Vehicle wheel tires with excellent wear resistance and grip.

Abstract

The present invention relates to a tire for winter, all-season, or summer use, characterized by reduced wear and improved grip. The tire comprises a tire component comprising a crosslinked elastomer compound obtained from a crosslinkable elastomer composition containing a specific conjugated diene polymer (I).

Description

[Technical Field]

[0001] The present invention relates to tires for vehicle wheels, and more particularly to tires for automobiles. In particular, the present invention relates to tires characterized by reduced wear for winter, all-season, or summer use, wherein the tire comprises a tire component comprising a crosslinkable elastomer compound obtained from a crosslinkable elastomer composition containing a specific conjugated diene polymer. [Background technology]

[0002] Patent documents US20050203251A1, US20090036567A1, JP11189616A, and EP1457501A1 disclose rubber compositions containing modified conjugated diene polymers obtained by reacting the active ends of conjugated diene polymers with alkoxysilanes containing amino groups and silica.

[0003] US2019023880A1 discloses rubber compositions comprising modified conjugated diene polymers with low vinyl content and a glass transition temperature (Tg) of up to -60°C.

[0004] US2021284827A1 discloses a rubber composition comprising a blend of modified conjugated diene polymers, particularly a blend of polymer A having a Tg of at least -20.0°C and polymer B being highly branched and having a Tg of up to -25°C.

[0005] The polymer described above does not contain polymer chains comprising two segments having different microstructures and characterized by different Tg values; rather, it is a conventional random styrene-butadiene modified copolymer.

[0006] According to the applicant, there is still room for improvement in the physical properties of known rubber compositions in terms of abrasion resistance and grip. [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] In the tire sector, automakers are increasingly demanding higher performance. For reasons of eco-sustainability, cost-effectiveness, and safety, it is desirable to reduce tire wear and extend tire life, minimize environmental pollution, and maintain tire grip over the long term, as tread wear generally leads to a deterioration in traction and braking performance.

[0008] The traction and braking characteristics of tires in cold temperatures, typical of winter on snow-covered and icy roads, are contrary to their behavior on dry or wet surfaces in hot summer conditions.

[0009] Therefore, providing highly wear-resistant tires with excellent grip performance on snowy, icy, wet (winter, all-season) or wet / dry roads (summer use) is a particularly challenging objective.

[0010] The applicant conducted research to reduce tread wear while achieving better tire performance at low temperatures, such as on wet, snowy ground, i.e., for winter or all-season applications. Furthermore, with regard to summer tires, the applicant aimed to reduce tread wear while still striving to improve grip on hot, wet surfaces. [Means for solving the problem]

[0011] The applicant has found that a tire component comprising a crosslinked elastomer compound obtained by crosslinking a crosslinkable elastomer composition containing a specific conjugated diene polymer (I) as defined below, wherein the polymer is appropriately selected with a lower Tg for winter or all-season applications and a higher Tg for summer applications, exhibits reduced wear and maintains or improves grip performance in either application. Increased wear resistance without altering other important properties of the final tire translates to long-term performance retention and a longer tire life.

[0012] Accordingly, the present invention relates to a vehicle wheel tire comprising at least one tire component comprising a crosslinked elastomer compound obtained by crosslinking a crosslinkable elastomer composition, wherein the crosslinkable elastomer composition comprises at least one conjugated diene polymer (I) comprising conjugated conjugated diene monomer units (Y) and possibly conjugated aromatic vinyl monomer units (X), and the conjugated diene polymer (I) comprises at least one first polymer segment and at least one second polymer segment.

[0013] In particular, the present invention relates to a vehicle wheel tire comprising at least one tire component comprising a crosslinked elastomer compound obtained by crosslinking a crosslinkable elastomer composition, wherein the crosslinkable elastomer composition comprises at least one conjugated diene polymer (I) which comprises conjugated conjugated diene monomer units and may also comprise conjugated aromatic vinyl monomer units, and the conjugated diene polymer (I) comprises at least one first polymer segment and at least one second polymer segment. Y1 (mol%) is the amount of vinyl units in the conjugated diene monomer units of the first polymer segment, Y2 (mol%) is the amount of vinyl units in the conjugated diene monomer units of the second polymer segment, and Y2 - Y1 (mol%) is 15% to 50%. If bonded aromatic vinyl monomer units are present, X1 (wt%) is the amount of bonded aromatic vinyl monomer units in the first polymer segment, X2 (wt%) is the amount of bonded aromatic vinyl monomer units in the second polymer segment, and |X1-X2| (wt%) is at most 5%. i) Calculated glass transition temperature (Tg) of conjugated diene polymer (I) CALC ) is -75.0℃ to -30.0℃, preferably -72.0℃ to -40.0℃, and / or ii) In a conjugated diene polymer (I), the calculated glass transition temperature (Tg) of the first polymer segment CALC1) is lower than the calculated glass transition temperature (Tg CALC2 ) of the second polymer segment, where the calculated glass transition temperature is determined according to the Gordon-Taylor equation, relating to a vehicle wheel tire.

[0014] Preferably, in the conjugated diene polymer (I), the calculated glass transition temperature (Tg CALC1 ) of the first polymer segment is lower than the calculated glass transition temperature (Tg CALC2 ) of the second polymer segment, and the calculated glass transition temperature is determined according to the Gordon-Taylor equation.

[0015] Preferably, in the conjugated diene polymer (I), there are aromatic vinyl monomer units, and preferably |X1 - X2| (wt%) is at most 5%, where X1 (wt%) is the amount of the bonded aromatic vinyl monomer units in the first polymer segment, and X2 (wt%) is the amount of the bonded aromatic vinyl monomer units in the second polymer segment.

[0016] In a preferred embodiment, in the conjugated diene polymer (I), Tg CALC1 is lower than Tg CALC2 , there are aromatic vinyl monomer units, and |X1 - X2| (wt%) is at most 5%.

[0017] Preferably, in the conjugated diene polymer (I), Y2 - Y1 (mol%) is 15% to 50%, where Y1 (mol%) is the amount of vinyl units in the bonded conjugated diene monomer units of the first polymer segment, and Y2 (mol%) is the amount of vinyl units in the bonded conjugated diene monomer units of the second polymer segment.

[0018] In a preferred embodiment, in the conjugated diene polymer (I), Tg CALC1 is lower than Tg CALC2 , there are aromatic vinyl monomer units, |X1 - X2| (wt%) is at most 5%, and Y2 - Y1 (mol%) is 15% to 50%.

[0019] Preferably, in the conjugated diene polymer (I), the bonded aromatic vinyl monomer units are present in both polymer segments (i.e., X1 > 0 wt% and X2 > 0 wt%).

[0020] Preferably, the calculated glass transition temperature (Tg) of the conjugated diene polymer (I) is calculated according to the Gordon-Taylor formula. CALC The temperature range is -75.0℃ to -30℃, more preferably -72.0℃ to -40.0℃.

[0021] Preferably, the conjugated diene polymer (I) has a single DSC glass transition temperature (Tg) measured according to the method of ISO 22768:2006 at a heating rate of 10°C / min. DSC ) only has.

[0022] In one embodiment, the calculated glass transition temperature Tg of the conjugated diene polymer (I) CALC The temperature range is -72.0℃ to -40.0℃, the Y2-Y1 (mol%) is 15% to 50%, and if aromatic vinyl monomer units are present, |X1-X2| (wt%) is a maximum of 5%.

[0023] In a preferred embodiment, in the conjugated diene polymer (I), Tg CALC1 is Tg CALC2) Lower than, aromatic vinyl monomer units are present in both polymer segments, |X1-X2| (wt%) is up to 5%, Y2-Y1 (mol%) is 15%-50%, and the conjugated diene polymer (I) has one Tg DSC It has only -75.0℃ to -30℃, preferably -72.0℃ to -40.0℃ Tg CALC It has.

[0024] In a conjugated diene polymer (I), where the aromatic vinyl monomer unit is styrene and the conjugated diene monomer unit is 1,3-butadiene, the Tg of the conjugated diene polymer (I) CALCThe temperature range is -75.0°C to -30°C, preferably -72.0°C to -40.0°C, and the approximate formula is (1A):

[0025]

number

[0026] The applicant noted that, by providing the tire of the present invention as defined above, surprisingly, improved wear resistance was achieved along with better grip performance under different conditions. [Modes for carrying out the invention]

[0027] General definition In the context of this specification and the following claims, the term "phr" (percentage of rubber) means parts by weight of a particular component per 100 parts by weight of a dry elastomer polymer.

[0028] Unless otherwise specified, all percentages are expressed as weight percentages.

[0029] The term "elastomer composition" refers to a composition comprising at least one diene elastomer polymer and one or more additives, which, when mixed, provides an elastomer compound suitable for use in tire components.

[0030] The components of an elastomer composition are generally not introduced into the mixer all at once, but are typically added sequentially. In particular, vulcanizing additives, such as vulcanizing agents and optionally accelerators and retarders, are usually added at a stage downstream from the incorporation and processing of all other components. In intermediate or final elastomer compounds, the individual components of the elastomer composition are not necessarily unchanged and are not individually traceable, as they may have been transformed, whole or partially, by interactions with other components, thermal and / or mechanical processing. The term “elastomer composition” as used herein is intended to include all components added in the preparation of an elastomer compound, regardless of whether they are all actually present at the same time, introduced sequentially, or subsequently traceable in the final elastomer compound or tire.

[0031] The term "crosslinkable elastomer composition" refers to an elastomer composition comprising at least one elastomerized polymer, a reinforcing filler, and a vulcanizing agent.

[0032] The term "elastomer compound" means a mixture that can be obtained by mixing at least one elastomerized polymer and at least one additive commonly used in the preparation of tire compounds under specific pressure and temperature conditions, preferably by heating.

[0033] The term "vulcanized or cross-linked elastomer compound" refers to a material that can be obtained by cross-linking or sulfur-curing an elastomer compound.

[0034] The term "conjugated diene polymer" refers to a polymer or copolymer derived from the polymerization of one or more monomers, at least one of which is a conjugated diene (conjugated diolefin).

[0035] The term "elastomer polymer" refers to a natural or synthetic polymer that, after vulcanization, can be repeatedly stretched at room temperature to at least twice its original length and, upon removal of the tensile load, forcefully returns to almost its original length virtually immediately (as defined in ASTM D1566-11 Standard terminology relating to Rubber).

[0036] The term "vulcanization" refers to the cross-linking reaction of natural or synthetic rubber induced, for example, by sulfur-based vulcanizing agents.

[0037] The terms "raw" or "green" refer to materials, compounds, parts, or tires that have not yet been vulcanized.

[0038] The term "vulcanizing agent" refers to a crosslinking agent that can transform natural or synthetic rubber into an elastic and resistant material by forming a three-dimensional network of intermolecular and intramolecular crosslinks.

[0039] The term "vulcanization accelerator" refers to chemical agents that can reduce the duration and / or operating temperature of the vulcanization process, such as TBBS, sulfenamides in general, thiazoles, dithiophosphates, dithiocarbamates, guanidines, and sulfur donors, such as thiurams.

[0040] The term "vulcanization activator" refers to a chemical agent that further accelerates curing, allowing curing to occur in a shorter time and, optionally, at a lower temperature. An example of an activator is the stearate-zinc oxide system.

[0041] The term "vulcanization retarder" refers to a chemical agent that can delay the initiation of a curing reaction and / or suppress undesirable secondary reactions, such as N-(cyclohexylthio)phthalimide (CTP).

[0042] The term "curing system" refers to a system of chemical agents comprising at least one vulcanizing agent, and optionally an accelerator, retarder, and vulcanization activator.

[0043] The term "reinforcement filler" refers to reinforcements commonly used in the industry to improve the mechanical properties of tires, preferably selected from carbon black, conventional silica (e.g., granular silica precipitated with a strong acid, preferably amorphous silica), diatomaceous earth, calcium carbonate, titanium dioxide, talc, alumina, aluminosilicate, kaolin, silicate fibers, and mixtures thereof.

[0044] The term "white filler" refers to conventional reinforcing materials used in the industry, selected from conventional silicas and silicates such as sepiolite, palygorskite (also known as attapulgite), montmorillonite, and halloysite, which may be modified by acid treatment and / or derivatization. White fillers typically have hydroxyl groups on their surface.

[0045] The term "mixing stage 1" refers to a step in an elastomer compound preparation method that can be incorporated by mixing one or more additives under specific pressure and temperature conditions and optionally heating them, with the exception of the vulcanizing agent fed in stage 2. Mixing stage 1 is also called a "non-productive stage." In compound preparation, there may be multiple "non-productive" mixing stages, which may be referred to as 1a, 1b, etc.

[0046] The term “Mixing Stage 2” refers to the next step in an elastomer compound preparation method, in which a vulcanizing agent and optionally other additives in the vulcanizing package are introduced and mixed into the elastomer compound obtained from Stage 1 at a controlled temperature, generally below 120°C, to provide a vulcanizable elastomer compound. Mixing Stage 2 is also referred to as the “Production Stage.” Each mixing stage may include several intermediate or sub-stages of the process, characterized in that mixing is temporarily interrupted to allow the addition of one or more materials, but no intermediate release of the compound occurs.

[0047] The terms "modification" or "functionalization" refer to a chain-end modification reaction between one end of a single polymer chain and one or more modifiers.

[0048] The terms "coupling" and "branching" reactions correspond to end-chain reactions between two and two or more single polymer chain ends and one or more coupling agents, respectively. End-chain modification reactions between two or more single polymer chain ends and coupling agents result in polymers containing three or more arms at the coupling point.

[0049] In this specification, coupling functional groups and modifying functional groups may be present in the same agent acting as a coupling and modifying agent, the coupling functional group providing branching, and the modifying functional group modifying the properties of the polymer, for example, by increasing compatibility with fillers, thereby allowing the fillers to disperse better in the compound.

[0050] The term "modification rate" refers to the weight ratio, expressed as a percentage, of the modified conjugated diene polymer component containing modified functional groups in the polymer, relative to the total amount of the conjugated diene polymer mixture.

[0051] The term "degree of branching" refers to the number of polymer arms / chains at a coupling point.

[0052] A “random” (or “statistical” polymer, as defined herein, contains two or more monomers polymerized in an irregular or non-coherent manner. That is, the arrangement of monomers within the polymer chain follows statistical laws.

[0053] As defined herein, “block copolymer” essentially consists of two types of monomers that are polymerized in a regular or coherent manner and thus form two or more homopolymer subunits linked by covalent bonds.

[0054] In this specification, the term "segment or polymer segment" refers to a portion of a conjugated diene polymer (I) consisting of conjugated diene monomer units and aromatic vinyl monomer units, or consisting solely of conjugated diene monomer units.

[0055] In this specification, the term "first polymer segment" refers to a polymer segment having a lower Tg than the second polymer segment.

[0056] In this specification, the term "second polymer segment" refers to a polymer segment having a higher Tg than the first polymer segment.

[0057] The term "polymer segment ratio in conjugated diene polymer (I)" refers to the average weight fraction of each polymer segment relative to the entire conjugated diene polymer (I).

[0058] In this specification, the term "conjugated conjugated diene" refers to the conjugated diene monomer unit incorporated into the conjugated diene polymer (I) by polymerization.

