Tire tread rubber composition and related methods

Abstract

A tire tread rubber composition comprising a specified elastomer component, a reinforcing silica filler, a specified hydrocarbon resin, a liquid plasticizer, and a curing package is disclosed herein. The elastomer component comprises styrene-butadiene rubber and high cis-polybutadiene having silica-reactive functional groups. The use of the disclosed components may result in tire treads having specific properties, as further discussed herein.

Description

[Technical Field]

[0001] This application relates to tire tread rubber compositions and related methods. [Background technology]

[0002] A tire consists of many components, including the tread that contacts the road surface. The specific components used to prepare the rubber composition, including the tire tread, can vary. Compounding tire tread rubber compositions is a complex science, as changes to the compound that result in an improvement in one property (e.g., wet performance) may lead to a deterioration in another property (e.g., dry traction). [Overview of the Initiative]

[0003] This specification discloses rubber compositions for tire treads and related methods.

[0004] In the first embodiment, a tire tread rubber composition is disclosed. The composition comprises (a) 100 parts of an elastomer component comprising (i) 30 to 45 parts, preferably 30 to 40 parts of at least one styrene-butadiene rubber having a Tg of at least about -20°C, preferably about -20 to about -10°C, and (ii) 55 to 70 parts, preferably 60 to 70 parts of polybutadiene rubber having a cis bond content of at least 95%, a Tg of less than -101°C, preferably -101 or -110°C, and silica-reactive functional groups, and (b) about 100 to about 300 m 2 / g, preferably about 150 to about 300m 2The product is made from components comprising: (c) at least one reinforcing silica filler with a surface area of ​​80 to 120 phr having a surface area of ​​1 / g; (d) at least one hydrocarbon resin with a Tg of 30 to 40 phr having a Tg of 15 phr or less, preferably 10 phr or less; (e) at least one liquid plasticizer with a Tg of 15 to 30 phr, preferably consisting of at least one oil; and (f) a cured package, wherein the total amount of (d) and (e) is 45 to 60 phr.

[0005] In a second embodiment, a tire tread rubber composition is disclosed. The composition comprises (a) 100 parts of an elastomer component comprising (i) 30 to 45 parts, preferably 30 to 40 parts of at least one oil-spreadable non-functionalized styrene-butadiene rubber having a Tg of at least about -20°C, preferably about -20 to about -10°C, and an Mw of at least 600,000 grams / mol, preferably 600,000 to 1,200,000 grams / mol, and (ii) 55 to 70 parts, preferably 60 to 70 parts of polybutadiene rubber having a cis bond content of at least 95%, a Tg of less than -101°C, preferably -101 or -110°C, and silica-reactive functional groups, and (b) about 100 to about 300 m 2 / g, preferably about 150 to about 300m 2 The components are made from (a) a liquid plasticizer comprising (a) an oil-spreadable non-functionalized styrene-butadiene rubber of (i) a liquid plasticizer of (a) a liquid plasticizer

[0006] In a third embodiment, which is a sub-embodiment of the first embodiment, a tire tread rubber composition is disclosed. The composition comprises (a) 100 parts of an elastomer component comprising (i) 30 to 45 parts, preferably 30 to 40 parts of at least one styrene-butadiene rubber having a Tg of at least about -20°C, preferably about -20 to about -10°C, and (ii) 55 to 70 parts, preferably 60 to 70 parts of polybutadiene rubber having a cis bond content of at least 95%, a Tg of less than -101°C, preferably -101 or -110°C, and silica-reactive functional groups, and (b) about 100 to about 300 m 2 / g, preferably about 150 to about 300m 2 The product is made from components comprising: (c) at least one reinforcing silica filler with a surface area of ​​80 to 120 phr having a surface area of ​​1 / g; (d) at least one hydrocarbon resin with a Tg of 30 to 40 phr having a Tg of 15 phr or less, preferably 10 phr or less; (e) at least one liquid plasticizer with a Tg of 15 to 30 phr, preferably consisting of at least one oil; and (f) a cured package, wherein the total amount of (d) and (e) is 45 to 60 phr. In addition, according to the third embodiment, the tire tread rubber composition has a tanδ value at 60°C of 0.18 to 0.26, preferably 0.19 to 0.24, and satisfies at least one of the following: (a) has a tanδ value at -30°C that is 3 times or less the tanδ value at 60°C, preferably 3 to 1.8 times the tanδ value at 60°C, more preferably 2.9 to 2 times the tanδ value at 60°C; (b) has a tanδ value at 30°C that is at least 1.3 times the tanδ value at 60°C, preferably 1.3 to 1.8 times the tanδ value at 60°C, more preferably 1.4 to 1.7 times the tanδ value at 60°C; or (c) has a tanδ value at 0°C that is at least 1.9 times the tanδ value at 60°C, preferably 1.9 to 2.7 times the tanδ value at 60°C, more preferably 2 to 2.5 times the tanδ value at 60°C.

[0007] In a fourth embodiment, which is a sub-embodiment of the second embodiment, a tire tread rubber composition is disclosed. The composition comprises (a) 100 parts of an elastomer component comprising (i) 30 to 45 parts, preferably 30 to 40 parts of at least one oil-spreadable non-functionalized styrene-butadiene rubber having a Tg of at least about -20°C, preferably about -20 to about -10°C, and an Mw of at least 600,000 grams / mol, preferably 600,000 to 1,200,000 grams / mol, and (ii) 55 to 70 parts, preferably 60 to 70 parts of polybutadiene rubber having a cis bond content of at least 95%, a Tg of less than -101°C, preferably -101 or -110°C, and silica-reactive functional groups, and (b) about 100 to about 300 m 2 / g, preferably about 150 to about 300m 2The components are made from (a) a liquid plasticizer comprising (a) an oil-spreadable non-functionalized styrene-butadiene rubber of (i) a liquid plasticizer of (a) a liquid plasticizer In addition, according to the fourth embodiment, the tire tread rubber composition has a tanδ value at 60°C of 0.18 to 0.26, preferably 0.19 to 0.24, and satisfies at least one of the following: (a) has a tanδ value at -30°C that is 3 times or less the tanδ value at 60°C, preferably 3 to 1.8 times the tanδ value at 60°C, more preferably 2.9 to 2 times the tanδ value at 60°C; (b) has a tanδ value at 30°C that is at least 1.3 times the tanδ value at 60°C, preferably 1.3 to 1.8 times the tanδ value at 60°C, more preferably 1.4 to 1.7 times the tanδ value at 60°C; or (c) has a tanδ value at 0°C that is at least 1.9 times the tanδ value at 60°C, preferably 1.9 to 2.7 times the tanδ value at 60°C, more preferably 2 to 2.5 times the tanδ value at 60°C. [Modes for carrying out the invention]

[0008] This specification discloses rubber compositions for tire treads and related methods.

[0009] In the first embodiment, a tire tread rubber composition is disclosed. The composition comprises components, (a) an elastomeric component consisting of 100 parts of (i) at least about -20°C, preferably about -20 to about -10°C Tg, 30 to 45 parts, preferably 30 to 40 parts of at least one styrene-butadiene rubber, and (ii) at least 95% cis bond content, Tg less than -101°C, preferably -101 or -110°C, and silica-reactive functional groups, 55 to 70 parts, preferably 60 to 70 parts of polybutadiene rubber, an elastomeric component, and (b) about 100 to about 300 m 2 / g, preferably about 150 to about 300 m 2 / g surface area, 80 to 120 phr of at least one reinforcing silica filler, (c) 15 phr or less carbon black, preferably 10 phr or less carbon black, (d) about 30 to about 50°C Tg, 30 to 40 phr of at least one hydrocarbon resin, (e) preferably consisting of at least one oil, 15 to 30 phr of at least one liquid plasticizer, (f) a curing package, and is made from components where the total amount of (d) and (e) is 45 to 60 phr.

[0010] In the second embodiment, a tire tread rubber composition is disclosed. The composition comprises (a) an elastomeric component consisting of 100 parts of (i) at least about -20°C, preferably about -20 to about -10°C Tg, and at least 600,000 grams / mol, preferably 600,000 to 1,200,00,0 grams / mol Mw, 30 to 45 parts, preferably 30 to 40 parts of at least one oil-extended non-functionalized styrene-butadiene rubber, and (ii) at least 95% cis bond content, Tg less than -101°C, preferably -101 or -110°C, and silica-reactive functional groups, 55 to 70 parts, preferably 60 to 70 parts of polybutadiene rubber, an elastomeric component, and (b) about 100 to about 300 m 2 / g, preferably about 150 to about 300 m 2The components are made from (a) a liquid plasticizer comprising (a) an oil-spreadable non-functionalized styrene-butadiene rubber of (i) a liquid plasticizer of (a) a liquid plasticizer

[0011] In a third embodiment, which is a sub-embodiment of the first embodiment, a tire tread rubber composition is disclosed. The composition comprises (a) 100 parts of an elastomer component comprising (i) 30 to 45 parts, preferably 30 to 40 parts of at least one styrene-butadiene rubber having a Tg of at least about -20°C, preferably about -20 to about -10°C, and (ii) 55 to 70 parts, preferably 60 to 70 parts of polybutadiene rubber having a cis bond content of at least 95%, a Tg of less than -101°C, preferably -101 or -110°C, and silica-reactive functional groups, and (b) about 100 to about 300 m 2 / g, preferably about 150 to about 300m 2The product is made from components comprising: (c) at least one reinforcing silica filler with a surface area of ​​80 to 120 phr having a surface area of ​​1 / g; (d) at least one hydrocarbon resin with a Tg of 30 to 40 phr having a Tg of 15 phr or less, preferably 10 phr or less; (e) at least one liquid plasticizer with a Tg of 15 to 30 phr, preferably consisting of at least one oil; and (f) a cured package, wherein the total amount of (d) and (e) is 45 to 60 phr. In addition, according to the third embodiment, the tire tread rubber composition has a tanδ value at 60°C of 0.18 to 0.26, preferably 0.19 to 0.24, and satisfies at least one of the following: (a) has a tanδ value at -30°C that is 3 times or less the tanδ value at 60°C, preferably 3 to 1.8 times the tanδ value at 60°C, more preferably 2.9 to 2 times the tanδ value at 60°C; (b) has a tanδ value at 30°C that is at least 1.3 times the tanδ value at 60°C, preferably 1.3 to 1.8 times the tanδ value at 60°C, more preferably 1.4 to 1.7 times the tanδ value at 60°C; or (c) has a tanδ value at 0°C that is at least 1.9 times the tanδ value at 60°C, preferably 1.9 to 2.7 times the tanδ value at 60°C, more preferably 2 to 2.5 times the tanδ value at 60°C.

[0012] In a fourth embodiment, which is a sub-embodiment of the second embodiment, a tire tread rubber composition is disclosed. The composition comprises (a) 100 parts of an elastomer component comprising (i) 30 to 45 parts, preferably 30 to 40 parts of at least one oil-spreadable non-functionalized styrene-butadiene rubber having a Tg of at least about -20°C, preferably about -20 to about -10°C, and an Mw of at least 600,000 grams / mol, preferably 600,000 to 1,200,000 grams / mol, and (ii) 55 to 70 parts, preferably 60 to 70 parts of polybutadiene rubber having a cis bond content of at least 95%, a Tg of less than -101°C, preferably -101 or -110°C, and silica-reactive functional groups, and (b) about 100 to about 300 m2 / g, preferably about 150 to about 300m 2 The components are: (c) at least one reinforcing silica filler with a surface area of ​​80 to 120 phr having a surface area of ​​1 / g; (d) at least one aromatic hydrocarbon resin with a Tg of about 30 to about 50°C and a Tg of 30 to 40 phr, preferably 30 to 35 phr; and (e) at least one liquid plasticizer with a Tg of 15 to 30 phr, preferably 15 to 25 phr, wherein the at least one liquid plasticizer with a Tg of 15 to 30 phr contains an oil from the oil-spreadable non-functionalized styrene-butadiene rubber of (a)(i); and (f) a cured package, wherein the total amount of (d) and (e) is 45 to 60 phr, preferably 45 to 55 phr. In addition, according to the fourth embodiment, the tire tread rubber composition has a tanδ value at 60°C of 0.18 to 0.26, preferably 0.19 to 0.24, and satisfies at least one of the following: (a) has a tanδ value at -30°C that is 3 times or less the tanδ value at 60°C, preferably 3 to 1.8 times the tanδ value at 60°C, more preferably 2.9 to 2 times the tanδ value at 60°C; (b) has a tanδ value at 30°C that is at least 1.3 times the tanδ value at 60°C, preferably 1.3 to 1.8 times the tanδ value at 60°C, more preferably 1.4 to 1.7 times the tanδ value at 60°C; or (c) has a tanδ value at 0°C that is at least 1.9 times the tanδ value at 60°C, preferably 1.9 to 2.7 times the tanδ value at 60°C, more preferably 2 to 2.5 times the tanδ value at 60°C.

[0013] definition The terms used herein are for illustrative purposes only and should not be construed as limiting the invention as a whole.

[0014] As used herein, the term “most” refers to more than 50%.

[0015] As used herein, the abbreviation Mn refers to the number-average molecular weight.

[0016] When used herein, the abbreviation Mp refers to peak molecular weight.

[0017] As used herein, the abbreviation Mw refers to the weight-average molecular weight.

[0018] Unless otherwise specified herein, the term "Mooney viscosity" refers to Mooney viscosity, ML. 1+4 This refers to the Mooney viscosity of a rubber composition, which will be understood by those skilled in the art.

[0019] As used herein, the term “natural rubber” means naturally derived rubber, including rubber harvested from raw materials such as the Hevea rubber tree, and rubber harvested from non-Hevea raw materials such as guayule rubber and dandelions such as TKS. In other words, the term “natural rubber” should be interpreted as excluding synthetic polyisoprene.

[0020] As used herein, the term "phr" means parts per 100 parts of rubber. 100 parts of rubber is also referred to herein as 100 parts of elastomer component.

[0021] As used herein, the term “polyisoprene” means synthetic polyisoprene. In other words, the term is used to refer to polymers produced from isoprene monomers and should not be interpreted to include naturally occurring rubbers (e.g., Hevea natural rubber, guayule-derived natural rubber, or dandelion-derived natural rubber). However, the term polyisoprene should be interpreted to include polyisoprene produced from natural sources of isoprene monomers.

[0022] As used herein, the term “tread” refers to both the portion of the tire that contacts the road under normal inflation and load conditions, and any sub-tread.

[0023] Tire tread rubber composition As described above, the first to fourth embodiments disclosed herein relate to tire tread rubber compositions made from specified components. The rubber compositions are generally used in preparing tire treads by a process that includes forming a tread pattern by molding and curing one of the rubber compositions. Thus, a tire tread includes a cured form of one of the tire tread rubber compositions. The tire tread rubber composition may exist in the form of a tread that has been formed but has not yet been incorporated into a tire, and / or may exist within a tread that forms part of a tire.

[0024] According to the first to fourth embodiments disclosed herein, the Tg of the entire rubber composition can vary. The Tg of the entire rubber composition may be referred to as the compound Tg or the rubber composition Tg. In certain embodiments of the first to fourth embodiments, the rubber composition has a compound Tg of -40 to -60°C (e.g., -40, -41, -42, -43, -44, -45, -46, -47, -48, -49, -50, -51, -52, -53, -54, -55, -56, -57, -58, -59, or -60°C), preferably -45 to -55°C (e.g., -45, -46, -47, -48, -49, -50, -51, -52, -53, -54, or -55°C). The Tg of rubber compounds can generally be measured according to the guidelines of ASTM D5992-96 (2011) using a dynamic mechanical thermal spectrometer (such as the Gabo analyzer described below, operating in tensile mode) and with a temperature sweep (-70 to 65°C) under specified test conditions (i.e., frequency 52 Hz, static strain 6%, dynamic strain 0.1%, sample form 4.75 mm wide × 29 mm long × 2 mm deep), the measurement is performed on the sample after curing at 170°C for 15 minutes, and the Tg is estimated from the resulting curve using the vibration method.

[0025] Elastomer components As described above, according to the first to fourth embodiments, the tire tread rubber composition is made from a composition containing 100 parts of an elastomer component. The elastomer component includes styrene-butadiene rubber and polybutadiene rubber. Since a total of 100 parts of elastomer or rubber is used, the amounts of other components can be listed in terms of phr or in parts per 100 parts of rubber (or 100 parts of elastomer component). As a non-limiting example, for a rubber composition containing 35 parts of styrene-butadiene rubber, 65 parts of polybutadiene rubber, and 110 parts of reinforcing silica filler, the amount of silica filler can be stated as 110 phr.

