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 crosslinked elastomer compound obtained from a crosslinkable elastomer composition containing a specific conjugated diene polymer. [Background technology]

[0002] US2022314696A1 discloses a rubber composition comprising a random styrene-butadiene polymer functionalized with aminoalkoxysilane groups and having a glass transition temperature (Tg) lower than -70°C. The corresponding vulcanized compound applied to tire treads is described as having superior wet grip.

[0003] JP3438317B2 discloses a tread rubber composition comprising a styrene-butadiene polymer having a Tg of -50°C to -10°C and silica, which improves the wet grip performance of tires. The styrene-butadiene polymer is a solution SBR characterized by a bond S / bond B ratio of (23 / 77) to (50 / 50), a molar ratio of 1,2 bond content / 1,4 bond content in the microstructure of the butadiene portion of the styrene-butadiene copolymer of 25 / 75 to 57 / 43, and a Mooney viscosity of 80 to 200.

[0004] The polymer described above does not contain polymer chains having two segments with different microstructures and different Tg values, but rather is a conventional random styrene-butadiene modified copolymer.

[0005] 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 project] [Problems that the invention aims to solve]

[0006] 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.

[0007] 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.

[0008] Therefore, providing highly wear-resistant tires with excellent grip performance on snowy, icy, wet (winter or all-season), or wet / dry roads (summer use) is a particularly challenging objective.

[0009] 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]

[0010] The applicant has found that, surprisingly, a tire comprising a tire component containing 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 / all-season applications and a higher Tg for summer applications, exhibits reduced wear and maintains or improves grip performance in both applications. Increased wear resistance without altering other important properties of the final tire translates to long-term performance retention and a longer tire life.

[0011] 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 bonded aromatic vinyl units (X) and bonded conjugated diene units (Y), and the conjugated diene polymer (I) comprises at least one first polymer segment and at least one second polymer segment.

[0012] 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) comprising bonded aromatic vinyl units and bonded conjugated diene units, the conjugated diene polymer (I) comprising at least one first polymer segment and at least one second polymer segment, and the conjugated diene polymer (I) has a single DSC glass transition temperature (Tg) measured at a heating rate of 10°C / min according to the method of ISO 22768:2006 DSC ) only has, i) The conjugated diene polymer (I) has a calculated glass transition temperature (Tg) of -75.0°C to -30.0°C, preferably -72.0°C to -45.0°C. CALC) and the Tg of the conjugated diene polymer (I) measured at a heating rate of 10 °C / min according to the method of ISO 22768:2006 DSC The extrapolated Tg end temperature (Tg DSC終了 ) and the extrapolated Tg start temperature (Tg DSC開始 ) have a difference of at least 12.0 °C and at most 35.0 °C, preferably at least 15.0 °C and at most 35.0 °C, more preferably at least 15.0 °C and at most 30.0 °C, and / or ii) 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 Relates to vehicle wheel tires

[0013] Preferably, the conjugated diene polymer (I) has only one DSC glass transition temperature (Tg DSC ) measured according to the method of ISO 22768:2006 at a heating rate of 10 °C / min

[0014] Preferably, the conjugated diene polymer (I) has a calculated glass transition temperature (Tg CALC ) of -75.0 °C to -30.0 °C, more preferably -72.0 °C to -45.0 °C, determined according to the Gordon-Taylor equation

[0015] In the conjugated diene polymer (I), the aromatic vinyl monomer unit is styrene, the conjugated diene monomer unit is 1,3-butadiene, and the Tg of the conjugated diene polymer (I) CALC is preferably -75.0 °C to -30 °C, more preferably -72.0 °C to -40.0 °C, and the approximate formula (1A):

[0016] [Number] (where X all(wt%) is the total amount of bonded aromatic vinyl monomer units in the conjugated diene polymer (I), Y all (mol%) represents the total amount of vinyl units in the bonded conjugated diene monomer units of conjugated diene polymer (I). It may also be calculated by using

[0017] In a preferred embodiment, the conjugated diene polymer (I) has a single DSC glass transition temperature (Tg) measured at a heating rate of 10°C / min according to the method of ISO 22768:2006. DSC ) only, preferably having a calculated glass transition temperature (Tg) determined according to the Gordon-Taylor formula, in the range of -75.0°C to -30.0°C, more preferably -72.0°C to -45.0°C. CALC ) has.

[0018] Preferably, in the conjugated diene polymer (I), the Tg of the conjugated diene polymer (I) is measured at a heating rate of 10°C / min according to the method of ISO 22768:2006. DSC Curve extrapolation Tg end temperature (Tg DSC終了 ) and extrapolated Tg onset temperature (Tg DSC開始 The difference from ) is at least 12.0°C and at most 35.0°C, preferably at least 15.0°C and at most 35.0°C, and more preferably at least 15.0°C and at most 30.0°C.

[0019] In a preferred embodiment, the conjugated diene polymer (I) has one Tg DSC It has only a Tg of -75.0°C to -30.0°C, more preferably -72.0°C to -45.0°C. CALC It has extrapolated Tg DSC終了 Temperature and Tg DSC開始 The temperature difference is at least 12.0°C and at most 35.0°C, preferably at least 15.0°C and at most 35.0°C, and more preferably at least 15.0°C and at most 30.0°C.

[0020] Preferably, in the conjugated diene polymer (I), the calculated glass transition temperature (Tg) of the first polymer segment is 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.

[0021] In a preferred embodiment, the conjugated diene polymer (I) has one DSC glass transition temperature (Tg DSC ) having only and preferably a calculated glass transition temperature (Tg) of -75.0°C to -30.0°C, and more preferably -72.0°C to -45.0°C. CALC ) has and / or Tg CALC1 is Tg CALC2 It is lower than that.

[0022] Preferably, in the conjugated diene polymer (I), the difference X2-X1(wt%) between the amount X2(wt%) of bonded aromatic vinyl monomer units in the second polymer segment and the amount X1(wt%) of bonded aromatic vinyl monomer units in the first polymer segment is greater than 5wt%.

[0023] In a preferred embodiment, the conjugated diene polymer (I) has one Tg DSC It has only a Tg of -75.0°C to -30.0°C, more preferably -72.0°C to -45.0°C. CALC It may have Tg CALC2 Lower Tg CALC1 It has the following characteristics, and the difference X2-X1(wt%) is greater than 5wt%.

[0024] In a preferred embodiment, the conjugated diene polymer (I) has one Tg DSC It has only a Tg of -75.0°C to -30.0°C, more preferably -72.0°C to -45.0°C. CALC It has extrapolated Tg DSC終了 Temperature and Tg DSC開始 The temperature difference is at least 12.0°C and at most 35.0°C, preferably at least 15.0°C and at most 35.0°C, and more preferably at least 15.0°C and at most 30.0°C.

[0025] Preferably, the amount X1 (wt%) of aromatic vinyl monomer units in the first polymer segment of the conjugated diene polymer (I) is at most 10 wt%, preferably at most 5 wt%, and more preferably, no aromatic vinyl monomer units are present in the first polymer segment (X1=0).

[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 by, for example, sulfur-based vulcanizing agents.

[0037] The term "raw" or "green" refers 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 / or 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 (step 1) in an elastomer compound preparation method, which 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 step 2. Mixing stage 1 is also called the "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 (Step 2) of an elastomer compound preparation method, in which a vulcanizing agent and optionally other additives to the vulcanizing package are introduced and mixed into the elastomer compound obtained from Step 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, a “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) that comprises conjugated diene monomer units and aromatic vinyl monomer units, which are referred to herein as a second polymer segment having a higher Tg, or, preferably, only conjugated diene monomer units, which are referred herein as a first polymer segment having a lower Tg.

[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 conjugated diene units incorporated into a conjugated diene polymer (I) by polymerization.

[0059] In this specification, the term “amount of bonded aromatic vinyl units” refers to the wt% of bonded aromatic vinyl 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 the mole fraction (mol%) of 1,2-vinyl units relative to the bound conjugated diene monomer units contained in the conjugated diene polymer (I) or a segment thereof.

[0061] In this specification, the term "microstructure" refers to the composition of a conjugated diene polymer consisting of aromatic vinyl units and conjugated diene 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 JP2023-072838, which is incorporated herein by reference.

[0070] The conjugated diene polymer (I) of the present invention comprises bonded conjugated diene units and bonded aromatic vinyl units.

[0071] Total amount of bonded aromatic vinyl units in conjugated diene polymer (I) X all (wt%) represents the weight fraction of bonded aromatic vinyl units relative to the total weight of the conjugated diene polymer (I).

[0072] The total amount of vinyl units of the conjugated conjugated diene in the conjugated diene polymer (I) of the present invention Y all (mol%) represents the mole fraction (mol%) of the 1,2-vinyl units of the conjugated diene in the conjugated diene polymer (I).

[0073] As explained below, X all (wt%) and Y all (mol%) satisfies the Gordon-Taylor formula, therefore the calculated Tg has a value of preferably -75.0°C to -30.0°C, and more preferably -72.0°C to -45.0°C. CALC To provide.

[0074] 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.

[0075] 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.

[0076] The conjugated diene polymer (I) comprises at least one first polymer segment and at least one second polymer segment, wherein the first polymer segment preferably does not contain aromatic vinyl monomer units, but the second polymer segment contains aromatic vinyl monomer units.

[0077] 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.

[0078] The first polymer segment and the second polymer segment may each contain multiple polymer segments, but preferably each contains a single polymer segment.

[0079] In conjugated diene polymers (I), polymer segments may be directly bonded to each other or bonded via a coupling agent.

[0080] 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%.