[0059] In this specification, the term “amount of bonded aromatic vinyl monomer units” refers to the wt% of bonded aromatic vinyl monomer units relative to the weight of the segment or the weight of the conjugated diene polymer (I).

[0060] In this specification, the term "amount of vinyl units" refers to conjugated diene polymer (I)(Y all This refers to the mole fraction (mol%) of 1,2-vinyl units relative to the bonded conjugated diene monomer units contained in the ) or its segments (Y1, Y2).

[0061] In this specification, the term "microstructure" refers to the composition of a conjugated diene polymer that is composed of conjugated diene units and may also be composed of aromatic vinyl units.

[0062] The term "essentially consisting of" means that there may be additional specific components, i.e., those that do not significantly affect the essential properties of the polymer compound or elastomer composition.

[0063] Detailed description of the invention The crosslinkable elastomer compositions used to prepare one or more tires and tire components according to the present invention may be interpreted individually or in any desired combination with each other, and may have one or more of the following preferred properties.

[0064] The numerical ranges listed as preferred ranges may be replaced with numerical ranges obtained by arbitrarily combining each of the values ​​listed as upper and lower limits, even if no specific combination is mentioned.

[0065] The tire of the present invention includes a tire component comprising a crosslinked elastomer compound obtained by crosslinking a crosslinkable elastomer composition as described below. Preferably, the tire component consists essentially of, and more preferably consists of, a crosslinked elastomer compound obtained by crosslinking the following crosslinkable elastomer compositions.

[0066] The crosslinking elastomer composition of the present invention comprises at least the following: One or more elastomer polymers with 100 phr (at least 20 phr of which is at least one conjugated diene polymer (I) as defined below), At least 10 phr of reinforcing filler, and A vulcanizing agent of at least 0.1 phr.

[0067] The crosslinkable elastomer composition comprises one or more elastomer polymers in a concentration of 100 phr, of which preferably at least 30 phr or 40 phr, more preferably at least 50 phr, 60 phr or 70 phr, and even more preferably at least 80 phr or 90 phr, one or more conjugated diene polymers (I). In a preferred embodiment, the crosslinkable elastomer composition comprises 100 phr of conjugated diene polymer (I) as the sole elastomer polymer.

[0068] The crosslinkable elastomer composition may contain one or more conjugated diene polymers (I) in a mixture.

[0069] A tire of the present invention and a conjugated diene polymer (I) suitable for its manufacture are disclosed, for example, in Asahi Patent Application JP2023-072878, which is incorporated herein by reference.

[0070] The conjugated diene polymer (I) contains bonded conjugated diene monomer units and may also contain bonded aromatic vinyl monomer units. Preferably, the conjugated diene polymer (I) contains bonded conjugated diene monomer units and bonded aromatic vinyl monomer units. Preferably, the conjugated diene polymer (I) contains bonded aromatic vinyl monomer units in both of at least two polymer segments, and therefore the amounts (wt%) of X1 and X2 are greater than zero (>0 wt%). More preferably, the conjugated diene polymer (I) contains bonded 1,3-butadiene units and bonded styrene units in both of at least two polymer segments.

[0071] Examples of conjugated diene monomer units 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, 1,3-heptadiene, and mixtures thereof. Among these, 1,3-butadiene and isoprene are preferred.

[0072] Examples of aromatic vinyl monomer units include, but are not limited to, styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene, and mixtures thereof. Styrene is preferred among these.

[0073] The conjugated diene polymer (I) is a conjugated diene polymer comprising at least two polymer segments. The polymer segments are portions of the conjugated diene polymer (I) consisting of conjugated diene monomer units and aromatic vinyl monomer units, or consisting of conjugated diene monomer units alone.

[0074] The first polymer segment and the second polymer segment may each contain multiple polymer segments, but preferably each contains a single polymer segment.

[0075] In conjugated diene polymers (I), polymer segments may be directly bonded to each other or bonded via a coupling agent.

[0076] Polymer segments other than the first and second polymer segments are not required but may be present. For example, a third segment may be included after the synthesis of the first and second segments to enhance the reactivity between the conjugated diene polymer and the coupling agent.

[0077] In the conjugated diene polymer (I), the percentage ratio of the sum of the weights of the first and second polymer segments to the total weight of the conjugated diene polymer (I) is preferably higher than 70%, more preferably higher than 80%, and even more preferably higher than 90%.

[0078] In the conjugated diene polymer (I), the first and second polymer segments preferably have a predetermined weight ratio r1 and r2, i.e., the ratio of the weight of the first polymer segment and the second polymer segment to the total weight of the conjugated diene polymer (I).

[0079] The conjugated diene polymer (I) is characterized by a ratio R = r1 / r2 (wherein r1 is the weight ratio of the first polymer segment having a lower Tg in the conjugated diene polymer (I), and r2 is the weight ratio of the second polymer segment having a higher Tg) preferably 0.25 to 4.00, more preferably 1.00 to 3.00, and even more preferably 1.50 to 2.40.

[0080] The polymer segments of conjugated diene polymers (I) have different microstructures from one another.

[0081] The distribution of conjugated diene monomer units and optional aromatic vinyl units within the polymer segment is peculiar.

[0082] In fact, in conjugated diene polymers (I), when aromatic vinyl units are present, the absolute difference (|X1-X2|) between the amount X1 (wt%) of bonded aromatic vinyl monomer units in the first polymer segment and the amount X2 (wt%) of bonded aromatic vinyl monomer units in the second polymer segment is less than 5% (wt%).

[0083] Preferably, the conjugated diene polymer (I) contains bonded aromatic vinyl monomer units.

[0084] Preferably, in the conjugated diene polymer (I), the polymer segments have few or no blocks containing four or more linked aromatic vinyl monomer units, which are referred to herein as "bonded aromatic vinyl monomer unit blocks." Preferably, the content of these blocks in the conjugated diene polymer (I) is at most 1.0 wt%, more preferably at most 0.1 wt%, and more preferably 0 wt% by the total weight of the conjugated diene polymer (I). If the conjugated diene polymer (I) is a butadiene-styrene polymer, the content of bonded aromatic vinyl monomer unit blocks can be measured by analyzing the amount of methanol-insoluble polystyrene according to the Kolthoff method (IMKolthoff, et al., J.Polym.Sci.1, 429 (1964)).

[0085] When there are few or no bonded aromatic vinyl monomer unit blocks, conjugated diene polymers (I) are more likely to have a single glass transition temperature (Tg).

[0086] If present, the amount of aromatic vinyl units in the first polymer segment X1 (wt%) and the second polymer segment X2 (wt%) is preferably at least 5 wt%, more preferably at least 7 wt%, even more preferably at least 9 wt%, preferably up to 30 wt%, more preferably up to 25 wt%, and even more preferably up to 23 wt%, in each polymer segment.

[0087] In the conjugated diene polymer (I), the absolute difference (│X1-X2│) between the amount X1 (wt%) of the bound aromatic vinyl monomer in the first polymer segment and the amount X2 (wt%) of the bound aromatic vinyl monomer in the second polymer segment is preferably at most 3 wt%, and more preferably at most 2.5 wt%.

[0088] When (│X1-X2│) is less than 5 wt%, the distribution of aromatic vinyl monomer units becomes more uniform, microphase separation of the conjugated diene polymer (I) is suppressed, and the tensile properties of the vulcanized compound tend to be better.

[0089] The absolute value of the difference in the amount of bonded aromatic vinyl monomers in polymer segments can be controlled within a numerical range by adjusting the amount of aromatic vinyl monomer added in the polymerization process of each polymer segment.

[0090] The amount of vinyl units Y1 (mol%) in the conjugated diene of the first polymer segment is preferably at least 14 mol%, more preferably at least 16 mol%, even more preferably at least 17 mol%, preferably up to 40 mol%, more preferably up to 35 mol%, even more preferably up to 30 mol%, and still more preferably up to 23 mol%.

[0091] The amount of vinyl units Y2 (mol%) in the conjugated diene of the second polymer segment is preferably at least 40 mol%, more preferably at least 45 mol%, even more preferably at least 50 mol%, still more preferably at least 55 mol%, preferably up to 65 mol%, more preferably up to 62 mol%, and even more preferably up to 61 mol%.

[0092] Furthermore, in the conjugated diene polymer (I), the difference (Y2-Y1) between the amount of vinyl units Y2 (mol%) in the conjugated conjugated diene of the second polymer segment and the amount of vinyl units Y1 (mol%) in the conjugated conjugated diene of the first polymer segment is preferably 20 mol% to 45 mol%, more preferably 25 mol% to 45 mol%.

[0093] A suitable range for the amounts Y1 and Y2 of vinyl units in the conjugated diene of the polymer segment can be obtained by arbitrarily combining the above upper and lower limits.

[0094] When (Y2-Y1) is 15 mol% or more, the vulcanized compound tends to have an excellent balance between wet grip performance and winter performance. On the other hand, when (Y2-Y1) is 50 mol% or less, microphase separation of the conjugated diene polymer (I) is suppressed, and the vulcanized compound tends to have excellent tensile strength.

[0095] The value of (Y2-Y1) can be controlled within the above numerical range, for example, by changing the amount of polar substance added in the polymerization steps (P1 and P2) described later.

[0096] Finally, the total amount X of bonded aromatic vinyl monomer units (if present) in the conjugated diene polymer (I) all (wt%) and total amount Y in vinyl units all (mol%) is the calculated Tg which satisfies the Gordon-Taylor formula and therefore preferably has a value of -75.0°C to -30.0°C, more preferably -72.0°C to -40.0°C. CALCTo provide.

[0097] X all and Y all The amount satisfies the Gordon-Taylor formula, preferably with a Tg of -75.0°C to -30.0°C, more preferably -72.0°C to -40.0°C. CALC Providing this improves the wet grip performance, winter performance, and wear resistance of the vulcanized compound.

[0098] Total amount of aromatic vinyl units in conjugated diene polymer (I) X all (wt%) and total amount Y in vinyl units all (mol%) can be determined by NMR according to the method of ISO 21561-1:20015, for example, as described in the experimental section below.

[0099] The conjugated diene polymer (I) may have more than one glass transition temperature, but preferably has a single glass transition temperature (Tg).

[0100] A conjugated diene polymer (I) comprising two or more polymer segments undergoes a glass transition over multiple temperature ranges because the polymer segments have different glass transition temperatures. In fact, according to the above, the conjugated diene polymer (I) comprises a segment referred herein as the second polymer segment, which has a higher vinyl unit content and a higher Tg, and a segment referred herein as the first polymer segment, which has a lower vinyl unit content and a lower Tg, wherein the first and second polymer segments, if present, have substantially the same content as aromatic vinyl units.

[0101] The estimated Tg of the polymer segment calculated as described below shows the same trend, i.e., the calculated glass transition temperature (Tg) of the first polymer segment CALC1 ) is the calculated glass transition temperature (Tg) of the second polymer segment. CALC2 It is lower than ).

[0102] Preferably, TgCALC2 and Tg CALC1 The difference is at least 10.0°C, more preferably at least 20.0°C, and even more preferably at least 25.0°C. Preferably, the difference is at most 40.0°C, and more preferably at most 35.0°C.

[0103] Of the two or more polymer segments contained in the conjugated diene polymer (I), Tg CALC The average Tg of conjugated diene polymer (I) CALC A polymer segment that is 5°C or more lower than the Tg is referred to herein as the “first polymer segment,” and its calculated Tg is Tg CALC1 On the other hand, if the temperature is 5°C or higher, it is referred to as the "second polymer segment" in this specification, and its calculated Tg is Tg CALC2 It is called that.

[0104] By setting the microstructure of the conjugated diene polymer (I) segments, that is, by selecting the appropriate amounts of bonded aromatic vinyl monomer units (X1, X2) and bonded vinyl units (Y1, Y2) for each polymer segment described above, and consequently selecting the respective glass transition temperatures within a certain range, a vulcanization compound with excellent wet grip performance and winter performance can be obtained.

[0105] This distribution causes the broadening of the DSC glass transition, whose inflection point typically correlates with the polymer Tg of the conjugated diene polymer (I), resulting in a rubber compound with excellent wet grip and winter performance, in addition to very good abrasion resistance and tensile properties.

[0106] Typically, in the tire industry, when winter performance is important, conventional conjugated diene polymers with low Tg are used to achieve sufficiently high flexibility at temperatures of -30°C to -10°C. However, conventional elastomer polymers have a relatively steep DSC glass transition profile, resulting in a relatively low Tan D value in the same -30°C to 0°C range, and therefore inferior snow and wet grip performance.

[0107] In conjugated diene polymers (I) containing at least two polymer segments, the greater the difference in Tg between the two polymer segments, the broader the DSC glass transition profile, and therefore the better the balance between winter performance and wet grip performance.

[0108] To broaden the DSC glass transition profile, both the amount of aromatic vinyl units and the difference in the amount of vinyl units between the first polymer segment and the second polymer segment can be increased.

[0109] However, if the aforementioned differences between the two polymer segments become too large, the compatibility of the two polymer segments decreases, and the tensile strength of the vulcanized product tends to decrease. To obtain a vulcanized product with appropriate tensile strength, it is effective to limit the difference in the amount of bonded aromatic vinyl monomer units between the two polymer segments (│ΔX=X1-X2│) within an appropriate range, and to increase the difference in the amount of bonded conjugated diene vinyl units between the two polymer segments (Y2-Y1) within the range listed above.

[0110] The glass transition temperature of a conjugated diene polymer (I) depends on its microstructure and is given by the following equation (1)

[0111]

number

[0112] The value obtained in this manner is the Tg(Tg) calculated in this specification. CALC ) is referred to as.

[0113] In equation (1) above, the subscript i of the variable represents each component of the microstructure in the conjugated diene polymer (I), and Δαi w is the difference in thermal expansion of the homopolymer of component i before and after the glass transition, and i This is the weight ratio of component i in the conjugated diene polymer (I), and Tg i ρ is the glass transition temperature of the polymer of single component i, i is the density of the polymer with single component i. Both literature values ​​and experimental measurements can be used for the variables in the above equation.

[0114] For example, if the conjugated diene polymer contains styrene and one of i is a styrene component, then the thermal expansion coefficient of polystyrene is (J. Brandrup et al, Polymer Handbook, Group 3, (US), John Wiley & Sons, Inc. 1966, VI-75)Δα i is 3.6 × 10 -4 K -1 Tg is measured by DSC. i The temperature is 105.3℃, and the measured density is ρ i = 1.02 g / cm³ 3 That is the case.

[0115] When the conjugated diene polymer (I) is a butadiene-styrene polymer, the amount of bonded aromatic vinyl units X all (wt%), amount of vinyl units in the conjugated diene Y all (mol%), the coefficient of thermal expansion (Δα), glass transition temperature (Tg), and density (ρ) of polystyrene (PS), poly-1,2-butadiene (1,2-PBd), and poly-1,4-butadiene (1,4-PBd) are known, therefore the Tg of the conjugated diene polymer (I) CALC This can be calculated by subsequent approximation, as shown in the following equation: Tg CALC =

[0116]

number

[0117]

number

[0118] If the conjugated diene polymer is a homopolymer of butadiene or a copolymer of butadiene and styrene, the glass transition temperature of the conjugated diene polymer (I) is determined by the amount of bonded aromatic vinyl units in the conjugated diene polymer (I) X all (wt%) and amount of vinyl units of conjugated dienes Y all It can be easily calculated using the above formula (1A) from values ​​that are commonly known in polymer design, such as (mol%).