[0026] As described above, according to the first and third embodiments, 100 parts of the elastomer component (i) has a Tg of at least -20°C, preferably about -20 to about -10°C or -20 to -10°C (e.g., -20, -19, -18, -17, -16, -15, -14, -13, -12, -11, or -10°C), and 30 to 45 parts (e.g., 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, or 45 parts), preferably 30 to 40 parts (e.g., 30, 31, 32, 33, 34, (ii) at least one styrene-butadiene rubber in 35, 36, 37, 38, 39, or 40 parts, and (ii) 55 to 70 parts (e.g., 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70 parts), preferably 60 to 70 parts (e.g., 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70 parts), of polybutadiene having at least 95% cis bond content, a Tg of less than -101°C, preferably -101 or -110°C, and silica-reactive functional groups.As described above, according to the second and fourth embodiments, and in certain embodiments of the first and third embodiments, 100 parts of the elastomer component is (i) 30 to 45 parts (e.g., 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, or 45 parts) of at least one oil-spreadable non-functionalized styrene-butadiene rubber with a Tg of at least -20°C, preferably about -20 to about -10°C or Tg at -20 to -10°C (e.g., -20, -19, -18, -17, -16, -15, -14, -13, -12, -11, or -10°C) and at least 600,000 grams / mol (e.g., 600,000, 650,000, 700,000, 750,000, 800,000, 850,000, 900,000, 950,000, 1,000,000, 1,050,000, 1,100,000, 1,150,000, 1,2 Mw of 00,000, 1,250,000, 1,300,000 grams / mol or more, preferably 600,000 to 1,200,000 grams / mol (for example, 600,000, 650,000, 700,000, 750,000, 800,000, 850,000, 900,000, 950,000, 1,000,000, 1,050,000, 1,100,000, 1,150,000, or 1,200,000 grams / mol) (ii) comprising (ii) 55 to 70 parts (e.g., 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70 parts) of polybutadiene having at least 95% cis bond content, a Tg of less than -101°C, preferably -101 or -110°C, and silica-reactive functional groups. In certain embodiments of the first to fourth embodiments, the amount of styrene-butadiene rubber (i) (discussed above) is 30 to 40 parts (e.g., 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 parts), and the amount of polybutadiene rubber (ii) (discussed above) is 60 to 70 parts (e.g., 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70 parts).

[0027] In certain embodiments of the first to fourth embodiments, the elastomer component (a) comprises 9 parts or less (e.g., 9, 8, 7, 6, 5, 4, 3, 2, 1 or even 0 parts), preferably 5 parts or less (e.g., 5, 4, 3, 2, 1 or even 0 parts) of natural rubber, polyisoprene, or a combination thereof. In certain embodiments of the first to fourth embodiments, the elastomer component (a) comprises 0 parts of natural rubber, polyisoprene, or a combination thereof. In certain embodiments of the first to fourth embodiments, the amount of 9 parts or less refers to 1 to 9 parts, and in other embodiments, it refers to 0 to 9 parts. Similarly, in certain embodiments of the first to fourth embodiments, the amount of 5 parts or less refers to 1 to 5 parts, and in other embodiments, it refers to 0 to 5 parts.

[0028] In certain embodiments of the first to fourth embodiments, 100 parts of the elastomer component consist of (i) (i.e., at least one specified styrene-butadiene rubber) and (ii) (i.e., a specified polybutadiene rubber) (only) in the amounts considered above. In other embodiments of the first embodiment, 100 parts of the elastomer component include (i) and (ii) plus one or more additional rubbers (iii). According to the first to fourth embodiments, if one or more additional rubbers (iii) are present, the amount is generally limited to preferably 20 parts or less (e.g., 20, 15, 10, 5, or less), more preferably 15 parts or less (e.g., 15, 10, 5, or less), 9 parts or less (e.g., 9, 8, 7, 6, 5, 4, 3, 2, 1, or even 0 parts), or 5 parts or less (e.g., 5, 4, 3, 2, 1, or even less). In certain embodiments of the first to fourth embodiments, an amount of 20 parts or less refers to 1 to 20 parts, while in other embodiments it refers to 0 to 20 parts. In certain embodiments of the first to fourth embodiments, an amount of 15 parts or less refers to 1 to 15 parts, while in other embodiments it refers to 0 to 15 parts. In certain embodiments of the first to fourth embodiments, an amount of 9 parts or less refers to 1 to 9 parts, while in other embodiments it refers to 0 to 9 parts. In certain embodiments of the first to fourth embodiments, an amount of 5 parts or less refers to 1 to 5 parts, while in other embodiments it refers to 0 to 5 parts. In certain embodiments of the first to fourth embodiments, one or more additional rubbers (iii) are selected from diene monomer-containing rubbers, and in certain such embodiments, one or more additional rubbers (iv) are selected from the group consisting of natural rubber, polyisoprene, styrene-isoprene rubber, butadiene-isoprene rubber, styrene-isoprene-butadiene rubber, butyl rubber (both halogenated and non-halogenated), ethylene-propylene rubber (EPR), ethylene-butylene rubber (EBR), ethylene-propylene-diene rubber (EPDM), and combinations thereof.In yet other embodiments of the first to fourth embodiments, the additional rubber may be selected from: natural rubber, polyisoprene, or a combination thereof; one or more styrene-butadiene rubbers other than styrene-butadiene rubber (i), e.g., SBR having a Tg above -10°C (e.g., -7°C, -5°C, -3°C or higher) or below -20°C (e.g., -25, -30, -35, -40, -45, -50, -55, -60°C or lower); polybutadiene other than polybutadiene (ii), e.g., polybutadiene with a low cis-1,4 bond content (e.g., less than 50%, less than 45%, less than 40%), unfunctionalized polybutadiene rubber with at least 95% cis bond content and a Tg of -101°C or lower, or a combination thereof; or a combination of the aforementioned types of rubbers.

[0029] The Tg values ​​referred to herein for elastomers represent Tg measurements performed on the elastomer without any oil application. In other words, for oil-spreadable elastomers, the above Tg values ​​refer to the Tg before oil application, or the non-oil-spread version of the same elastomer. The Tg values ​​of elastomers or polymers can be measured using a differential scanning calorimeter (DSC) instrument such as those manufactured by TA Instruments (New Castle, Delaware), and the measurement is performed using a temperature rise of 10°C / min after cooling to -120°C. The tangent is then drawn on the baseline before and after the sharp rise in the DSC curve. The temperature on the DSC curve (read at the point corresponding to the midpoint between the two junctions) can be used as the Tg.

[0030] In certain embodiments of the first to fourth embodiments, the average Tg of the elastomer components is -60 to -85°C (e.g., -60, -61, -62, -63, -64, -65, -66, -67, -68, -69, -70, -71, -72, -73, -74, -75, -76, -77, -78, -79, -80, -81, -82, -83, -84, or -85°C), preferably -65 to -75°C (e.g., -65, -66, -67, -68, -69, -70, -71, -72, -73, -74, or -75°C). The average Tg of the elastomer components can be calculated using the Tg of each rubber present in 100 parts of the elastomer components, taking into account their relative weight percentages. When one (or more) types of rubber are oil-applied, only the amount of rubber (i.e., excluding any amount of oil) is used to calculate the average Tg of the elastomer components. When one (or more) types of rubber are oil-applied, the Tg of the oil-applied rubber in its non-oil-applied form (i.e., rubber only) is used to calculate the average Tg of the elastomer components.

[0031] Styrene-butadiene rubber (i) As described above, according to the first to fourth embodiments, the elastomer component of the tire tread rubber composition comprises, in the amounts considered above, at least one styrene-butadiene rubber (i) having a Tg of at least -20°C, preferably about -20 to about -10°C or -20 to -10°C (e.g., -10, -11, -12, -13, -14, -15, -16, -17, -18, -19, or -20°C).

[0032] According to the first and third embodiments, the Mw of the styrene-butadiene rubber used in (i) can vary. In certain embodiments of the first and third embodiments, and according to the second and fourth embodiments, the Mw of the styrene-butadiene rubber used in (i) is at least 600,000 grams / mol, preferably 600,000 to 1,200,000 grams / mol. In certain embodiments of the first to fourth embodiments, the elastomer component (i) has a Tg of about -20 to about -10°C or -20 to -10°C (e.g., -10, -11, -12, -13, -14, -15, -16, -17, -18, -19, or -20°C) and a Tg of 700,000 to 1,200,000 grams / mol (e.g., 700,000, 725,000, 750,000). 00, 775,000, 800,000, 825,000, 850,000, 875,000, 900,000, 925,000, 950,000, 975,000, 1,000,000, 1,025,000, 1,050,000, 1,075,000, 1,100,000, 1,125,000, 1,150,000, 1,175,000, or 1,200,000 Mw of gram / mol (e.g., 700,000-950,000 grams / mol (e.g., 700,000, 725,000, 750,000, 775,000, 800,000, 825,000, 850,000, 875,000, 900,000, 925,000, or 950,000 grams / mol) or Mw of 800,000-950,000 grams / mol (e.g., 800 It consists of at least one type of styrene-butadiene rubber having at least one of the following Mw values ​​(grams / mol): 000, 825,000, 850,000, 875,000, 900,000, 925,000, or 950,000 grams / mol, in a particular such embodiment, (i) comprises only one type of SBR having both Tg and Mw within one of the aforementioned ranges.In certain embodiments of the first to fourth embodiments, (i) of the elastomer component is a Tg at approximately -10 to approximately -20°C and 700,000 to 1,200,000 grams / mol (e.g., 700,000, 725,000, 750,000, 775,000, 800,000, 825,000, 850,000, 875,000, 90 Mw (0,000, 925,000, 950,000, 975,000, 1,000,000, 1,025,000, 1,050,000, 1,075,000, 1,100,000, 1,125,000, 1,150,000, 1,175,000, or 1,200,000 grams / mol), 700,000-950,000 The material comprises at least one styrene-butadiene rubber having an Mw of gram / mol (e.g., 700,000, 725,000, 750,000, 775,000, 800,000, 825,000, 850,000, 875,000, 900,000, 925,000, or 950,000 grams / mol) or an Mw of 800,000 to 950,000 grams / mol (e.g., 800,000, 825,000, 850,000, 875,000, 900,000, 925,000, or 950,000 grams / mol), wherein in certain such embodiments, (i) comprises only one SBR having an Mw of no more than one of the aforementioned ranges. The Mw values ​​referred to herein are weight-average molecular weights, which can be determined by using gel permeation chromatography (GPC) calibrated with a styrene-butadiene standard and the Mark-Haucink constant for the polymer of interest.

[0033] According to the first to fourth embodiments, the Mn of at least one styrene-butadiene rubber used in (i) can vary. In certain embodiments of the first to third embodiments, elastomer component (i) comprises at least one styrene-butadiene rubber having a Tg of about -10 to about -20°C, or at least one Mw of 600,000 grams / mol, preferably 600,000 to 1,200,000 grams / mol (or any range within the aforementioned range as considered above), and Mn of 300,000 to 500,000 grams / mol (e.g., 300,000, 325,000, 350,000, 375,000, 400,000, 425,000, 450,000, 475,000, or 500,000 grams / mol), and in certain such embodiments, (i) comprises only one SBR, which has Mn within the aforementioned range. In certain embodiments of the first to fourth embodiments, elastomer component (i) comprises at least one styrene-butadiene rubber having a Tg of about -10 to about -20°C and a Mn of 350,000 to 450,000 (e.g., 350,000, 375,000, 400,000, 425,000, or 450,000 grams / mol), and in certain such embodiments, (i) comprises only one SBR, which has a Mn within the aforementioned ranges. The SBR of (i) may have a Mn within one of the aforementioned ranges in combination with a Mw within one of the aforementioned ranges, optionally in combination with an Mw / Mn value as considered below. The Mn values ​​referred to herein are number-average molecular weights, which can be determined by using gel permeation chromatography (GPC) calibrated with a styrene-butadiene standard and the Mark-Hauck constant for the polymer of interest.

[0034] In certain embodiments of the first to fourth embodiments disclosed herein, elastomer component (i) comprises at least one styrene-butadiene rubber having a Tg of about -10 to about -20°C, or at least one Mw of at least 600,000 grams / mol, preferably 600,000 to 1,200,000 grams / mol (or any range within this range as considered above), and also having an Mw / Mn (polydispersible) of 1.5 to 2.5 (e.g., 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, or 2.5), preferably 1.7 to 2.5 (e.g., 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, or 2.5). In certain such embodiments, (i) comprises only one type of SBR, which has an Mw / Mn of no more than one of the aforementioned ranges.

[0035] According to certain embodiments of the first to fourth embodiments, as discussed above, the (i) of the elastomer component comprises at least one styrene-butadiene rubber having a Tg of about -10 to about -20°C and / or an Mw of at least 600,000 grams / mol, more preferably 600,000 to 1,200,000 grams / mol (or any range within this range, as discussed above). According to certain preferred embodiments of the first and third embodiments, and according to the second and fourth embodiments, the at least one styrene-butadiene rubber comprises an oil-spreadable styrene-butadiene rubber, and in certain such embodiments, the Tg of the oil-spreadable SBR is about -10 to about -20°C. When oil-spreadable styrene-butadiene rubber is used as (i), the SBR may be spread with a variety of amounts of oil, preferably 30 to 40 parts (e.g., 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 parts) per 100 parts of styrene-butadiene rubber. As a non-limiting example, an oil-spreadable SBR spread with 35 parts of oil per 100 parts of styrene-butadiene rubber would provide 14 parts of oil for every 40 parts of SBR used in the rubber composition. The amount (parts) of at least one type of styrene-butadiene rubber (i) discussed above refers to the polymer amount of styrene-butadiene rubber and does not include the amount of oil that contributes when oil-spreadable SBR is used as (ii). In preferred embodiments of the first to fourth embodiments, at least one styrene-butadiene rubber (i) has a styrene content of at least 20% (e.g., 20%, 25%, 30%, 35%, 40%, 45%, 50%, or more), more preferably at least 25% (e.g., 25%, 30%, 35%, 40%, 45%, 50%, or more), or 20-50% (e.g., 20%, 25%, 30%, 35%, 40%, 45%, or 50%), or 20-40% (e.g., 20%, 25%, 30%, 35%, or 40%).In certain such embodiments, at least one styrene-butadiene rubber also has a vinyl bond content of 30-60% (e.g., 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, or 60%), 35-55% (e.g., 35, 37, 39, 41, 43, 45, 47, 49, 51, 53, or 55%), 40-50% (e.g., 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, or 50%), or 42-48% (e.g., 42%, 43%, 44%, 45%, 46%, 47%, or 48%). The vinyl bond content referred to herein should be understood as the total vinyl bond content in the SBR polymer chain, not the vinyl bond content in the butadiene portion of the SBR polymer chain, and H. 1 -NMR and C 13 - This can be measured by NMR (for example, using a 300 MHz Gemini 300 NMR spectrometer system (Varian)). In certain embodiments of the first to fourth embodiments, the styrene-butadiene rubber used in (i) may have a vinyl bond content and styrene content within one of the aforementioned ranges, in an optional combination with one or more of the above-mentioned Mw, Mn, and / or Mw / Mn ranges.

[0036] In certain preferred embodiments of the first to fourth embodiments, at least one of the following is satisfied: (a) at least one of the styrene-butadiene rubbers of (a)(i) is unfunctionalized, (b) at least one of the styrene-butadiene rubbers of (a)(i) is oil-fiber

[0037] According to the first and third embodiments, at least one styrene-butadiene rubber of (i) may be functionalized or defunctionalized. According to the second and fourth embodiments, and in preferred embodiments of the first and third embodiments, at least one styrene-butadiene rubber of (i) is defunctionalized. As used herein, the term functionalization should be understood to encompass the use of both functional groups and coupling agents. One or more functional groups may be utilized in each SBR. Generally, functional groups may be present at the leading edge of the polymer, at the terminal edge of the polymer, along the backbone of the polymer chain, or in combination thereof. Functional groups present at one or both ends of the polymer are generally the result of the use of a functional initiator, a functional arrestor, or both. Alternatively or further, functional groups may be present as a result of the coupling of multiple polymer chains using a coupling agent (described below). In certain embodiments of the first and third embodiments, at least one styrene-butadiene rubber of (i) is functionalized, preferably with a silica-reactive functional group. In certain such embodiments of the first and third embodiments, (i) consists of only one type of styrene-butadiene rubber as described above, which is functionalized with a silica-reactive functional group. In other embodiments of the first and third embodiments, and according to the second and fourth embodiments, at least one type of styrene-butadiene rubber in (i) is unfunctionalized or un-functionalized. In certain such embodiments of the first and third embodiments (and according to the second and third embodiments), (i) consists of only one type of styrene-butadiene rubber as described above, which is unfunctionalized (i.e., does not contain functional groups and coupling agents). In other embodiments of the first and third embodiments, (i) consists of two or more types (e.g., two, three, or more) of styrene-butadiene rubber as described above, and in certain such embodiments, at least one of the styrene-butadiene rubbers is functionalized with a silica-reactive functional group. Non-limiting examples of silica-reactive functional groups include, generally speaking, nitrogen-containing functional groups, silicon-containing functional groups, oxygen- or sulfur-containing functional groups, and metal-containing functional groups, as will be described in more detail below.