[0081] In particular, in the conjugated diene polymer (I), preferably the weight of the copolymer containing styrene as a bonded aromatic vinyl monomer unit and butadiene as a bonded conjugated diene monomer unit 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).

[0082] In the conjugated diene polymer (I), the first and second polymer segments preferably have a predetermined weight ratio with respect to the total weight of the conjugated diene polymer (I), i.e., a predetermined weight ratio of the weight of the first polymer segment (r1) and the weight of the second polymer segment (r2), respectively.

[0083] In the conjugated diene polymer (I), preferably, the weight ratio (r1) of the first polymer segment to the total weight of the conjugated diene polymer (I) is at least 30 wt%, more preferably at least 40 wt%, and even more preferably at least 50 wt%.

[0084] In the conjugated diene polymer (I), preferably, the weight ratio (r1) of the first polymer segment to the total weight of the conjugated diene polymer (I) is at most 80 wt%, more preferably at most 75 wt%, and even more preferably at most 70 wt%.

[0085] In the conjugated diene polymer (I), preferably, the weight ratio (r1) of the first polymer segment to the total weight of the conjugated diene polymer (I) is at least 30 wt% and at most 80 wt%, more preferably at least 40 wt% and at most 75 wt%, and even more preferably at least 50 wt% and at most 70 wt%.

[0086] In the conjugated diene polymer (I), preferably, the weight ratio (r2) of the second polymer segment to the total weight of the conjugated diene polymer (I) is at least 20 wt%, more preferably at least 25 wt%, and even more preferably at least 30 wt%.

[0087] In the conjugated diene polymer (I), preferably, the weight ratio (r2) of the second polymer segment to the total weight of the conjugated diene polymer (I) is at most 60 wt%, more preferably at most 55 wt%, and even more preferably at most 50 wt%.

[0088] In the conjugated diene polymer (I), preferably, the weight ratio (r2) of the second polymer segment to the total weight of the conjugated diene polymer (I) is at least 20 wt% and at most 60 wt%, more preferably at least 25 wt% and at most 55 wt%, and even more preferably at least 30 wt% and at most 50 wt%.

[0089] When the ratio of the first polymer segment (r1) diene to the second polymer segment (r2) in the conjugated diene polymer (I) falls within the above preferred range, wet grip is improved, as long as the stiffness of the compound is kept under control.

[0090] The polymer segments of the conjugated diene polymer (I) differ from one another in their microstructure. Each polymer segment may differ, for example, in the amount of bonded aromatic vinyl units and the amount of vinyl units of the bonded conjugated diene.

[0091] The conjugated diene polymer (I) preferably has a first polymer segment (X1=0) that does not contain aromatic vinyl monomer units, and a second polymer segment (X2>0) that contains aromatic vinyl monomer units.

[0092] The distribution of conjugated diene units and aromatic vinyl units within polymer segments is peculiar.

[0093] Preferably, in the first polymer segment, the amount of vinyl units Y1 (mol%) in the conjugated diene is greater than 10 mol%, more preferably at least 12 mol%, and even more preferably at least 15 mol%. Preferably, the amount of vinyl units Y1 (mol%) is up to 50 mol%, more preferably up to 45 mol%, and even more preferably up to 40 mol%.

[0094] Preferably, the amount of vinyl units Y1 (mol%) in the conjugated diene is 10 mol% to 50 mol%, more preferably 12 mol% to 45 mol%, and even more preferably 15 mol% to 40 mol%.

[0095] Preferably, in the first polymer segment, the amount X1 of aromatic vinyl monomer units is at most 10 wt%, more preferably at most 5 wt%, and even more preferably, there are no aromatic vinyl monomer units in the first polymer segment (X1=0).

[0096] When the amount Y1 of vinyl units is within the above range, the flexibility of the conjugated diene polymer (I) improves in the low-temperature range, and its vulcanized compound tends to have excellent abrasion resistance.

[0097] In the second polymer segment, the amount X2 (wt%) of aromatic vinyl monomer units is at least 10 wt% and at most 40 wt%, more preferably at least 20 wt% and at most 30 wt%.

[0098] In the second polymer segment, preferably, the amount of vinyl units Y2 (mol%) is at least 25 mol% and at most 65 mol%, more preferably at least 40 mol% and at most 60 mol%.

[0099] In the conjugated diene polymer (I), when the amounts of aromatic vinyl units X2 and Y2 are within the above range, wet grip is improved as long as the rigidity of the compound is kept under control.

[0100] The difference X2-X1(wt%) between the amount of bonded aromatic vinyl monomer units X2(wt%) in the second polymer segment and the amount of bonded aromatic vinyl monomer units X1(wt%) in the first polymer segment is greater than 5wt%, and more preferably at least 10wt%. Preferably, the difference is a maximum of 35wt%, and more preferably a maximum of 30wt%.

[0101] Preferably, the difference is greater than 5 wt% and up to 35 wt%, more preferably 10 wt% to 30 wt%.

[0102] At higher differences, the compatibility between segments may decrease, and the polymer may exhibit a deterioration in properties.

[0103] The difference between the amount of vinyl monomer units Y2 in the second polymer segment and the amount of vinyl monomer units Y1 in the first polymer segment is 0 mol% to 45 mol%, preferably 5 mol% to 35 mol%, when Y2 = Y1.

[0104] By appropriately combining r1, r2, X1, X2, Y1, and Y2 within the preferred ranges described above, it is possible to optimize low-temperature performance, wet grip, wear rate, and rolling resistance according to the overall performance balance required by specific winter, all-season, or summer applications.

[0105] 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)).

[0106] When there are few or no bonded aromatic vinyl monomer unit blocks, the conjugated diene polymer (I) has a single glass transition temperature (Tg DSC ) is more likely to be present.

[0107] When the conjugated diene polymer (I) of the present invention is a polymer of butadiene and styrene, the amount of vinyl units contained in the conjugated butadiene can be calculated by Hampton's method (RRHampton, Analytical Chemistry, 21, 923 (1949)).

[0108] Ultimately, the total amount of bonded aromatic vinyl monomer units in the conjugated diene polymer (I) X all (wt%) and total amount Y in vinyl units all (mol%) provides a calculated Tg that satisfies the Gordon-Taylor formula and therefore preferably has a value of -75.0°C to -30.0°C, and more preferably -72.0°C to -45.0°C.

[0109] Units: Y1, Y2, X1, X2, X all and Y allWhen the amounts of each of these elements fall within the preferred ranges described above, the wet grip, winter performance, wear resistance, and strength of the vulcanized compound are improved.

[0110] Total amount of aromatic vinyl units in conjugated diene polymer (I) X all and the total amount Y in vinyl units all This can be determined, for example, by NMR according to the method of ISO 21561-1:20015, as described in the experimental section below.

[0111] The conjugated diene polymer (I) has a single glass transition temperature (Tg) which is preferably measured by differential scanning calorimetry (DSC) according to ISO 22768:2006. DSC ) has.

[0112] Tg of conjugated diene polymer (I) DSC The measured temperature is preferably at least -75.0°C, more preferably at least -70.0°C, preferably at most -35.0°C, and more preferably at most -40.0°C. Tg of conjugated diene polymer (I) DSC This is measured according to the method reported to the laboratory in accordance with ISO 22768:2006. More specifically, differential scanning calorimetry (DSC) is performed while increasing the temperature within a predetermined temperature range, and the DSC curve is recorded. The inflection point of the DSC curve is considered to be the glass transition temperature.

[0113] Preferably, the Tg of the conjugated diene polymer (I) DSC The temperature range is -75.0℃ to -35.0℃, more preferably -70.0℃ to -40.0℃.

[0114] 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.

[0115] Preferably, the Tg of the conjugated diene polymer (I) DSCFor summer tires, the optimal operating temperature range is -55.0°C to -35.0°C, more preferably -55.0°C to -40.0°C.

[0116] 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 economy) for each specific application (winter, all-season, or summer).

[0117] From the DSC thermogram of conjugated diene polymer (I), Tg DSC Starting temperature and Tg DSC The termination temperature is recorded in this experimental section and can be extrapolated as shown in Figure 4.

[0118] Extrapolation Tg of conjugated diene polymer (I) DSC The starting temperature is preferably at least -90.0°C, more preferably at least -85.0°C, preferably up to -60.0°C, and more preferably up to -65.0°C.

[0119] Extrapolation Tg of conjugated diene polymer (I) DSC The termination temperature is preferably at least -70.0°C, more preferably at least -65.0°C, preferably up to -40.0°C, and more preferably up to -45.0°C.

[0120] Preferably, extrapolate Tg DSC Termination temperature and extrapolated Tg DSC The difference from the starting temperature is at least 12.0°C, more preferably at least 13.0°C.

[0121] Preferably, extrapolate Tg DSC Termination temperature and extrapolated Tg DSC The difference from the starting temperature is at least 12.0°C and at most 35.0°C, more preferably at least 15.0°C and at most 35.0°C, and even more preferably at least 15.0°C and at most 30.0°C.

[0122] 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) preferably comprises a segment containing vinyl units and aromatic vinyl units having a higher Tg (i.e., a second polymer segment), and preferably a segment containing only vinyl units having a lower Tg (i.e., a first polymer segment).

[0123] 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 ) is lower than. 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 the 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 the calculated Tg is Tg CALC2 It is called that.

[0124] 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 vinyl units (Y1, Y2) for each polymer segment described above, and consequently setting the respective glass transition temperatures within a certain range, a vulcanized compound with excellent wet grip performance and winter performance can be obtained.

[0125] The unique distribution of units within the polymer segment causes broadening of the Tg peak and TanD curve 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.

[0126] 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.

