 37 109 / 124 Petition 870250088816, dated 09 / 30 / 2025, pp. 117 / 146 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Sample 10 Sample 11 Sample 12 Sample 13 Sample 14 Sample 15 Sample 16 Sample 17 Sample 18 Sample 19 (Physical Property 4) Difference in Polymerization Conversion Rate (%) 4.4 4.4 4.4 4.4 4.2 4.2 4.4 4.4 4.4 9.3 (Physical Property 5) Estimated Glass Transition Temperature (°C) -60 -60 -60 -60 -60 -60 -60 -60 -60 -62 (Physical Property 6) Weight-Average Molecular Weight Mw (104 g / mol) 34 45 62 138 48 54 51 72 85 63 (Physical Property 6) Number-Average Molecular Weight Mn (104 g / mol) 18.5 24 33 76 25 26 29.5 38 47 35 (Physical Property 6) Molecular Weight Distribution Mw / Mn 1.84 1.88 1.88 1.81 1.92 2.08 1.73 1.89 1.81 1.81 (Physical Property 7) Mooney Viscosity of the Polymer 30.0 52.0 89.0 110.0 57.0 68.0 63.0 120.0 80.0 110.0 (Physical Property 8) Extrapolated Initial Glass Transition Temperature (°C) -68.0 -68.0 -68.0 -68.0 -67.9 -67.9 -68.0 -68.0 -68.0 -68.2 110 / 124 Petition 870250088816, dated 09 / 30 / 2025, pp. 118 / 146 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Sample 10 Sample 11 Sample 12 Sample 13 Sample 14 Sample 15 Sample 16 Sample 17 Sample 18 Sample 19 (Physical Property 8) Glass Transition Temperature (°C) -60.8 -60.8 -60.8 -60.8 -60.8 -60.8 -60.8 -60.8 -60.8 -60.9 (Physical Property 8) Extrapolated Final Glass Transition Temperature (°C) -54.3 -54.3 -54.3 -54.3 -54.4 -54.4 -54.3 -54.3 -54.3 -53.9 (Physical Property 8) Extrapolated Final-Initial Glass Transition Temperature (°C) 13.7 13.7 13.7 13.7 13.5 13.5 13.7 13.7 13.7 14.3 (Physical Property 9) Modification Ratio (%) 79 79 74 72 59 55 0 74 74 83 111 / 124 Petition 870250088816, dated 09 / 30 / 2025, pp. 119 / 146 [Table 3] Sample 20 Sample 21 Sample 22 Sample 23 Sample 24 Sample 25 Sample 26 Sample 27 Polymerization conditions for n-Butyllithium treatment (mmol / min) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 Polymerization initiator n-Butyllithium (mmol / min) 0.239 0.239 0.239 0.239 0.187 0.198 0.239 0.203 Butadiene added in P1 (g / min) 20.3 16.8 23.3 20.3 20.3 20.3 21 21.3 Styrene added to P1 (g / min) 4.31 9.33 1.00 4.31 4.31 4.31 1.34 6.7 Normal Hexane added to P1 (g / min) 173 173 173 173 173 173 172 205 Polar Material added to P1 (mmol / min) 0.136 0.0235 0.0235 0.168 0.106 0.115 0.145 0.12 Polymerization Temperature in reactor P1 (°C) 68 78 78 78 78 68 78 55 Butadiene added to P2 (g / min) 8.71 7.20 9.70 8.71 8.71 8.71 8.99 5.3 Styrene added in P2 (g / min) 0 0 0 0 0 0 2.01 0 Normal hexane added in P2 (g / min) 32.1 32.1 32.1 32.1 32.1 32.1 32.9 36 Polar material added to P2 (mmol / min) 0 0.45 0.45 0 0 0 0 2.23, 112 / 124 Petition 870250088816, dated 09 / 30 / 2025, pages 120 / 146 Sample 20 Sample 21 Sample 22 Sample 23 Sample 24 Sample 25 Sample 26 Sample 27 Polymerization Temperature in reactor P2 (°C) 73 78 78 78 78 73 78 60 Coupling