[0038] In certain embodiments of the first to third embodiments, when a functionalized SBR is used, the functionalization can be achieved by adding a functional group to one or both ends of the polymer, by adding a functional group to the poly backbone (or by a combination thereof), or by bonding two or more polymer chains to a coupling agent, or by a combination thereof, and such effects can be achieved by treating a living polymer with a coupling agent, a functionalizing agent, or a combination thereof, which helps to bond and / or functionalize other chains. In certain embodiments of the first to third embodiments, the functionalized SBR of (ii) contains one or more functional groups but is not bonded (i.e., does not contain any coupling agent). The coupling agent and / or functionalizing agent can be used in various molar ratios. Alternatively, in certain embodiments of the first to third embodiments, the functionalized styrene-butadiene rubber of (ii) may simply be silica reactivity resulting from the use of a coupling agent. Although the use of both coupling agents and functionalizing groups (and the compounds used therefor) is referred to herein, those skilled in the art will understand that certain compounds may perform both functions. In other words, certain compounds can both bond polymer chains and provide polymer chains along with functional groups. Those skilled in the art will also understand that the ability to bond polymer chains may depend on the amount of coupling agent reacted with the polymer chains. For example, favorable bonding can be achieved by adding the coupling agent in a 1:1 ratio of lithium equivalents of the reaction initiator to equivalents of the leaving group (e.g., halogen atom) of the coupling agent. Non-limiting examples of coupling agents include metal halides, metalloid halides, alkoxysilanes, alkoxystannanes, and combinations thereof.

[0039] In certain embodiments of the first to third embodiments, non-limiting examples of nitrogen-containing functional groups that can be used as silica-reactive functional groups in the styrene-butadiene rubber of (ii) include, but are not limited to, substituted or unsubstituted amino groups, amide residues, isocyanate groups, imidazolyl groups, indolyl groups, imino groups, nitrile groups, pyridyl groups, and ketimine groups. The substituted or unsubstituted amino groups should be understood to include primary alkylamines, secondary alkylamines, or cyclic amines, and amino groups derived from substituted or unsubstituted imines. In certain embodiments of the first to third embodiments, the styrene-butadiene rubber of (ii) contains one silica-reactive functional group selected from the list of nitrogen-containing functional groups described above.

[0040] In certain embodiments of the first to third embodiments, the styrene-butadiene rubber of (ii) contains silica-reactive functional groups from compounds containing nitrogen in the form of imino groups. Such imino-containing functional groups may be added by reacting the active ends of polymer chains with a compound having the following formula (I):

[0041] [ka] In the formula, R, R', R'', and R''' are each independently selected from a group having 1 to 18 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms) selected from the group consisting of alkyl groups, allyl groups, and aryl groups, and m and n are integers from 1 to 20 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) and 1 to 3 (1, 2, or 3), respectively. Each of R, R', R'', and R''' is preferably a hydrocarbyl and does not contain a heteroatom. In certain embodiments of the first to third embodiments, each R and R' is independently selected from alkyl groups having 1 to 6 carbon atoms (e.g., 1, 2, 3, 4, 5, or 6 carbon atoms), preferably 1 to 3 carbon atoms (e.g., 1, 2, or 3 carbon atoms). In certain embodiments of the first to third embodiments, m is an integer of 2 to 6 (e.g., 2, 3, 4, 5, or 6), preferably 2 or 3. In certain embodiments of the first to third embodiments, R''' is selected from groups having 1 to 6 carbon atoms (e.g., 1, 2, 3, 4, 5, or 6 carbon atoms), preferably 2 to 4 carbon atoms (e.g., 2, 3, or 4 carbon atoms). In certain embodiments of the first to third embodiments, R'' is selected from alkyl groups having 1 to 6 carbon atoms (e.g., 1, 2, 3, 4, 5, or 6 carbon atoms), preferably 1 to 3 carbon atoms (e.g., 1, 2, or 3 carbon atoms), most preferably 1 carbon atom (e.g., methyl). In certain embodiments of the first to third embodiments, n is 3, resulting in a compound having a trihydrocarboxysilane moiety, such as a trialkoxysilane moiety.Non-limiting examples of compounds having an imino group and satisfying formula (I) above, which are suitable for providing silica-reactive functional groups for styrene-butadiene rubber of (i), include, but are not limited to, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N-methylethylidene)-3-(triethoxysilyl)-1-propanamine, N-ethylidene-3-(triethoxysilyl)-1-propanamine, N-(1-methylpropyridene)-3-(triethoxysilyl)-1-propanamine, and N-(4-N,N-dimethylaminobenzylidene)-3-(triethoxysilyl)-1-propanamine.

[0042] Non-limiting examples of silicon-containing functional groups that can be used as silica-reactive functional groups in the styrene-butadiene rubber of (ii) in certain embodiments of the first to third embodiments include, but are not limited to, organosilyl or siloxy groups, and more precisely, such functional groups may be selected from alkoxysilyl groups, alkylhalosilyl groups, siloxy groups, alkylaminosilyl groups, and alkoxyhalosilyl groups. Optionally, organosilyl or siloxy groups may also contain one or more nitrogen atoms. Other examples of silicon-containing functional groups suitable for use in the functionalization of diene elastomers include those disclosed in U.S. Patent No. 6,369,167, the entire disclosure of which is incorporated herein by reference. In certain embodiments of the first to third embodiments, the styrene-butadiene rubber of (ii) comprises at least one silica-reactive functional group selected from the list of silicon-containing functional groups described above.

[0043] In certain embodiments of the first to third embodiments, the styrene-butadiene rubber of (ii) comprises silica-reactive functional groups including silicon-containing functional groups having a siloxy group (e.g., hydrocarbyloxysilane-containing compounds), the compound optionally comprising a monovalent group having at least one functional group. Such silicon-containing functional groups may be added by reacting the active end of a polymer chain with a compound having the following formula (II) and / or a partial condensation product thereof.

[0044] [ka] In the formula, A 1 R represents a monovalent group having at least one functional group selected from epoxy, isocyanate, imine, cyano, carboxylic acid ester, carboxylic acid anhydride, cyclic tertiary amine, acyclic tertiary amine, pyridine, silazane, and sulfide. c R represents a divalent hydrocarbon group having a single bond or 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), d R represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms), and R represents a monovalent aromatic hydrocarbon group or reactive group having 1 to 20 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms). e represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms), where b is an integer from 0 to 2, and there are two or more R d OR e When each R exists, d and / or OR e These may be the same or different from each other, and the active proton is not contained within the molecule. As used herein, a partial condensation product refers to a product in which some (but not all) of the SiOR groups in the hydrocarbyloxysilane compound are fused into SiOSi bonds. In certain embodiments of the first to third embodiments, the following applies: (a)R c(b)R e However, it represents a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms), 2 to 6 carbon atoms (e.g., 2, 3, 4, 5, or 6 carbon atoms), or 1 to 2 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 8 carbon atoms, (c)R d However, at least one of the following is satisfied: that it represents a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms), 2 to 6 carbon atoms (e.g., 2, 3, 4, 5, or 6 carbon atoms), or 1 to 2 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 8 carbon atoms; in certain such embodiments, each of (a), (b), and (c) is satisfied, and R c , R e and R d It is selected from one of the aforementioned bases.

[0045] In certain embodiments of the first to third embodiments, the functional group of the styrene-butadiene rubber of (ii) is derived from a compound represented by formula (II), where A 1It has at least one epoxy group. Non-limiting specific examples of such compounds include 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-glycidoxyethyl)methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl)-methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyl(methyl)dimethoxysilane. Among these, 3-glycidoxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are particularly suitable.

[0046] In certain embodiments of the first to third embodiments, the functional group of the styrene-butadiene rubber of (ii) is derived from a compound represented by formula (II), where A 1 It has at least one isocyanate group. Non-limiting specific examples of such compounds include 3-isocyanate-propyltrimethoxysilane, 3-isocyanate-propyltriethoxysilane, 3-isocyanate-propylmethyldiethoxysilane, and 3-isocyanate-propyltriisopropoxysilane, among which 3-isocyanate-propyltrimethoxysilane is particularly preferred.

[0047] In certain embodiments of the first to third embodiments, the functional group of the styrene-butadiene rubber of (ii) is derived from a compound represented by formula (II), where A 1Each compound has at least one imine group. Non-limiting specific examples of such compounds include N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N-(1-methylethylidene)-3-(triethoxysilyl)-1-propanamine, N-ethylidene-3-(triethoxysilyl)-1-propanamine, N-(1-methylpropyridene)-3-(triethoxysilyl)-1-propanamine, N-(4-N,N-dimethylaminobenzylidene)-3-(triethoxysilyl)-1-propanamine, N-(cyclohexylidene)-3-(triethoxysilyl)-1-propanamine, and trimethoxysilyl compounds, methyldiethoxysilyl compounds, and ethyldimethoxysilyl compounds corresponding to the above triethoxysilyl compounds. Among these, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine and N-(1-methylpropyridene)-3-(triethoxysilyl)-1-propanamine are particularly suitable. Furthermore, examples of imine (amidine) group-containing compounds include 1-[3-trimethoxysilyl]propyl]-4,5-dihydroimidazole, 3-(1-hexamethyleneimino)propyl(triethoxy)silane, (1-hexamethyleneimino)methyl(trimethoxy)silane, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole, N-(3-isopropoxysilylpropyl)-4,5-dihydroimidazole, and N-(3-methyldiethoxysilylpropyl)-4,5-dihydroimidazole, among which N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole and N-(3-isopropoxysilylpropyl)-4,5-dihydroimidazole are preferred.

[0048] In certain embodiments of the first to third embodiments, the functional group of the styrene-butadiene rubber of (ii) is derived from a compound represented by formula (II), where A 1It has at least one carboxylic acid ester group. Non-limiting specific examples of such compounds include 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, and 3-methacryloyloxypropyltriisopropoxysilane, among which 3-methacryloyloxypropyltriethoxysilane is preferred.

[0049] In certain embodiments of the first to third embodiments, the functional group of the styrene-butadiene rubber of (ii) is derived from a compound represented by formula (II), where A 1 It has at least one carboxylic acid anhydride group. Non-limiting specific examples of such compounds include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, and 3-methyldiethoxysilylpropyl succinic anhydride, among which 3-triethoxysilylpropyl succinic anhydride is preferred.

[0050] In certain embodiments of the first to third embodiments, the functional group of the styrene-butadiene rubber of (ii) is derived from a compound represented by formula (II), where A 1 It has at least one cyano group. Non-limiting specific examples of such compounds include 2-cyanoethylpropyltriethoxysilane.

[0051] In certain embodiments of the first to third embodiments, the functional group of the styrene-butadiene rubber of (ii) is derived from a compound represented by formula (II), where A 1It has at least one cyclic tertiary amine group. Non-limiting specific examples of such compounds include 3-(1-hexamethyleneimino)propyltriethoxysilane, 3-(1-hexamethyleneimino)propyltrimethoxysilane, (1-hexamethyleneimino)methyltriethoxysilane, (1-hexamethyleneimino)methyltrimethoxysilane, 2-(1-hexamethyleneimino)ethyltriethoxysilane, 3-(1-hexamethyleneimino)ethyltrimethoxysilane, 3-(1-pyrrolidinine Examples include propyltrimethoxysilane, 3-(1-pyrrolidinyl)propyltriethoxysilane, 3-(1-heptamethyleneimino)propyltriethoxysilane, 3-(1-dodecamethyleneimino)propyltriethoxysilane, 3-(1-hexamethyleneimino)propyldiethoxymethylsilane, 3-(1-hexamethyleneimino)propyldiethoxyethylsilane, and 3-[10-(triethoxysilyl)decyl]-4-oxazoline. Among these, 3-(1-hexamethyleneimino)propyltriethoxysilane and (1-hexamethyleneimino)methyltriethoxysilane are particularly preferred.

[0052] In certain embodiments of the first to third embodiments, the functional group of the styrene-butadiene rubber of (i) is derived from a compound represented by formula (II), where A 1 It has at least one acyclic tertiary amine group. Non-limiting specific examples of such compounds include 3-dimethylaminopropyltriethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 3-diethylaminopropyltriethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 2-dimethylaminoethyltriethoxysilane, 2-dimethylaminoethyltrimethoxysilane, 3-dimethylaminopropyldiethoxymethylsilane, and 3-dibutylaminopropyltriethoxysilane, among which 3-dimethylaminopropyltriethoxysilane and 3-diethylaminopropyltriethoxysilane are suitable.

[0053] In certain embodiments of the first to third embodiments, the functional group of the styrene-butadiene rubber of (ii) is derived from a compound represented by formula (II), where A 1 It has at least one pyridine group. Non-specific examples of such compounds include 2-trimethoxysilylethylpyridine.

[0054] In certain preferred embodiments of the first to third embodiments, the functional group of the styrene-butadiene rubber of (ii) is derived from a compound represented by formula (II), where A 1 It has at least one silazane group. Non-limiting specific examples of such compounds include N,N-bis(trimethylsilyl)aminopropylmethyldimethoxysilane, 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane, N,N-bis(trimethylsilyl)aminopropyltrimethoxysilane, N,N-bis(trimethylsilyl)aminopropyltriethoxysilane, N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane, N,N-bis(trimethylsilyl)aminoethyltrimethoxysilane, N,N-bis(trimethylsilyl)aminoethyltriethoxysilane, N,N-bis(trimethylsilyl)aminoethylmethyldimethoxysilane, and N,N-bis(trimethylsilyl)aminoethylmethyldiethoxysilane. N,N-bis(trimethylsilyl)aminopropyltriethoxysilane, N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane, or 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane are particularly preferred.

[0055] A silica-reactive functional group according to formula (II) is used, in which A 1In embodiments of the first to third embodiments, which contain one or more protected nitrogens (as discussed in detail above), the nitrogen may be deprotected or deblocked by hydrolysis or other procedures to convert the protected nitrogen into primary nitrogen. As a non-limiting example, nitrogen bonded to two trimethylsilyl groups may be deprotected and converted to primary amine nitrogen (such nitrogen is still bonded to the remainder of the compound of formula (II)). Thus, the silica-reactive functional group of styrene-butadiene rubber arises from the use of the compound according to formula (II), where A 1 In certain embodiments of the first to third embodiments, in which the functionalized polymer contains one or more protected nitrogen atoms, the functionalized polymer can be understood as containing functional groups resulting from a deprotected (or hydrolyzed) version of the compound.

[0056] In certain embodiments of the first to third embodiments, non-limiting examples of oxygen or sulfur-containing functional groups that can be used as silica-reactive functional groups in the styrene-butadiene rubber of (ii) include, but are not limited to, hydroxyl groups, carboxyl groups, epoxy groups, glycidoxy groups, diglycidylamino groups, cyclic dithiane-derived functional groups, ester groups, aldehyde groups, alkoxy groups, ketone groups, thiocarboxyl groups, thioepoxy groups, thioglycidoxy groups, thiodiglycidylamino groups, thioester groups, thioaldehyde groups, thioalkoxy groups, and thioketone groups. In certain embodiments of the first to third embodiments, the aforementioned alkoxy groups may be benzophenone-derived alcohol-derived alkoxy groups. In certain embodiments of the first to third embodiments, the styrene-butadiene rubber of (ii) contains at least one silica-reactive functional group selected from the list of oxygen or sulfur-containing functional groups described above.

[0057] According to the first to third embodiments, one or more styrene-butadiene rubbers having silica-reactive functional groups in (ii) can be prepared by either solution polymerization or emulsion polymerization. In certain preferred embodiments of the first to third embodiments, the styrene-butadiene rubbers having silica-reactive functional groups used in (ii) are only those prepared by solution polymerization. In other embodiments of the first to third embodiments, the styrene-butadiene rubbers having silica-reactive functional groups used in (ii) are only those prepared by emulsion polymerization. In certain embodiments of the first to third embodiments, when two or more styrene-butadiene rubbers having silica-reactive functional groups are used for (ii), the rubber is a combination of solution-polymerized SBR and emulsion-polymerized SBR (e.g., one solution SBR and one emulsion SBR). As described above, in certain embodiments of the first to third embodiments, the styrene-butadiene rubbers (including SBRs having silica-reactive functional groups) present in the elastomer components are only solution SBRs (i.e., emulsion SBRs are not present).