[0127] 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 T profile, resulting in a better balance between winter performance and wet grip performance.

[0128] 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.

[0129] However, if the difference between the two polymer segments becomes 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 suitable tensile strength, as described above, it is effective to increase the difference in the amount of bonded aromatic vinyl monomer units between the two polymer segments (making X2 greater than X1) while keeping the amount of bonded conjugated dienes vinyl units (Y2 and Y1) between the two polymer segments within an appropriate range.

[0130] The glass transition temperature of a conjugated diene polymer (I) depends on its microstructure and is given by the following equation (1)

[0131]

number

[0132] The value obtained in this manner is the Tg(Tg) calculated in this specification. CALC ) is referred to as.

[0133] In equation (1) above, the subscript i of the variable represents each component of the microstructure in the conjugated diene polymer, and Δα i w is the difference in thermal expansion of the polymer of single component i before and after the glass transition, and i This is the mass ratio of component i in the conjugated diene polymer, 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.

[0134] 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.

[0135] For example, if the conjugated diene polymer 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:

[0136]

number

[0137]

number

[0138] 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%).

[0139] In conjugated diene polymers (I), the calculated glass transition temperature (Tg) depends on the microstructure of the conjugated diene polymer (I). CALC The temperature range is preferably -75.0°C to -30.0°C, more preferably -72.0°C to -45.0°C, by satisfying formula (1) / (1A).

[0140] Preferably, in the case of a conjugated diene polymer (I), Tg CALC The temperature is at least -75.0°C, more preferably at least -72.0°C, even more preferably at least -70.0°C, still more preferably at least -68.0°C, preferably at most -30.0°C, more preferably at most -45.0°C, and still more preferably at most -50.0°C.

[0141] The best performance of the conjugated diene polymer (I) of the present invention is obtained when the amount X all (wt%) of the combined aromatic vinyl units and the amount Y all (mol%) of the vinyl units in the combined conjugated diene satisfy the above formula (1) / (1A), and thus preferably have a Tg of at least -75.0 °C and at most -30.0 °C CALC .

[0142] The glass transition temperature of the conjugated diene polymer (I) can be controlled within the above numerical range by adjusting the microstructure of the polymer. For example, in the case of a butadiene-styrene polymer, according to formula (1A), by adjusting the total amount X all (wt%) of the combined styrene and the total amount Y all (mol%) of the vinyl units of the combined butadiene, it can be controlled.

[0143] By preferably setting the Tg (Tg CALC ) calculated by the above formula (1) or (1A) to -75.0 °C to -30.0 °C, more preferably -72.0 °C to -45.0 °C, the actually measured glass transition temperature is also approximately in its preferred range.

[0144] However, the calculated Tg CALC temperature of the conjugated diene polymer (I) by formula (1) / (1A) may differ from the observed Tg measured by DSC depending on the microstructure of the polymer and / or specific settings of the DSC measurement, particularly the cooling and heating rates.

[0145] Specifically, when the difference (Tg CALC -Tg CALC2 -Tg CALC1 ) in the Tg values between polymer segments is 33 or more, or when the mass ratio r1 of the above first polymer segment is in the range of 40 to 60, the discrepancy between the glass transition temperature estimated from formula (1) / (1A) and the actual glass transition temperature measured by DSC tends to become more significant.

[0146] Conjugated diene polymers (I) containing two or more polymer segments undergo glass transitions over multiple temperature ranges because the polymer segments have different glass transition temperatures.

[0147] In fact, according to the foregoing, the conjugated diene polymer (I) comprises a segment having a higher aromatic vinyl unit content and a higher Tg, which is referred to herein as the second polymer segment, and a segment having a lower aromatic vinyl unit content and a lower Tg, which is referred herein as the first polymer.

[0148] 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.

[0149] 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 ).

[0150] When applied to the first polymer segment, the value of equation (1) / (1A) is lower than the value obtained when applied to the conjugated diene polymer (I). CALC1 The value provided is, namely, the first polymer segment, the Tg of the entire conjugated diene polymer (I). CALC Lower Tg CALC1 It holds.

[0151] If the conjugated diene polymer is a butadiene-styrene polymer or a butadiene homopolymer, Tg CALC1 In equation (1A), X all and Y all Instead, it is calculated by inserting the amount of bound styrene in the first polymer segment (X1, preferably zero) and the amount of vinyl units in the bound butadiene of the first polymer segment (Y1).

[0152] When applied to the second polymer segment, the value obtained from formula (1) / (1A) is higher than the value obtained when applied to the conjugated diene polymer (I). CALC2 The second polymer segment provides the Tg of the entire conjugated diene polymer (I). CALC Higher Tg CALC2 It holds.

[0153] If the conjugated diene polymer is a butadiene-styrene polymer or a butadiene homopolymer, Tg CALC2 In equation (1A), X all and Y all Instead, it is calculated by inserting the amount of bound styrene (X2) in the second polymer segment and the amount of vinyl units (Y2) in the bound butadiene.

[0154] Preferably, the amount X2 (wt%) of bonded aromatic vinyl units in the second polymer segment and the amount Y2 (mol%) of bonded conjugated diene vinyl units in the second polymer segment are such that the Tg is higher than -45.0°C and lower than -5.0°C. CALC2 To provide.

[0155] Preferably, the Tg of the second polymer segment CALC2 The temperature is at least -44.0°C, more preferably at least -43.0°C, and at most -10.0°C, and more preferably at most -15.0°C.

[0156] Tg CALC1 and Tg CALC2 The value can be adjusted by adjusting the amount of aromatic vinyl units and vinyl units in the first and second polymer segments, that is, by adjusting their microstructure.

[0157] Preferably, Tg CALC2 and Tg CALC1The difference is at least 10.0°C, more preferably at least 20.0°C, and even more preferably at least 35°C. To prevent mismatch between polymer segments, preferably the difference is at most 70.0°C, more preferably at most 60.0°C, and even more preferably at most 55.0°C.

[0158] Preferably, Tg CALC2 and Tg CALC1 The difference is 10.0℃ to 70.0℃, more preferably 20.0℃ to 60℃, and even more preferably 35.0℃ to 55.0℃.

[0159] The weight-average molecular weight (Mw) of the conjugated diene polymer (I), as measured by gel permeation chromatography (GPC), is preferably at least 270,000 g / mol, more preferably at least 300,000, even more preferably at least 400,000 g / mol, and / or preferably up to 1,350,000 g / mol, more preferably up to 900,000 g / mol, and even more preferably up to 700,000 g / mol.

[0160] Preferably, the weight-average molecular weight (Mw) of the conjugated diene polymer (I) is 300,000 g / mol to 1,350,000 g / mol, preferably 400,000 g / mol to 1,000,000 g / mol, and more preferably 400,000 g / mol to 700,000 g / mol.

[0161] The number-average molecular weight (Mn) of the conjugated diene polymer (I), as measured by GPC, is preferably at least 170,000 g / mol, more preferably at least 190,000 g / mol, even more preferably at least 230,000 g / mol, and / or up to 800,000 g / mol, more preferably up to 500,000 g / mol, and even more preferably up to 450,000 g / mol.

[0162] 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 amount of polymerization initiator used relative to the amount of monomer used, as well as the type and amount of coupling agent used.

[0163] 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).

[0164] The conjugated diene polymer (I) preferably has a polydispersity index Mw / Mn of at least 1.2 and at most 2.5. Preferably, the polydispersity index Mw / Mn of the conjugated diene polymer (I) is at least 1.3, more preferably at least 1.4, and / or at most 2.4, more preferably at most 2.2, and even more preferably at most 2.0.

[0165] The conjugated diene polymer (I) preferably contains nitrogen-containing modifying groups and preferably has a modification rate of at least 60%. The modification rate represents the weight ratio of the modified conjugated diene polymer (I) containing nitrogen-containing modifying groups to the total amount of the mixture of modified and unmodified conjugated diene polymers. The modification rate can be measured by chromatography, which can separate the modified and 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%.

[0166] In the conjugated diene polymer (I), a pair of polymer segments may be directly bonded to each other or bonded via a coupling agent.

[0167] The degree of branching obtained depends on the type of coupling agent used.

[0168] Preferably, the degree of branching of the conjugated diene polymer (I) is greater than 2.

[0169] In preferred embodiments, 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. - The aromatic vinyl monomer unit is styrene. - Tg of conjugated diene polymer (I) DSC For winter / all-season tires, the operating temperature range is -65.0°C to -55.0°C, and for summer tires, it's -55.0°C to -40.0°C. - The first polymer segment does not contain aromatic vinyl units (X1=0), - The difference (wt%) between X2 and X1 is 5 wt% or more. - In the first polymer segment, the amount of vinyl units Y1 (mol%) is at least 15 mol% and at most 40 mol%. - In the second segment, the amount of aromatic vinyl monomer units X2 (wt%) is at least 20 wt% and at most 30 wt%. - In the second polymer segment, the amount of vinyl units Y2 (mol%) is at least 40 mol% and at most 60 mol%. - In the second polymer segment, the amount of bonded aromatic vinyl units X2 (wt%) and the amount of vinyl units Y2 (mol%) in the bonded conjugated diene is at a Tg of at least -43.0°C and at most -15.0°C. CALC2 To provide - The difference X2-X1(wt%) between the amount of bonded aromatic vinyl monomer units X2(wt%) in the second polymer segment and the amount of bonded aromatic vinyl monomer units X1(wt%) in the first polymer segment is at least 10wt%. - The difference between the amount of vinyl monomer units Y2 in the second polymer segment and the amount of vinyl monomer units Y1 in the first polymer segment, Y2-Y1 (mol%), is between 5 mol% and 35 mol%. - Tg CALC2 and Tg CALC1 The difference is at least 10.0℃. - The weight ratio (r1) of the first polymer segment is at least 40 wt% and at most 75 wt%. - The weight ratio (r2) of the second polymer segment is at least 30 wt% and at most 50 wt%. - The weight-average molecular weight (Mw) is between 400,000 g / mol and 700,000 g / mol. - The number-average molecular weight (Mn) is between 230,000 g / mol and 450,000 g / mol. - The multivariance index Mw / Mn is between 1.3 and 2.0. - The modification rate is at least 70%. - The coupling agent is selected from 1-methyl-4-[3-(trimethoxysilyl)propyl]piperazine and tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine. It features one or more, preferably all, of the following characteristics.