Agent A (mmol / min) 0.0103 0.0103 0.0103 0.0125 0.00839 0 0.0103 0 Coupling Agent B (mmol / min) 0.0965 0.0965 0.0965 0.117 0.0783 0 0.0965 0.12 Coupling Agent C (mmol / min) 0 0 0 0 0 0 0 0 First Polymer Segment (Physical Property 1) Mass Ratio of Polymer Segments r1 75 62 70 62 62 75 62 80 (Physical Property 2) Amount of Styrene Bonded X1 (mass%) 10 28 3 10 10 10 5 19.5 (Physical Property 3) Amount of Vinyl Bonds Y1 (mol%) 38 20 20 38 38 37 30 42 Second Polymer Segment (Physical Property 1) Mass Ratio of Polymer Segments r2 25 38 30 38 38 25 38 20 (Physical Property 2) Amount of Styrene Bonded X2 (mass%) 10 28 3 10 10 10 20 23 113 / 124 Petition 870250088816, dated 09 / 30 / 2025, pp. 121 / 146 Sample 20 Sample 21 Sample 22 Sample 23 Sample 24 Sample 25 Sample 26 Sample 27 (Physical Property 3) Amount of Vinyl Bonds Y2 (mol%) 37 58 58 37 37 37 50 76 Conjugated Diene Polymer (Physical Property 1) Mass Ratio of Polymer Segments R=r1 / r2 3.00 1.63 2.33 1.63 1.63 3.00 1.63 4.00 (Physical Property 2) Amount of Bonded Styrene Xall (mass%) 10 28 3 10 10 10 10 20 (Physical Property 3) Amount of Vinyl Bonds Yall (mol%) 37 33 31 37 37 37 32 49 (Physical Property 2) Difference in the Amount of Styrene Bonded |AX| (mass%) 0 0 0 0 0 0 15 4 (Physical Property 3) Difference in the Amount of Vinyl Bonds AY (mol%) 1 38 38 1 1 0 20 34 (Physical Property 4) Difference in Polymerization Conversion Rate (%) 2.2 4.2 4.2 2.2 2.2 2.7 37 2.5 114 / 124 Petition 870250088816, dated 09 / 30 / 2025, pp. 122 / 146 Sample 20 Sample 21 Sample 22 Sample 23 Sample 24 Sample 25 Sample 26 Sample 27 (Physical Property 5) Estimated Glass Transition Temperature (°C) -61 -39 -75 -61 -61 -61 -65 -38 (Physical Property 6) Weight-Average Molecular Weight Mw (10⁴ g / mol) 51 51 51 45 62 51 51 48 (Physical Property 6) Number-Average Molecular Weight Mn (10⁴ g / mol) 27 27 27 24 33 30 27 31 (Physical Property 6) Molecular Weight Distribution Mw / Mn 1.89 1.89 1.89 1.88 1.88 1.73 1.89 1.56 (Physical Property 7) Mooney Viscosity of the Polymer 63.0 63.0 63.0 52.0 89.0 63.0 63.0 60.0 (Physical Property 8) Extrapolated Initial Glass Transition Temperature (°C) -65.0 -47.0 -82.0 -68.0 -68.0 -65.0 -67.9 -46.5 (Physical Property 8) Glass Transition Temperature (°C) -61.4 -39.0 -75.5 -60.8 -60.8 -61.8 -60.8 -38.5 115 / 124 Petition 870250088816, dated 09 / 30 / 2025, pp. 123 / 146 Sample 20 Sample 21 Sample 22 Sample 23 Sample 24 Sample 25 Sample 26 Sample 27 (Physical Property 8) Extrapolated Final Glass Transition Temperature (°C) -57.9 -34.8 -68.1 -54.3 -54.3 -57.9 -54.4 -34.4 (Physical Property 8) Extrapolated Initial Final Glass Transition Temperature (°C) 7.1 12.2 13.9 13.7 13.7 7.1 13.5 12.1 (Physical Property 9) Modification Ratio (%) 83 73 79 85 77 0 77 77 116 / 124 Petition 870250088816, dated 09 / 30 / 2025, pages 124 / 146 117 / 124 [Examples 20 to 38], [Reference Example 2], and [Comparative Examples 8 to 14]