[0058] In one or more embodiments of the first to third embodiments, the coupling agent for styrene-butadiene rubber of formula (ii) is formula (1)R * n M 1 Y (4-n) , Equation (2)M 1 Y4 and formula (3)M 2 It comprises a metal halide or semimetallic halide selected from the group including the compound represented by Y3, where each R * M is a monovalent organic group that independently has 1 to 20 carbon atoms. 1 is a tin atom, a silicon atom, or a germanium atom, M 2 is a phosphorus atom, Y is a halogen atom, and n is an integer between 0 and 3.

[0059] Examples of compounds represented by formula (1) include organometallic halides, and examples of compounds represented by formulas (2) and (3) include metal halides.

[0060] M 1 When represents a tin atom, compounds represented by formula (1) can include, for example, triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, trihexyltin chloride, trioctyltin chloride, diphenyltin dichloride, dibutyltin dichloride, dihexyltin dichloride, dioctyltin dichloride, phenyltin trichloride, butyltin trichloride, octyltin trichloride, and so on. Furthermore, compounds represented by formula (2) can include tin tetrachloride and tin tetrabromide.

[0061] M 1 When represents a silicon atom, the compounds represented by formula (1) can be, for example, triphenylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tributylchlorosilane, trimethylchlorosilane, diphenyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane, dibutyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, hexyltrichlorosilane, octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane, etc. Furthermore, examples of compounds represented by formula (2) include silicon tetrachloride and silicon tetrabromide. 1 When represents a germanium atom, the compound represented by formula (1) can be, for example, triphenylgermanium chloride, dibutylgermanium dichloride, diphenylgermanium dichloride, butylgermanium trichloride, etc. Furthermore, examples of compounds represented by formula (2) include germanium tetrachloride and germanium tetrabromide. Examples of compounds represented by formula (3) include phosphorous trichloride and phosphorous tribromide. In one or more embodiments, a mixture of metal halides and / or metalloid halides can be used.

[0062] In one or more embodiments of the first to third embodiments, the coupling agent for styrene-butadiene rubber of formula (ii) is formula (4)R * n M 1 (OR^) 4-n The compound comprises an alkoxysilane or alkoxy stannane selected from the group including the compound represented by the formula, where each R * M is a monovalent organic group that independently has 1 to 20 carbon atoms. 1 R^ is a tin atom, a silicon atom, or a germanium atom, OR^ is an alkoxy group, R^ is a monovalent organic group, and n is an integer from 0 to 3.

[0063] Exemplary compounds represented by formula (4) include tetraethyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate, tetraethoxytin, tetramethoxytin, and tetrapropoxytin.

[0064] Polybutadiene rubber (ii) According to the first to fourth embodiments, elastomer component (ii) consists of polybutadiene rubber having a cis bond content of at least 95% (e.g., 95%, 96%, 97%, 98%, 99%, or more), a Tg of less than -101°C (e.g., -102, -103, -104, -105, -106, -107, -108, -109, -110, -111, -112°C or less), preferably -101 or -110°C (e.g., -102, -103, -104, -105, -106, -107, -108, -109, or -110°C), and silica-reactive functional groups. In certain such embodiments, the Tg of polybutadiene rubber (ii) is -101 to -110°C. The cis bond content refers to the cis-1,4- bond content. The cis-1,4- bond content and vinyl bond content of polybutadiene rubber referred to herein are determined by FTIR (Fourier Transform Infrared Spectroscopy), in which case the polymer sample is dissolved in CS2 and then subjected to FTIR. In certain embodiments of the first to fourth embodiments, the polybutadiene rubber of (ii) has a cis-1,4- bond content of at least 98% (e.g., 98%, 99%, or more) or at least 99% (e.g., 99%, 99.5%, or more). Since the cis bond content of polybutadiene rubber (ii) is high (i.e., at least 95%, as discussed above), the vinyl bond content is low. In certain embodiments of the first to fourth embodiments, the polybutadiene rubber of (ii) has a vinyl bond content of less than 4% (e.g., 3.9%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, 0.5%, etc.), preferably less than 3% (e.g., 2.5%, 2%, 1.5%, 1%, 0.5%, etc.), and more preferably less than 2% (e.g., 1.5%, 1.4%, 1.3%, 1.2%, 1.1%, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, etc.). In certain embodiments of the first to fourth embodiments, any polybutadiene rubber used in the tire tread rubber composition has a Tg of -105°C or below (e.g., -105, -106, -107, -108, -109°C or below), such as -105 to -110°C.In certain embodiments of the first to fourth embodiments, any polybutadiene rubber used in the tire tread rubber composition contains less than 3% by weight (e.g., 3%, 2%, 1%, 0.5%, or less), preferably less than 1% by weight (e.g., 1%, 0.5%, or less), or 0% by weight of syndiotactic 1,2-polybutadiene. Generally, according to the first to fourth embodiments, one or more polybutadiene rubbers having at least 95% cis bond content, a Tg below -101°C, and silica-reactive functional groups may be used for (ii). In certain embodiments of the first to fourth embodiments, (ii) consists of only one polybutadiene rubber having at least 95% (e.g., 95%, 96%, 97%, 98%, 99%, or more) cis bond content, a Tg below -101°C, and silica-reactive functional groups. In preferred embodiments of the first to fourth embodiments, the amount of any polybutadiene rubber having a high vinyl content (i.e., more than about 70%) is limited to less than 25 parts, more preferably less than 10 parts, and even more preferably less than 5 parts or 0 parts (in the total tread rubber composition).

[0065] As described above, according to the first to fourth embodiments, a polybutadiene rubber having at least 95% cis bond content, a Tg of less than -101°C, and silica-reactive functional groups exists as (ii). In certain embodiments of the first to fourth embodiments, the Tg of this polybutadiene rubber (ii) is -101 to -110°C (e.g., -101, -102, -103, -104, -105, -106, -107, -108, -109, or -110°C), or -105 to -110°C (e.g., -105, -106, -107, -108, -109, or -110°C).

[0066] As described above, according to the first and third embodiments, 100 parts of the elastomer component (i) has a Tg of at least -20°C, preferably about -20 to about -10°C or -20 to -10°C (e.g., -20, -19, -18, -17, -16, -15, -14, -13, -12, -11, or -10°C), and 30 to 45 parts (e.g., 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, or 45 parts), preferably 30 to 40 parts (e.g., 30, 31, 32, 33, 34 (ii) at least one styrene-butadiene rubber in (ii) 35, 36, 37, 38, 39, or 40 parts, and (ii) 55 to 70 parts (e.g., 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70 parts), preferably 60 to 70 parts (e.g., 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70 parts), of polybutadiene having at least 95% cis bond content, a Tg of less than -101°C, preferably -101 or -110°C, and silica-reactive functional groups.As described above, according to the second and fourth embodiments, and in certain embodiments of the first and third embodiments, 100 parts of the elastomer component is (i) 30 to 45 parts (e.g., 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, or 45 parts) of at least one oil-spreadable non-functionalized styrene-butadiene rubber with a Tg of at least -20°C, preferably about -20°C to about Tg of -10℃ or -20~-10℃ (e.g., -20, -19, -18, -17, -16, -15, -14, -13, -12, -11, or -10℃), and at least 600,000 grams / mol (e.g., 600,000, 650,000, 700,000, 750,000, 800,000, 850,000, 900,000, 950,000, 1,000,000, 1,050,000, 1,100,000, 1, 150,000, 1,200,000, 1,250,000, 1,300,000 grams / mol or more), preferably 600,000 to 1,200,000 grams / mol (for example, 600,000, 650,000, 700,000, 750,000, 800,000, 850,000, 900,000, 950,000, 1,000,000, 1,050,000, 1,100,000, 1,150,000, or 1,20 The material comprises (ii) at least one oil-spreadable, non-functionalized styrene-butadiene rubber having Mw of 0,000 grams / mol, and (ii) 55 to 70 parts (e.g., 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70 parts) of polybutadiene having a cis bond content of at least 95%, a Tg of less than -101°C, preferably -101 or -110°C, and silica-reactive functional groups. In certain embodiments of the first to fourth embodiments, the amount of styrene-butadiene rubber (i) (discussed above) is 30 to 40 parts (e.g., 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 parts), and the amount of polybutadiene rubber (ii) (discussed above) is 60 to 70 parts (e.g., 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70 parts).

[0067] According to the first to fourth embodiments disclosed herein, the Mw of a polybutadiene rubber having at least 95% cis bond content, a Tg of less than -101°C, preferably -101 to -110-101°C, and the silica-reactive functional group of (ii) can vary. In certain embodiments of the first to fourth embodiments, the polybutadiene rubber having a cis bond content of at least 95%, a Tg of less than -101°C, preferably -101 to -110-101°C, and the silica-reactive functional group of (ii), has an Mw of 450,000 to 700,000 grams / mol (e.g., 450,000, 500,000, 550,000, 600,000, 650,000, or 700,000 grams / mol), preferably 500,000 to 650,000 grams / mol (e.g., 500,000, 525,000, 550,000, 575,000, 600,000, 625,000, or 650,000 grams / mol). Mw ranges falling within the aforementioned ranges, such as 500,000 to 600,000 grams / mol, 550,000 to 600,000 grams / mol, 450,000 to 600,000 grams / mol, and 500,000 to 700,000 grams / mol, can also be utilized in certain embodiments of the first to fourth embodiments. In certain embodiments of the first to fourth embodiments, the polybutadiene rubber having at least 95% cis bond content, a Tg of less than -101°C, preferably -101 to -110-101°C, and the silica-reactive functional group of (ii), is 180,000 to 300,000 grams / mol (e.g., 180,000, 200,000, 220,000, 240,000, 25 It has Mn of 0,000, 260,000, 280,000, or 300,000 grams / mol), preferably 200,000 to 280,000 grams / mol (for example, 200,000, 210,000, 220,000, 230,000, 240,000, 250,000, 260,000, 270,000, or 280,000 grams / mol).Mn ranges falling within the aforementioned ranges, such as 200,000 to 250,000 grams / mol, 230,000 to 280,000 grams / mol, 180,000 to 280,000 grams / mol, and 200,000 to 280,000 grams / mol, can also be utilized in certain embodiments of the first to fourth embodiments. In certain embodiments of the first to fourth embodiments, the polybutadiene rubber having at least 95% cis bond content, a Tg of less than -101°C, preferably -101 to -110-101°C, and the silica-reactive functional group of (ii), has Mw of 450,000 to 700,000 grams / mol (or any range within the aforementioned ranges as described above), and Mn of 180,000 to 300,000 grams / mol (or any range within the aforementioned ranges as described above). The aforementioned Mw and Mn values ​​for polybutadiene in (ii) refer to values ​​measured by GPC using polystyrene standards. Similarly, the aforementioned Mw and Mn values ​​for polybutadiene in (ii) refer to bound Mw and bound Mn, not base polymer values.

[0068] In certain embodiments of the first to fourth embodiments disclosed herein, the at least one polybutadiene rubber (ii) as described above is an oil-spreadable rubber incorporating oil in amounts further discussed below. In other preferred embodiments of the first to fourth embodiments disclosed herein, the at least one polybutadiene rubber (ii) as described above is a non-oil-spreadable rubber (i.e., BR is not spreadable with any oil).

[0069] The use of claimed amounts of polybutadiene having at least 95% cis bond content, a Tg of less than -101°C, preferably between -101 and -110-101°C, and silica-reactive functional groups in the tire tread rubber compositions according to the first to fourth embodiments disclosed herein (preferably in combination with other components of the tire tread rubber compositions according to the first to fourth embodiments) can, in certain embodiments, result in improved wear and rolling resistance compared to a control rubber composition using a non-functionalized version of polybutadiene having at least 95% cis bond content and a Tg of less than -101°C. In certain embodiments of the first to fourth embodiments, the tire tread rubber composition exhibits at least 2% (e.g., 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 2-13%, 2-10%, etc.), at least 5% (e.g., 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 5-13%, 5-10%, etc.), or even further at least 10% (e.g., 10%, 11%, 12%, 13%, 10-13%, etc.). As will be further considered, the wear improvement can be measured by the DIN wear value, where the lower limit (i.e., less material loss) indicates good wear. In certain embodiments of the first to fourth embodiments, the tire tread rubber composition contains at least 5% (e.g., 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 5-20%, 5-19%, 5-18%, 5-17%, 5-16%, 5-15%, 5-14%, 5-13%, 5-10%, etc.), preferably at least 10% (e.g., 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%) This exhibits an improvement in rolling resistance of 18%, 19%, 20%, 10-20%, 10-19%, 10-18%, 10-17%, 10-16%, 10-15%, 10-14%, 10-13%, etc., more preferably at least 15% (e.g., 15%, 16%, 17%, 18%, 19%, 20%, 15-20%, etc.), or 5-20%, 5-15%, 10-20%, 10-15%, etc. (as can be seen in more detail below, as evidenced by its value tanδ at -60°C).

[0070] According to certain embodiments of the first to fourth embodiments disclosed herein, the polybutadiene rubber of (i) comprises silica-reactive functional groups including silicon-containing functional groups having a siloxy group (e.g., hydrocarbyloxysilane-containing compounds), the compound optionally comprising a monovalent group having at least one functional group. Such silicon-containing functional groups may be added by reacting the active ends of polymer chains with a compound having the following formula (II) and / or a partial condensation product thereof,

[0071] [ka] A 1 represents a monovalent epoxy group, R c R represents a divalent hydrocarbon group having a single bond or 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), d R represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms), and R represents a monovalent aromatic hydrocarbon group or reactive group having 1 to 20 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms). e represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms), where b is an integer from 0 to 2, and there are two or more R d OR e When each R exists, d and / or OR eThese may be the same or different from each other, and the active proton is not contained within the molecule. As used herein, a partial condensation product refers to a product in which some (but not all) of the SiOR groups in the hydrocarbyloxysilane compound are fused into SiOSi bonds. In certain embodiments of the first to fourth embodiments, the following applies: (a)R c (b)R e However, it represents a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms), 2 to 6 carbon atoms (e.g., 2, 3, 4, 5, or 6 carbon atoms), or 1 to 2 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 8 carbon atoms, (c)R d However, at least one of the following is satisfied: that it represents a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms), 2 to 6 carbon atoms (e.g., 2, 3, 4, 5, or 6 carbon atoms), or 1 to 2 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 8 carbon atoms; in certain such embodiments, each of (a), (b), and (c) is satisfied, and R c , R e and R d It is selected from one of the aforementioned bases.

[0072] According to the first to fourth embodiments, the specific epoxy group present in the functionalized compound of formula (II) can vary. In a particular preferred embodiment among the first to fourth embodiments, the epoxy group (i.e., A in formula (II) above) 1) is glycidoxy, 3,4-epoxycyclohexyl, or has a total number of carbon atoms of 3 to 8 (e.g., 3, 4, 5, 6, 7, or 8), preferably 3 to 6 (e.g., 3, 4, 5, or 6) (with two terminal carbons in the epoxy ring and the other end of the carbon chain being R c Selected from glycidyl groups (bonded to) in the first to fourth embodiments. In certain embodiments of the first to fourth embodiments, the polybutadiene rubber of (ii) has silica-reactive functional groups resulting from the use of the functionalized compound of formula (II) and epoxy groups (i.e., A 1 ) is selected from glycidoxy. In certain embodiments of the first to fourth embodiments, the polybutadiene rubber of (ii) has silica-reactive functional groups resulting from the use of the functionalized compound of formula (II) and epoxy groups (i.e., A 1 ) is selected from 3,4-epoxycyclohexyl. In certain embodiments of the first to fourth embodiments, the polybutadiene rubber of (ii) has silica-reactive functional groups resulting from the use of the functionalized compound of formula (II) and epoxy groups (i.e., A 1 ) has a total number of carbon atoms of 3 to 8 (e.g., 3, 4, 5, 6, 7, or 8), preferably 3 to 6 (e.g., 3, 4, 5, or 6) (two terminal carbons are in the epoxy ring, and the other end of the carbon chain is R cSelected from glycidyl groups (bonded to). Non-limiting specific examples of such functionalized compounds by formula (II) containing epoxy groups include 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-glycidoxyethyl)methyldimethoxysilane, (2-glycidoxyethyl)methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl)-methyldimethoxysilane, (3-glycidoxypropyl)-methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(methyl)dimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyl(methyl)diethoxysilane. Among these, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are particularly preferred.