[0170] There are no particular limitations on the method for introducing multiple polymer segments into the molecule of the conjugated diene polymer of the present invention.

[0171] The conjugated diene polymer (I) can be produced by a method that, according to conventional polymerization techniques, for example, includes a first polymerization process (PR1) in which two or more continuous reactors are used and a conjugated diene, a polymerization initiator, and a polar substance are added to the continuous reactor to continuously prepare a first polymer segment, and a second polymerization process (PR2) in which an aromatic vinyl monomer and a polar substance are added to the continuous reactor to form a second polymer segment at the end of the first polymer segment. The method may further include a process for coupling the active end of the conjugated diene polymer obtained by the polymerization process with a coupling agent such as a trifunctional or more reactive agent, and / or a process for modifying it with a modifier having a nitrogen atom-containing group (preferably a coupling agent having a nitrogen atom-containing group). In this specification, the coupling process and the modification process are collectively referred to as the coupling process (PR3).

[0172] Preferably, the weight ratio of the conjugated diene added in the first polymerization process (PR1) to the total amount of conjugated diene and aromatic vinyl monomer added is 50 wt% to 80 wt%.

[0173] Preferably, in the second polymerization process (PR2) described above, the weight ratio of the amount of aromatic vinyl monomer added to the amount of conjugated diene added is 0.35 to 0.70.

[0174] Preferably, in the second process (PR2), a larger amount of polar substance is added than the amount of polar substance added in the first polymerization process (PR1).

[0175] Preferably, in the manufacturing method, the coupling agent is an aminoalkoxysilane.

[0176] At least one organic monolithium compound can be used as a polymerization initiator. Non-limiting examples of 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. The amount of organic monolithium compound used as a polymerization initiator depends on the desired molecular weight of the conjugated diene polymer, as is known in the art.

[0177] When nitrogen atoms are introduced into a conjugated diene polymer using a polymerization initiator, the organic monolithium agent is preferably an alkyllithium agent having a substituted amino group, i.e., an amino group that does not have active hydrogen or has protected active hydrogen. Non-limiting examples of alkyllithium agents having an amino group without active hydrogen include 3-dimethylaminopropyllithium, 3-diethylaminopropyllithium, 4-(methylpropylamino)butyllithium, and 4-hexamethyleneiminobutyllithium. Non-limiting examples of alkyllithium agents having an amino group with protected active hydrogen include 3-bistrimethylsilylaminopropyllithium and 4-trimethylsilylmethylaminobutyllithium.

[0178] Polar substances may be added during the polymerization process. Polar substances allow aromatic vinyl agents to randomly copolymerize with conjugated dienes. Non-limiting examples of polar substances include ethers, tertiary amines, alkali metal alkoxides, phosphines, and mixtures thereof.

[0179] The polymerization temperature in the polymerization process is preferably the temperature at which living anionic polymerization proceeds, and from the viewpoint of productivity, it is preferably at least 0°C and at most 120°C, more preferably at least 50°C and at most 100°C.

[0180] The conjugated diene polymer (I) may be prepared as described in JP2023-072838 or WO2018128285A1.

[0181] The coupling agent may have any structure as long as it is a reactive agent having three or more functional groups, but a reactive agent having three or more functional groups containing silicon atoms is preferred.

[0182] Examples of coupling agents having three or more preferred functional groups include halogenated silanes, epoxidized silanes, vinylinated silanes, alkoxysilanes, and nitrogen-containing alkoxysilanes.

[0183] 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.

[0184] Examples of coupling agents that also act as modifiers include epoxy agents having nitrogen atom-containing groups, such as hydrocarbon agents that contain an epoxy group bonded to an amino group and may further have an epoxy group bonded to an ether group.

[0185] 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.

[0186] 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.

[0187] 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).

[0188] 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.

[0189] Among coupling agents having nitrogen atom-containing groups, 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.

[0190] Suitable coupling and / or modifiers incorporated herein by reference are disclosed, for example, in Japanese Patent Application JP2023-072838.

[0191] In this method, the conjugated diene polymer (I) is further preferably to which an extender oil, liquid rubber and / or resin is added.

[0192] Conjugated diene polymers (I) exhibit excellent abrasion resistance and tensile properties, and when incorporated into rubber compositions, they enhance grip performance.

[0193] 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.

[0194] In conventional elastomer polymers, the distribution of vinyl units and aromatic vinyl units is random or, in any case, does not match that of the conjugated diene polymer (I) of the present invention as described above.

[0195] 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.

[0196] 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.

[0197] 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.

[0198] Monoolefins 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.

[0199] 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.

[0200] 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.

[0201] 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.

[0202] 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. Preferably: 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.

[0203] 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).

[0204] The polymers described above may be functionalized along the main chain or at their ends.

[0205] 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).

[0206] Alternatively, functionalization may be introduced by reaction with a suitable end-terminating agent or coupling agent.

[0207] The crosslinkable elastomer composition of the present invention preferably comprises 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.

[0208] The composition of the present invention may contain at least one reinforcing filler in the range of 1 phr to 150 phr, 5 phr to 120 phr, or 10 phr to 90 phr.

[0209] Preferably, the reinforcing filler is selected from carbon black, white filler, silicate fibers, derivatives, and mixtures thereof.

[0210] 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.

[0211] 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.

[0212] In one embodiment, the reinforcing filler includes silica mixed with carbon black.

[0213] In one embodiment, the reinforcing filler includes modified silica.

[0214] Silica may be modified by reaction with, for example, silsesquioxane (as in WO2018078480A1), pyrrole (as in WO2016050887A1), or a silanating agent.

[0215] Suitable commercially available silanes include Si69, Dynasilan AMEO, and Dynasilan GLYEO from Evonik.

[0216] Modified silica may also be silica sulfide silane.

[0217] Silica sulfide is silica prepared by the reaction of silica or a metal silicate with at least one silane sulfide agent.

[0218] A suitable commercially available example of silica sulfide silane is Agilon 400 silica manufactured by PPG.

[0219] In one embodiment, the reinforcing filler includes modified silica mixed with carbon black.

[0220] In one embodiment, the reinforcing filler includes a silicate, such as a layered silicate (e.g., bentonite, halloysite, laponite, saponite, vermiculite or hydrotalcite), or a silicate fiber which may be modified (e.g., sepiolite fiber, palygorskite fiber known also as attapulgite, wollastonite fiber, imogolite fiber), or a mixture thereof.

[0221] In one embodiment, the reinforcing filler includes silicate fibers mixed with carbon black.

[0222] In one embodiment, the silicate fibers are modified silicate fibers, for example, those described in WO2016174629A1, WO2016174628A1, for example, those organically modified by reaction with a quaternary ammonium salt or a silanizing agent.

[0223] In one embodiment, the reinforcing filler preferably has a surface area not less than 20 m 2 / g and preferably greater than 50 m 2 / g (STSA according to ISO18852:2005, determined by statistical thickness surface area) and is carbon black selected from such.

[0224] 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.

[0225] The crosslinkable elastomer composition of the present invention contains at least 0.1 phr of a vulcanizing agent.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] Preferably, the vulcanizing agent is sulfur selected from soluble sulfur (crystalline sulfur), insoluble sulfur (polymeric sulfur), oil-dispersed sulfur, and mixtures thereof.

[0230] A commercially available example of a vulcanizing agent suitable for use in crosslinkable elastomer compositions is soluble sulfur from Zolfindustria (Italy).

[0231] 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.

[0232] The crosslinkable elastomer composition may contain at least one vulcanizing activator.

[0233] Suitable vulcanizing activators for use in the crosslinkable elastomer composition of the present invention are zinc agents, particularly ZnO, ZnCO3, and zinc salts of saturated or unsaturated fatty acids containing 8 to 18 carbon atoms, which are preferably formed in situ in the crosslinkable elastomer composition by the reaction of ZnO with fatty acids or mixtures thereof. 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.

[0234] 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.

[0235] The preferred activator is derived from the reaction between zinc oxide and stearic acid.

[0236] An example of an activator is Aktiplast ST, a product sold by Rheinchemie.

[0237] The crosslinkable elastomer composition may further contain at least one vulcanization accelerator.

[0238] Commonly used vulcanization accelerators may be selected from, for example, dithiocarbamates, guanidines, thioureas, thiazoles, sulfenamides, sulfenimides, thiurams, amines, xanthetes, or mixtures thereof.

[0239] Preferably, the accelerator is selected from mercaptobenzothiazole (MBT), N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N-tert-butyl-2-benzothiazole sulfenamide (TBBS), and mixtures thereof.

[0240] 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.

[0241] 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.

[0242] The crosslinkable elastomer composition may contain at least one vulcanization retarder.

[0243] The vulcanization retarder suitable for use in the crosslinkable elastomer composition of the present invention is preferably selected from urea, phthalic anhydride, N-nitrosodiphenylamine, N-cyclohexylthiophthalimide (CTP or PVI), and mixtures thereof.