[00395] Samples 1 to 27 shown in Tables 1 to 3 were respectively used as the rubber raw materials to obtain rubber compositions containing the respective rubber raw materials according to the following composition:

[00396] Conjugated diene polymer (any of samples 1 to 27): 100 parts by mass (excluding oil)

[00397] Silica (trade name Ultrasil 7000GR, produced by Evonik Degussa, specific surface area for nitrogen adsorption: 170 m2 / g): 85.0 parts by mass

[00398] Coal black (trade name Seast 7HM (N234), produced by Tokai Carbon Co., Ltd.): 2.0 parts by mass

[00399] Silane-type coupling agent: (trade name Si69, produced by Evonik Degussa, bis(triethoxysilylpropyl)tetrasulfide): 6.8 parts by mass

[00400] SRAE oil (trade name Process NC140, produced by JX Nippon Oil & Energy Corporation): 40 parts by mass Zinc oxide: 2.4 parts by mass Stearic acid: 1.25 parts by mass Anti-aging agent: (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine): 3.5 parts by mass Sulfur: 1.0 part by mass Vulcanization accelerator 1: tetrabenzylthiuram disulfide: 0.5 parts by mass Vulcanization accelerator 2: N-(tert-butyl)-2-benzothiazolsulfenamide: 2.5 parts by mass Total: 246.95 parts by mass

[00401] The materials described above were crushed using the following method to obtain a rubber composition. Petition 870250088816, dated 09 / 30 / 2025, pages 125 / 146 118 / 124

[00402] A closed mixer (having an internal volume of 0.3 L) equipped with a temperature controller was used to mix, as a first mixing stage, the rubber raw material (any of samples 1 to 26), the fillers (silica and carbon black), the silane-type coupling agent, the process oil, zinc oxide, and stearic acid under conditions of a filling rate of 65% and a rotation speed of 30 to 50 rpm. Here, the temperature of the closed mixer was controlled to obtain each rubber composition (compound) at a discharge temperature of 145 to 150°C.

[00403] Next, after cooling the compound obtained as described above to room temperature, as a second kneading stage, the anti-aging agent was added to it, and the resulting product was kneaded once more to improve the dispersibility of the silica. Also in this case, the discharge temperature of the compound was set to 120°C by the temperature control of the kneader.

[00404] After cooling, as a third stage of kneading, with sulfur and vulcanization accelerators 1 and 2 being added, the resulting product was kneaded with an open roller at a temperature of 70°C.

[00405] After that, the resulting product was molded and vulcanized at 160°C for 20 minutes using a vulcanizing press.

[00406] The composition of rubbers before vulcanization, and the composition of rubbers after vulcanization were evaluated.

[00407] Specifically, the assessments were conducted in the manner described below. [Assessments 1 and 2: Viscoelasticity Parameter]

[00408] An ARES viscoelasticity testing machine manufactured by Rheometric Scientific, Inc. was used to measure the parameter Petition 870250088816, dated 09 / 30 / 2025, pages 126 / 146 119 / 124 viscoelasticity in a torsional mode.

[00409] Every measurement value was presented as an index obtained by assuming that the result obtained in the rubber composition of Reference Example 2 was equal to 100. (Assessment 1)

[00410] The tan δ measured at 0°C at a frequency of 10 Hz and an effort of 1% was used as an index of the adhesion property on wet surfaces. A higher index indicates a better adhesion property on wet surfaces.

[00411] It was determined that the composition exhibited sufficient wet surface adhesion property in the form of a vulcanizate when the index value was 80 or higher. (Assessment 2)

[00412] The storage coefficient G' measured at -20°C at a frequency of 10 Hz and a stress of 1% was used as an index of the low temperature property.

[00413] A higher index indicates a property with better winter conditions.

[00414] It was determined that the composition exhibited sufficient winter performance in the form of a vulcanized compound when the index value was 50 or more. [Assessment 3: Abrasion Resistance]

[00415] An Akron abrasion meter (produced by Yasuda Seiki Seisakusho, Ltd.) was used to measure the amount of abrasion through 1,000 rotations at a load of 44.4 N according to JIS K6264-2 standard, and every measured value was presented as an index obtained assuming that the result of Reference Example 2 was equal to 100.