[0119] In the case of conjugated diene polymer (I), Tg CALC The temperature is preferably at least -72.0°C, preferably at least -70.0°C, more preferably at least -68°C, preferably at most -40.0°C, more preferably at most -42.0°C, and more preferably at most -44.0°C.

[0120] The same equation (1) / (1A) is given by Tg of segment n. CALC This can be applied to calculate the respective Xn and Yn content within that segment.

[0121] The glass transition temperature of conjugated diene polymer (I) is determined by the total amount of bonded aromatic vinyl monomer units in conjugated diene polymer (I) X all (wt%) and total amount Y in vinyl units all By adjusting the (mol%), it is possible to control the value within the above range.

[0122] Tg(Tg) is calculated using the above formula (1) or (1A). CALC By setting the temperature to preferably -72.0°C to -40.0°C, the measured glass transition temperature will also generally fall within that preferred range.

[0123] However, Tg calculated according to equation (1) CALCThe observed Tg measured by DSC may differ from the Tg calculated by DSC (e.g., a difference of 2-5°C) depending on the polymer microstructure and / or the specific settings of the DSC measurement, particularly the cooling and heating rates. Specifically, the difference between the Tg calculated from equation (1) or (1A) above and the measured DSC glass transition temperature is the Tg of the segment calculated by applying equation (1) or (1A). CALC The difference (Tg CALC2 -Tg CALC1 The ratio tends to be larger when the ratio is 33 or higher, or when the weight ratio R of the polymer segments is in the range of 0.67 to 1.50.

[0124] Preferably, Tg is determined by DSC in accordance with ISO 22768:2006. DSC The experimental Tg of the conjugated diene polymer (I) referred to as is -75.0°C to -30.0°C, or preferably at least -72.0°C, more preferably -72.0°C to -40.0°C.

[0125] Tg of conjugated diene polymer (I) DSC For winter or all-season use, the optimal temperature is preferably -70.0°C to -40.0°C, more preferably -65.0°C to -55.0°C.

[0126] Preferably, the Tg of the conjugated diene polymer (I) DSC For summer tires, the optimal operating temperature range is -55.0°C to -20.0°C, more preferably -55.0°C to -40.0°C.

[0127] Tg DSC If the above range is met, the vulcanized compound of conjugated diene polymer (I) tends to have an overall optimized performance balance (i.e., wet grip, wear, and RR, i.e. fuel efficiency) for a specific application (winter, all-season, or summer).

[0128] From the DSC thermogram of conjugated diene polymer (I), Tg DSC Starting temperature and Tg DSCThe termination temperature can be extrapolated, for example, as described in the experimental section of the present invention and shown in Figure 4.

[0129] Tg of conjugated diene polymer (I) DSC Extrapolated Tg DSC Termination temperature and extrapolated Tg DSC The difference from the starting temperature may be less than 15.0°C, less than 14.5°C, or less than 14.0°C. Preferably, the difference is greater than 10.0°C, preferably greater than 12.0°C, and typically between 10.0°C and 15.0°C.

[0130] The weight-average molecular weight (Mw) of the conjugated diene polymer (I), as measured by gel permeation chromatography (GPC), is preferably at least 350,000 g / mol, more preferably at least 400,000. Furthermore, the weight-average molecular weight is preferably up to 1,350,000 g / mol, more preferably up to 1,000,000 g / mol, even more preferably up to 950,000 g / mol, and still more preferably up to 800,000 g / mol, 750,000 g / mol, or 650,000 g / mol.

[0131] Preferably, the weight-average molecular weight (Mw) of the conjugated diene polymer (I) is 350,000 g / mol to 1,350,000 g / mol, preferably 350,000 g / mol to 1,000,000 g / mol, and more preferably 400,000 g / mol to 650,000 g / mol.

[0132] The number-average molecular weight (Mn) of the conjugated diene polymer (I), as measured by GPC, is preferably at least 100,000 g / mol, more preferably at least 150,000 g / mol, and even more preferably at least 200,000 g / mol. Furthermore, the number-average molecular weight is preferably up to 1,000,000 g / mol, more preferably up to 700,000 g / mol, and even more preferably up to 500,000 g / mol.

[0133] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the conjugated diene polymer (I) can be controlled within the above numerical range by adjusting the ratio of the polymerization initiator used to the monomer used, as well as the type and amount of coupling agent used.

[0134] The molecular weight distribution of a conjugated diene polymer (I) is expressed by the ratio of its weight-average molecular weight (Mw) to its number-average molecular weight (Mn) (polydispersion index Mw / Mn). The conjugated diene polymer (I) preferably has a polydispersion index Mw / Mn of at least 1.20, more preferably at least 1.30, and even more preferably at least 1.40. Furthermore, this is preferably up to 2.20, more preferably up to 2.00, and even more preferably 1.80.

[0135] The conjugated diene polymer (I) preferably contains nitrogen-containing modifying groups and preferably has a modification rate of at least 60%. The modification rate can be measured by chromatography, which can separate the functional group-containing modified components from the unmodified components. In the conjugated diene polymer (I), the modification rate can be controlled by adjusting the amount of modifying agent added and the reaction method. The conjugated diene polymer (I) preferably has a modification rate of at least 60%, more preferably at least 65%, and even more preferably at least 70%.

[0136] Preferably, the degree of branching of the conjugated diene polymer (I) is greater than 2.

[0137] The degree of branching obtained depends on the type of coupling agent used.

[0138] In a preferred embodiment, the conjugated diene polymer (I) has the following characteristics: - The conjugated diene monomer unit is selected from 1,3-butadiene, isoprene, and mixtures thereof, preferably 1,3-butadiene. - Aromatic vinyl monomer units are present, and they are styrene. - The percentage ratio of the sum of the weights of the first and second polymer segments to the total weight of the conjugated diene polymer (I) is greater than 90%. - The ratio R=r1 / r2 of the first polymer segment to the second polymer segment is 1.50 to 2.40. - The absolute value of the difference (│X1-X2│) is at most 2.5 wt%. - The difference (Y2-Y1) is between 25 mol% and 45 mol%. - Tg CALC2 and Tg CALC1 The difference is at least 10.0℃. - Tg DSC For winter or all-season tires, the temperature range is -65.0°C to -55.0°C, and for summer tires, it is -55.0°C to -40.0°C. - The weight-average molecular weight (Mw) is 400,000 to 800,000 g / mol. - The number-average molecular weight (Mn) is preferably 200,000 to 500,000 g / mol. - The multivariance index Mw / Mn is between 1.30 and 2.00. - The modification rate is at least 70%. It features one or more, preferably all, of the following characteristics.

[0139] Preferably, in the conjugated diene polymer (I), the weight of the copolymer containing styrene and butadiene is at least 70 wt%, more preferably at least 80 wt%, and even more preferably at least 90 wt%, of the total weight of the conjugated diene polymer (I).

[0140] The conjugated diene polymer (I) can be produced by a method comprising a polymerization process (PR1) for synthesizing a first polymer segment and a polymerization process (PR2) for forming a second polymer segment at the end of the first polymer segment obtained in PR1, according to conventional polymerization techniques.

[0141] A method for introducing multiple polymer segments into the molecule of a conjugated diene polymer (I) is carried out by sequentially adding the conjugated diene monomer, aromatic vinyl monomer (if present), polar substance, and solvent to each reactor using a continuous solution polymerization method in which multiple reactors are arranged in series.

[0142] Suitable polymerization initiators include n-BuLi, sec-BuLi, tert-BuLi, Li-(CH2)(Me)2Si-N-(C4H9)2, and Li-(CH2)(Me)2Si-N-(C2H5)2.

[0143] In particular, the conjugated diene polymer (I) can be produced according to a method comprising a polymerization process (PR1) for synthesizing a first polymer segment in two or more successive reactors, and a polymerization process (PR2) for forming a second polymer segment at the ends of the first polymer segment obtained in PR1, wherein a polar substance is additionally added in polymerization process PR2.

[0144] Polar substances can be randomly copolymerized with aromatic vinyl monomers and conjugated diene monomers. Examples of polar substances include ethers, tertiary amines, alkali metal alkoxides, and phosphines.

[0145] Polymerization process PR2 for obtaining the second polymer segment uses one or more linked reactors, similar to the first polymerization PR1. In PR2, by adding new conjugated diene monomers, aromatic vinyl monomers, inert solvents, and polar substances after the previous polymerization process, a second polymer segment with a higher amount of vinyl units in the conjugated conjugated diene can be synthesized. This allows for the formation of a second polymer segment with a higher Tg than the first polymer segment. The method for producing conjugated diene polymer (I) involves the following steps: - A step of coupling the active ends of a conjugated diene polymer obtained by a polymer segment polymerization step using a coupling agent such as a reactive agent having three or more functional groups, and / or - A process of modification using a modifier having a nitrogen atom-containing group. This can be implemented.

[0146] The coupling agent may have any structure as long as it is a reactive compound having three or more functional groups, but a reactive compound having three or more functional groups having silicon atoms is preferred.

[0147] The coupling agent preferably includes a modifier, for example, the coupling agent preferably includes a nitrogen atom-containing group.

[0148] Preferred coupling agents having three or more functional groups containing silicon atoms include halogenated silanes, epoxidized silanes, vinylinated silanes, alkoxysilanes, and alkoxysilanes containing nitrogen groups.

[0149] Examples of nitrogen atom-containing modifiers include, but are not limited to, isocyanates, isothiocyanates, isocyanuric acid derivatives, carbonyl agents containing nitrogen atom groups, vinyl agents containing nitrogen atom groups, and epoxy agents containing nitrogen atom groups. Preferably, in the modifier, the nitrogen atom-containing functional group is an amine that does not have active hydrogen, such as a tertiary amine or a protected amine.

[0150] An example of a coupling agent that also acts as a modifier is an epoxy compound having nitrogen atom-containing groups, such as a hydrocarbon compound that contains an epoxy group bonded to an amino group and may further have an epoxy group bonded to an ether group.

[0151] Examples of modifiers include alkoxysilanes having nitrogen atom-containing groups, such as tris(3-trimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl)amine, tris(3-tripropoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]amine, tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine ("N,N,N',N'-tetrakis(3-trimethoxysilylpropyl Tris(3-trimethoxysilylpropyl)-[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-propanediamine, Tris(3-trimethoxysilylpropyl)-[3-(1-methoxy-2-methyl-1-sila-2-azacyclopentane)propyl]-1,3-propanediamine, Bis(3-triethoxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl] -[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane, tris(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, tetrakis(3-trimethoxysilylpropyl)-1,6-hexamethylenediamine, pentaquis(3-trimethoxysilylpropyl) (Rylpropyl)-diethylenetriamine, Tris(3-trimethoxysilylpropyl)-methyl-1,3-propanediamine, Tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane, Bis(3-trimethoxysilylpropyl)-bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane, Tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)silane, Tris[3-(2,[2-Dimethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-Methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]silane, 3-Tris[2-(2,2-Dimethoxy-1-aza-2-silacyclopentane)ethoxy]silyl-1-trimethoxysilylpropane, 1-[3-(1-Methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-3,4,5-Tris(3-tri These are (methoxysilylpropyl)-cyclohexane, 1-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-3,4,5-tris(3-trimethoxysilylpropyl)-cyclohexane, 3,4,5-tris(3-trimethoxysilylpropyl)-cyclohexyl-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl] ether, and (3-trimethoxysilylpropyl) phosphate.

[0152] Also, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]phosphate, bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)phosphate, tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]phosphate, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N-(1,3-dimethylbutylidene)-3-(trimethoxysilyl)-1-propanamine, N-ben Examples include zylidene-3-(triethoxysilyl)propan-1-amine, N-benzylidene-3-(trimethoxysilyl)propan-1-amine, 1,1-(1,4-phenylene)bis(N-(3(triethoxysilyl)propyl)methaneamine), 1,1-(1,4-phenylene)bis(N-(3(trimethoxysilyl)propyl)methaneamine), 2-methoxy-2-methyl-1-(benzylideneaminoethyl)-1-aza-2-silacyclopentane, and 2-methoxy-2-methyl-1-(4-methoxybenzylideneaminoethyl)-1-aza-2-silacyclopentane.

[0153] Furthermore, 1-methyl-4-[3-(trimethoxysilyl)propyl]piperazine, 1-methyl-4-[3-(triethoxysilyl)propyl]piperazine, 1-methyl-4-[3-(methyldimethoxysilyl)propyl]piperazine, 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropane-1-amine), 3,3'-(1,1,3, Examples include 3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropane-1-amine), and 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropane-1-amine).

[0154] Furthermore, 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethane-1-amine), 3,3'-(1,1 ,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethane-1-amine) Roxane-1,3-diyl)bis(N,N-dimethylmethane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis Other examples include s(N,N-dipropylmethane-1-amine), 1,3-bis(3-(1H-imidazole-1-yl)propyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(3-(1H-imidazole-1-yl)propyl)-1,1,3,3-tetraethoxydisiloxane, and 1,3-bis(3-(1H-imidazole-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane.

[0155] Among coupling modifiers containing nitrogen atoms, examples include protected amine agents in which the active hydrogen is substituted with a protecting group, and in particular, agents having an alkoxysilane moiety and a protected amine.

[0156] Suitable coupling and / or modifiers incorporated herein by reference are disclosed, for example, in Japanese Patent Application JP2023-072878 (see formulas A-D described herein).

[0157] In the method for preparing the conjugated diene polymer (I) of the present invention, an extender oil, liquid rubber and / or resin is preferably further added to the conjugated diene polymer (I) produced.

[0158] Conjugated diene polymers (I) exhibit excellent abrasion resistance and tensile properties, and when incorporated into rubber compositions, they enhance grip performance.

[0159] In the crosslinkable elastomer composition of the present invention, the complement of the conjugated diene polymer (I) up to 100 phr may be one or more conventional elastomer polymers, as described below.

[0160] Conventional elastomer polymers are commonly used in sulfur-vulcanizable elastomer compositions and are particularly suitable for tire production. These can be selected from solid elastomer polymers or copolymers having unsaturated chains and generally having a glass transition temperature (Tg) lower than 20°C, preferably in the range of 0°C to -110°C.

[0161] These polymers or copolymers may be of natural origin or may be obtained by solution polymerization, emulsion polymerization, or gas-phase polymerization of one or more conjugated dienes, which may be mixed with at least one comonomer, preferably selected from monoolefins, monovinylarenes, and / or polar comonomers, in an amount not exceeding 60% by weight.

[0162] The conjugated diene generally contains 4 to 12, preferably 4 to 8, carbon atoms, and may be selected from the group including, for example: 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene, and mixtures thereof. 1,3-butadiene and isoprene are particularly preferred.

[0163] Monoolefins can be selected from ethylene and α-olefins, which generally contain 3 to 12 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or mixtures thereof.

[0164] Monovinylarenes, which may be used as comonomers, generally contain 8 to 20, preferably 8 to 12, carbon atoms and can be selected from, for example: styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, various alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl derivatives of styrene, such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-p-tolylstyrene, 4-(4-phenylbutyl)styrene, and mixtures thereof. Styrene is particularly preferred.