[0244] A commercially available example of a suitable retarder is N-cyclohexylthiophthalimide VULKALENT G from Lanxess.

[0245] The vulcanization retarder may preferably be present in the crosslinkable elastomer composition of the present invention in an amount of 0.05 phr to 2 phr.

[0246] The crosslinkable elastomer composition of the present invention may contain one or more vulcanization retarders as defined above in the mixture.

[0247] The crosslinkable elastomer composition may further contain at least one silane coupling agent of at least 0.05 phr, preferably at least 0.1 phr or 0.5 phr, more preferably at least 1 phr or 2 phr.

[0248] Preferably, the crosslinkable elastomer composition contains at least one silane coupling agent of 0.1 phr to 20.0 phr, or 0.5 phr to 10.0 phr, even more preferably 1.0 phr to 5.0 phr.

[0249] Preferably, the coupling agent has, 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].

[0250] 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.

[0251] An example of a silane coupling agent is TESPT bis(3-triethoxysilylpropyl)tetrasulfide Si69, sold by Evonik.

[0252] 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.

[0253] For example, the crosslinkable elastomer composition according to the present invention may further contain at least one plasticizer, preferably a plasticizing oil, to improve the workability of the compound. The amount of plasticizer is preferably in the range of 5 to 50 phr, preferably 10 to 40 phr. The term "plasticizing oil" means petroleum-derived process oil, mineral oil, vegetable oil, synthetic oil, or a combination thereof. The plasticizing oil may be a petroleum-derived process oil selected from paraffin (saturated hydrocarbon), naphthene, aromatic polycyclic, and mixtures thereof.

[0254] 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 known in the industry. Plasticizing oils may also be oils of natural or synthetic origin derived from the esterification of glycerol and fatty acids, including glycerol triglycerides, diglycerides, monoglycerides, or mixtures thereof.

[0255] Suitable vegetable oils include sunflower oil, soybean oil, linseed oil, rapeseed oil, castor oil, and cottonseed oil. The plasticizing oil may also be a synthetic oil selected from phthalic acid or alkyl or aryl esters of phosphoric acid.

[0256] The crosslinkable elastomer composition may further contain at least one resin. The resin is preferably a non-reactive resin selected from hydrocarbon resins, phenolic resins, natural resins, and mixtures thereof. The amount of resin is preferably in the range of 5 to 30 phr, more preferably 10 to 20 phr.

[0257] 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.

[0258] 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.

[0259] The crosslinkable elastomer composition may contain at least one type of wax. The wax may be, for example, a mixture of petroleum wax or paraffin.

[0260] Suitable commercially available waxes include Repsol N-paraffin mixture and Antilux® 654 microcrystalline wax from Rhein Chemie.

[0261] 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.

[0262] The crosslinkable elastomer composition may contain at least one antioxidant.

[0263] The antioxidants are preferably 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'- Dityl-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, and mixtures thereof are selected, and preferably N-1,3-dimethylbutyl-N-phenyl-p-phenylenediamine (6-PPD).

[0264] Suitable commercially available antioxidants include Eastman's Solutia or Santoflex 6PPD.

[0265] The antioxidant may be present in the crosslinkable elastomer composition in a total amount of preferably 0.1 phr to 20 phr, more preferably 0.5 phr to 10 phr.

[0266] In one embodiment, a preferred crosslinkable elastomer composition for winter or all-season use includes: - One or more elastomer polymers of 100 phr, wherein at least 50 phr of the elastomer polymer (I) is conjugated diene polymer (I), and the conjugated diene polymer (I) has a Tg of -70.0°C to -40.0°C, preferably -65.0°C to -55.0°C. DSC Elastomer polymer having, - At least one reinforcing filler with a density of at least 50 phr, preferably 80 to 130 phr, preferably silica. - At least 10 phr, preferably 15-25 phr of plasticizer, preferably oil, - Optionally, a resin of at least 20 phr, preferably 30-40 phr, - Optionally, at least 10 phr, preferably 15-25 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.

[0267] One embodiment includes the following preferred crosslinkable elastomer compositions for summer use: - One or more elastomer polymers of 100 phr, wherein at least 50 phr of the elastomer polymer (I) is conjugated diene polymer (I), and the conjugated diene polymer (I) has a Tg of -50.0°C to -35.0°C, preferably -50.0°C to -40.0°C. DSC Elastomer polymer having, - A reinforcing filler of at least 50 phr, preferably 70 to 110 phr, preferably silica. - At least 10 phr, preferably 15-20 phr of plasticizer, preferably oil, - Optionally, a resin of at least 10 phr, preferably 15-25 phr, - Optionally, a liquid polymer of at least 5 phr, preferably 10-20 phr, - A vulcanizing agent of at least 0.5 phr, preferably 1.0 to 2.0 phr, preferably sulfur. - One or more vulcanization accelerators in an amount of at least 1 phr, preferably 3 to 4 phr.

[0268] Next, the above-mentioned crosslinkable elastomer composition is crosslinked to provide the crosslinked elastomer compound of the present invention.

[0269] The crosslinked elastomer compound of the present invention is characterized by a specific hysteresis pattern.

[0270] In fact, unlike known elastomer compounds including conventional SBR, such as the reference compounds in Examples 1, Figure 2B and 2, 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 3, 4, Figure 2B and 5, 6, Figure 3B) 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.

[0271] Furthermore, as the temperature decreases from -30°C to -50°C, the crosslinked elastomer compounds of the present invention (Examples 3, 4, Figure 2A and Examples 5, 6, 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.

[0272] Furthermore, the tire compounds of the present invention (Examples 3, 4, 5, and 6) exhibit a significantly lower pain effect (see Table 5) and, as is evident from the lower hardness values ​​(Table 4), demonstrate better dispersion of the filler in the polymer matrix.

[0273] Finally, the crosslinked elastomer compounds of the present invention (Examples 3, 4, 5, and 6) exhibit lower Mooney viscosity compared to the reference compounds of Examples 1 and 2, and show good compounding processability along with suitable static properties for use (see Table 4).

[0274] 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.

[0275] 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 comprising at least one vulcanizing agent and optionally at least one 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.

[0276] 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.

[0277] 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.

[0278] 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.

[0279] 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.

[0280] In production process 2, the temperature is generally controlled to avoid unwanted pre-vulcanization.

[0281] At the end of the second step, the crosslinkable elastomer compound is incorporated into one or more components of the green tire and subjected to vulcanization according to known techniques.

[0282] In the method of the present invention, any of the conventional vulcanization processes may be used, such as heating with a press or mold, or heating with superheated steam or hot air.

[0283] The tire component, which includes, preferably is essentially, or more preferably consists of the above-mentioned crosslinked elastomer compound, is preferably selected from tread bands, underlayers, anti-abrasion strips, sidewalls, sidewall inserts, mini-sidewalls, liners, underliners, rubber layers, bead fillers, bead reinforcement layers (flippers), bead protection layers (chafers), and sheets. Preferably, the tire component is a tread band.

[0284] The vehicle wheel tire of the present invention comprises at least one component comprising a crosslinked elastomer compound obtained by crosslinking the above-described crosslinkable elastomer composition. Preferably, the component is at least a tread band.

[0285] In one embodiment, the vehicle tire according to the present invention is - A carcass structure comprising at least one carcass ply having opposing side edges bonded to each bead structure, - Optionally, a pair of sidewalls applied to the lateral surfaces of the carcass structure at axially outward positions; - Optionally, a belt structure applied to a radially outward position relative to the carcass structure. - The tread band applied to the carcass structure, or, if present, the belt structure, at a radially outward position. - 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.

[0286] 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.

[0287] 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.

[0288] 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.

[0289] 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.

[0290] The tire according to the present invention may be a tire for a two-wheeled, three-wheeled, or four-wheeled vehicle.

[0291] 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 the crosslinked elastomer compound of the present invention.

[0292] Vehicle wheel tires may be constructed, formed, molded and vulcanized in various ways known to those skilled in the art.

[0293] 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].

[0294] 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.

[0295] 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".

[0296] 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).

[0297] 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).

[0298] 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.

[0299] 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.

[0300] An anti-wear strip (105), which may be made of an elastomer material, is positioned on the outer side of each bead structure (103).

[0301] 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.

[0302] 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.

[0303] 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.

[0304] 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.

[0305] 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).

[0306] 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.

[0307] A lower layer (111) of elastomer material may be placed between the belt structure (106) and the tread band (109).

[0308] 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).

[0309] 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).

[0310] 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."

[0311] 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).

[0312] The flipper (120) typically includes multiple fiber cords incorporated within a layer of elastomer material.

[0313] 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).

[0314] 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).

[0315] 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.

[0316] 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.

[0317] 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.

[0318] 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.

[0319] 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.

[0320] 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.

[0321] 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]

[0322] [Figure 1] This is a schematic half-cross-sectional view showing a tire for a vehicle wheel according to the present invention. [Figure 2] These graphs show the E'-to-temperature (Figure 2A) and TanD-to-temperature (Figure 2B) of the compounds in Example 1 (reference), Example 3, and Example 4 (invention), each containing diene polymers A, P1, and P2, and having a TgDSC lower than -58.0°C. [Figure 3] These graphs show the E'-to-temperature (Figure 3A) and TanD-to-temperature (Figure 3B) of the compounds in Example 2 (reference), Example 5, and Example 6 (invention), each containing diene polymers B, P3, and P4, respectively, with a TgDSC higher than -58.0°C. [Figure 4]This graph shows the extrapolation of the TgDSC start and end temperatures from the DSC thermogram of an exemplary polymer.