[0073] Natural rubber, polyisoprene, or combinations thereof. In certain embodiments of the first to fourth embodiments, the elastomer component may consist of up to 9 parts (e.g., 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0 parts) of natural rubber, polyisoprene, or a combination thereof, which may be referred to as (iii). In certain embodiments of the first to fourth embodiments, the amount of (iii) is 0 to 9 parts, and in other embodiments, 1 to 9 parts. In other embodiments of the first to fourth embodiments, elastomer component (iii) consists of up to 5 parts, 0 to 5 parts, or 1 to 5 parts of natural rubber, polyisoprene, or a combination thereof. In certain embodiments of the first to fourth embodiments, (iii) consists of (only) natural rubber. In other embodiments of the first to fourth embodiments, (iii) consists of (only) polyisoprene. In yet other embodiments of the first to fourth embodiments, as described above, natural rubber or polyisoprene is not present in or used in the tire tread rubber composition. If natural rubber is present in (iii) of the elastomer components, the natural rubber may include Para rubber natural rubber, non-Para rubber natural rubber (e.g., guayule natural rubber), or a combination thereof. When natural rubber is used in the tire tread rubber compositions of the first to fourth embodiments, the natural rubber preferably has an Mw of 1,000,000 to 2,000,000 grams / mol (e.g., 1 million, 1.1 million, 1.2 million, 1.3 million, 1.4 million, 1.5 million, 1.6 million, 1.7 million, 1.8 million, 1.9 million, 2 million grams / mol), 1,250,000 to 2,000,000 grams / mol, or 1,500,000 to 2,000,000 grams / mol (measured by GPC using polystyrene standards). When natural rubber is used in the tire tread rubber composition of the first to fourth embodiments, the Tg of the natural rubber can vary. Preferably, according to the first to fourth embodiments, when natural rubber is used, the natural rubber has a Tg of -65 to -80°C (e.g., -65, -66, -67, -68, -69, -70, -71, -72, -73, -74, -75, -76, -77, -78, -79, or -80°C), more preferably a Tg of -67 to -77°C (e.g., -67, -68, -69, -70, -71, -72, -73, -74, -75, -76, or -77°C).When polyisoprene is used in the tire tread rubber compositions of the first to fourth embodiments, the Tg of the polyisoprene can vary. Preferably, according to the first to fourth embodiments, when polyisoprene is used, it has a Tg of -55 to -75 °C (for example, -55, -56, -57, -58, -59, -60, -61, -62, -63, -64, -65, -66, -67, -68, -69, -70, -71, -72, -73, -74, or -75 °C), more preferably -58 to -74 °C (for example, -58, -59, -60, -61, -62, -63, -64, -65, -66, -67, -68, -69, -70, -71, -72, -73, or -74 °C).

[0074] Filler As used herein, the term "reinforcing" as used for "reinforcing carbon black filler", "reinforcing silica filler", and "reinforcing filler" is generally understood to encompass both fillers that have been conventionally described as reinforcing and fillers that may have been conventionally described as semi-reinforcing. Conventionally, the term "reinforcing filler" has been used to refer to particulate materials having a nitrogen adsorption specific surface area (N2SA) greater than about 100 m 2 / g, and in certain instances greater than 100 m 2 / g, greater than about 125 m 2 / g, greater than 125 m 2 / g, or even greater than about 150 m 2 / g, or greater than 150 m 2 / g. Alternatively (or in addition), the term "reinforcing filler" has also been used conventionally to refer to particulate materials having a particle size of about 10 nm to about 50 nm (including 10 nm to 50 nm). Conventionally, the term "semi-reinforcing filler" has been used to refer to fillers that are intermediate between non-reinforcing fillers (as discussed below) and reinforcing fillers in terms of either particle size, surface area (N2SA), or both. In certain embodiments of the first to fourth embodiments disclosed herein, the term "reinforcing filler" refers to a filler having a nitrogen adsorption specific surface area (N2SA) of about 20 m 2 / g or more (including 20 m 2 / g or more), about 50 m 2 / g ultra, 50 m 2 / g ultra, approximately 100 m 2 / g ultra, or 100 m 2 / g ultra, which is used to refer to particulate materials. In certain embodiments of the first to fourth embodiments disclosed herein, the term "reinforcing filler" is used to refer to particulate materials having a particle size of about 10 nm to a maximum of about 1000 nm (including 10 nm to 1000 nm), about 10 nm to a maximum of about 50 nm (including 10 nm to 50 nm).

[0075] Reinforcing silica filler As described above, according to the first to fourth embodiments disclosed herein, the tire tread rubber composition is about 100 to about 300 m 2 / g (e.g., 110, 120, 130, 140, 150, 160, 180, 200, 220, 240, 260, 280, or 300 m 2 / g), preferably about 150 to about 300 m 2 / g, more preferably about 180 to about 250 m 2 / g, and comprises (includes) 80 to 120 phr (e.g., 80, 81, 82, 84, 85, 86, 88, 90, 92, 94, 95, 96, 98, 100, 102, 104, 105, 106, 108, 110, 112, 114, 115, 116, 118, or 120 phr) of at least one reinforcing silica filler. In certain embodiments of the first to fourth embodiments disclosed herein, the tire tread rubber composition is about 100 to about 300 m 2 / g (e.g., 110, 120, 130, 140, 150, 160, 180, 200, 220, 240, 260, 280, or 300 m 2 / g), preferably about 150 to about 300 m 2 / g, more preferably about 180 to about 250 m 2The tire tread rubber composition comprises at least one reinforcing silica filler in an amount of 85 to 95 phr (e.g., 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or 95) having a surface area of ​​ / g. In other embodiments of the first to fourth embodiments disclosed herein, the tire tread rubber composition comprises about 100 to about 300 m 2 / g (for example, 110, 120, 130, 140, 150, 160, 180, 200, 220, 240, 260, 280, or 300m) 2 ( / g), preferably about 150 to about 300m 2 / g, more preferably about 180 to about 250m 2 The tire tread rubber composition comprises at least one reinforcing silica filler in an amount of 100 to 120 phr (e.g., 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, or 120 phr) having a surface area of ​​ / g. In certain preferred embodiments of the first to fourth embodiments, the tire tread rubber composition comprises 150 to 300 m 2 / g (for example, 150, 160, 180, 200, 220, 240, 260, 280, or 300m) 2 The tire tread rubber composition comprises at least one reinforcing silica filler having a surface area of ​​( / g). In certain more preferred embodiments of the first to fourth embodiments, the tire tread rubber composition should be understood to include intermediate ranges such as 180-240, 180-230, 180-220, 180-210, 190-240, 190-230, 190-220, 190-210, 180-250m 2 / g (for example, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, or 250m) 2The composition includes at least one reinforcing silica filler having a surface area of ​​0 phr. According to the first to fourth embodiments, one or more reinforcing silica fillers having the surface areas considered above may be used. In those embodiments in which two or more such reinforcing silica fillers are used, the aforementioned amounts refer to the total amount of all reinforcing silica fillers. In certain embodiments of the first to fourth embodiments, only one reinforcing silica filler having the surface area considered above is used. In preferred embodiments of the first to fourth embodiments, the reinforcing silica fillers used in the tire tread rubber composition are only those having the surface areas considered above, and in such embodiments, the tire tread rubber composition can be understood as not containing any reinforcing silica fillers having a surface area outside the range considered above (i.e., containing 0 phr of reinforcing silica fillers).

[0076] According to the first to fourth embodiments, the specific type of silica used for at least one reinforcing silica filler having the surface area discussed above can vary. Non-limiting examples of reinforcing silica fillers suitable for use in certain embodiments of the first to fourth embodiments include, but are not limited to, precipitated amorphous silica, wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), fumed silica, and calcium silicate. Other reinforcing silica fillers suitable for use in certain embodiments of the first to fourth embodiments include, but are not limited to, aluminum silicate, magnesium silicate (Mg2SiO4, MgSiO3, etc.), magnesium calcium silicate (CaMgSiO4), calcium silicate (Ca2SiO4, etc.), aluminum silicate (Al2SiO5, Al4.3SiO4.5H2O, etc.), and aluminum calcium silicate (Al2O3.CaO2SiO2, etc.). Among the listed reinforcing silica fillers, precipitated amorphous wet process and hydrated silica fillers are preferred. Such reinforcing silica fillers are generated by chemical reactions in water and from there precipitate as ultrafine spherical particles, which strongly bind to aggregates and subsequently to primary particles that bind slightly more strongly to the aggregates. Surface area, measured by the BET method, is a preferred measure for characterizing the reinforcing properties of different reinforcing silica fillers. In certain embodiments of the first to fourth embodiments disclosed herein, the rubber composition comprises a reinforcing silica filler having a surface area (measured by the BET method) as discussed below. In certain embodiments of the first to fourth embodiments disclosed herein, the rubber composition comprises a reinforcing silica filler having a pH of about 5.5 to about 8, 5.5 to 8 (e.g., 5.5, 5.7, 5.9, 6.1, 6.3, 6.5, 6.7, 6.9, 7.1, 7.3, 7.5, 7.7, 7.9, or 8), about 6 to about 8, 6 to 8 (e.g., 6, 6.2, 6.4, 6.6, 6.8, 7, 7.2, 7.4, 7.6, 7.8, or 8), about 6 to about 7.5, 6 to about 7.5, about 6.5 to about 8, 6.5 to 8, about 6.5 to about 7.5, 6.5 to 7.5, about 5.5 to about 6.8, or 5.5 to 6.8.Some commercially available reinforcing silica fillers that can be used in certain embodiments of the first to fourth embodiments include Hi-Sil® EZ120G, Hi-Sil® EZ120G-D, Hi-Sil® 134G, Hi-Sil® EZ 160G, Hi-Sil® EZ 160G-D, Hi-Sil® 190, Hi-Sil® 190G-D, Hi-Sil® EZ 200G, and Hi-Sil® EZ, manufactured by PPG Industries (Pittsburgh, Pa.). Examples include, but are not limited to, 200G-D, Hi-Sil® 210, Hi-Sil® 233, Hi-Sil® 243LD, Hi-Sil® 255CG-D, Hi-Sil® 315-D, Hi-Sil® 315G-D, Hi-Sil® HDP 320G, etc.Similarly, many useful commercial grades of different reinforcing silica fillers are also available from Evonik Corporation (e.g., Ultrasil® 320 GR, Ultrasil® 5000 GR, Ultrasil® 5500 GR, Ultrasil® 7000 GR, Ultrasil® VN2 GR, Ultrasil® VN2, Ultrasil® VN3, Ultrasil® VN3 GR, Ultrasil® 7000 GR, Ultrasil® 7005, Ultrasil® 7500 GR, Ultrasil® 7800 GR, Ultrasil® 9500 GR, Ultrasil® 9000 G, Ultrasil® 9100 Available from GR) and Solvay (e.g., Zeosil® 1115MP, Zeosil® 1085GR, Zeosil® 1165MP, Zeosil® 1200MP, Zeosil® Premium, Zeosil® 195HR, Zeosil® 195GR, Zeosil® 185GR, Zeosil® 175GR, and Zeosil® 165GR).

[0077] Silica coupling agent In certain embodiments of the first to fourth embodiments disclosed herein, one or more silica coupling agents may also be used (optionally). In preferred embodiments of the first to fourth embodiments, at least one silica coupling agent is used. Silica coupling agents are useful for preventing or reducing the aggregation of silica fillers in the rubber composition. Aggregation of silica filler particles is thought to increase the viscosity of the rubber composition, and therefore, by preventing this aggregation, viscosity is reduced, and the processability and blendability of the rubber composition are improved.

[0078] In general, any type of conventional silica coupling agent can be used, such as those having silanes and constituent components, or parts that can react with polymers, particularly vulcanizable polymers. The silica coupling agent acts as a linking crosslink between silica and polymer. Suitable silica coupling agents for use in certain embodiments of the first to fourth embodiments disclosed herein include those containing groups such as alkylalkoxy, mercapto, blocked mercapto, sulfide-containing (e.g., monosulfide-based alkoxy-containing, disulfide-based alkoxy-containing, tetrasulfide-based alkoxy-containing), amino, vinyl, epoxy, and combinations thereof. In certain embodiments of the first to fourth embodiments, the silica coupling agent can be added to the rubber composition in the form of pre-treated silica. The pre-treated silica is pre-surface-treated with silane before being added to the rubber composition. The use of pre-treated silica makes it possible to add two components (i.e., silica and silica coupling agent) to one component, which generally tends to facilitate rubber compounding.

[0079] Alkylalkoxysilanes have the general formula R 10 p Si(OR 11 ) 4-p It has each R 11 These are independently monovalent organic groups, and p is an integer from 1 to 3, but at least one R 10 The condition is that is an alkyl group. Preferably, p is 1. Generally, each R 10 These are, independently, C1~C 20 Aliphatic, C5~C 20 cyclic aliphatic, or C6~C 20 Contains aromatic compounds, each R 11 These independently include C1-C6 aliphatic atoms. In certain exemplary embodiments, each R 10 It is independent of C6~C 15 Includes aliphatic elements, and in further embodiments, each R 10 It is independently C8~C 14 It contains aliphatic compounds. Mercaptosilane has the general formula HS-R 13 -Si(R14 )(R 15 ) has 2, R 13 R is a divalent organic group, 14 R is a halogen atom or an alkoxy group, and each R 15 These are independently a halogen, an alkoxy group, or a monovalent organic group. The halogen is chlorine, bromine, fluorine, or iodine. The alkoxy group preferably has 1 to 3 carbon atoms. Blocked mercaptosilanes have the general formula BSR. 16 It has -Si-X3, the silyl group is available for reaction with silica in silica-silane reactions, and the blocking group B substitutes a mercapto hydrogen atom to block the reaction between the sulfur atom and the polymer. In the general formula above, B is a blocking group that can be in the form of an unsaturated heteroatom or a carbon directly bonded to sulfur via a single bond. 16 X is a C1-C6 linear or branched alkylidene, where each X is independently selected from the group consisting of C1-C4 alkyl or C1-C4 alkoxy.

[0080] Non-limiting examples of alkylalkoxysilanes suitable for use in certain embodiments of the 1st to 4th embodiments include octyltriethoxysilane, octyltrimethoxysilane, trimethylethoxysilane, cyclohexyltriethoxysilane, isobutyltriethoxysilane, ethyltrimethoxysilane, cyclohexyltributoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, propyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, nonyltriethoxysilane, and decyltriethoxysilane. Examples include, but are not limited to, dodecyltriethoxysilane, tetradecyltriethoxysilane, octadecyltriethoxysilane, methyloctyldiethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, octadecyl-trimethoxysilane, methyloctyldimethoxysilane, and mixtures thereof.

[0081] Non-limiting examples of bis(trialkoxysilylorgano) polysulfides suitable for use in certain embodiments of the first to fourth embodiments include bis(trialkoxysilylorgano) disulfides and bis(trialkoxysilylorgano) tetrasulfides. Specific non-limiting examples of bis(trialkoxysilylorgano) disulfides include 3,3'-bis(triethoxysilylpropyl) disulfide, 3,3'-bis(trimethoxysilylpropyl) disulfide, 3,3'-bis(tributoxysilylpropyl) disulfide, 3,3'-bis(tri-t-butoxysilylpropyl) disulfide, 3,3'-bis(trihexoxysilylpropyl) disulfide, and 2,2'-bis(dimethylmethoxysilylethyl) disulfide. Examples include, but are not limited to, sulfides, 3,3'-bis(diphenylcyclohexoxysilylpropyl) disulfide, 3,3'-bis(ethyl-di-sec-butoxysilylpropyl) disulfide, 3,3'-bis(propyldiethoxysilylpropyl) disulfide, 12,12'-bis(triisopropoxysilylpropyl) disulfide, 3,3'-bis(dimethoxyphenylsilyl-2-methylpropyl) disulfide, and mixtures thereof. Non-limiting examples of bis(trialkoxysilylorgano)tetrasulfide silica coupling agents suitable for use in certain embodiments of the first to fourth embodiments include, but are not limited to, bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropyl-benzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, and mixtures thereof.Bis(3-triethoxysilylpropyl)tetrasulfide is commercially available as Si69® from Evonik Degussa Corporation. In preferred embodiments of the first to fourth embodiments, the tire tread rubber composition comprises a silica coupling agent in the form of bis(trialkoxysilylorgano)polysulfide, more preferably bis(trialkoxysilylorgano)disulfide.

[0082] Non-limiting examples of mercaptosilanes suitable for use in certain embodiments of the first to fourth embodiments disclosed herein include, but are not limited to, 1-mercaptomethyltriethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 2-mercaptoethyltrippropoxysilane, 18-mercaptooctadecyldiethoxychlorosilane, and mixtures thereof.