[0165] The polar comonomers that may be used can be selected from, for example, acrylic acids and alkyl acrylic acid esters, acrylonitriles, or mixtures thereof, such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylonitrile, and mixtures thereof.

[0166] Preferably, the elastomer polymer can be selected from, for example, cis-1,4-polyisoprene (natural or synthetic, preferably natural rubber), 3,4-polyisoprene, polybutadiene (especially polybutadiene with a high 1,4-cis content), isoprene / isobutene copolymer, halogenated isoprene / isobutene copolymer, 1,3-butadiene / acrylonitrile copolymer, styrene / 1,3-butadiene copolymer, styrene / isoprene / 1,3-butadiene copolymer, styrene / 1,3-butadiene / acrylonitrile copolymer, and mixtures thereof.

[0167] The crosslinkable elastomer composition may contain one or more monoolefins and at least one polymer of an olefin comonomer or derivative thereof. The monoolefin can be selected from ethylene and α-olefins generally containing 3 to 12 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or mixtures thereof. The following are preferred: copolymers selected from ethylene and α-olefins, which may contain a diene; homopolymers of isobutene, which may be at least partially halogenated, or copolymers thereof containing a small amount of diene. The diene, which may be present, generally contains 4 to 20 carbon atoms and is preferably selected from: 1,3-butadiene, isoprene, 1,4-hexadiene, 1,4-cyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, vinylnorbornene, or mixtures thereof. Of these, the following are particularly preferred: ethylene / propylene (EPR) copolymer or ethylene / propylene / diene (EPDM) copolymer; polyisobutene; butyl rubber; halobutyl rubber, especially chlorobutyl rubber or bromobutyl rubber; and mixtures thereof.

[0168] In conventionally known elastomer polymers, the distribution of vinyl units and aromatic vinyl units is random or does not provide first and second polymer segments like those of the present invention, such as in the conjugated diene polymer (I).

[0169] The polymers described above may be functionalized along the main chain or at their ends.

[0170] The functional groups may be introduced into the elastomer polymer by methods known in the art, for example, by copolymerization with at least one corresponding functionalized monomer containing at least one ethylene unsaturated group during the formation of the elastomer polymer, or by subsequent modification of the elastomer polymer by graft polymerization of at least one functionalized monomer in the presence of a free radical initiator (e.g., an organic peroxide).

[0171] Alternatively, functionalization may be introduced by reaction with a suitable end-terminating agent or coupling agent.

[0172] The crosslinkable elastomer composition preferably contains at least one reinforcing filler in an amount of at least 10 phr, 20 phr, 30 phr, or 40 phr, more preferably at least 40 phr or 50 phr, and even more preferably at least 60 phr or 70 phr.

[0173] The composition of the present invention may contain at least one reinforcing filler in the range of 10 phr to 150 phr, 10 phr to 120 phr, or 10 phr to 90 phr.

[0174] Preferably, the reinforcing filler is selected from carbon black, white filler, silicate fibers, derivatives, and mixtures thereof.

[0175] In one embodiment, the reinforcing filler is a white filler selected from hydroxides, oxides and hydrated oxides, metal salts and hydrated salts, silicate fibers, derivatives thereof, and mixtures thereof. Preferably, the white filler is silica.

[0176] Suitable commercially available silica products include Zeosil 1165 MP, Zeosil 1115 MP, Zeosil 185 GR, Solvay Efficium, Wuxi Newsil HD90 and Newsil HD200, Wilmar K160 and K195, IQE H160AT and H180AT, Huber Zeopol 8755 and 8745, Grace Perkasil TF100, PPG Hi-Sil EZ 120 G, EZ 160 G, and EZ 200 G, and Evonik Ultrasil 7000 GR and Ultrasil 9100 GR.

[0177] In one embodiment, the reinforcing filler includes silica mixed with carbon black.

[0178] In one embodiment, the reinforcing filler includes modified silica.

[0179] Silica may be modified by reaction with, for example, silsesquioxane (as in WO2018078480A1), pyrrole (as in WO2016050887A1), or a silanating agent.

[0180] Suitable commercially available silanes include Si69, Dynasilan AMEO, and Dynasilan GLYEO from Evonik.

[0181] Modified silica may also be silica sulfide silane.

[0182] Silica sulfide is silica prepared by the reaction of silica or a metal silicate with at least one silane sulfide agent.

[0183] A suitable commercially available example of silica sulfide silane is Agilon 400 silica manufactured by PPG.

[0184] In one embodiment, the reinforcing filler includes modified silica mixed with carbon black.

[0185] In one embodiment, the reinforcing filler comprises silicates, such as layered silicates (e.g., bentonite, alloysite, laponite, saponite, vermiculite, or hydrotalcite), or possibly modified silicate fibers (e.g., sepiolite fibers, palygorskite fibers also known as attapulgite, wollastonite fibers, imogolite fibers), or mixtures thereof.

[0186] In one embodiment, the reinforcing filler includes silicate fibers mixed with carbon black.

[0187] In one embodiment, the silicate fiber is a modified silicate fiber, for example, one described in WO2016174629A1, WO2016174628A1, which is organically modified by reaction with a quaternary ammonium salt or a silanating agent.

[0188] In one embodiment, the reinforcing filler is preferably 20m 2 A surface area not less than / g, preferably 50m² 2 This carbon black is selected from those with a surface area greater than / g (determined by STSA, statistical thickness surface area according to ISO 18852:2005).

[0189] The carbon black may be, for example, N110, N115, N121, N134, N220, N234, N326, N330, N375 or N550, N660 sold by Birla Group (India) or Cabot Corporation, Vulcan® 1391 supplied by Cabot Corporation, or Birla Carbon® 2115 supplied by Birla Group.

[0190] The crosslinkable elastomer composition contains at least 0.1 phr of vulcanizing agent.

[0191] Preferably, the crosslinkable elastomer composition contains at least one vulcanizing agent in an amount of at least 0.2 phr, 0.5 phr, 0.8 phr, or 1 phr.

[0192] Preferably, the composition contains at least one vulcanizing agent in an amount of 0.1 to 10 phr, 0.2 to 10 phr, 1 to 10 phr, or 1.5 to 5 phr.

[0193] At least one vulcanizing agent is preferably selected from sulfur, sulfurizing agents (sulfur donors), such as bis[(trialkoxysilyl)propyl]polysulfide, caprolactam-disulfide, or peroxides, and mixtures thereof.

[0194] Preferably, the vulcanizing agent is sulfur selected from soluble sulfur (crystalline sulfur), insoluble sulfur (polymeric sulfur), oil-dispersed sulfur, and mixtures thereof.

[0195] A commercially available example of a vulcanizing agent suitable for use in crosslinkable elastomer compositions is soluble sulfur from Zolfindustria (Italy).

[0196] In the crosslinkable elastomer composition of the present invention, the vulcanizing agent may be used together with adjuvants such as vulcanizing activators, accelerators and / or retarders known to those skilled in the art.

[0197] The crosslinkable elastomer composition may contain at least one vulcanizing activator.

[0198] Suitable vulcanizing activators for use in the crosslinkable elastomer composition of the present invention are zinc salts of saturated or unsaturated fatty acids containing 8 to 18 carbon atoms, or mixtures thereof, which are formed in situ in the crosslinkable elastomer composition by the reaction of zinc compounds, particularly ZnO, ZnCO3, preferably ZnO and fatty acids. For example, zinc stearate, preferably zinc stearate formed in situ in the crosslinkable elastomer composition from ZnO and fatty acids, or magnesium stearate formed from MgO, or mixtures thereof can be used.

[0199] The vulcanizing activator may be present in the crosslinkable elastomer composition in an amount of preferably 0.2 phr to 15 phr, more preferably 1 phr to 5 phr.

[0200] The preferred activator is derived from the reaction between zinc oxide and stearic acid.

[0201] An example of an activator is Aktiplast ST, a product sold by Rheinchemie.

[0202] The crosslinkable elastomer composition may further contain at least one vulcanization accelerator.

[0203] Commonly used vulcanization accelerators may be selected from, for example, dithiocarbamates, guanidines, thioureas, thiazoles, sulfenamides, sulfenimides, thiurams, amines, xanthetes, or mixtures thereof.

[0204] Preferably, the accelerator is selected from mercaptobenzothiazole (MBT), N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N-tert-butyl-2-benzothiazole sulfenamide (TBBS), and mixtures thereof.

[0205] Examples of commercially available accelerators suitable for use in the crosslinkable elastomer composition of the present invention include N-cyclohexyl-2-benzothiadyl sulfenamide Vulkacit® (CBS or CZ), and N-terbutyl 2-benzothiadyl sulfenamide, Vulkacit® NZ / EGC, sold by Lanxess.

[0206] The vulcanization accelerator may be used in the crosslinkable elastomer composition of the present invention in an amount of preferably 0.05 phr to 10 phr, preferably 0.1 phr to 7 phr, and more preferably 0.5 phr to 5 phr.

[0207] The crosslinkable elastomer composition may contain at least one vulcanization retarder.

[0208] Suitable vulcanization retarders for use in the crosslinkable elastomer composition of the present invention are preferably selected from urea, phthalic anhydride, N-nitrosodiphenylamine N-cyclohexylthiophthalimide (CTP or PVI), and mixtures thereof.

[0209] A suitable commercially available retarder is Lanxess's N-cyclohexylthiophthalimide VULKALENT G.

[0210] A vulcanization retarder may be present in the crosslinkable elastomer composition of the present invention in an amount of preferably 0.05 phr to 2 phr.

[0211] The crosslinkable elastomer composition of the present invention may contain one or more vulcanization retarders as defined above in the mixture.

[0212] The crosslinkable elastomer composition may further contain at least one silane coupling agent in an amount of at least 0.05 phr, preferably at least 0.1 phr or 0.5 phr, and more preferably at least 1 phr or 2 phr.

[0213] Preferably, the crosslinkable elastomer composition contains at least one silane coupling agent in a concentration of 0.1 phr to 20.0 phr, or 0.5 phr to 10.0 phr, and more preferably 1.0 phr to 5.0 phr.

[0214] Preferably, the coupling agent is, for example, the following general formula: (R')3Si-C n H 2n -X (In the formula, the groups R' which are equal or different from each other are selected from alkyl, alkoxy or aryloxy groups or halogen atoms, provided that at least one of the groups R' is an alkoxy or aryloxy group, n is an integer from 1 to 6, and X is nitrite, mercapto, amino, epoxide, vinyl, imide, chloro, -(S) m C n H 2n (The group is selected from -Si-(R')3 and -S-COR' groups, where m and n are integers from 1 to 6, and the R' group is defined as above.) A silane coupling agent selected from those having at least one hydrolyzable silane group, which can be identified by [specific method / method].

[0215] Particularly preferred silane coupling agents are bis(3-triethoxysilylpropyl)tetrasulfide and bis(3-triethoxysilylpropyl)disulfide. The coupling agents may be added either on their own or mixed with an inert filler (e.g., carbon black) to facilitate their incorporation into the crosslinkable elastomer composition.

[0216] An example of a silane coupling agent is TESPT bis(3-triethoxysilylpropyl)tetrasulfide Si69, sold by Evonik.

[0217] The crosslinkable elastomer composition may further contain one or more additional materials commonly used in the art, such as plasticizers, resins, antioxidants and / or anti-ozone agents (anti-aging agents), waxes, adhesives, and the like.

[0218] For example, the crosslinkable elastomer composition according to the present invention may further contain at least one plasticizer, preferably a plasticizing oil, in order to improve the workability of the compound.

[0219] The amount of plasticizer is preferably in the range of 5 to 50 phr, and preferably 10 to 40 phr.

[0220] The term "plasticizing oil" refers to process oils, mineral oils, vegetable oils, synthetic oils, or combinations thereof derived from petroleum.

[0221] The plasticizing oil may be a process oil derived from petroleum, selected from paraffin (saturated hydrocarbons), naphthenes, aromatic polycyclics, and mixtures thereof.

[0222] Suitable process oils derived from petroleum include aromatic, paraffinic, and naphthenic oils such as MES (Mild Extract Solvated), DAE (Distillate Aromatic Extract), TDAE (Treated Distillate Aromatic Extract), TRAE (Treated Residual Aromatic Extract), and RAE (Residual Aromatic Extract), which are well known in the industry.

[0223] The plasticizing oil may be an oil of natural or synthetic origin derived from the esterification of glycerol and fatty acids, including glycerol triglycerides, diglycerides, monoglycerides, or mixtures thereof.

[0224] Suitable examples of vegetable oils include sunflower oil, soybean oil, linseed oil, rapeseed oil, castor oil, and cottonseed oil.

[0225] The plasticizing oil may be a synthetic oil selected from phthalic acid or alkyl or aryl esters of phosphoric acid.

[0226] The crosslinkable elastomer composition may further contain at least one resin.

[0227] The resin is preferably a non-reactive resin selected from hydrocarbon resins, phenolic resins, natural resins, and mixtures thereof.

[0228] The amount of resin is preferably in the range of 5 to 30 phr, more preferably in the range of 10 to 20 phr.

[0229] The crosslinkable elastomer composition may contain one or more liquid polymers. The liquid polymer is preferably selected from functionalized or unfunctionalized liquid BR, liquid SBR, or liquid IR, and its Mw is preferably lower than 20,000 g / mol.

[0230] The amount of liquid polymer is preferably in the range of 5 to 30 phr, more preferably in the range of 10 to 20 phr.

[0231] The crosslinkable elastomer composition may contain at least one type of wax.

[0232] The wax may be, for example, a mixture of petroleum wax or paraffin.

[0233] Suitable commercially available waxes include Repsol N-paraffin mixture and Antilux® 654 microcrystalline wax from Rhein Chemie.

[0234] The wax may be present in the crosslinkable elastomer composition in a total amount of generally 0.1 phr to 20 phr, preferably 0.5 phr to 10 phr, and more preferably 1 phr to 5 phr.

[0235] The crosslinkable elastomer composition may contain at least one antioxidant.

[0236] The antioxidant is preferably selected from N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), N-(-1,3-dimethyl-butyl)-n'-phenyl-p-phenylenediamine (6PPD), N,N'-bis-(1,4-dimethyl-pentyl)-p-phenylenediamine (77PD), N,N'-bis-(1-ethyl-3-methyl-pentyl)-p-phenylenediamine (DOPD), N,N'-bis-(1,4-dimethyl-pentyl)-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine (DPPD), N,N'-ditolyl-p-phenylenediamine (DTPD), N,N'-di-beta-naphthyl-p-phenylenediamine (DNPD), N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine (44PD), N-phenyl-N-cyclohexyl-p-phenylenediamine, N-phenyl-N'-1-methylheptyl-p-phenylenediamine, etc., and mixtures thereof, preferably N-1,3-dimethylbutyl-N-phenyl-p-phenylenediamine (6-PPD).

[0237] Commercially available examples of suitable antioxidants are 6PPD from Eastman's Solutia or Santoflex.

[0238] The antioxidant may preferably be present in the crosslinkable elastomer composition in an overall amount of 0.1 phr to 20 phr, more preferably 0.5 phr to 10 phr.