[0323] Experiment Department Unless otherwise specified, the components of the composition will be expressed in PHR (percentage of rubber) in this experimental department.

[0324] 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.

[0325] 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).

[0326] 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.

[0327] 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.

[0328] 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 baseline on the high-temperature side to the low-temperature side and a tangent line drawn to the point where the slope of the curve representing the stepwise change portion of the glass transition is maximum.

[0329] Tg DSC and Tg DSC Figure 4 shows an example of extrapolation of the start / end temperatures into a graph.

[0330] Calculated glass transition temperature (Tg CALC ) The estimated glass transition temperatures of the styrene-butadiene polymer (I) (P1~P4) and its segments used in this experiment were calculated using the approximation formula (1A) described above.

[0331] Total vinyl and styrene content in conjugated diene(I) All vinyl (Y all ) and total styrene (X all The content was determined according to ISO 21561-1:20015, using a BRUKER Avance NMR spectrometer (400 MHz) and a 5 mm dual probe, with CDCl3 (purity higher than 99.8%) containing 0.03% tetramethylsilane (TMS) as the solvent. 1 It was measured by 1H-NMR.

[0332] Amount of bound styrene in the first polymer segment (X1) A 100 mg sample of the polymer solution from the waste portion of polymerization process 1 for synthesizing the first polymer segment was diluted with chloroform to 100 ml and dissolved to obtain a sample for measurement. 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").

[0333] Amount of bound styrene in the second polymer segment (X2) The segment ratio (r1) of the first polymer segment and the segment ratio (r2) of the second polymer segment are calculated by the method described later, and the amount of bound styrene (X2) in the second polymer segment is calculated from the amount of bound styrene X in the conjugated diene polymer (I) calculated from previous measurements. all And using the amount of bound styrene X1 in the first polymer segment, equation (2):

[0334]

number

[0335] Total amount of vinyl units in conjugated diene polymer (I) (Y all ) A conjugated diene polymer without rubber softeners was used as the sample. 50 mg of the sample was dissolved in 10 ml of carbon disulfide to prepare the measurement sample. The infrared spectrum of each sample was recorded at 600-1000 cm⁻¹ using a Fourier transform infrared spectrophotometer (JASCO Corporation, product name "FT-IR230"). -1 Measurements were taken within the specified range. The amount (mol%) of 1,2-vinyl units in the bound butadiene was determined from the absorbance at a given wavenumber using the Hampton method (RR Hampton, Analytical Chemistry 21, 923 (1949)).

[0336] Amount of vinyl units in the first polymer segment (Y1) The vinyl unit content of the first polymer segment was determined in the same manner as for the conjugated diene polymer (I), except that the sample was changed from conjugated diene polymer (I) to the first polymer segment.

[0337] Amount of vinyl units in the second polymer segment (Y2) The segment ratio (r1) of the first polymer segment and the segment ratio (r2) of the second polymer segment are calculated by the method described later, and the amount of vinyl units in the second polymer segment (Y2) is given by equation (3).

[0338]

number

[0339] Ratio of the first polymer segment (r1) The ratio of polymer segments in the first polymerization process (PR1) to the total amount of conjugated diene compound and aromatic vinyl compound added per hour during the polymerization of conjugated diene polymer (I) was calculated from the amount of solid conjugated diene polymer (I) per hour after the first polymerization process (PR1).

[0340] The solid content in the conjugated diene polymer solution was determined from the amount of non-volatile components in the polymer solution flowing out of the first polymerization process (PR1) per unit time.

[0341] The total volume of the polymer solution flowing through the outlet of the first polymerization process (PR1) was collected for 3 minutes, and a polymerization inhibitor was immediately added. The mixture was then transferred to a heat-resistant dish and dried in an oven at 140°C for at least 30 minutes, and the weight M1 of the solid residue was measured.

[0342] The solid content m1 and the ratio of the first polymer segment were calculated using the following formula (4):

[0343]

number

[0344] Ratio of the second polymer segment (r2) The ratio of the second polymer segment in the second polymerization process (PR2) for forming the second polymer segment was calculated from the amount of solid conjugated diene polymer per hour after the second polymerization process (PR2) relative to the total amount of conjugated diene compound and aromatic vinyl compound added per hour during polymerization of the conjugated diene polymer, and was calculated from the difference between this amount and the amount of solid conjugated diene polymer per hour after the first polymerization process (PR1).

[0345] The amount of solid in the conjugated diene polymer solution was determined from the amount of non-volatile components in the polymer solution flowing out of the second polymerization process (PR2) per unit time.

[0346] The total volume of polymer solution flowing out of the second polymerization process (PR2) outlet was collected for 3 minutes, and a polymerization inhibitor was immediately added. The mixture was then transferred to a heat-resistant dish and dried in an oven at 140°C for at least 30 minutes, and the weight M2 of the solid residue was measured. From the weights M1 and M2 of the solid obtained in the first polymerization process (PR1), the second polymer segment ratio r2 was obtained using formula (5).

[0347] The ratio of the second polymer segment (r2) was calculated using the following equation (5):

[0348]

number

[0349] Qualification rate The modification rate of conjugated diene polymer (I) was measured by column adsorption GPC as follows.

[0350] 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.

[0351] 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.

[0352] - 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.

[0353] - 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.

[0354] 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.

[0355] - 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.

[0356] 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.

[0357] - 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 (6): Modification rate (%)=[1-(PA2×PA3) / (PA1×PA4)]×100 (6) (In the equation, PA1 + PA2 = PA3 + PA4 = 100) The modification rate (%) was obtained from this.

[0358] 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.

[0359] Properties of crosslinkable elastomer compounds The green crosslinkable elastomer compound was subjected to the following evaluations:

[0360] 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.

[0361] Properties of cross-linked compounds After crosslinking (vulcanization), the elastomer compound was subjected to the following evaluations:

[0362] Density: Density was measured using Alpha Technologies' automated Densitron according to ISO 2781 Method A.

[0363] 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.

[0364] 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.

[0365] The dynamic mechanical properties were measured using a dynamic Instron device under compression-tension operations according to the following method.

[0366] 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.

[0367] 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'').

[0368] 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%.

[0369] 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.

[0370] 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.

[0371] 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.

[0372] Abrasion resistance (LAT 100 under dry conditions) Abrasion resistance was determined according to ISO 23233:2009 by using a driven vertical abrasion disc (LAT 100: Laboratory Abrasion Tester 100).

[0373] 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).

[0374] 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 or Example 2 compound), and is expressed by the following equations (7) and (8):

[0375]

number

[0376] The lower the AR index, the better the abrasion resistance of the compound compared to the reference compound.

[0377] 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.

[0378] 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 or Example 2) to 100.

[0379] The higher the frictional force, the better the wet grip of the test specimen. [Examples]

[0380] The following embodiments are provided for the purpose of further illustrating the present invention and should not be construed as limiting.

[0381] Reference polymer In the examples, commercially available reference polymers A and B, differing in Tg and functional groups, were used. These reference polymers were random solution styrene-butadiene copolymers having a uniform Tg along the polymer chain, i.e., no segments, and a steep DSC glass transition temperature profile. Polymer A was chain-end functionalized, while polymer B contained multiple functional groups.

[0382] These polymers were characterized as shown in Table 1 below:

[0383] [Table 1]

[0384] 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 polymers of the present invention." Polymers P1 and P2 of the present invention have a Tg suitable for winter / all-season use. DSC It has a Tg suitable for summer use, while polymers P3 and P4 have a Tg suitable for summer use. DSC The polymers P1 to P4 of the present invention contained 5 phr of oil.

[0385] Preparation of conjugated diene polymer (I) Preparation of polymer P1 The polymerization reactor consisted of two connected tank-type pressure vessels, each with an internal volume of 10 liters, an internal height (L) to diameter (D) ratio (L / D) of 4.0, an inlet at the bottom and an outlet at the top, and equipped with a stirrer. Each vessel also had a temperature control stirrer and jacket.

[0386] A mixed solution was obtained by mixing 19.3 g / min of 1,3-butadiene with 161.5 g / min of n-hexane from which water had been removed beforehand. This mixed solution was supplied to the inlet of the reaction group using a static mixer installed in the middle of the piping, and n-butyllithium was added at a rate of 0.104 mmol / min to deactivate residual impurities. After mixing, it was continuously supplied to the bottom of reactor 1. Furthermore, 2,2-bis(2-oxolanil)propane was supplied to the bottom of reactor 1 at a rate of 0.145 mmol / min as a polar substance, and n-butyllithium was added at a rate of 0.239 mmol / min as a polymerization initiator, and the mixture was vigorously mixed to maintain the internal temperature of the reactor at 78°C. After the polymerization reaction stabilized, a small amount of the conjugated diene polymer was withdrawn from the top of the reactor, and an antioxidant (BHT) of 0.2 g per 100 g of polymer was added. After removing the solvent, the amount of vinyl units (Y1) in the conjugated diene of the first polymer segment was measured.

[0387] Next, the polymer solution was continuously supplied from the top of reactor 1 to the bottom of reactor 2 and stirred. At the same time, 1,3-butadiene was added to reactor 2 at a rate of 8.3 g / min, styrene at 2.9 g / min, n-hexane at 33.6 g / min, and 2,2-bis(2-oxophenol)propane as a polar substance at a rate of 0.222 mmol / min, and the reaction was continued at 78°C.

[0388] Next, 1-methyl-4-[3-(trimethoxysilyl)propyl]piperazine ("Coupling Agent A" in Table 2 below) was added at a rate of 0.097 mmol / min to the polymer solution flowing out from the top of the second reactor. Tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (referred to as "Coupling Agent B" in Table 2 below) was then continuously added at a rate of 0.010 mmol / min. These were mixed using a static mixer and subjected to the coupling reaction. At this time, it took 4.8 minutes for the coupling agent to be added to the polymer solution flowing out from the reactor outlet, and the temperature was 68°C. The difference between the polymerization process temperature and the temperature until the coupling agent was added was 2°C.