[0083] Non-limiting examples of blocked mercaptosilanes suitable for use in certain embodiments of the first to fourth embodiments disclosed herein include, but are not limited to, those described in U.S. Patents 6,127,468, 6,204,339, 6,528,673, 6,635,700, 6,649,684, and 6,683,135 (these disclosures are incorporated herein by reference). Representative examples of blocked mercaptosilanes include 2-triethoxysilyl-1-ethylthioacetate, 2-trimethoxysilyl-1-ethylthioacetate, 2-(methyldimethoxysilyl)-1-ethylthioacetate, 3-trimethoxysilyl-1-propylthioacetate, triethoxysilylmethylthioacetate, trimethoxysilylmethylthioacetate, triisopropoxysilylmethylthioacetate, methyldiethoxysilylmethylthioacetate, methyldimethoxysilylmethylthioacetate, methyldiisopropoxysilylmethylthioacetate, dimethylethoxysilylmethylthioacetate, dimethylmethoxysilylmethylthioacetate, dimethylisopropoxysilylmethylthioacetate, 2-triisopropoxysilyl-1-ethylthioacetate, 2-(methyldiethoxysilyl)-1-ethylthioacetate, 2-( Methyldiisopropoxysilyl)-1-ethylthioacetate, 2-(dimethylethoxysilyl-1-ethylthioacetate, 2-(dimethylmethoxysilyl)-1-ethylthioacetate, 2-(dimethylisopropoxysilyl)-1-ethylthioacetate, 3-triethoxysilyl-1-propylthioacetate, 3-triisopropoxysilyl-1-propylthioacetate, 3-methyldiethoxysilyl-1-propyl- Oacetate, 3-methyldimethoxysilyl-1-propylthioacetate, 3-methyldiisopropoxysilyl-1-propylthioacetate, 1-(2-triethoxysilyl-1-ethyl)-4-thioacetylcyclohexane, 1-(2-triethoxysilyl-1-ethyl)-3-thioacetylcyclohexane, 2-triethoxysilyl-5-thioacetylnorbornene, 2-triethoxysilyl-4-thioacetylnorbornene,2-(2-triethoxysilyl-1-ethyl)-5-thioacetylnorbornene, 2-(2-triethoxy-silyl-1-ethyl)-4-thioacetylnorbornene, 1-(1-oxo-2-thia-5-triethoxysilylphenyl)benzoic acid, 6-triethoxysilyl-1-hexylthioacetate, 1-triethoxysilyl-5-hexylthioacetate, 8-triethoxysilyl-1-octylthioacetate, 1-triethoxysilyl-7-octylthioacetate, 6-triethoxysilyl-1-hexylthioacetate, 1- Triethoxysilyl-5-octylthioacetate, 8-trimethoxysilyl-1-octylthioacetate, 1-trimethoxysilyl-7-octylthioacetate, 10-triethoxysilyl-1-decylthioacetate, 1-triethoxysilyl-9-decylthioacetate, 1-triethoxysilyl-2-butylthioacetate, 1-triethoxysilyl-3-butylthioacetate, 1-triethoxysilyl-3-methyl-2-butylthioacetate, 1-triethoxysilyl-3-methyl-3-butylthioacetate, 3- Dimethoxysilyl-1-propylthiooctanoate, 3-triethoxysilyl-1-propyl-1-propylthiopalmitate, 3-triethoxysilyl-1-propylthiooctanoate, 3-triethoxysilyl-1-propylthiobenzoate, 3-triethoxysilyl-1-propylthio-2-ethylhexanoate, 3-methyldiacetoxysilyl-1-propylthioacetate, 3-triacetoxysilyl-1-propylthioacetate, 2-methyldiacetoxysilyl-1-ethylthioacetate, 2-triacetoxysilyl Lyl-1-ethylthioacetate, 1-methyldiacetoxysilyl-1-ethylthioacetate, 1-triacetoxysilyl-1-ethyl-thioacetate, tris-(3-triethoxysilyl-1-propyl)trithiophosphate, bis-(3-triethoxysilyl-1-propyl)methyldithiophosphonate, bis-(3-triethoxysilyl-1-propyl)ethyldithiophosphonate, 3-triethoxysilyl-1-propyldimethylthiophosphinate, 3-triethoxysilyl-1-propyldiethylthiophosphinate,Tris-(3-triethoxysilyl-1-propyl)tetrathiophosphate, bis-(3-triethoxysilyl-1-propyl)methyltrithiophosphonate, bis-(3-triethoxysilyl-1-propyl)ethyltrithiophosphonate, 3-triethoxysilyl-1-propyldimethyldithiophosphinate, 3-triethoxysilyl-1-propyldiethyldithiophosphinate, Tris-(3-methyldimethoxysilyl-1-propyl)trithiophosphate, bis-(3-methyldimethoxysilyl-1-propyl)-methyldithiophosphonate, bis-(3-methyldimethoxysilyl-1-propyl)-ethyldithiophosphonate, 3-methyldimethoxysilyl-1-propyldimethylthiophosphinate, 3-methyldimethoxysilyl-1-propyldiethylthiophosphinate, 3-triethoxysilyl-1-propylmethylthiophosphonate Examples include, but are not limited to, ruphet, 3-triethoxysilyl-1-propylmethanethiosulfate, 3-triethoxysilyl-1-propylethanethiosulfate, 3-triethoxysilyl-1-propylbenzenethiosulfate, 3-triethoxysilyl-1-propyltoluenethiosulfate, 3-triethoxysilyl-1-propylnaphthalenthiosulfate, 3-triethoxysilyl-1-propylxylentiosulfate, triethoxysilylmethylmethylthiosulfate, triethoxysilylmethylmethanethiosulfate, triethoxysilylmethylethanethiosulfate, triethoxysilylmethylbenzenethiosulfate, triethoxysilylmethyltoluenethiosulfate, triethoxysilylmethylnaphthalenthiosulfate, and triethoxysilylmethylxylentiosulfate. Various mixtures of blocked mercaptosilanes can be used. A further example of a blocked mercaptosilane suitable for use in certain exemplary embodiments is NXT® silane (3-octanoylthio-1-propyltriethoxysilane), available from Momentive Performance Materials Inc. (Albany, NY).

[0084] Examples of pre-treated silica (i.e., silica pre-surface-treated with silane) suitable for use in certain embodiments of the first to fourth embodiments disclosed herein include, but are not limited to, Ciptane® 255 LD and Ciptane® LP (PPG Industries) silica pre-treated with mercaptosilane, and Coupsil® 8113 (Degussa), a product of the reaction between organosilane bis(triethoxysilylpropyl) polysulfide (Si69) and Ultrasil® VN3 silica. Other examples include Coupsil 6508, Agilon 400® silica (PPG Industries), Agilon 454® silica (PPG Industries), and 458® silica (PPG Industries). In embodiments in which the silica includes pre-treated silica, the pre-treated silica is used in amounts already disclosed for silica fillers (i.e., 81–120 phr or about 90–about 120 phr, etc.).

[0085] In one embodiment of the first to fourth embodiments, when a silica coupling agent is used, the amount used may vary. In certain embodiments of the first to fourth embodiments, the rubber composition does not contain any silica coupling agent. In other preferred embodiments of the first to fourth embodiments, the silica coupling agent is present in an amount sufficient to provide ratios of total amount of silica coupling agent to silica filler of about 0.1:100 to about 1:5 (i.e., about 0.1 to about 20 parts by weight per 100 parts of silica), for example, 0.1:100 to 1:5, about 1:100 to about 1:10, 1:100 to 1:10, about 1:100 to about 1:20, 1:100 to 1:20, about 1:100 to about 1:25, and 1:100 to 1:25, as well as about 1:100 to about 0:100, and 1:100 to 0:100. In preferred embodiments of the first to fourth embodiments, the ratio of the total amount of silica coupling agent to the silica packing agent is within the range of 1:10 to 1:20 (i.e., 10 to 5 parts by weight per 100 parts of silica).In certain embodiments according to the first to fourth embodiments, the rubber composition contains a silica coupling agent in an amount of about 0.1 to about 15 phr, for example, 0.1 to 15 phr (e.g., 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 phr), about 0.1 to about 12 phr, 0.1 to 12 phr, about 0.1 to about 10 phr, 0.1 ~10 phr, approximately 0.1~7 phr, 0.1~7 phr, approximately 0.1~5 phr, 0.1~5 phr, approximately 0.1~3 phr, 0.1~3 phr, approximately 1~15 phr, 1~15 phr (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 phr), approximately 1~12 phr, 1~12 phr (for example, 1, 2, 3, 4 5, 6, 7, 8, 9, 10, 11, or 12 phr), approximately 1 to approximately 10 phr, 1 to 10 phr (for example, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10 phr), approximately 1 to approximately 7 phr, 1 to 7 phr, approximately 1 to approximately 5 phr, 1 to 5 phr, approximately 1 to approximately 3 phr, 1 to 3 phr , including about 3 to about 15 phr, 3 to 15 phr, about 3 to about 12 phr, 3 to 12 phr, about 3 to about 10 phr, 3 to 10 phr, about 3 to about 7 phr, 3 to 7 phr, about 3 to about 5 phr, 3 to 5 phr, about 5 to about 15 phr, 5 to 15 phr, about 5 to about 12 phr, 5 to 12 phr, about 5 to about 10 phr, 5 to 10 phr, about 5 to about 7 phr, or 5 to 7 phr. In preferred embodiments of the first to fourth embodiments, the rubber composition contains 8 to 12 phr, or one of the aforementioned ranges falling within this range, of the silica coupling agent.

[0086] Carbon black filler According to the first to fourth embodiments disclosed herein, the amount of carbon black filler used in the tire tread rubber composition is limited. More specifically, according to the first to fourth embodiments disclosed herein, the tire tread rubber composition contains 15 phr or less of carbon black filler (e.g., 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or even 0 phr), and in preferred embodiments of the first to fourth embodiments disclosed herein, the tire tread rubber composition contains 10 phr or less of carbon black filler (e.g., 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or even 0 phr). In certain embodiments of the first to fourth embodiments disclosed herein, the tire tread rubber composition contains about 5 to about 10 phr of carbon black, or 5 to 10 phr of carbon black (e.g., 5, 6, 7, 8, 9, or 10 phr). In certain embodiments of the first to fourth embodiments, the tire tread rubber composition contains 1 to 15 phr, 5 to 15 phr, 1 to 10 phr, 5 to 10 phr, 1 to 9 phr, 1 to 8 phr, 8 phr or less (e.g., 8, 7, 6, 5, 4, 3, 2, 1, or even 0 phr), 0 to 9 phr, or 0 to 8 phr of carbon black filler. In certain embodiments of the first to fourth embodiments, the tire tread rubber composition contains 0 phr of carbon black filler. In certain embodiments of the first to fourth embodiments, the aforementioned limited amounts of carbon black filler should be understood to refer to reinforced carbon black filler. In other embodiments of the first to fourth embodiments, the aforementioned limited amounts of carbon black filler should be understood to refer to unreinforced carbon black filler. In yet another embodiment of the first to fourth embodiments, the aforementioned limited amounts of carbon black filler should be understood to refer to all carbon black fillers (i.e., both reinforced and unreinforced carbon black fillers).

[0087] In the embodiments of the first to fourth embodiments in which a carbon black filler is present, the specific one or more types of carbon black used may vary. Generally, a suitable carbon black for use as a reinforcing filler in a rubber composition in a particular embodiment of the first to fourth embodiments is at least about 20 m 2 / g (at least 20m) 2 (including / g), and more preferably at least about 35m 2 / g ~ up to approximately 200m 2 / g or more (35m 2 / g ~ up to 200m 2This includes any of the commercially available carbon blacks having a surface area of ​​(including / g). The surface area values ​​used herein for carbon black are determined by ASTM D-1765 using the cetyltrimethyl-ammonium bromide (CTAB) technique. Useful carbon blacks include furnace black, channel black, and lamp black. More specifically, examples of useful carbon blacks include super abrasion furnace (SAF) black, high abrasion furnace (HAF) black, fast extrusion furnace (FEF) black, fine furnace (FF) black, intermediate super abrasion furnace (ISAF) black, semi-reinforcing furnace (SRF) black, moderately processable channel black, difficult-to-process channel black, and conductive channel black. Other carbon blacks that can be used include acetylene black. In certain embodiments of the first to fourth embodiments, the rubber composition comprises a mixture of two or more of the aforementioned blacks. Preferably, according to the first to fourth embodiments, if a carbon black filler is present, it consists of only one type (or grade) of reinforcing carbon black. Typical and suitable carbon blacks used in certain embodiments of the first to fourth embodiments are N-110, N-220, N-339, N-330, N-351, N-550, and N-660, as specified by ASTM D-1765-82a. The carbon black used can be in pelletized form or in non-pelletized cotton-like form. Preferably, non-pelletized carbon black is preferred for a more homogeneous mixture.

[0088] Other reinforcing fillers In certain embodiments of the first to fourth embodiments, the tire tread rubber composition includes reinforcing fillers other than carbon black or silica (i.e., additional reinforcing fillers). One or more additional reinforcing fillers may be used, but their total amount is preferably limited to 10 phr or less (e.g., 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0 phr) or 5 phr or less (e.g., 5, 4, 3, 2, 1 or 0 phr). In certain preferred embodiments of the first to fourth embodiments, the tire tread rubber composition does not contain additional reinforcing fillers (i.e., 0 phr), in other words, in such embodiments, there are no reinforcing fillers other than silica and optionally carbon black.

[0089] In the embodiments of the first to fourth embodiments, where additional reinforcing fillers are used, one or more additional reinforcing fillers may vary. Non-limiting examples of additional reinforcing fillers suitable for use in the tire tread rubber composition of certain embodiments of the first to fourth embodiments include, but are not limited to, alumina, aluminum hydroxide, clay (reinforcing grade), magnesium hydroxide, boron nitride, aluminum nitride, titanium dioxide, reinforcing zinc oxide, and combinations thereof.

[0090] Unreinforced filler In certain embodiments of the first to fourth embodiments, the tire tread rubber composition further comprises at least one non-reinforced filler. In other preferred embodiments of the first to fourth embodiments, the tire tread rubber composition does not contain a non-reinforced filler (i.e., 0 phr). In embodiments of the first to fourth embodiments in which at least one non-reinforced filler is utilized, the at least one non-reinforced filler may be selected from clay (non-reinforced grade), graphite, magnesium dioxide, aluminum oxide, starch, boron nitride (non-reinforced grade), silicon nitride, aluminum nitride (non-reinforced grade), calcium silicate, silicon carbide, pulverized rubber, and combinations thereof. The term "non-reinforced filler" is used for approximately 20 m 2 Less than / g (20m 2 In a particular embodiment, it is about 10 m (including less than / g).2 Less than / g (10m 2 The term is used to mean particulate materials having a nitrogen adsorption specific surface area (N2SA) of less than 1 / g. The N2SA surface area of ​​particulate materials can be determined according to various standard methods, including ASTM D6556. In certain embodiments, the term “unreinforced filler” refers, alternatively or further, to particulate materials having a particle size greater than about 1000 nm (including greater than 1000 nm). In those embodiments of the first to fourth embodiments, where the unreinforced filler is present in the rubber composition, the total amount of unreinforced filler can vary, but is preferably 10 phr or less (e.g., 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 phr), and in certain embodiments, 1 to 10 phr, 5 phr or less (e.g., 5, 4, 3, 2, or 1 phr), 1 to 5 phr, or 1 phr or less.

[0091] hydrocarbon resins As described above, according to the first and third embodiments, the tire tread rubber composition comprises (d) at least one hydrocarbon resin having a Tg of about 30 to about 50°C, or 30 to 50°C (e.g., 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 42, 44, 45, 46, 48, or 50°C) and a Tg of 30 to 40 phr (e.g., 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 phr). In preferred embodiments of the first and third embodiments, the at least one hydrocarbon resin (d) is an aromatic hydrocarbon resin. As described above, according to the second and fourth embodiments, the tire tread rubber composition comprises (d) at least one aromatic hydrocarbon resin with a Tg of about 30 to about 50°C, or 30 to 50°C (e.g., 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 42, 44, 45, 46, 48, or 50°C) and a Tg of 30 to 40 phr (e.g., 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 phr). In certain embodiments of the first to fourth embodiments, the tire tread rubber composition comprises (d) at least one of the aforementioned hydrocarbon resins having a Tg of about 30 to about 50°C or 30 to about 35 phr or 30 to 35 phr (e.g., 30, 31, 32, 33, 34, or 35 phr). The Tg of the hydrocarbon resin can be measured by DSC following the procedure discussed above for measuring the Tg of elastomers. In certain preferred embodiments of the first to fourth embodiments, at least one hydrocarbon resin of (d) may have a Tg of about 35 to about 50°C, 35 to 50°C (e.g., 30, 32, 34, 35, 36, 38, 40, 42, 44, 45, 46, 48, or 50°C), about 35 to about 45°C, or 35 to 45°C (e.g., 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, or 45°C), and may be present in one of the amounts considered above.As will be discussed in more detail below, according to the second and fourth embodiments, and in certain embodiments of the first and third embodiments, at least one hydrocarbon resin of (d) includes an aromatic resin.