[0239] In one embodiment, a preferred crosslinkable elastomer composition for winter or all-season use comprises the following: - 100 phr of one or more elastomeric polymers (at least 50 phr being a conjugated diene polymer (I), and the conjugated diene polymer (I) having a Tg of -70.0 °C to -40.0 °C, preferably -65.0 °C to -55.0 °C) DSC ), - at least 50 phr, preferably 80 to 130 phr of at least one reinforcing filler, preferably silica. - At least 10 phr, preferably 15 to 25 phr of a plasticizer, preferably an oil, - Optionally at least 20 phr, preferably 30 to 40 phr of a resin, - Optionally at least 10 phr, preferably 15 to 25 phr of a liquid polymer, - At least 0.2 phr, preferably 0.5 to 1.0 phr of a vulcanizing agent, preferably sulfur, - At least 0.5 phr, preferably 0.8 to 1.5 phr of one or more vulcanization accelerators.

[0240] In one embodiment, a preferred crosslinkable elastomer composition for summer use comprises: - 100 phr of one or more elastomeric polymers (where at least 50 phr is a conjugated diene polymer (I) having a Tg of -55.0 °C to -20.0 °C, preferably -55.0 °C to -40.0 °C) DSC ), - At least 50 phr, preferably 70 to 110 phr of a reinforcing filler, preferably silica, - At least 10 phr, preferably 15 to 20 phr of a plasticizer, preferably an oil, - Optionally at least 10 phr, preferably 15 to 25 phr of a resin, - Optionally at least 5 phr, preferably 10 to 20 phr of a liquid polymer, - At least 0.5 phr, preferably 1.0 to 2.0 phr of a vulcanizing agent, preferably sulfur, - At least 1 phr, preferably 3 to 4 phr of one or more vulcanization accelerators.

[0241] Next, the above crosslinkable elastomer composition is crosslinked to provide the crosslinked elastomer compound of the present invention.

[0242] The crosslinked elastomer compound of the present invention is characterized by a specific hysteresis pattern.

[0243] In fact, unlike known elastomer compounds including conventional SBR, such as the reference compounds in Examples 1 and 2 (Figure 2B) and Examples 3 and 3 (Figure 3B), where the hysteresis shows a narrow, high peak centered around the compound's Tg temperature, which then decreases sharply after the peak as T increases, resulting in a low TanD value in the -30°C to +30°C range, the tire compounds of the present invention (Examples 4, 5, 6, Figure 2B) instead show a broadly flattened Tan D peak in the -30°C to +30°C temperature range, which is of interest for improving snow grip / wet grip performance, with less of a steep decline and a higher TanD value.

[0244] Furthermore, as the temperature decreases from -30°C to -50°C, the crosslinked elastomer compounds of the present invention (Examples 4, 5, 6, Figure 2A and Example 7, Figure 3A) exhibit a smoother or similar increase in stiffness (E') compared to the corresponding reference compound. This behavior, along with the broadening of the Tan D peak at temperatures from -30°C to +30°C, predicts higher wet grip.

[0245] Furthermore, the tire compounds of the present invention (Examples 4, 5, 6, and 7) exhibit a lower pain effect (see Table 5), which indicates better dispersion of the filler in the polymer matrix, as evidenced by the lower hardness values.

[0246] Finally, the crosslinked elastomer compounds of the present invention (Examples 4, 5, 6, and 7) exhibit lower or similar Mooney viscosity compared to the reference compounds of Examples 1, 2, and 3, and show well-balanced compound processability and static properties (see Table 4).

[0247] The crosslinked elastomer compound of the present invention may be prepared, for example, by a conventional method comprising a first non-productive step and a second productive step, followed by crosslinking.

[0248] This method typically includes the following: - In a first non-productive step, an elastomer polymer containing the conjugated diene polymer (I) of the present invention, a reinforcing filler, and optionally other optional materials, excluding antioxidants, compatibilizers, anti-ozone agents and / or waxes, and vulcanizing agents, are mixed at a temperature of 110 to 190°C to obtain a first elastomer compound. - In the second production step, a curing system containing at least one vulcanizing agent and optionally an accelerator, retarder, and vulcanization activator is added to the first elastomer compound, and the components are mixed at a temperature preferably lower than 120°C to obtain a crosslinkable elastomer compound, and - A crosslinkable elastomer compound is crosslinked at a temperature of preferably 150°C to 180°C to obtain a crosslinked elastomer compound.

[0249] The method according to the present invention typically comprises one or more thermomechanical mixing steps in at least one suitable mixer, in particular, at least a first mixing step (step 1, non-productive) and a second mixing step (step 2, productive), as defined above.

[0250] Each mixing step may include a number of intermediate processing steps or sub-steps, characterized in that mixing is temporarily interrupted to allow the addition of one or more materials, but no intermediate discharge of the compound occurs.

[0251] Mixing may be carried out using, for example, an open mill type open mixer, or a closed mixer with a tangential rotor (Banbury®) or an interpenetrating rotor (Intermix), or a Ko-Kneader® type (Buss®) or a twin-screw or multi-screw continuous mixer.

[0252] Generally, though not always, the initial elastomer compound is removed at the end of process 1 and refilled into the same or another suitable mixer after a varying period for the next productive process 2.

[0253] In the production process 2, the temperature is generally controlled in order to avoid an undesired pre-vulcanization phenomenon.

[0254] At the end of the second step, the crosslinkable elastomer compound is incorporated into one or more parts of the green tire and subjected to vulcanization according to known techniques.

[0255] In the method of the present invention, any of the usual vulcanization processes may be used, such as heating with a press or mold, heating with superheated steam or hot air.

[0256] The tire part containing, preferably consisting essentially of, or more preferably consisting of the above crosslinked elastomer compound is preferably selected from a tread band, a lower layer, a wear prevention strip, a sidewall, a sidewall insert, a mini-sidewall, a liner, an underliner, a rubber layer, a bead filler, a bead reinforcement layer (flipper), a bead protection layer (chafer) and a sheet. Preferably, the tire part is a tread band.

[0257] The tire for a vehicle wheel according to the present invention includes at least one part containing a crosslinked elastomer compound obtained by crosslinking the above crosslinkable elastomer composition. Preferably, the part is at least a tread band.

[0258] In one embodiment, the vehicle tire according to the present invention - includes a carcass structure including at least one carcass ply having opposing side edges coupled to respective bead structures, - optionally, a pair of sidewalls each applied to a lateral surface of the carcass structure at an axially outer position; - optionally, a belt structure applied at a radially outer position relative to the carcass structure; - a tread band applied at a radially outer position relative to the carcass structure or, if present, the belt structure, - Optionally, a layer of elastomer material referred to as the lower layer, applied to a radially inward position relative to the tread band. The tire comprises at least one component, preferably a tread band, which comprises, preferably essentially, or more preferably consists of, the crosslinked elastomer compound of the present invention. In a preferred embodiment, the tire component of the tire according to the present invention is a tread band.

[0259] In a preferred embodiment, the tire according to the present invention is (a) To produce a green tire including a green tread band applied to the radially outer position of the tire, (b) The green tire is subjected to molding and vulcanization to obtain a finished tire. The raw tread band may be prepared by comprising the above-mentioned crosslinkable elastomer composition or by a method which preferably comprises essentially the same.

[0260] The tire according to the present invention may be for summer use. Alternatively, the tire according to the present invention may be for winter and all-season use, depending on the structural features and the selection of a conjugated diene polymer (I) having a suitable Tg in the crosslinkable elastomer composition of the present invention. In a preferred embodiment, the vehicle tire of the present invention is a winter tire or a snow tire.

[0261] In one embodiment, the tire according to the present invention is a passenger car tire with normal or high performance, or an off-road vehicle tire, and is preferably a passenger car tire designed for personal use vehicles such as sedans, coupes, crossovers, SUVs, minivans, and small pickups.

[0262] In one embodiment, the tire according to the present invention is a motorcycle tire in which at least one component comprises, preferably essentially, or more preferably consists of the crosslinked elastomer compound of the present invention.

[0263] The tire according to the present invention may be a tire for a two-wheeled, three-wheeled, or four-wheeled vehicle.

[0264] In one embodiment, the tire according to the present invention is a tire for a bicycle wheel. A bicycle wheel tire typically includes a carcass structure wound around a pair of bead cores of a bead, and a tread band positioned radially outward relative to the carcass structure. Preferably, at least the tread band contains, or preferably consists of, the crosslinked elastomer compound of the present invention.

[0265] Vehicle wheel tires may be constructed, formed, molded and vulcanized in various ways known to those skilled in the art.

[0266] The tire according to the present invention is - To construct the components of the green tire on at least one forming drum, - To shape, mold, and vulcanize tires. This includes constructing at least one component of the green tire. - To manufacture at least one green component, preferably a tread band, comprising, preferably essentially, or more preferably consisting of, the crosslinkable elastomer compound of the present invention. It may be manufactured according to a method that includes [a specific component].

[0267] Description of a tire according to the present invention A tire for a vehicle wheel according to the present invention, comprising at least one component containing the elastomer compound of the present invention, is shown in a radial half-section in Figure 1.

[0268] In Figure 1, "a" indicates the axial direction, "X" indicates the radial direction, and in particular, XX indicates the outline of the equatorial plane. For simplicity, Figure 1 shows only a portion of the tire; the remaining unillustrated portion is identical and positioned symmetrically with respect to the equatorial plane "XX".

[0269] A four-wheeled vehicle tire (100) includes at least one carcass structure, each having opposing end flaps that engage with each annular anchor structure (102) called a bead core, which may be bonded to a bead filler (104).

[0270] The tire region, including the bead core (102) and filler (104), forms a bead structure (103) intended to secure the tire to a corresponding mounting rim (not shown).

[0271] The carcass structure is generally radial, meaning that the reinforcing elements of at least one carcass layer (101) are located in a plane that includes the tire's axis of rotation and is substantially perpendicular to the tire's equatorial plane. The reinforcing elements generally consist of fiber cords such as rayon, nylon, or polyester (e.g., polyethylene naphthalate, PEN). Each bead structure is joined to the carcass structure by folding the opposing side edges of at least one carcass layer (101) around an annular anchor structure (102) to form a so-called carcass flap (101a), as shown in Figure 1.

[0272] In one embodiment, the coupling between the carcass structure and the bead structure may be provided by a second carcass layer (not shown in Figure 1) which is applied axially outward with respect to the first carcass layer.

[0273] An anti-wear strip (105), which may be made of an elastomer material, is positioned on the outer side of each bead structure (103).

[0274] The carcass structure is bonded to a belt structure (106) which includes one or more belt layers (106a), (106b) arranged to overlap each other and radially with respect to the carcass layer, each having fibers and / or metal reinforcing cords incorporated within a layer of elastomer material.

[0275] Such reinforcing cords may have an orientation that intersects with the circumferential deployment direction of the tire (100). The "circumferential" direction generally refers to the direction in which the tire rotates.

[0276] At least one zero-degree reinforcing layer (106c), generally known as a "0° belt" (106b), may be applied to the radially outermost position of the belt layer (106a), which is generally substantially circumferentially oriented and thus forms an angle of several degrees (e.g., an angle of about 0° to 6°) with respect to the direction parallel to the equatorial plane of the tire, and incorporates a plurality of elongated reinforcing elements, typically metal or fiber cords, coated with an elastomer material.

[0277] The tread band (109) containing the crosslinked elastomer compound of the present invention is applied to the belt structure (106) at a radially outer position.

[0278] Furthermore, each sidewall (108) of the elastomer material is applied to an axially lateral position on the lateral surface of the carcass structure, with each extending from one of the side edges of the tread (109) to its respective bead structure (103).

[0279] At the radially outer position, the tread band (109) has a rolling surface (109a) intended to contact the ground. Circumferential grooves, generally formed on this surface (109a) and connected by lateral notches (not shown in Figure 1), define multiple blocks of various shapes and sizes distributed on this surface (109a), which are shown as smooth in Figure 1 for simplicity.

[0280] A lower layer (111) of elastomer material may be placed between the belt structure (106) and the tread band (109).

[0281] A strip (110) made of an elastomer material, generally known as a "mini-sidewall," may be provided in the connecting zone between the sidewall (108) and the tread band (109). This mini-sidewall is generally obtained by co-extrusion with the tread band (109) and allows for improved mechanical interaction between the tread band (109) and the sidewall (108). Preferably, the end portion of the sidewall (108) directly covers the side edge of the tread band (109).

[0282] In the case of tubeless tires, a rubber layer (112), generally known as a "liner," which provides the necessary airtightness for the expanding air in the tire, may also be provided at a radially inward position relative to the carcass layer (101).

[0283] The robustness of the tire sidewall (108) can be improved by providing the bead structure (103) with a reinforcing layer (120) or additional strip-like insert, commonly known as a "flipper."

[0284] The flipper (120) is a reinforcing layer that is wrapped around each bead core (102) and bead filler (104) so ​​as to be at least partially surrounding them, and the reinforcing layer is positioned between at least one carcass layer (101) and the bead structure (103). Typically, the flipper is in contact with the at least one carcass layer (101) and the bead structure (103).

[0285] The flipper (120) typically includes multiple fiber cords incorporated within a layer of elastomer material.

[0286] The reinforcing ring structure or bead (103) of the tire is commonly known by the terms “chafer” (121) or protective strip and may include an additional protective layer that serves to enhance the robustness and integrity of the bead structure (103).

[0287] A chafer (121) typically contains multiple cords embedded within a rubber layer of elastomer material. Such cords are generally made from fibrous material (e.g., aramid or rayon) or metallic material (e.g., steel cord).

[0288] A layer or sheet of elastomer material may be placed between the belt structure and the carcass structure (not shown). The layer may have a uniform thickness, or it may have a variable thickness in the axial direction. For example, the layer may have a greater thickness near the axial outer edge relative to the central (crown) zone. Advantageously, the layer or sheet may extend over a surface substantially corresponding to the extended surface of the belt structure.

[0289] In a preferred embodiment, a layer of elastomer material referred to as the lower layer (111) may be positioned between the belt structure and the tread band, wherein the lower layer preferably extends onto a surface substantially corresponding to the extended surface of the belt structure.

[0290] In the preferred tire according to the present invention, the crosslinked elastomer compound of the present invention may, advantageously, be incorporated into one or more of the other tire components in addition to the tread band.

[0291] The construction of the tire (100) described above may be carried out by assembling each semi-finished product, each consisting of a respective green compound and adapted to form a tire component, on a forming drum (not shown) using at least one assembly device.

[0292] At least some of the components intended to form the tire carcass structure may be constructed and / or assembled on a forming drum. More specifically, the forming drum is intended to first receive a possible liner and then receive the carcass structure. A device (not shown) then shaped the carcass sleeve according to a toroidal form by radial expansion of the carcass structure, such that one of the annular anchor structures coaxially engages around each of the end flaps, positioning the outer sleeve, which includes the belt structure and tread band, at a coaxial center position around the cylindrical carcass sleeve and applying it to the radial inner surface of the outer sleeve.

[0293] After the construction of the green tire, molding and vulcanization processes are generally performed to determine the structural stabilization of the tire by crosslinking the elastomer composition, as well as to impart the desired tread pattern to the tread band and to add identification graphic markings to the sidewall.