[0389] A small amount of the conjugated diene polymer solution after the coupling reaction is extracted, an antioxidant (BHT) is added at a rate of 0.2 g per 100 g of polymer, the solvent is removed, and the amount of bound styrene (X all ), amount in vinyl units (Y all ), glass transition temperature (T DSC ), and the extrapolated glass transition start and end temperatures were identified.

[0390] Next, an antioxidant (BHT) was continuously added to the polymer solution undergoing a coupling reaction at a rate of 0.055 g / min (n-hexane solution) per 100 g of polymer at a rate of 0.2 g, and the coupling reaction was carried out until complete. Simultaneously with the antioxidant, 5.0 g of SRAE oil (JOMO Process NC140, manufactured by JX Nippon Oil & Energy Corporation) was continuously added to 100 g of polymer as a rubber softener and mixed in a static mixer. The solvent was removed by vapor stripping to obtain the conjugated diene polymer P1. The molecular weight, Mooney viscosity, and modification rate were determined.

[0391] 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:

[0392] 1,3-butadiene was added to the first reactor at a rate of 21.4 g / min, n-hexane at a rate of 170.3 g / min, and 2,2-bis(2-oxolanyl)propane as a polar substance at a rate of 0.054 mmol / min. Then, 1,3-butadiene was added to the second reactor at a rate of 9.2 g / min, styrene at a rate of 3.5 g / min, n-hexane at a rate of 36.8 g / min, and 2,2-bis(2-oxolanyl)propane at a rate of 0.394 mmol / min. All other conditions were the same as in Example 1.

[0393] 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:

[0394] In the first reactor, 19.3 g / min of 1,3-butadiene, 161.5 g / min of n-hexane, and 0.145 mmol / min of 2,2-bis(2-oxolanil)propane as a polar substance were added. Then, in the second reactor, 8.3 g / min of 1,3-butadiene, 2.9 g / min of styrene, 33.6 g / min of n-hexane, and 0.222 mmol / min of 2,2-bis(2-oxolanil)propane were added. All other conditions were the same as in Example 1.

[0395] 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:

[0396] In the first reactor, 15.4 g / min of 1,3-butadiene, 166.0 g / min of n-hexane, and 0.072 mmol / min of 2,2-bis(2-oxolanil)propane as a polar substance were added. Then, in the second reactor, 12.6 g / min of 1,3-butadiene, 5.3 g / min of styrene, 48.2 g / min of n-hexane, and 0.340 mmol / min of 2,2-bis(2-oxolanil)propane were added. All other conditions were the same as in Example 1.

[0397] The conditions applied to the manufacturing process and the characteristics of the polymer thus obtained are summarized in Table 2 below:

[0398] [Table 2]

[0399] Compositions and compounds (Examples 1-6) Reference compositions and corresponding compounds were prepared using polymers A (S-SBR, SLR3402, Example 1) and B (S-SBR, HPR621, Example 2). Compositions and compounds for tires of the present invention were produced using polymers P1 (Example 3), P2 (Example 4), P3 (Example 5), and P4 (Example 6). The recipes for the compositions are shown in Table 3 below:

[0400] [Table 3]

[0401] The above composition is used in a chamber with a total volume of 1100 cm³. 3 The 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 (step 1) 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 this temperature was maintained 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 a vulcanizing agent and TBBS and TBZTD as accelerators, the second mixing step (step 2) 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''.

[0402] 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 1-6:

[0403] [Table 4]

[0404] Tg lower than -58.0°C, as shown in Table 4 above. DSC The properties of the compounds containing the polymer (the reference compound of Example 1, and the compounds of the present invention of Examples 3 and 4) were as follows: - The compounds of the present invention in Examples 3 and 4, containing polymers P1 and P2, exhibit a lower Mooney viscosity compared to the reference compound of Example 1, which contains polymer A, and therefore exhibit good compounding properties. - The mechanical properties of the compound of this invention (T300%, TB, EB, and energy) were slightly inferior to those of the reference compound, but were still sufficiently suitable for tread applications. - The vulcanization kinetics of the compound of the present invention, particularly T90, were comparable to or slightly slower than 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 being lower in hardness, which means that the physical contact between the rubber and the asphalt for the tire increases, and consequently leads to improved grip.

[0405] Tg higher than -58.0℃ as shown in Table 4 above. DSC The properties of the compounds containing the polymer characterized by (the reference compound of Example 2, and the compounds of the present invention of Examples 5 and 6) were as follows: - The compounds of the present invention in Examples 5 and 6, containing polymers P3 and P4, exhibited a much lower Mooney viscosity compared to the reference compound of Example 2, which contained polymer B, and therefore showed better compounding properties. - The mechanical properties (T300%, TB, EB, and energy) of the compounds of the present invention in Examples 5 and 6 were slightly inferior to those of the reference compound in Example 2 due to the large difference in the Mw of the polymers (see note that the Mw of reference polymer B is 610,000 g / mol compared to 457,600 g / mol and 569,000 g / mol for polymers P3 and P4, respectively), but they were still suitable for tread applications.

[0406] [Table 5]

[0407] As shown in Table 5 above, Tg DSCRegarding the properties of compounds containing polymers with a temperature lower than -58.0℃ (reference compound in Example 1, and the compounds of the present invention in Examples 3 and 4), the following was observed: - ΔG', G', TanD(9%): The Pain effect (ΔG') is lower in the compounds of the present invention in Examples 3 and 4 compared to the reference compound in Example 1, indicating better dispersion of fillers in the polymer matrix in the compounds of the present invention. The compounds of the present invention also show a lower G'(9%) value at 70°C, indicating better interaction between the polymers P1 and P2 of the present invention and silica compared to reference polymer A. The TanD(9%) of the compounds of the present invention 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): With respect to these dynamic properties, the low-temperature behavior (snow and wet grip) of the compounds of the present invention in Examples 3 and 4 was better than that of the reference compound in Example 1, 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.

[0408] The viscoelastic properties of the compounds in Example 1 (reference), Example 3, and Example 4 (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.

[0409] In the compounds of the present invention in Example 3, and particularly in Example 4, a smooth increase in stiffness (E') relative to the reference compound was observed as the temperature decreased from -30°C to -50°C (Figure 2A), and a broadening of the Tan D peak and higher Tan D values ​​were observed from -30°C to +30°C (Figure 2B). In contrast, the reference compound of Example 1 showed a steep increase in E' (Figure 2A) and a narrow Tan D peak profile (Figure 2B).

[0410] The combination of a smoother increase in E' and a wider TanD peak in the T-30 / +30℃ range of the present invention's compound predicted higher wet grip.

[0411] The broadening of the Tan D curve observed in the compounds of Examples 3 and 4, each containing polymers P1 and P2 of the present invention, is due to the Tg between the two polymer segments. CALC This may be due to differences in P1 (the Tg of the first polymer segment). CALC1 -70.6℃, Tg of the second polymer segment CALC2 P2 (Tg of the first polymer segment) is better than -32.5℃ CALC1 -83.2℃, Tg of the second polymer segment CALC2 The -33.6℃ range is wider (see Table 2).

[0412] Tg higher than -58.0℃ as shown in Table 5 above. DSC Regarding the properties of the compounds containing the polymer (the reference compound of Example 2 and the compounds of the present invention of Examples 5 and 6), the following was observed: - ΔG', G', Tan D (9%): The Payne effect (ΔG') was significantly lower in the compounds of the present invention in Examples 5 and 6 (polymers P3 and P4, respectively) than in the reference compound of Example 2 (reference polymer B), and the compounds of the present invention also showed a slightly lower value of G' (9%) at 70°C, indicating better dispersion of the filler in the polymer matrix. The Tan D (9%) at 70°C of the compounds of the present invention (Examples 5 and 6, polymers P3 and P4, respectively) was very close to that of the reference compound (Example 2, polymer B), suggesting similar rolling resistance. - E', Tan D at -10℃ / 0℃ (winter / wet performance): The dynamic properties of the compounds of the present invention in Examples 5 and 6 (polymers P3 and P4, respectively) show that the hysteresis (Tan D) was much higher than that of the reference compound (polymer B) in Example 2 for equivalent or even lower stiffness (E') at low temperatures, suggesting improved grip.

[0413] The viscoelastic properties of the compounds in Example 2 (reference), Example 5, and Example 6 (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.

[0414] In Example 5, the compound of the present invention (polymer P3) showed a similar stiffness profile (E') compared to the reference compound (polymer B) of Example 2, but the Tan D curve profile was broader. In Example 6, the compound of the present invention (polymer P4) showed a less steep stiffness trend (E') compared to the reference compound (Example 2, polymer B) because the Tg of the compound of the present invention in Example 6 was higher, but the Tan D curve was broader.

[0415] Overall, the temperature sweep experiments highlighted the decreased dependence of the modulus (E') on temperature decrease in the compounds of the present invention (Examples 5 and 6), and the broader Tan D curve of the compounds of the present invention, regardless of Tg.

[0416] Table 6 below shows the key performance indicators (KPIs) for crosslinked polymer compositions according to Examples 1-6 on snow, wet, and abrasion surfaces.