[0092] In addition to controlling the amount of hydrocarbon resin (d) used in the tire tread rubber composition, it is also preferable to control the total amount (or sum) of plasticizers, i.e., hydrocarbon resin (d) and liquid plasticizer (e), within the amounts considered elsewhere in this specification, as will be further discussed below by the first to fourth embodiments.

[0093] According to the first to fourth embodiments, one or more hydrocarbon resins may be used in the tire tread rubber composition, and the specific types of one or more hydrocarbon resins may vary. When two or more hydrocarbon resins are used, the amounts discussed above should be understood to refer to the total amount of all hydrocarbon resins.

[0094] According to the second and fourth embodiments, and in certain embodiments of the first and third embodiments, the hydrocarbon resin of (d) optionally includes an aromatic resin in combination with one or more additional resins selected from aliphatic resins, cyclic aliphatic resins, and terpene resins, and in those embodiments of the first to fourth embodiments, the total amount of such additional resins is preferably 5 phr or less, less than 5 phr, less than 4 phr, less than 3 phr, less than 2 phr, or less than 1 phr (and in each case, 10% by weight or less, preferably 5% by weight or less, of the total amount of the hydrocarbon resin of (d)). In other embodiments of the first to fourth embodiments, the hydrocarbon resin of (d) consists of an aromatic hydrocarbon resin (only). When an aromatic resin is used, one or more aromatic hydrocarbon resins may be used. In certain preferred embodiments of the first to fourth embodiments, the hydrocarbon resin of (d) includes less than 5 phr of terpene resin, and preferably does not include any terpene resin (i.e., 0 phr of terpene resin is present in the tire tread rubber composition). As used herein, the terms aromatic resin or aromatic hydrocarbon resin should be understood to include both aromatic homopolymer resins and aromatic copolymer resins. An aromatic copolymer resin refers to a hydrocarbon resin comprising a combination of one or more aromatic monomers and one or more other (non-aromatic) monomers, wherein the maximum amount of any type of monomer is aromatic. An aromatic copolymer resin may include a hydrocarbon resin having 25% by weight of a cyclic aliphatic monomer and 30% by weight of an aliphatic monomer, in addition to 45% by weight of an aromatic monomer, and a hydrocarbon resin having 30% by weight of a cyclic aliphatic monomer and 15% by weight of an aliphatic monomer, in addition to 55% by weight of an aromatic monomer. In certain embodiments of the first to fourth embodiments, the hydrocarbon resin of (d) comprises one or more aromatic copolymer resins, wherein the majority of the weight of the total monomers (e.g., 51%, 55%, 60%, 65%, etc.) is aromatic.Non-limiting examples of aromatic resins suitable for use as hydrocarbon resin (d) in certain embodiments of the first to fourth embodiments include coumarone-indene resins and alkyl-phenol resins, as well as vinyl aromatic homopolymer or copolymer resins containing one or more of the following monomers: α-methylstyrene, styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, vinyltoluene, para(tert-butyl)styrene, methoxystyrene, chlorostyrene, hydroxystyrene, vinyl mesitylene, divinylbenzene, vinylnaphthalene, or any vinyl aromatic monomer obtained from the C9 fraction or C8-C10 fractions. Non-limiting examples of vinyl aromatic copolymer resins include vinyl aromatic / terpene copolymer resins (e.g., limonene / styrene copolymer resins), vinyl aromatic / C5 fraction resins (e.g., C5 fraction / styrene copolymer resins), and vinyl aromatic / aliphatic copolymer resins (e.g., CPD / styrene copolymer resins and DCPD / styrene copolymer resins). Non-limiting examples of alkylphenol resins include alkylphenol-acetylene resins such as p-tert-butylphenol-acetylene resins and alkylphenol-formaldehyde resins (e.g., resins with a low degree of polymerization). Exemplary such aromatic resins are commercially available under various trade names from various companies, including Chemfax, Dow Chemical Company, Eastman Chemical Company, Idemitsu, Neville Chemical Company, Nippon, Polysat Inc., Resinall Corp., and Zeon.

[0095] In certain embodiments of the first to fourth embodiments, the hydrocarbon resin (d) comprises an aromatic resin based on one or more of the vinyl aromatic monomers described above (e.g., styrene, α-methylstyrene), wherein in certain such embodiments, at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, at least 99% by weight, or even 100% by weight of the monomers in the aromatic resin are aromatic monomers. In certain embodiments of the first to fourth embodiments, the hydrocarbon resin (d) comprises an aromatic resin based on one or more of the vinyl aromatic monomers described above (e.g., styrene, α-methylstyrene), wherein in certain such embodiments, at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, at least 99% by weight, or even 100% by weight of the monomers in the aromatic resin are aromatic monomers. In certain embodiments of the first to fourth embodiments, the aromatic resin of (d) may comprise a hydrogenated form of one of the above aromatic resins (i.e., a hydrogenated aromatic resin). In other embodiments of the first to fourth embodiments, the aromatic resin of (d) excludes any hydrogenated aromatic resin; in other words, in such embodiments, the aromatic resin is not hydrogenated.

[0096] As described above, in certain embodiments of the first to fourth embodiments, at least one hydrocarbon resin of (d) comprises (i) an aromatic resin in combination with (ii) an aliphatic resin. Non-limiting examples of aliphatic resins include C5 fraction homopolymers and copolymer resins. The amount of any aliphatic resin used in (d) is preferably limited. According to the first to fourth embodiments, the total amount of any aliphatic resin used in combination with the aromatic resin is preferably 5 phr or less, less than 5 phr, less than 4 phr, less than 3 phr, less than 2 phr, or less than 1 phr (and in each case, 20% by weight or less, preferably 15% by weight or less, or 10% by weight or less, of the total amount of hydrocarbon resin of (d)).

[0097] As described above, in certain embodiments of the first to fourth embodiments, at least one hydrocarbon resin of (d) comprises (i) an aromatic resin in combination with (ii) a cyclic aliphatic resin. Non-limiting examples of the cyclic aliphatic resin include cyclopentadiene ("cyclopentadiene, CPD") homopolymer or copolymer resins, dicyclopentadiene ("dicyclopentadiene, DCPD") homopolymer or copolymer resins, and combinations thereof. The amount of any cyclic aliphatic resin used in (d) is preferably limited. According to the first to fourth embodiments, the total amount of any cyclic aliphatic resin used in combination with the aromatic resin is preferably 5 phr or less, less than 5 phr, less than 4 phr, less than 3 phr, less than 2 phr, or less than 1 phr (and in each case, 20% by weight or less, preferably 15% by weight or less, or 10% by weight or less, of the total amount of hydrocarbon resin of (d)).

[0098] As described above, in certain embodiments of the first to fourth embodiments, at least one hydrocarbon resin of (d) comprises (i) an aromatic resin in combination with (ii) a terpene resin. Non-limiting examples of terpene resins include α-pinene resins, β-pinene resins, limonene resins (e.g., L-limonene, D-limonene, dipentene which is a racemic mixture of L-isomers and D-isomers), β-phellandrene, δ-3-carene, δ-2-carene, and combinations thereof. The amount of any terpene resin used in (d) is preferably limited. According to the first to fourth embodiments, the total amount of any terpene resin used in combination with the aromatic resin is preferably 5 phr or less, less than 5 phr, less than 4 phr, less than 3 phr, less than 2 phr, or less than 1 phr (and in each case, 20% by weight or less, preferably 15% by weight or less, or 10% by weight or less, of the total amount of hydrocarbon resin in (d)). As described above, in the preferred embodiments of the first to fourth embodiments, the hydrocarbon resin (d) does not contain a terpene resin (i.e., 0 phr).

[0099] In certain preferred embodiments of the first to fourth embodiments, the hydrocarbon resin (d) has a softening point of about 70 to about 100°C or 70 to 100°C (e.g., 70, 75, 80, 85, 90, 95, or 100°C), preferably about 75 to about 95°C or 75 to 95°C (e.g., 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or 95°C), more preferably about 80 to about 90°C or 80 to 90°C (e.g., 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, or 90°C). Generally, the softening point of a hydrocarbon resin has a relationship with its Tg such that the Tg is lower than the softening point, and the lower the Tg, the lower the softening point. As a non-limiting example, in the case of two hydrocarbon resins with Tgs of 70°C and 100°C, the resin with a Tg of 70°C has a lower softening point than the resin with a Tg of 100°C.

[0100] In certain embodiments of the first to fourth embodiments, the hydrocarbon resin (d) satisfies at least one of the following: (a) 1000 to about 4000 grams / mol, 1000 to 4000 grams / mol (e.g., 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, or 4 1000 grams / mol), approximately 1000 to approximately 3000 grams / mol, 1000 to approximately 3000 grams / mol (for example, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, or 3000 grams / mol), approximately 1000 to approximately 2500 grams / mol, 1000 to approximately 2500 grams / mol (for example, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 19 (b) Mw of 00, 2000, 2100, 2200, 2300, 2400, or 2500 grams / mol), about 1000 to about 2000 grams / mol, 1000 to 2000 grams / mol (e.g., 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, or 2000 grams / mol), about 1100 to about 1800 grams / mol, or 1100 to 1800 grams / mol (e.g., 1100, 1200, 1300, 1400, 1500, 1600, 1700, or 1800 grams / mol), (b) about 700 to about 1 500 grams / mol, 700-1500 grams / mol (e.g., 700, 800, 900, 1000, 1100, 1200, 1300, 1400, or 1500 grams / mol), approximately 800-1400 grams / mol, 800-1400 grams / mol (e.g., 800, 900, 1000, 1100, 1200, 1300, or 1400 grams / mol), approximately 800-1300 grams / mol, 800-1300 grams / mol (e.g., 800, 900, 1000, 1100, 1200, or 1300 grams / mol), approximately 900-1200 grams / mol,Or Mn of 900-1200 grams / mol (e.g., 900, 950, 1000, 1050, 1100, 1150, or 1200 grams / mol), or (c) about 1-2, 1-2 (e.g., 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2), about 1.1-1.8, 1.1-1.8 ( For example, polydispersity (Mw / Mn) of 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, or 1.8), about 1.1 to about 1.7, 1.1 to 1.7 (for example, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, or 1.7), about 1.2 to about 1.5, or 1.2 to 1.5 (for example, 1.2, 1.3, 1.4, or 1.5). In certain preferred embodiments of the first to fourth embodiments, the hydrocarbon resin (d) has Mw according to one of the above ranges, combined with Mn according to one of the above ranges, and further combined with Mw / Mn according to one of the above ranges. In certain such embodiments, the hydrocarbon resin (d) is an aromatic resin.

[0101] In certain embodiments of the first to fourth embodiments, the hydrocarbon resin (d) is at least about 40% by weight, at least 40% by weight (e.g., 40, 45, 50, 51, 55, 60% by weight, or more), about 40% to about 65% by weight, 40% to about 65% by weight (e.g., 40, 42, 44, 45, 46, 48, 50, 52, 54, 55, 56, 58, 60, 62, 64, or 65% by weight), at least about 45% by weight, at least 45% by weight (e.g., 45, 50, 51, 55, 60% by weight, or more), about 45% to about 65% by weight, 45% to about 65% by weight (e.g., 45, 47, 49, 50, 51, 53, 55, 57 The aromatic resins (as discussed above) have aromatic monomer content of 59, 60, 61, 63, or 65% by weight, at least 51% by weight (e.g., 51, 55, 60, 65%, or more), about 51% to about 65% (e.g., 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, or 65%), 51% to about 65%, about 51% to about 60%, 51% to about 60% (e.g., 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, or 60%), about 51% to about 55%, or 51% to about 55% (e.g., 51, 52, 53, 54, or 55%). The amount of aromatic monomer content is a weight percentage based on the total weight of each hydrocarbon resin.

[0102] Liquid plasticizers (including oils and non-oils) As described above, according to the first to fourth embodiments, the tire tread rubber composition comprises 15 to 30 phr of liquid plasticizer (e.g., 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 phr). In certain embodiments of the first to fourth embodiments, the tire tread rubber composition comprises 15 to 25 phr of liquid plasticizer (e.g., 15, 16, 17, 28, 19, 20, 21, 22, 23, 24, or 25 phr), 15 to 20 phr of liquid plasticizer (e.g., 15, 16, 17, 18, 1, or 20 phr), or 20 to 25 phr of liquid plasticizer (e.g., 20, 21, 22, 23, 24, or 25 phr). The term liquid plasticizer refers to a plasticizer component that is liquid at room temperature (i.e., liquid above 25°C) and is used to distinguish it from hydrocarbon resin plasticizers that are generally solid at room temperature. Generally, liquid plasticizers will have a Tg below 0°C, generally well below -30°C, below -40°C, or below -50°C. In certain embodiments of the first to fourth embodiments, the liquid plasticizer has a Tg of below 0°C to -100°C, a Tg of -30°C to -100°C, or a Tg of -50°C to -100°C. As will be discussed in more detail below, liquid plasticizers include both oils (e.g., petroleum oils and vegetable oils) and other non-oil liquid plasticizers, including but not limited to ether plasticizers, ester plasticizers, phosphate plasticizers, and sulfonate plasticizers. Furthermore, the term liquid plasticizer means that it encompasses both free oils (usually added during the compounding process) and drawable oils (used to draw out rubber). Therefore, by mentioning that the tire tread rubber composition contains 15-30 phr of liquid plasticizer, it should be understood that the total amount of any free liquid plasticizer (both oil-based and non-oil-based liquid plasticizers) and any draw oil is 15-30 phr. In certain embodiments of the first and third embodiments, the tire tread rubber composition contains only free liquid plasticizer in one of the aforementioned amounts (e.g., 15-30 phr, 15-25, 15-20, 20-25 phr, etc.).In other embodiments of the first and third embodiments, and in certain embodiments of the second and fourth embodiments, the tire tread rubber composition contains only the spreader oil in one of the aforementioned amounts (e.g., 15-30 phr, 15-25, 15-20, 20-25 phr, etc.). In yet other (preferred) embodiments of the first to fourth embodiments, the tire tread rubber composition contains both a free liquid plasticizer and a spreader oil, wherein at least 50% by weight (e.g., 50%, 55%, 60%, 65%, 70%, 75%, 80% or more), preferably at least 60% by weight of the liquid plasticizer in the tire tread rubber composition is provided by an oil from an oil-spreadable polymer, e.g., the oil-spreadable SBR of (ii). In certain embodiments of the first to fourth embodiments, 60-80% by weight, 60-90% by weight, 60-100%, 70-80% by weight, 70-90% by weight, 70-100% by weight, 80-90% by weight, 80-100% by weight, or 90-100% by weight of liquid plasticizer in the tire tread rubber composition is provided from an oil-spreadable polymer, e.g., oil-spreadable SBR of (i). In those embodiments of the first to fourth embodiments in which the oil-spreadable rubber is used, the amount of oil used to prepare the oil-spreadable rubber may vary. In the embodiments of the first and third embodiments in which an oil-spreadable rubber is used (e.g., an oil-spreadable SBR for (i)), and according to the second and fourth embodiments in which the SBR of (i) is oil-spread, the amount of oil used to prepare the oil-spreadable rubber may vary, and in certain such embodiments, the amount of spreading oil present in the oil-spreadable rubber (polymer) or SBR is 10 to 50 parts of oil per 100 parts of rubber (e.g., 10, 15, 20, 25, 30, 35, 40, 45, or 50 parts of oil per 100 parts of rubber), preferably 10 to 40 parts of oil per 100 parts of rubber or 20 to 40 parts of oil per 100 parts of rubber. As a non-limiting example, the spreader oil may be used in the SBR of (i) in an amount of 40 parts oil per 100 parts rubber, where 40 parts SBR (40 parts is the amount of polymer of the oil-spreadable SBR, as discussed earlier) is used throughout the tread rubber composition, and therefore the amount of oil contributed to the tire tread rubber composition by the oil-spreadable SBR would be 16 phr.Oil spreading of rubber (particularly styrene-butadiene rubber) can be beneficial to the ease of processing or mixing when the SBR has a relatively high Mw and / or a relatively high Mooney viscosity. In certain embodiments of the first to fourth embodiments disclosed herein, the styrene-butadiene rubber used in (i) has a polymer Mooney viscosity of at least 100 ML at 100°C. 1+4 It is an oil-spreadable styrene-butadiene rubber having [a certain property]. Polymer Mooney viscosity means the Mooney viscosity of the rubber or polymer before oil spreading. When the oil-spreadable rubber is used in the elastomer components of the tire tread rubber compositions disclosed herein, the amounts specified for (i) (and (ii)) should be understood to refer to the amount of rubber only, and not the amount of oil-spreadable rubber. As used herein, oil refers to both petroleum oils (e.g., aromatic oils, naphthenic oils, and low PCA oils) and vegetable oils (such as those that can be harvested from vegetables, nuts, and seeds). Vegetable oils generally contain triglycerides, and this term should be understood to include synthetic triglycerides and those actually derived from plants.