[0294] The applicant has found that the properties of the crosslinkable elastomer compositions described herein make it possible to provide tires with increased wear resistance that offer better driving performance in snowy / wet winter conditions or on wet / dry summer roads. [Brief explanation of the drawing]

[0295] [Figure 1] This is a schematic half-cross-sectional view showing a tire for a vehicle wheel according to the present invention. [Figure 2] This graph shows the E'-to-temperature (Figure 2A) and Tan D-to-temperature (Figure 2B) of compounds from Examples 1, 2, and 4-8 containing diene polymers with a TgDSC lower than -55℃. [Figure 3] This graph shows the E'-to-temperature (Figure 3A) and Tan D-to-temperature (Figure 3B) of the compounds in Example 3 (reference) and Example 7 (invention) containing a diene polymer having a TgDSC higher than -55℃. [Figure 4] This graph shows the extrapolation of the TgDSC start and end temperatures from the DSC thermogram of an exemplary polymer.

[0296] Experiment Department Unless otherwise specified, the components of the composition will be expressed in PHR (percentage of rubber) in this experimental department.

[0297] Test method Properties of polymers Weight-average molecular weight (Mw) and number-average molecular weight (Mn) The molecular weight (Mw) and number-average molecular weight (Mn) of polymers were measured by gel permeation chromatography (GPC) using a system consisting of a Waters HPLC instrument, Wyatt Multi-Angle Light Scattering (MALS), and a refractive index (RI) detector. The chromatography column bank consisted of three Shodex columns (KF802.5 + KF805 + KF806) with an inner diameter of 8.0 mm and a length of 300 mm. Column calibration was unnecessary due to the combined use of MALS and the RI detector. A polymer sample (10 mg) was dissolved in tetrahydrofuran (10 ml). The resulting solution was filtered using a 0.45 μm PTFE filter in an amber HPLC vial and analyzed to determine the weight-average molecular weight (Mw) and number-average molecular weight (Mn). The analysis was performed under the following conditions: mobile phase tetrahydrofuran (THF), eluent flow rate of 1 ml / min, and temperature of 30°C.

[0298] Glass transition temperature (Tg) of reference polymer determined by DSC DSC ) The glass transition temperatures of reference polymers A-C were determined by differential scanning calorimetry (DSC) using a DSC Mettler Toledo instrument under the following conditions: Test samples weighing 5 mg to 20 mg were weighed, placed in a pan without processing, the pan was sealed with a lid, and placed in the cell of the instrument set to 50°C. The nitrogen gas flow rate was set to 80 ml / min. The samples were cooled to -120°C at a cooling rate of 10°C / min and maintained at this temperature for 5 minutes. To determine the glass transition temperature, a thermogram was recorded during the final heating step from -120°C to +50°C at a heating rate of 10°C / min. The glass transition temperature was measured at the inflection point of the DSC curve (i.e., the minimum value of the first derivative of the DSC thermogram line) (see Figure 4).

[0299] Glass transition temperature (Tg) of polymers P1-P4 of the present invention by DSC. DSC ) When the polymer of the present invention is an oil-extracted product, the extender oil was first extracted, and then the sample was subjected to measurement of the glass transition temperature according to ISO 22768:2006 under the following conditions. The DSC thermogram was recorded using a MacScience "DSC 3200S" differential scanning calorimeter under a helium flow of 50 ml / min by raising the temperature from -120°C to +40°C at a heating rate of 10°C / min.

[0300] Extrapolated glass transition onset temperature (Tg DSC The starting point was determined as the temperature at the intersection of a straight line obtained by extending the baseline on the low-temperature side towards the high-temperature side and a tangent line drawn to the point where the slope of the curve representing the stepwise transition portion of the glass transition reaches its maximum.

[0301] Extrapolated glass transition end temperature (Tg DSC The end point was determined as the temperature at the intersection of a straight line obtained by extending the high-temperature baseline to the low-temperature side and a tangent line drawn to the point where the slope of the curve representing the stepwise transition portion of the glass transition is maximum.

[0302] Tg DSC and Tg DSC Figure 4 shows an example of extrapolation of the start / end temperatures into a graph.

[0303] Calculated glass transition temperature (Tg CALC ) The estimated glass transition temperatures of the styrene-butadiene polymers (I) (P1 to P4) and their segments used in this experimental section were calculated using the above approximate formula (1A).

[0304] Total vinyl and styrene content in conjugated diene (I) Total vinyl (Y all ) and total styrene (X all ) contents were measured by 1H-NMR using a NMR spectrometer BRUKER Avance (400 MHz) and a 5 mm dual probe, and CDCl3 (purity higher than 99.8%) containing 0.03% tetramethylsilane (TMS) as an internal standard as a solvent according to ISO 21561-1:20015. 1 was measured by 1H-NMR.

[0305] Determination of the weight ratios r1 and r2 of the first polymer segment and the second polymer segment, and their R ratios From the amount of non-volatile components (solid residue) in the conjugated diene polymer (I) solution, the amount of solid in the conjugated diene polymer (I) solution flowing through the measurement point per unit time was obtained. The total amount of the conjugated diene polymer (I) solution flowing through the measurement point was sampled for 3 minutes, and a polymerization terminator was immediately added. Then, the sample was transferred to a heat-resistant dish and dried in an oven at 140 °C for at least 30 minutes, and the weight (wt) of the solid residue was measured. The amount of solid (wt) was calculated by the following formula (2) Amount of solid wt [g / min] = Amount of solid wt [g / 3 min] : 3 (2) was determined by.

[0306] Similarly, the amounts of solid m1 and m2 referring to the first polymer segment and the second polymer segment were measured respectively. The measurement points were the discharge parts of the polymerization process 1 (PR1) for synthesizing the first polymer segment and the discharge part of the polymerization process 2 (PR2) for forming the second polymer segment.

[0307] The weight ratios r1 and r2 of the first and second polymer segments are given by the following equations (3) and (4): First polymer segment ratio

[0308]

number

[0309]

number

[0310] The weight ratio R of the polymer segments is given by the following formula (5): R = r1 / r2 (5) It is obtained from.

[0311] Determination of the content of bonded monomer units in the polymer segment of a conjugated diene polymer (I) and their differences (X1, X2, Y1, Y2, ΔX, ΔY) A 100 mg sample of the polymer solution from the waste portion of polymerization process PR1 for synthesizing the first polymer segment was diluted with chloroform to 100 ml and dissolved to obtain the measurement sample.

[0312] The amount of bound styrene (X1) (wt%) in the first polymer segment relative to 100% by weight of the first polymer segment was measured from the UV absorption of the phenyl group of styrene (wavelength approximately 254 nm, Shimadzu Corporation spectrophotometer "UV-2450").

[0313] The amount of bound styrene (X2) in the second polymer segment is given by the following equation (6):

[0314]

number

[0315] The difference │ΔX│ in the amount of bound styrene between the first polymer segment and the second polymer segment is given by the following formula (7): │Δx│ = |x1 - x2| (7) and is determined in accordance with

[0316] The amount (Y1) of vinyl units in the first polymer segment was determined as follows: 50 mg of a sample of the polymer solution in the effluent portion of the polymerization process (PR1) for synthesizing the first polymer segment was dissolved in 10 ml of carbon disulfide. Using a Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, trade name "FT-IR230"), the infrared spectrum of each sample was measured in the range of 600 to 1000 cm -1 of the range

[0317] The total amount (mol%) of 1,2-vinyl units in the bound butadiene of the conjugated diene polymer (I) was determined from the absorbance at a given wave number according to the method described in the Hampton method (R.R. Hampton, Analytical Chemistry 21, 923 (1949)).

[0318] The amount (Y2) (mol%) of vinyl units of the bound conjugated diene in the second polymer segment is given by the following formula (8):

[0319] [Number] (where X all , Y all , r1, X1, Y1, X2, and r2 have the meanings described above and are determined as described above) is calculated from

[0320] The difference ΔY in the amount of conjugated vinyl units of the diene between the first polymer segment and the second polymer segment is given by the following equation (9): ΔY = Y2 - Y1 (9) It was decided by [the organization / group].

[0321] Qualification rate The modification rates of polymers P1 to P4 of the present invention were measured as follows by column adsorption GPC.

[0322] Modified conjugated diene polymers were used as samples, and the modification rate was measured by utilizing the characteristic adsorption of the modified polymer components onto a GPC column loaded with silica gel.

[0323] Specifically, the amount adsorbed by the silica column was determined by comparing the chromatogram of a sample solution containing modified polymers and low molecular weight internal standard polystyrene, measured using a polystyrene column, with the chromatogram of the same sample solution, measured using a silica column.

[0324] - Preparation of sample solution: 10 mg of the sample and 5 mg of standard polystyrene were dissolved in 20 ml of THF (tetrahydrofuran) to obtain the sample solution.

[0325] - GPC measurement conditions using a polystyrene column: Using Tosoh Corporation's "HLC-8320GPC" column and 5 mmol / l triethylamine-containing THF as the eluent, 10 μl of sample solution was injected into the device at a column oven temperature of 40°C and a THF flow rate of 0.35 ml / min. A chromatogram was recorded using an RI detector.

[0326] Three "TSKgel SuperMultiporeHZ-H" units manufactured by Tosoh Corporation were connected, and a "TSK guard column SuperMP(HZ)-H" unit, also manufactured by Tosoh Corporation, was connected to the front of them.

[0327] - GPC measurement conditions using a silica column: GPC measurements were performed using the Tosoh Corporation's "HLC-8320GPC," an RI detector (Tosoh Corporation's product name "HLC-8020"), and THF as the eluent. 50 μl of the sample solution was injected into the device at a column oven temperature of 40°C and a THF flow rate of 0.5 ml / min, and the chromatogram was recorded.

[0328] The columns "Zorbax PSM-1000S," "PSM-300S," and "PSM-60S" were connected in this order, and a "DIOL 4.6x12.5mm 5micron" guard column was connected before them.

[0329] - Method for calculating modification rate: Assuming the total peak area of ​​the chromatogram using a polystyrene column is 100, the peak area of ​​the sample is PA1, the peak area of ​​standard polystyrene is PA2, the total peak area of ​​the chromatogram using a silica column is 100, the peak area of ​​the sample is PA3, and the peak area of ​​standard polystyrene is PA4, use the following formula (10): Modification rate (%)=[1-(PA2×PA3) / (PA1×PA4)]×100 (10) (In the equation, PA1 + PA2 = PA3 + PA4 = 100) The modification rate (%) was obtained from this.

[0330] Mooney viscosity and relaxation The Mooney stress relaxation rate (MSR) was determined using an Alpha Technologies MV2000 viscometer according to standard ISO 289. After the viscosity test at 100°C, the disc rotation was stopped within 0.1 seconds to reset the zero torque point to static zero of the stationary rotor, and the torque was recorded at least every 0.2 seconds. Relaxation data was collected starting 1.6 seconds after the rotor stopped and continuing until 5.0 seconds, typically yielding a total of 18 data points.

[0331] Properties of crosslinkable elastomer compounds The green crosslinkable elastomer compound was subjected to the following evaluations:

[0332] Mooney viscosity and relaxation (same test as above) MDR Rheometry Analysis: Following the standard ISO 6502, the test was performed using an MDR2000 Alpha Technologies rheometer at 170°C for 20 minutes with a frequency of 1.66 Hz (100 vibrations per minute) and an amplitude of ±0.5°. The time required to reach 90% of the final torque (T90) was measured. The maximum torque MH was also measured.

[0333] Properties of cross-linked compounds After crosslinking (vulcanization), the elastomer compound was subjected to the following evaluations:

[0334] Density: Density was measured using Alpha Technologies' automated Densitron according to ISO 2781 Method A.

[0335] Static mechanical properties were measured at 23°C according to the standard ISO 37:2005. Specifically, tensile stress at 300% elongation (T300%), tensile stress at fracture TB, and elongation at fracture EB were measured for elastomer compound samples vulcanized at 170°C for 10 minutes. Tensile tests were performed on ring-shaped specimens with a linear axis.

[0336] Hardness at IRHD (23°C) was measured in samples of elastomer compound vulcanized at 170°C for 10 minutes, according to the standard ISO 48:2007.

[0337] The dynamic mechanical properties were measured using a dynamic Instron device under compression-tension operations according to the following method.

[0338] E', E'' modulus of elasticity and TanD A sample of raw elastomer compound, vulcanized at 170°C for 10 minutes, having a cylindrical shape (length = 25 mm, diameter = 14 mm), pre-loaded and compressed until longitudinal deformation of 25% compared to the initial length, and held at a preset temperature (-10°C, 0°C, or 23°C) throughout the test, was subjected to dynamic sinusoidal deformation at a frequency of 100 Hz with an amplitude of ±3.5% with respect to the length under static pre-strain.

[0339] The dynamic mechanical properties were expressed in terms of the dynamic modulus of elasticity (E'), tan delta (Tan D - dielectric loss tangent or hysteresis), and loss compliance D'' (wet grip index). The value of TanD was calculated as the ratio of the viscosity coefficient (E'') to the modulus of elasticity (E'). The value of D'' was calculated as the ratio of TanD to the modulus of elasticity E * (complex modulus of elasticity E * It was calculated as the ratio of (=E'+iE'').

[0340] Dynamic testing using RPA (Rubber Process Analyzer) This test was used to measure the dynamic parameters and curing kinetics of the cured compound, the Payne effect (ΔG') due to strain sweep, and G' and tandelta at 9% strain. The procedure included the following steps and conditions: The sample is vulcanized at 170°C for 10 minutes under dynamic conditions. Wait 10 minutes to allow the material to recover after vulcanization and ensure it reaches a temperature of 70°C. • Strain sweep of 0.3% to 10% at 10Hz and 70℃. • Mechanical pretreatment of 100 cycles at 70°C, 10Hz, and 9% strain. • Dynamic characterization at 70°C, 10Hz, and strains of 9% and 3%.

[0341] Glass transition temperature (Tg) determined by temperature sweep This technique was used to determine the glass transition temperature Tg (tensile mode) of an elastomer compound subjected to sinusoidal vibrations of constant amplitude (strain) and constant frequency at increasing temperatures.

[0342] The application conditions were as follows: initial temperature: -80°C, final temperature: +30°C, heating rate: 2°C / min, pre-strain: 3%, strain: 0.1%, frequency: 1Hz.

[0343] The results are reported as curves of storage modulus (E') and TanD (ratio E'' / E') versus temperature (see Figures 2 and 3). The temperature peak in the tandelta curve corresponds to the glass transition temperature (Tg) of the compound.

[0344] Abrasion resistance (LAT 100 under dry conditions) The abrasion resistance was determined according to ISO 23233:2009 by using a driven vertical abrasion disc (LAT 100: Laboratory Abrasion Tester 100).

[0345] The test specimen was a single wheel made from the vulcanized compound under test, which was then driven under load on an abrasive disc rotating at a slip angle relative to the direction of rotation. Weight loss due to abrasion was determined from the slip generated by setting different slip angles and rotation speeds between the wheel-shaped rubber test piece and the abrasive disc, rotating them in planes perpendicular to each other, and pressing them under a predetermined load. The test results were reported as the Abrasion Resistance Index (ARI).