[00416] A higher index indicates better resistance to adhesion. [Assessment 4: Processability] Petition 870250088816, dated 09 / 30 / 2025, pp. 127 / 146 120 / 124

[00417] With respect to each of the modified diene-based polymers or the diene-based polymers before vulcanization produced, respectively, by the methods described in the Examples, Reference Examples, and Comparative Examples, a block (shape) obtained immediately after being discharged from a pressurizing mixer (immediately after being discharged after the kneading was completed with the pressurizing mixer in the first stage of kneading) was visually observed by panelists to carry out the evaluation based on the following criteria, each on a scale of 1 to 5.

[00418] An agglomeration property is an index of the processability of a vulcanizate.

[00419] A higher index indicates better processability. <Critérios de Avaliação> 1: Part of the sheet edge was smooth by 50% or less, and the processability was very poor. 2: Part of the sheet's edge was smooth in more than 50% and 60% or less, and the processability was poor. 3: Part of the sheet edge was smooth in more than 60% and 80% or less, and the processability was good. 4: Part of the sheet edge was smooth in more than 80% and 90% or less, and the processability was excellent. 5: One part of the sheet edge was smooth by more than 90%, and the processability was very excellent. [Assessment 5: Tensile Properties]

[00420] According to the tensile test method of the JIS K6251 standard, tensile strength and tensile limit were measured, and the product of these values ​​is shown as an index obtained assuming that the result of Reference Example 2 was equal to 100. Petition 870250088816, dated 09 / 30 / 2025, pages 128 / 146 121 / 124

[00421] A higher index indicates better tensile strength and tensile limit (fracture resistance).

[00422] It was determined that the composition had sufficient tensile properties in the form of a vulcanizate when the index value was 80 or more. [Table 4] Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Conjugated Diene Polymer Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8 Sample 9 (Evaluation 1) 0°C tannin (strain 1%) 112 134 145 107 92 112 104 126 106 (Evaluation 2) 20°C 98 75 60 106 125 99 108 77 99 (Evaluation 3) Abrasion Resistance 103 80 70 106 111 110 107 80 100 (Assessment 4) Processability 4 4 4 4 4 3 4 4 4 (Assessment 5) Tensile strength 110 115 118 104 100 110 108 102 107 Average of Assessments 1 + 2 105 105 103 107 109 106 106 102 103 [Table 5] Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Example 38 Polymer of Amo Amo Amo Amo Amo Amo Amo Amo Amo diene Conjugate- stra stra stra stra stra stra stra stra stra do 10 11 12 13 14 15 16 17 18 19 Petition 870250088816, dated 09 / 30 / 2025, pp. 129 / 146 122 / 124 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Example 38 (Assessment 1) 0°C tan₂ (strain 1%) 112 112 112 112 112 114 112 112 112 120 (Assessment 2) 20°C 108 105 87 60 92 69 55 77 71 93 (Assessment 3) Abrasion Resistance 80 96 112 120 98 97 90 115 120 112 (Assessment 4) Processability 5 5 4 2 4 4 4 4 4 4 (Assessment 5) Tensile strength 92 105 113 116 107 110 85 116 118 118 Average of Assessments 1 + 2 110 109 100 86 102 92 84 95 92 107 [Table 6] Ref, Ex, 2 Com, Ex, 8 Com, Ex, 9 Com, Ex, 10 Com, Ex, 11 Com, Ex, 12 Com, Ex, 13 Com, Ex, 14 Conjugated Diene Polymer Sample 20 Sample 21 Sample 22 Sample 23 Sample 24 Sample 25 Sample 26 Sample 27 (Evaluation 1) 0°C tannin (strain 1%) 100 151 75 100 100 100 112 151 (Evaluation 2) 20°C 100 45 145 107 89 51 98 45 (Evaluation 3) Abrasion Resistance 100 65 118 93 109 87 103 65 Petition 870250088816, dated 09 / 30 / 2025, pages 130 / 146 123 / 124 Ref, Ex, 2 Com, Ex, 8 Com, Ex, 9 Com, Ex, 10 Com, Ex, 11 Com, Ex, 12 Com, Ex, 13 Com, Ex, 14 (Evaluation 4) Processability 4 4 4 5 4 4 4 3 (Evaluation 5) Tensile Strength 100 111 90 95 103 85 75 105 Average of Evaluations 1+2 100 98 110 104 95 76 105 98

[00423] As shown in Tables 4 to 6, by comparing the rubber compositions of Examples 20 to 38 using samples 1 to 19, taking into account the difference in the amount of styrene bonded, the difference in the amount of vinyl bonds, and the estimated glass transition temperature value within the preferred ranges with the rubber compositions of Reference Example 2, and Comparative Examples 8 to 14 using samples 20 to 27, the rubber composition of the Examples is excellent in terms of the balance between wet grip performance and winter performance obtained in the form of a vulcanizate, and has sufficient abrasion resistance and tensile properties.