[0417] [Table 6]

[0418] As shown in Table 6 above, Tg DSCRegarding the properties of compounds containing polymers with a temperature lower than -58.0℃ (reference compound in Example 1, and the compounds of the present invention in Examples 3 and 4), 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℃ 100Hz was used. * The compound of the present invention in Examples 3 and 4, which included polymers P3 and P4, was higher compared to the reference compound of Example 1. The increased hysteresis (TanD) associated with the high mobility of the polymer chains, and the low stiffness, are beneficial for low-temperature wet performance, so a higher D'' (at 0°C and 100Hz) is expected to improve wet grip.

[0419] LAT100 (Wet): The coefficient of friction of the reference compound (Example 1) was set to 100. In the temperature range of 2 to 15°C, the coefficients of friction of the compounds of the present invention in Examples 3 and 4 were consistent with that of the reference compound in Example 1.

[0420] The different trends observed between the D'' value and frictional force may be due to the lower styrene content of the present polymers P1 and P2 compared to the reference polymer A. This difference had a positive effect on the D'' value without significantly increasing the frictional force.

[0421] Regarding wear, it was evaluated using the LAT100 (dry conditions) test, with the weight loss of the reference compound in Example 1 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.

[0422] The wear performance of the compounds of the present invention in Examples 3 and 4 was better than that of the reference compound in Example 1, and the performance of Compound Example 4, which showed a 10% improvement, was particularly excellent.

[0423] Tg higher than -58.0℃ as shown in Table 6 above.DSC Regarding the properties of the compounds containing the polymer (the reference compound of Example 2 and the compounds of the present invention of Examples 5 and 6), the following was observed: The wetness index D'' (Tan D / E*) at 0℃ and 100Hz is higher for the compounds of the present invention in Examples 5 and 6 (polymers P3 and P4, respectively) compared to the reference compound in Example 2, suggesting improved wet grip. LAT100 Wet: The normalized coefficient of friction values ​​of the compounds of the present invention (Examples 5 and 6) in the temperature range of 2 to 15°C were similar to those of the reference compound (Example 2). The different trends observed between the D'' value and the frictional force may be due to the lower styrene content of the polymers P3 and P4 of the present invention compared to the reference polymer B. This difference had a positive effect on the D'' value without significantly increasing the frictional force.

[0424] Finally, the LAT100 (dry) abrasion test showed that the normalized abrasion index of the compounds of the present invention in Examples 5 and 6 (polymers P3 and P4, respectively) was 10% higher compared to the reference compound (Example 2) (i.e., weight loss was significantly reduced by 10%).

[0425] 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).

[0426] Conjugated diene polymer (I) Tg DSCBy appropriately selecting from the perspectives of both snow grip and wet grip, 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) comprising bonded aromatic vinyl units and bonded conjugated diene units, the conjugated diene polymer (I) comprising at least one first polymer segment and at least one second polymer segment, and the conjugated diene polymer (I) has one DSC glass transition temperature (Tg) measured at a heating rate of 10°C / min according to the method of ISO 22768:2006 ＤＳＣ ) only has, i) The conjugated diene polymer (I) has a calculated glass transition temperature (Tg) of -75.0°C to -30.0°C, preferably -72.0°C to -45.0°C. ＣＡＬＣ The Tg of the conjugated diene polymer (I) is measured at a heating rate of 10°C / min according to the method of ISO 22768:2006. ＤＳＣ Curve extrapolation Tg end temperature (Tg ＤＳＣ終了 ) and extrapolated Tg start temperature (Tg ＤＳＣ開始 The difference between the temperature and the temperature is at least 12.0°C and a maximum of 35.0°C, preferably at least 15.0°C and a maximum of 35.0°C, more preferably at least 15.0°C and a maximum of 30.0°C, and / or ii) 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 difference X2 - X1 (wt%) between the amount of bonded aromatic vinyl monomer units X2 (wt%) in the second polymer segment and the amount of bonded aromatic vinyl monomer units X1 (wt%) in the first polymer segment is greater than 5 wt%.

3. The amount X1 (wt%) of aromatic vinyl monomer units in the first polymer segment is at most 10 wt%, preferably at most 5 wt%, and more preferably there are no aromatic vinyl monomer units in the first polymer segment (X1 = 0). A tire according to any one of claims 1 to 2.

4. In conjugated diene polymers (I), - Calculated glass transition temperature (Tg) ＣＡＬＣ The temperature range is -72.0°C to -45.0°C. - The amount of vinyl units Y1 (mol%) in the conjugated diene of the first polymer segment is between 10 mol% and 50 mol%, - The amount of vinyl units Y2 (mol%) in the conjugated diene of the second polymer segment is 25 mol% to 65 mol%, and / or - The amount X2 of aromatic vinyl monomer units in the second polymer segment is at least 10 wt% and at most 40 wt%. A tire according to any one of claims 1 to 3.

5. Tg ＣＡＬＣ１ is lower than Tg ＣＡＬＣ２ more preferably, Tg ＣＡＬＣ２ and Tg ＣＡＬＣ１ The difference between them is 10.0°C to 70.0°C, more preferably 20.0°C to 60°C, and even more preferably 35.0°C to 55.0°C. The tire according to any one of claims 1 to 4.

6. - 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 5, wherein the aromatic vinyl monomer unit is selected from styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene and mixtures thereof, preferably styrene.

7. Conjugated diene polymer (I) has the following characteristics: - The aromatic vinyl monomer unit is styrene, and the conjugated diene monomer unit is 1,3-butadiene. - The percentage ratio of the total weight of the first polymer segment and the second polymer segment 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 weight ratio (r1) of the first polymer segment to the total weight of the conjugated diene polymer (I) is at least 30 wt%, preferably at least 40 wt%, more preferably at least 50 wt%, up to 80 wt%, preferably up to 75 wt%, and more preferably up to 70 wt%. - The weight ratio (r2) of the second polymer segment to the total weight of the conjugated diene polymer (I) is at least 20 wt% and at most 60 wt%, preferably at least 25 wt% and at most 55 wt%, more preferably at least 30 wt% and at most 50 wt%. - The amount of vinyl units Y1 (mol%) in the conjugated diene of the first polymer segment is higher than 10 mol%, preferably at least 12 mol%, more preferably at least 15 mol%, and lower than 50 mol%, preferably up to 45 mol%, more preferably up to 40 mol%. - The weight-average molecular weight (Mw) measured by GPC is 300,000 g / mol to 1,350,000 g / mol, preferably 400,000 g / mol to 1,000,000 g / mol, more preferably 400,000 g / mol to 700,000 g / mol. - The number-average molecular weight (Mn) measured by GPC is at least 170,000 g / mol, preferably at least 190,000 g / mol, more preferably at least 230,000 g / mol, and / or up to 800,000 g / mol, preferably up to 500,000 g / mol, more preferably up to 450,000 g / mol, and / or - The polyvariance index Mw / Mn (Mw / Mn) is at least 1.3, preferably at least 1.4, and / or at most 2.4, preferably at most 2.2, and more preferably at most 2.

0. A tire according to any one of claims 1 to 6, characterized by one or more of the above.

8. The DSC glass transition temperature (Tg) of conjugated diene polymer (I) is measured at a heating rate of 10°C / min according to the method of ISO 22768:2006. ＤＳＣ The tire according to any one of claims 1 to 7, wherein the temperature is at least -75.0°C, preferably at least -70.0°C, and at most -35.0°C, preferably at most -40.0°C.

9. Tg of conjugated diene polymer (I) ＤＳＣ The tire according to claim 8, wherein the temperature range for winter or all-season tires is -70.0°C to -40.0°C, preferably -65.0°C to -55.0°C, and for summer tires it is -55.0°C to -35.0°C, preferably -55.0°C to -40.0°C.

10. Tg of conjugated diene polymer (I) measured at a heating rate of 10°C / min according to the method of ISO 22768:2006 ＤＳＣ Curve extrapolation Tg end temperature (Tg ＤＳＣ終了 ) and extrapolated Tg start temperature (Tg ＤＳＣ開始 The tire according to any one of claims 1 to 9, wherein the difference with ) is at least 12.0°C and at most 35.0°C, preferably at least 15.0°C and at most 35.0°C, and more preferably at least 15.0°C and at most 30.0°C.

11. In the conjugated diene polymer (I), the aromatic vinyl monomer unit is styrene, and the conjugated diene monomer unit is 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 -45.0°C, and the approximate formula is (1A): [Math 1] (In the formula, X ａｌｌ (wt%) is the total amount of bonded aromatic vinyl monomer units in the conjugated diene polymer (I), Y ａｌｌ (mol%) represents the total amount of vinyl units in the bonded conjugated diene monomer units of conjugated diene polymer (I). A tire according to any one of claims 1 to 10, calculated using

12. The tire according to any one of claims 1 to 11, 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%.

13. One or more elastomer polymers, of which at least 20 phr is at least one conjugated diene polymer (I) as defined in any one of claims 1 to 12, 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].

14. - 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, of which one or more elastomer polymers are conjugated diene polymers (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 13, comprising:

15. - One or more elastomer polymers of 100 phr, wherein at least 50 phr is a conjugated diene polymer (I), and the conjugated diene polymer (I) has a Tg of -70.0°C to -40.0°C, preferably -65.0°C to -55.0°C. ＤＳＣ Elastomer polymer 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 or 14, comprising, for use in winter or all seasons.

16. - One or more elastomer polymers in 100 phr, wherein at least 50 phr is a conjugated diene polymer (I), and the conjugated diene polymer (I) has a Tg of -55.0°C to -35.0°C, preferably -55.0°C to -40.0°C. ＤＳＣ Elastomer polymer 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 or 14, comprising:

17. 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 13 to 16, 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.

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

19. A vehicle wheel tire according to any one of claims 1 to 13 or claim 18, for winter, all-season, or summer use.

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