[0346] The abrasion resistance index is defined as the weight loss due to abrasion per unit distance traveled, normalized based on a reference compound (Example 1, Example 2, or Example 3 compound), and is given by the following equations (11) and (12):

[0347]

number

[0348] A lower Abrasion Resistance Index (ARI) indicated that the compound had better abrasion resistance compared to the reference compound.

[0349] Grip in wet conditions (LAT100 under wet conditions) In this case, the surface of the rotating abrasive disc was moistened with water at different temperatures. The test measured the frictional force (in Newtons) which is directly proportional to the sliding resistance against the road surface and the wheel. The frictional force that determines the traction ability of the tread compound depends on the viscoelastic properties of the compound, the contact temperature, the sliding speed, and the composition of the road surface. The application conditions were as follows: water temperature 2°C, 8°C, 15°C; constant speed of the rotating abrasive disc 0.4 km / h; speed angle 0°, constant load 75 N, wheel lock.

[0350] The friction force values ​​were calculated as the average of four iterations and normalized by setting the friction force of the reference compound (Example 1, Example 2, or Example 3) to 100.

[0351] The higher the frictional force, the better the wet grip of the test specimen. [Examples]

[0352] The following embodiments are provided for the purpose of further illustrating the present invention and should not be construed as limiting.

[0353] Reference polymer In the examples, commercially available reference polymers A, B, and C, differing in Tg and functional groups, were used. These reference polymers were random solution styrene-butadiene copolymers, lacking a uniform Tg along the polymer chain, i.e., segments, and exhibiting a steep DSC glass transition temperature profile. Polymer A was chain-end functionalized, polymer B was difunctionalized, and polymer C contained multiple functional groups.

[0354] These polymers were characterized as shown in Table 1 below:

[0355] [Table 1]

[0356] Conjugated diene polymer (I) for tire composition of the present invention In the following examples, polymers P1-P4, comprising a first polymer segment and a second polymer segment, were used in the tire composition and compound of the present invention. For brevity, polymers P1-P4 suitable for manufacturing the tire of the present invention are referred to herein as "the polymer of the invention." The polymers P1-P3 of the invention are suitable for winter or all-season use. DSC It has a Tg suitable for summer use, while polymer P4 has a Tg DSC The polymers P1 to P4 of the present invention contained 5 phr of oil.

[0357] Preparation of conjugated diene polymer (I) Preparation of polymer P1 The polymerization reactor consisted of two connected tank-type reactors equipped with a stirrer and a tank-type pressure vessel with a temperature control jacket. The internal volume was 10 L, the ratio of internal height (L) to diameter (D) (L / D) was 4.0, and there was an inlet at the bottom and an outlet at the top.

[0358] A polymerization process (PR1) for synthesizing the first polymer segment was carried out using the first polymerization reactor. Pre-dehydrated 1,3-butadiene, styrene, and n-hexane were mixed at rates of 20.3 g / min, 4.31 g / min, and 173 g / min, respectively. Using a static mixer installed in the piping supplying this mixture to the inlet of the reaction group, 0.104 mmol / min of n-BuLi was added to deactivate any residual impurities, and after mixing, the mixture was continuously fed to the bottom of the reactor. Furthermore, 2,2-bis(2-oxolanil)propane as a polar substance and n-BuLi as a polymerization initiator were supplied to the bottom of the first reactor at rates of 0.0235 mmol / min and 0.239 mmol / min, respectively, and vigorously mixed with a stirrer to maintain the reactor's internal temperature at 78°C. Once the polymerization reaction stabilized, the entire amount of conjugated diene polymer was withdrawn from the top of the reactor. After adding 0.2 g of antioxidant (BHT) per 100 g of conjugated diene polymer, the solvent was removed. Subsequently, the amount of bonded aromatic vinyl monomer units (X1) in the first polymer segment, the amount of bonded vinyl monomer in the bonded conjugated diene (Y1), and the solids content concentration (m1) were measured.

[0359] Next, a second polymerization reactor was used to form a second polymer segment (PR2). A solution of the conjugated diene polymer was continuously supplied from the top of the first reactor to the bottom of the second reactor. Furthermore, 1,3-butadiene, n-hexane, and 2,2-bis(2-oxolanil)propane were added to the second reactor as polar substances at rates of 8.71 g / min, 32.1 g / min, and 0.450 mmol / min, respectively, while stirring, and the reaction was continued at 78°C.

[0360] Next, in the modification step, tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (referred to as "Coupling Agent A" in Table 2 below) and 1-methyl-4-[3-(trimethoxysilyl)propyl]piperazine (referred to as "Coupling Agent B" in Table 2 below) were continuously added at rates of 0.0103 mmol / min and 0.0965 mmol / min to the conjugated diene polymer solution flowing out from the top of the second reactor, and the mixture was mixed using a static mixer to carry out the coupling reaction. At this point, the time until the coupling agent was added to the polymer solution flowing out from the outlet of the reactor was 4.8 minutes, and the temperature was 68°C.

[0361] Subsequently, the entire amount of the conjugated diene polymer solution was withdrawn after the coupling reaction. After adding 0.2 g of antioxidant (BHT) per 100 g of conjugated diene polymer, the solvent was removed. Various molecular weights and the total amount of bonded aromatic vinyl units (X all ), the total amount of vinyl units in the bonded conjugated diene (Y all The solid content (m²), glass transition temperature, and other parameters were measured.

[0362] Next, to the conjugated diene polymer (I) solution after the coupling reaction, an antioxidant (BHT) was added at a rate of 0.055 g / min at a rate of 0.2 g per 100 g of polymer (n-hexane solution) to stop the coupling reaction.

[0363] Simultaneously with the antioxidant, SRAE oil (JOMO Process NC140, manufactured by JX Nippon Oil & Energy Corporation) was added as a rubber softener at a rate of 5.0 g per 100 g of polymer and mixed in a static mixer. The solvent was removed by vapor stripping to obtain modified conjugated diene polymer P1.

[0364] Preparation of polymer P2 Conjugated diene polymer P2 was obtained using the same procedure as described above for the production of polymer P1, with the following differences: - The amounts of 2,2-bis(2-oxolanil)propane and n-BuLi supplied to the first reactor, and the amounts of 2,2-bis(2-oxolanil)propane supplied to the second reactor were changed to 0.0271 mmol / min, 0.297 mmol / min, and 0.461 mmol / min, respectively. - The amounts of coupling agent A and coupling agent B added during the modification process were changed to 0.0125 mmol / min and 0.1168 mmol / min, respectively.

[0365] Preparation of polymer P3 Conjugated diene polymer P3 was obtained using the same procedure as described above for the production of polymer P1, with the following differences: - The amounts of 2,2-bis(2-oxolanil)propane and n-BuLi supplied to the first reactor, and the amounts of 2,2-bis(2-oxolanil)propane supplied to the second reactor were changed to 0.0190 mmol / min, 0.187 mmol / min, and 0.362 mmol / min, respectively. - The amounts of coupling agent A and coupling agent B added during the modification process were changed to 0.0084 mmol / min and 0.0783 mmol / min, respectively.

[0366] Preparation of polymer P4 Conjugated diene polymer P4 was obtained using the same procedure as described above for the production of polymer P1, with the following differences: - The amounts of 1,3-butadiene and styrene supplied to the first reactor, and the amount of 1,3-butadiene added to the second reactor, were changed to 18.7 g / min, 6.67 g / min, and 8.00 g / min, respectively.

[0367] Preparation of polymer P5 Conjugated diene polymer P5 was prepared using the same procedure, but in the quantities specified in Table 2 below.

[0368] The conditions applied to the manufacturing process and the characteristics of the polymer thus obtained are summarized in Table 2 below:

[0369] [Table 2-1]

[0370] [Table 2-2]

[0371] Compositions and compounds (Examples 1-7) Reference compositions and corresponding compounds were prepared using polymers A (S-SBR, SLR3402, Example 1), B (S-SBR, XB120, Example 2), and C (S-SBR, HPR621, Example 3). The tire compositions and compounds of the present invention were manufactured using polymers P1 (Example 4), P2 (Example 5), P3 (Example 6), P4 (Example 7), and P5 (Example 8) of the present invention.

[0372] The recipe for the composition is shown in Table 3 below:

[0373] [Table 3-1]

[0374] [Table 3-2]

[0375] The above composition is used in a chamber with a total volume of 1100 cm³. 3The compound was formulated using a standard two-step compounding process by kneading in a laboratory closed-circuit mixer (Banbury rotor type). The first mixing step was performed at an initial temperature of 40°C. After adding all materials except the polymer, fillers, and curing system, the rotor speed of the closed-circuit mixer was set to reach a temperature of 145°C to 160°C, and the mixture was held at that temperature for 4 minutes to allow the silanization reaction to complete. The total mixing time for the first step was 2'30''. After releasing the compound, the mixture was cooled and stored, and then the curing system was added in the second mixing step. After adding sulfur as the vulcanizing agent and TBBS and TBZTD as accelerators, the second mixing step was performed on the compound from the first mixing step using the same equipment at an initial temperature of 50°C for a total time of 2'15''.

[0376] Compound properties Tables 4 and 5 below show the results of the static, rheometric, and dynamic mechanical properties of the crosslinked polymer compositions according to Examples 1-8:

[0377] [Table 4]

[0378] The performance of each compound of the present invention is similar to that of a Tg. DSC The compounds were evaluated in comparison to reference compounds containing polymers having the specified polymer (i.e., the compounds of the present invention in Examples 4, 5, 6, and 8 were compared to the reference compounds of Examples 1 and 2, and the compound of the present invention in Example 7 was compared to the reference compound of Example 3).

[0379] As shown in Table 4 above, Tg DSC Regarding the properties of compounds containing polymers with a temperature lower than -55°C (reference compounds in Examples 1 and 2, and the compounds of the present invention in Examples 4, 5, 6, and 8), the following was observed: - The compounds of the present invention in Examples 4, 5, and 6, containing polymers P1, P2, and P3, exhibited lower or similar Mooney viscosity compared to the reference compounds of Examples 1 and 2, containing polymers A and B, respectively, and therefore showed good compound processability. The compound of the present invention in Example 8, containing polymer P5, exhibited a higher Mooney viscosity compared to the reference compounds of Examples 1 and 2, but was still within a processable range. - The mechanical properties of the compound of the present invention (T300%, TB, EB, and energy) were consistent with those of the reference compound. - The vulcanization kinetics of the compound of the present invention, particularly T90, were comparable to those of the reference compound. The MH of the compound of the present invention was lower than that of the reference compound, likely due to more effective filler dispersion (lower Pain effect). - The compound of the present invention has the advantage of having low hardness, which means that the physical contact between the rubber and asphalt for the tire increases, and in turn leads to improved grip.

[0380] Tg higher than -55.0℃ as shown in Table 4 above. DSC The properties of the compounds containing the polymer characterized by (the reference compound of Example 3 and the compound of the present invention of Example 7) were as follows: - The compound of the present invention in Example 7, which contains polymer P4, exhibits a lower Mooney viscosity compared to the reference compound of Example 3, which contains polymer C, and therefore exhibits better compounding properties. - The mechanical properties of the compound of the present invention (T300%, TB, EB, and energy) were consistent with those of the reference compound.

[0381] [Table 5]

[0382] As shown in Table 5 above, Tg DSCRegarding the properties of compounds containing polymers with a temperature lower than -55°C (reference compounds in Examples 1 and 2, and the compounds of the present invention in Examples 4, 5, 6, and 8), the following was observed: - ΔG', G', TanD(9%): The Pain effect (ΔG') is lower in all of the present invention compounds from Examples 4 to 6 compared to the reference compounds of Examples 1 and 2, indicating better dispersion of fillers in the polymer matrix in the present invention compounds. The present invention compounds also show lower values ​​of G'(9%) at 70°C, indicating better interaction between the present invention polymers P1-P3 and P5 and silica compared to reference polymer B. The TanD(9%) of the present invention compounds at 70°C is consistent with the value of the reference compound, predicting similar tire rolling resistance. - E', TanD at -10°C / 0°C (Snow / Wet Performance): Regarding these dynamic properties, the low-temperature behavior (snow and wet grip) of the compounds of the present invention in Examples 4-6 and Example 8 was better than that of the reference compounds in Examples 1 and 2, because they exhibited similar or lower stiffness (E') and a significant increase in hysteresis (TanD). This combination of lower stiffness and higher hysteresis predicted better grip in winter applications.

[0383] The viscoelastic properties of the compounds in Examples 1, 2 (reference), 4, 5, 6, and 8 (the present invention), namely the modulus of elasticity E' and hysteresis TanD over temperature, were measured by temperature sweep experiments and reported in the graphs in Figures 2A and 2B.

[0384] In the compounds of the present invention in Examples 4, 5, and 6, a smoother increase in stiffness (E') was observed compared to the reference compound as the temperature decreased from -30°C to -50°C (Figure 2A), and a broadening of the TanD peak was observed as the TanD value increased from -30°C to +30°C (Figure 2B). In contrast, the reference compounds of Examples 1 and 2 showed a steep increase in E' (Figure 2A) and a narrow TanD peak profile (Figure 2B). The combination of a smoother increase in E' and a broader TanD peak in the T-30 / +30°C range of the compounds of the present invention predicted higher wet grip.

[0385] The broadening of the TanD curve observed in compounds using polymers P1, P2, P3, and P5 of the present invention may be due to differences in Tg between two polymer segments (see Tg in Table 2). CALC2 -Tg CALC1 (See the difference.)

[0386] Tg higher than -55.0℃ as shown in Table 5 above. DSC Regarding the properties of the compounds containing the polymer (reference compound of Example 3 and the compound of the present invention of Example 7), the following was observed: - ΔG', G', TanD(9%): The Pain effect (ΔG') was significantly lower for the compound of the present invention (polymer P4) in Example 7 compared to the reference compound (reference polymer C) in Example 3, and the lower G'(9%) value at 70°C also indicated that the compound of the present invention had better dispersion of the filler in the polymer matrix. The TanD(9%) at 70°C for the compound of the present invention (Example 7, polymer P4) was similar to that of the reference compound (Example 3, polymer C), and similar rolling resistance is expected. - E', TanD (snow / wet performance) at -10℃ / 0℃: The dynamic properties of the compound (polymer P4) of the present invention in Example 7 show that at low temperatures, the hysteresis (TanD) is much higher than that of the reference compound (polymer C) in Example 3 for similar stiffness (E'), suggesting improved grip.

[0387] The viscoelastic properties of the compounds in Example 3 (reference) and Example 7 (invention), namely the modulus of elasticity E' and hysteresis TanD over temperature, were measured by temperature sweep experiments and reported in the graphs in Figures 3A and 3B.

[0388] The compound of the present invention (Example 7, polymer P4) showed moderately high stiffness (E') (Figure 3A) with a similar slope to the reference compound (Example 3, polymer C), while the TanD curve profile was flattened and slightly wider.

[0389] Table 6 below shows the key performance indicators (KPIs) for crosslinked polymer compositions according to Examples 1-7 on snow, wet, and abrasion surfaces.

[0390] [Table 6]

[0391] The performance of each compound of the present invention is similar to that of a Tg. DSC The compounds were evaluated in comparison to reference compounds containing polymers having the specified polymer (i.e., the compounds of the present invention in Examples 4, 5, and 6 were compared to the reference compounds of Examples 1 and 2, and the compound of the present invention in Example 7 was compared to the reference compound of Example 3).