[00424] It has been confirmed, by comparison between Example 30 and Comparative Example 10, and between Example 31 and Comparative Example 11 using, respectively, modified diene-based polymers having equivalent molecular weight and estimated glass transition temperature, that the rubber compositions of the Examples are excellent in terms of the balance between wet grip performance and winter performance, and have sufficient abrasion resistance and tensile properties.

[00425] Furthermore, it was confirmed, by comparison between Example 35 and Comparative Example 12, that the rubber composition of Petition 870250088816, dated 09 / 30 / 2025, pages 131 / 146 124 / 124 Example is excellent in terms of the balance between wet grip performance and winter performance, abrasion resistance, and tensile properties, even when an unmodified conjugated diene polymer is used.

[00426] This application is based on the Japanese Patent Application filed with the Japan Patent Office on April 27, 2023 (Japanese Patent Application No. 2023-072878), the full text of which is incorporated herein by reference. Industrial Application

[00427] A conjugated diene polymer of the present invention has industrial application as materials in various areas such as tire treads, vehicle interiors and exteriors, anti-vibration rubbers, belts, footwear, foam bodies, and various industrial products. Petition 870250088816, dated 09 / 30 / 2025, pp. 132 / 146

Claims

1 / 2 CLAIMS 1. A conjugated diene polymer characterized in that it comprises two or more polymer segments, wherein an absolute value of a difference (|Xi - X2|) between the amount of linked aromatic vinyl monomer units Xi (% by mass) in a first polymer segment and the amount of linked aromatic vinyl monomer units X2 (% by mass) in a second polymer segment is 5% by mass or less, a difference (Y2 - Y1) between an amount of vinyl linkages Y1 (% by mol) in the linked conjugated diene of the first polymer segment and an amount of vinyl linkages Y2 (% by mol) in the linked conjugated diene of the second polymer segment is 15% by mol or more and 50% by mol or less, and an estimated glass transition temperature (estimated Tg) of the conjugated diene polymer is -72°C or lower and -40°C or lower.

2. Conjugated diene polymer, according to claim 1, characterized in that the ratio Mw / Mn between a weight-average molecular weight Mw and a number-average molecular weight Mn is 1.7 or more.

3. Conjugated diene polymer, according to claim 1 or 2, characterized in that the ratio (R = n / r2) of the mass ratio (n) of the first polymer segment to the mass ratio (r2) of the second polymer segment varies from 0.25 to 4.

4. Conjugated diene polymer, according to any one of claims 1 to 3, characterized in that it has a weight-average molecular weight Mw of 350,000 or more and 1,350,000 or less.

5. Conjugated diene polymer, according to any of claims 1 to 4, characterized in that it has a nitrogen-containing modifying group and has a modification ratio of 60% or more.

6. Method for producing conjugated diene polymer as defined in any one of claims 1 to 5, characterized in that it comprises: a polymerization step (P1) for forming the first polymer segment with two or more continuous reactors; and a polymerization step (P2) for forming the second polymer segment at one end of the first polymer segment obtained in step (P1), wherein a polar material is additionally added in polymerization step (P2).

7. Method for producing a conjugated diene polymer according to claim 6, characterized in that a conjugated diene compound is additionally added in the polymerization step (P2).

8. A method for producing a conjugated diene polymer according to claim 6 or 7, characterized in that it comprises, after the polymerization step (P2), a coupling step involving the reaction of the conjugated diene polymer with a coupling agent having a group containing a nitrogen atom.

9. Method for producing a conjugated diene polymer according to claim 7 or 8, characterized in that the amount of conjugated diene compound additionally added in the polymerization step (P2) is 15% by mass or more relative to the total amount of conjugated diene compound added. Petition 870250088816, dated 09 / 30 / 2025, pp. 138 / 146