[0392] As shown in Table 6 above, Tg DSC Regarding the properties of compounds containing polymers with a temperature lower than -55.0℃ (reference compounds in Examples 1 and 2, and the compounds of the present invention in Examples 4, 5, and 6), the wet grip index (D'' and LAT100 wet) was used to predict the wet performance according to specific test conditions. In particular, the wet grip index D'' (TanD / E) at 0℃ and 100Hz was used. *The hysteresis (TanD) was higher in all of the present invention compounds in Examples 4 to 6, which included polymers P1 to P3, compared to the reference compounds in Examples 1 and 2. The increased hysteresis (TanD) associated with the high mobility of the polymer chains, and the lower stiffness, are beneficial for low-temperature wet performance, so a higher D'' (at 0°C and 100Hz) is expected to improve wet grip.

[0393] LAT100 (Wet): The coefficient of friction of the reference compound (Examples 1 and 2) was set to 100. In the temperature range of 2 to 15°C, the coefficient of friction of the present invention compounds (Examples 4 to 6) is higher than the reference, and an improvement in wet grip is expected.

[0394] Regarding wear, evaluation was performed using the LAT100 (dry conditions) test, with the weight loss of the reference compounds in Example 1 and Example 2 set to 100 (reference, wear resistance, or wear index). An improvement of 10% or more in weight loss was considered very significant in terms of its impact on wear performance, while a value of less than 5% resulted in minimal wear reduction for the tire.

[0395] The wear performance of the compounds of the present invention in Examples 4 to 6 differed and was directly related to the molecular weight of the polymer.

[0396] In particular, P2 had the lowest molecular weight, and the wear performance of the corresponding compound in Example 5 was similar to that of the reference compounds (polymers A and B) in Examples 1 and 2. However, P1, which had a higher MW than P2, actually improved the wear index by 5% (Example 4 vs. Example 1 / Example 2). Finally, P3, characterized by the highest molecular weight, provided the best wear performance (10% improvement in the Example 6 compound compared to the reference).

[0397] Tg higher than -55.0℃ as shown in Table 6 above. DSC Regarding the properties of the compounds containing the polymer (reference compound of Example 3 and the compound of the present invention of Example 7), the following was observed: Wetness index D'' (TanD / E) at 0℃ 100Hz * The compound of the present invention (polymer P4) in Example 7 shows a higher value compared to the reference compound in Example 3, suggesting an improvement in wet grip. LAT100 Wet: The normalized friction coefficient values ​​of the compound of the present invention (Example 7) in the temperature range of 2 to 15°C were comparable to those of the reference compound (Example 3). Finally, the LAT100 (dry) abrasion test showed that the normalized abrasion index of the compound of the present invention (polymer P4) in Example 7 was 5% higher compared to the reference compound (Example 3) (i.e., a 5% reduction in weight loss).

[0398] In conclusion, the above experiments demonstrate that by using a conjugated diene polymer (I) having the characteristics described above, a crosslinkable elastomer composition with a unique combination of physical properties was obtained. The main advantageous properties of the elastomer compound prepared from the above elastomer composition were a smooth increase in stiffness (E') with decreasing temperature, a wider hysteresis curve over the -30°C / +30°C temperature range with an increase in grip index (D''), appropriate levels of mechanical properties (T300%, TB, EB, energy at fracture), and optimal filler dispersion (Pain effect and hardness reduction).

[0399] By appropriately selecting conjugated diene polymers (I) in terms of Tg and Mw, we were able to optimize the overall compound performance for winter applications (snow grip and wet grip indices) or summer applications (wet grip and RR indices), while simultaneously improving wear rate performance in both applications.

Claims

1. A vehicle wheel tire comprising at least one tire component comprising a crosslinked elastomer compound obtained by crosslinking a crosslinkable elastomer composition, wherein the crosslinkable elastomer composition comprises at least one conjugated diene polymer (I) which comprises conjugated conjugated diene monomer units and may also contain conjugated aromatic vinyl monomer units, and the conjugated diene polymer (I) comprises at least one first polymer segment and at least one second polymer segment. Y1 (mol%) is the amount of vinyl units in the conjugated diene monomer units of the first polymer segment, Y2 (mol%) is the amount of vinyl units in the conjugated diene monomer units of the second polymer segment, and Y2 - Y1 (mol%) is between 15% and 50%. If bonded aromatic vinyl monomer units are present, X1 (wt%) is the amount of bonded aromatic vinyl monomer units in the first polymer segment, X2 (wt%) is the amount of bonded aromatic vinyl monomer units in the second polymer segment, and |X1 - X2| (wt%) is at most 5%. i) Calculated glass transition temperature (Tg) of conjugated diene polymer (I) ＣＡＬＣ ) is -75.0°C to -30.0°C, preferably -72.0°C to -40.0°C, and / or ii) In a conjugated diene polymer (I), the calculated glass transition temperature (Tg) of the first polymer segment ＣＡＬＣ１ ) is the calculated glass transition temperature (Tg) of the second polymer segment. ＣＡＬＣ２ ) is lower than The calculated glass transition temperature is determined according to the Gordon-Taylor equation. Vehicle wheels and tires.

2. The tire according to claim 1, wherein the bonded aromatic vinyl monomer units are present on both of the polymer segments.

3. Calculated glass transition temperature (Tg) ＣＡＬＣ The tire according to claim 1 or 2, wherein the temperature range is -75.0°C to -30.0°C, preferably -72.0°C to -40.0°C, more preferably at least -70.0°C, at least -68°C, preferably up to -42.0°C, more preferably up to -44.0°C.

4. - The conjugated diene monomer unit is selected from 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, and mixtures thereof, preferably 1,3-butadiene. - The tire according to any one of claims 1 to 3, wherein, if present, the aromatic vinyl monomer unit is selected from styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene and mixtures thereof, preferably styrene.

5. Conjugated diene polymer (I) has the following characteristics: - Aromatic vinyl monomer units, preferably styrene units, are present, and preferably the conjugated diene monomer unit is 1,3-butadiene. - Calculated glass transition temperature (Tg) of the first polymer segment ＣＡＬＣ１ ) is the calculated glass transition temperature (Tg) of the second polymer segment. ＣＡＬＣ２ The calculated glass transition temperature is lower than ) and is determined according to the Gordon-Taylor equation. - The percentage ratio of the sum of the weights of the first and second polymer segments to the total weight of the conjugated diene polymer (I) is higher than 70%, preferably higher than 80%, and more preferably higher than 90%. - The ratio R = r1 / r2 in the conjugated diene polymer (I) (wherein r1 is the weight ratio of the first polymer segment and r2 is the weight ratio of the second polymer segment) is 0.25 to 4.00, preferably 1.00 to 3.00, more preferably 1.50 to 2.

40. - Aromatic vinyl units are present, and the amount of aromatic vinyl units X1 (wt%) in the first polymer segment and the amount of aromatic vinyl units X2 (wt%) in the second polymer segment are at least 5 wt%, preferably at least 7 wt%, more preferably at least 9 wt%, up to 30 wt%, preferably up to 25 wt%, and more preferably up to 23 wt%, in each polymer segment. - The absolute value of the difference (│X1-X2│) between the amount of bonded aromatic vinyl monomer X1 (wt%) in the first polymer segment and the amount of bonded aromatic vinyl monomer X2 (wt%) in the second polymer segment is at most 3 wt%, more preferably at most 2.5 wt%, - The amount of vinyl units Y1 (mol%) in the conjugated diene of the first polymer segment is at least 14 mol%, preferably at least 16 mol%, more preferably at least 17 mol%, up to 40 mol%, preferably up to 35 mol%, more preferably up to 30 mol%, and even more preferably up to 23 mol%, - The amount of vinyl units Y2 (mol%) in the conjugated diene of the second polymer segment is at least 40 mol%, preferably at least 45 mol%, more preferably at least 50 mol%, even more preferably at least 55 mol%, up to 65 mol%, preferably up to 62 mol%, and more preferably up to 61 mol. - The difference (Y2 - Y1) between the amount of vinyl units Y2 (mol%) in the conjugated diene of the second polymer segment and the amount of vinyl units Y1 (mol%) in the conjugated diene of the first polymer segment is 20 mol% to 45 mol%, preferably 25 mol% to 45 mol%. A tire according to any one of claims 1 to 4, characterized by one or more of the above.

6. In the conjugated diene polymer (I), aromatic vinyl monomer units are present and are styrene, the conjugated diene monomer units are 1,3-butadiene, and the Tg of the conjugated diene polymer (I) ＣＡＬＣ However, the temperature range is -75.0°C to -30.0°C, preferably -72.0°C to -40.0°C, and the approximate formula is (1A): [Math 1] (wherein X ａｌｌ（ wt%) is the total amount of the bonded aromatic vinyl monomer units in the conjugated diene polymer (I), and Y ａｌｌ (mol%) is the total amount of the vinyl units of the bonded conjugated diene monomer units in the conjugated diene polymer (I)) A tire according to any one of claims 1 to 5, calculated by the method described above.

7. The glass transition temperature Tg of the conjugated diene polymer (I), measured according to the DSC method of ISO 22768:2006, is -75.0°C to -30.0°C, preferably -72.0°C to -40.0°C. ＤＳＣ A tire according to any one of claims 1 to 6, having the following characteristics.

8. Extrapolated Tg of conjugated diene polymer (I) whose glass transition differs by more than 10.0°C and less than 15.0°C, as measured according to the DSC method of ISO 22768:2006. ＤＳＣ Starting temperature and extrapolated Tg ＤＳＣ The tire according to claim 7, having an end temperature.

9. Conjugated diene polymer (I) - A weight-average molecular weight (Mw) of at least 350,000 g / mol, preferably at least 400,000, preferably up to 1,350,000 g / mol, or up to 1,000,000 g / mol, more preferably up to 950,000 g / mol, even more preferably up to 800,000 g / mol, 750,000 g / mol, or 650,000 g / mol, and / or - Number average molecular weight (Mn) of at least 100,000 g / mol, preferably at least 150,000 g / mol, more preferably at least 200,000 g / mol, up to 1,000,000 g / mol, preferably up to 700,000 g / mol, more preferably up to 500,000 g / mol, and / or - A polyvariance index (Mw / Mn) of at least 1.30, preferably at least 1.40, and at most 2.20, preferably at most 2.

00. A tire according to any one of claims 1 to 8, wherein Mw and Mn are measured by GPC.

10. The tire according to any one of claims 1 to 9, wherein the conjugated diene polymer (I) contains a nitrogen-containing modifying group and has a modification rate of at least 60%, preferably at least 65%, and more preferably at least 70%.

11. Conjugated diene polymer (I) has the following characteristics: - The conjugated diene monomer unit is selected from 1,3-butadiene, isoprene, and mixtures thereof, preferably 1,3-butadiene. - Aromatic vinyl monomer units are present and it is styrene, - The percentage ratio of the sum of the weights of the first and second polymer segments to the total weight of the conjugated diene polymer (I) is greater than 90%. - The ratio R = r1 / r2 of the first polymer segment to the second polymer segment is 1.50 to 2.

40. - The absolute value of the difference (│X1-X2│) is at most 2.5 wt%, - The difference (Y2 - Y1) is between 25 mol% and 45 mol%. - Tg ＣＡＬＣ２ and Tg ＣＡＬＣ１ The difference is at least 10.0°C. - Tg ＤＳＣ However, with winter or all-season tires, the temperature range is -65.0°C to -55.0°C, or with summer tires, the temperature range is -55.0°C to -40.0°C. - The weight-average molecular weight (Mw) is between 400,000 and 800,000 g / mol. - The number-average molecular weight (Mn) is preferably 200,000 to 500,000 g / mol. - The polyvariance index Mw / Mn is between 1.30 and 2.

00. - The modification rate is at least 70%. A tire according to any one of claims 1 to 10, characterized by one or more, preferably all of the above.

12. 100 phr of one or more elastomer polymers (where at least 20 phr of which is at least one conjugated diene polymer (I) as defined in any one of claims 1 to 11), At least 10 phr of reinforcing filler, and At least 0.1 phr of vulcanizing agent A crosslinkable elastomer composition comprising at least [a certain element].

13. - 100 phr of one or more elastomer polymers (of which at least 30 phr or 40 phr, preferably at least 50 phr, 60 phr or 70 phr, more preferably at least 80 phr or 90 phr or more is at least one conjugated diene polymer (I)), - At least one reinforcing filler material with a strength of 10 phr to 150 phr, 10 phr to 120 phr, or 10 phr to 90 phr. - At least one vulcanizing agent in the range of 0.1 phr to 10 phr, 0.2 phr to 10 phr, 1 phr to 10 phr, or 1.5 phr to 5 phr. A crosslinkable elastomer composition according to claim 12, comprising:

14. - 100 phr of one or more elastomer polymers (of which at least 50 phr is a conjugated diene polymer (I), and the conjugated diene polymer (I) has a Tg of -72.0°C to -40.0°C, preferably -65.0°C to -55.0°C) ＤＳＣ (having), - At least 50 phr, preferably 80 to 130 phr of at least one reinforcing filler, preferably silica. - At least 10 phr, preferably 15 to 25 phr of plasticizer, preferably oil, - Optionally, a resin of at least 20 phr, preferably 30 to 40 phr, - Optionally, at least 10 phr, preferably 15 to 25 phr of liquid polymer, - A vulcanizing agent in an amount of at least 0.2 phr, preferably 0.5 to 1.0 phr, preferably sulfur. - One or more vulcanization accelerators in an amount of at least 0.5 phr, preferably 0.8 to 1.5 phr. A crosslinkable elastomer composition according to claim 13, for use in winter or all seasons, comprising the above.

15. - 100 phr of one or more elastomer polymers (of which at least 50 phr is a conjugated diene polymer (I), and the conjugated diene polymer (I) has a Tg of -55.0°C to -20.0°C, preferably -55.0°C to -40.0°C) ＤＳＣ (having), - A reinforcing filler of at least 50 phr, preferably 70 to 110 phr, preferably silica. - At least 10 phr, preferably 15 to 25 phr of plasticizer, preferably oil, - Optionally, a resin of at least 10 phr, preferably 15 to 25 phr, - Optionally, at least 5 phr, preferably 10 to 20 phr of liquid polymer, - A vulcanizing agent in an amount of at least 0.5 phr, preferably 1.0 to 2.0 phr, preferably sulfur. - One or more vulcanization accelerators, at least 1 phr, preferably 3 to 4 phr. A crosslinkable elastomer composition for summer use according to claim 13, comprising the above.

16. A tire component comprising, preferably essentially, more preferably consisting of, a crosslinked elastomer compound obtained by crosslinking a crosslinkable elastomer composition according to any one of claims 12 to 15, wherein the component is selected from a tread band, a bottom layer, an anti-wear strip, a sidewall, a sidewall insert, a mini-sidewall, a liner, an underliner, a rubber layer, a bead filler, a bead reinforcing layer (flipper), a bead protective layer (chafer), and a sheet.

17. A vehicle wheel tire comprising at least one tire component as described in claim 16, wherein the tire component is preferably a tread band.

18. A vehicle wheel tire for winter, all-season, or summer use, according to any one of claims 1 to 11 or claim 17.

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