[0103] According to the first to fourth embodiments, various types of processing oils and drawer oils may be used as at least one liquid plasticizer, including but not limited to aromatic, naphthenic, and low-PCA oils (petroleum-derived or plant-derived). Suitable low-PCA oils include those having a polycyclic aromatic content of less than 3 weight percent as measured by the IP346 method. The IP346 method procedure can be found in Standard Methods for Analysis & Testing of Petroleum and Related Products and British Standard 2000 Parts, 2003, 62nd edition, published by the Institute of Petroleum (UK). Exemplary petroleum-derived low-PCA oils include mild extraction solvate (MES), treated distillate aromatic extract (TDAE), TRAE, and heavy naphthenic oils. Exemplary MES oils are commercially available as CATENEX SNR (SHELL), PROREX 15 and FLEXON 683 (EXXONMOBIL), VIVATEC 200 (BP), PLAXOLENE MS (TOTAL FINA ELF), TUDALEN 4160 / 4225 (DAHLEKE), MES-H (REPSOL), MES (Z8), and OLIO MES S201 (AGIP). Exemplary TDAE oils are available as TYREX 20 (EXXONMOBIL), VIVATEC 500, VIVATEC 180, and ENERTHENE 1849 (BP), and EXTENSOIL 1996 (REPSOL). Exemplary heavy naphthenic oils are available as SHELLFLEX 794, ERGON BLACK OIL, ERGON H2000, CROSS C2000, CROSS C2400, and SAN JOAQUIN 2000L. Exemplary low PCA oils also include various plant-derived oils, such as those harvested from vegetables, nuts, and seeds.Non-limiting examples include, but are not limited to, soybean oil, sunflower oil (including high-oleic sunflower oil), safflower oil, corn oil, linseed oil, cottonseed oil, rapeseed oil, cashew oil, sesame oil, camellia oil, jojoba oil, macadamia nut oil, coconut oil, and palm oil. The aforementioned processed oils can also be used as spreadable oils, i.e., for the preparation of oil-spreadable polymers or copolymers, or as processed oils or free oils.

[0104] As described above, according to the first to fourth embodiments, the liquid plasticizer may, in certain embodiments, include non-oil plasticizers, non-limiting examples of which include ether plasticizers, ester plasticizers, phosphate plasticizers, and sulfonate plasticizers. In embodiments where a non-oil plasticizer is present, preferably only a portion of the liquid plasticizer (e.g., less than 50%, 40% or less, 30% or less, 20% or less, 10% or less, or even 5% or less) is provided by the non-oil plasticizer. Exemplary ether plasticizers include polyethylene glycol and polypropylene glycol. Exemplary ester plasticizers include triesters and diesters in particular (which may be selected from the group consisting of diesters and triesters of carboxylic acids, diesters and triesters of phosphoric acid, or diesters and triesters of sulfonic acid, and mixtures thereof). More specifically, exemplary carboxylic acid ester plasticizers include compounds selected from the group consisting of trimellitic acid, pyromellitic acid, phthalic acid, 1,2-cyclohexanedicarboxylic acid, azidic acid, azelate, sebacate, glycerol triesters, and mixtures thereof. More specifically, with respect to glycerol triesters, these may contain more than 50% by weight, more preferably more than 80% by weight, of unsaturated C18 fatty acids (e.g., oleic acid, linoleic acid, linolenic acid, and mixtures thereof). Other exemplary carboxylic acid ester plasticizers include stearates, ricinoleates, phthalates (e.g., di-2-ethylhexyl phthalate and diosodesyl phthalate), isophthalates, tetrahydrophthalates, adipates (e.g., di(2-ethylhexyl)adipate and diisooctyladipate), malates, sebaicates (e.g., di(2-ethylhexyl)sebacate and diisooctylsebacate), and fumarates.Examples of exemplary phosphate plasticizers include those having trihydrocarbyl phosphate and dihydrocarbyl phosphate structures (where each hydrocarbyl is independently selected from C1-C12 alkyl, preferably C1-C8 alkyl, and C6-C12 aromatic (both substituted and unsubstituted), preferably aromatic C6, which is either substituted or unsubstituted). More specifically, examples of phosphate plasticizers include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, dioctyl phosphate, 2-ethylhexyldiphenyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyldiphenyl phosphate, isodecyldiphenyl phosphate, tricresyl phosphate, trityl phosphate, trixylenyl phosphate, tris(chloroethyl) phosphate, and diphenyl mono-o-xenyl phosphate. Examples of sulfonate plasticizers include sulfonic acid esters such as sulfonbutylamide, toluenesulfonamide, N-ethyl-toluenesulfonamide, and N-cyclohexyl-p-toluenesulfonamide. Among the aforementioned non-oil liquid plasticizers, phosphate plasticizers, particularly phosphate derivatives (which can be understood as phosphate esters), are preferred.

[0105] According to the first to fourth embodiments, the Tg of the oil used can vary. In certain embodiments of the first to fourth embodiments, any oil used may have a Tg of about -40 to about -100°C, -40 to -100°C (e.g., -40, -45, -50, -55, -60, -65, -70, -75, -80, -85, -90, -95, or -100°C), about -40 to about -90°C, -40 to -90°C (e.g., -40, -45, -50, -55, -60, It has a Tg of -65, -70, -75, -80, -85, or -90°C), approximately -45 to approximately -85°C, -45 to -85°C (for example, -45, -50, -55, -60, -65, -70, -75, -80, or -85°C), approximately -50 to approximately -80°C, or -50 to -80°C (for example, -50, -55, -60, -65, -70, -75, or -80°C).

[0106] In certain embodiments of the first to fourth embodiments, the tire tread rubber composition contains less than 5 phr of MES or TDAE oil (e.g., 4.5, 4, 3, 2, 1, or 0 phr), or no MES or TDAE oil at all (i.e., 0 phr). In preferred embodiments of the first to fourth embodiments, the tire tread rubber composition contains vegetable oil as at least a portion of at least one liquid plasticizer(e). In certain embodiments of the first to fourth embodiments, the tire tread rubber composition does not contain petroleum-based oil (i.e., 0 phr), and instead, any oil used is a vegetable oil. In certain embodiments of the first to fourth embodiments, the tire tread rubber composition contains soybean oil in one of the amounts described above. In certain embodiments of the first to fourth embodiments, the tire tread rubber composition does not contain sunflower oil (i.e., 0 phr).

[0107] In certain embodiments of the first to fourth embodiments, the tire tread rubber composition comprises one or more ester-based plasticizers. Suitable ester-based plasticizers are known to those skilled in the art and include, but are not limited to, phosphate esters, phthalate esters, adipic esters, and oleate esters (i.e., derived from oleic acid). Given that esters are chemical compounds derived from acids in which at least one -OH group is substituted with an -O-alkyl group, a variety of alkyl groups may be used in suitable ester-based plasticizers for use in tire tread rubber compositions, including C1-C20 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20) or generally linear or branched alkyl groups of C6-C12. Certain of the aforementioned esters are based on acids having two or more -OH groups and can therefore be adapted to one or more O-alkyl groups (e.g., trialkyl phosphate, dialkyl phthalate, dialkyl adipate). Non-limiting examples of suitable ester plasticizers include trioctyl phosphate, dioctyl phthalate, dioctyl adipate, nonyl oleate, octyl oleate, and combinations thereof. The use of ester plasticizers, such as one or more of the aforementioned, may be beneficial to the snow or ice performance of tires made from tread rubber compositions containing such ester plasticizers, at least in part due to the relatively low Tg of the ester plasticizers. In certain embodiments of the first to fourth embodiments, the tire tread rubber composition comprises one or more ester plasticizers having a Tg of -40°C to -70°C (e.g., -40, -45, -50, -55, -60, -65, or -70°C) or -50°C to -65°C (e.g., -50, -51, -52, -53, -54, -55, -56, -57, -58, -59, -60, -61, -62, -63, -64, or -65°C). In those embodiments of the first to fourth embodiments in which one or more ester plasticizers are used, the amounts used may vary.In certain embodiments of the first to fourth embodiments, one or more ester plasticizers are used in total amounts of 1 to 12 phr (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 phr), 1 to 10 phr (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 phr), 2 to 6 phr (e.g., 2, 3, 4, 5, or 6 phr), or 2 to 5 phr (e.g., 2, 3, 4, or 5 phr). In certain embodiments of the first to fourth embodiments, one or more ester plasticizers are used in combination with oil in one of the aforementioned amounts.

[0108] Hydrocarbon resin + liquid plasticizer As described above, according to the first to fourth embodiments disclosed herein, the total amount of at least one hydrocarbon resin (d) and at least one liquid plasticizer (e) is 45 to 60 phr (e.g., 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60 phr). In certain preferred embodiments of the first to fourth embodiments, the total amount of hydrocarbon resin (d) and liquid plasticizer (e) is 45 to 55 phr (e.g., 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, or 55 phr). In certain embodiments of the first to fourth embodiments, the total amount of hydrocarbon resin (d) and liquid plasticizer (e) is 59 phr or less (e.g., 59, 58, 57, 56, 55, 54, 50 phr, or less). In certain embodiments of the first to fourth embodiments, the total amount of hydrocarbon resin (d) and liquid plasticizer (e) is 55 phr or less (e.g., 55, 54, 53, 52, 51, 50, 49 phr, or less). In certain embodiments of the first to fourth embodiments, the total amount of hydrocarbon resin (d) and liquid plasticizer (e) is 45 to 59 phr (e.g., 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, or 59 phr), 45 to 55 phr (e.g., 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, or 55 phr), 45 to 54 phr (e.g., 45, 46, 47, 48, 49, 50, 51, These are 52, 53, 54 phr), 45-50 phr (e.g., 45, 46, 47, 48, 49, 50, 51, 52, 53, or 54 phr), 50-60 phr (e.g., 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60 phr), 50-59 phr (e.g., 51, 52, 53, 54, 55, 56, 57, 58, or 59 phr), or 50-55 phr (e.g., 50, 51, 52, 53, 54, or 55 phr).

[0109] In certain preferred embodiments of the first to fourth embodiments, the amount of hydrocarbon resin (d) is greater than the amount of liquid plasticizer (e). In certain such embodiments, the hydrocarbon resin (d) and liquid plasticizer (e) are present in a weight ratio of at least 1.4:1, preferably 1.4:1 to 3:1 (e.g., 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, or 3:1), more preferably 1.4:1 to 2:1 (e.g., 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1).

[0110] Hardened package As discussed above, according to the first to fourth embodiments disclosed herein, the tire tread rubber composition includes a curing package. The components of the curing package may vary depending on the first to fourth embodiments, but generally, the curing package includes at least one of a vulcanizing agent, a vulcanization accelerator, a vulcanization activator (e.g., zinc oxide, stearic acid, etc.), a vulcanization inhibitor, and a scorch inhibitor. In certain embodiments of the first to fourth embodiments, the curing package includes at least one vulcanizing agent, at least one vulcanization accelerator, at least one vulcanization activator, and optionally, a vulcanization inhibitor and / or a scorch inhibitor. The vulcanization accelerator and vulcanization activator act as catalysts for the vulcanizing agent. Various vulcanization inhibitors and scorch inhibitors are known in the art and can be selected by those skilled in the art based on desired vulcanization properties.

[0111] Examples of suitable types of vulcanizing agents for use in certain embodiments of the first to fourth embodiments include, but are not limited to, sulfur or peroxide-based curing components. Therefore, in certain such embodiments, the curing component may be a sulfur-based curing agent or a peroxide-based curing agent. In preferred embodiments of the first to fourth embodiments, the vulcanizing agent is a sulfur-based curing agent, and in certain such embodiments, the vulcanizing agent consists of a sulfur-based curing agent (only). Examples of specific suitable sulfur vulcanizing agents include sulfur-donating curing agents such as soluble sulfur, disulfide amines, polymeric polysulfides, or sulfur olefin adducts from "rubbermaker," and insoluble polymeric sulfur. Preferably, the sulfur vulcanizing agent is soluble sulfur, or a mixture of soluble sulfur polymer and insoluble sulfur polymer. For a general disclosure of suitable curing agents and other components used in curing (e.g., vulcanization inhibitors and scorch inhibitors), refer to Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd ed., Wiley Interscience, NY 1982, Vol. 20, pp. 365-468, in particular Vulcanization Agents and Auxiliary Materials, pp. 390-402, or Vulcanization by AYCoran (Encyclopedia of Polymer Science and Engineering, Second Edition (1989 John Wiley & Sons, Inc.)), both of which are incorporated herein by reference. The vulcanizing agents can be used alone or in combination. In general, in certain embodiments of the first to fourth embodiments, the vulcanizing agent may be used in amounts ranging from 0.1 to 10 phr (e.g., 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 phr), for example, 1 to 7.5 phr (e.g., 1, 2, 3, 4, 5, 6, 7, or 7.5 phr), for example, 1 to 5 phr (e.g., 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 phr), and preferably 1 to 3.5 phr (e.g., 1, 1.5, 2, 2.5, 3, or 3.5 phr).

[0112] Vulcanization accelerators are used to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanized product. Examples of suitable vulcanization accelerators for use in certain embodiments of the first to fourth embodiments disclosed herein include, but are not limited to, thiazole vulcanization accelerators, such as 2-mercaptobenzothiazole, 2,2'-dithiobis(benzothiazole) (MBTS), N-cyclohexyl-2-benzothiazole sulfenamide (CBS), and N-tert-butyl-2-benzothiazole sulfenamide (TBBS); guanidine vulcanization accelerators, such as diphenyl guanidine (DPG); thiram vulcanization accelerators; and carbamic acid vulcanization accelerators. Generally, the amount of vulcanization accelerator used is in the range of 0.1 to 10 phr (e.g., 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 phr), preferably 0.5 to 5 phr (e.g., 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 phr). Preferably, any vulcanization accelerator used in the tire tread rubber composition of the first to fourth embodiments is any thiuram such as thiuram monosulfide and thiuram polysulfide (for example, TMTM (tetramethyl thiuram monosulfide), TMTD (tetramethyl thiuram disulfide), DPTT (dipentamethylene thiuram tetrasulfide), TETD (tetraethyl thiuram disulfide), TiBTD (tetraisobutyl thiuram disulfide), and TBzTD (tetrabenzyl thiuram) Excluding disulfides (such as tetrabenzyl thiuram disulfide), in other words, the tire tread rubber compositions of the first to fourth embodiments preferably do not contain thiuram promoters (i.e., 0 phr).

[0113] Vulcanization activators are additives used to assist in vulcanization. Generally, vulcanization activators contain both inorganic and organic components. Zinc oxide is the most widely used inorganic vulcanization activator. Various organic vulcanization activators, including stearic acid, palmitic acid, lauric acid, and the respective zinc salts mentioned above, are commonly used. Generally, in certain embodiments of the first to fourth embodiments, the amount of vulcanization activator used is in the range of 0.1 to 6 phr (e.g., 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, or 6 phr), preferably 0.5 to 4 phr (e.g., 0.5, 1, 1.5, 2, 2.5, 3, 3.5, or 4 phr). In certain embodiments of the first to fourth embodiments, one or more vulcanization activators containing one or more thiourea compounds (used in one of the amounts mentioned above) are used and optionally combined with one or more of the vulcanization activators mentioned above. Generally, thiourea compounds have a structure (R 1 )(R 2 )NS(=C)N(R 3 )(R 4 It can be understood as a compound having ), where R 1 , R 2 , R 3 , and R 4 Each of these is independently selected from H, alkyl, aryl, and N-containing substituents (e.g., guanyl). Optionally, two of the aforementioned structures can be bonded together in the dithioviurea compound via N (by removing one of the R groups). In certain embodiments, R 1 or R 2 On the other hand, and R 3 or R 4 One of them can be bonded together with one or more methylene groups (-CH2-) between them. In certain embodiments of the first to fourth embodiments, thiourea is R selected from one of the aforementioned groups. 1 , R 2 , R 3 , and R 4It has one or two of the following groups, and the remaining R group is hydrogen. Examples of alkyl groups include C1-C6 linear, branched, or cyclic groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, and cyclohexyl. Examples of aryl groups include C6-C12 aromatic groups such as phenyl, tolyl, and naphthyl. Examples of thiourea compounds include, but are not limited to, dihydrocarbylthioureas such as dialkylthioureas and diarylthioureas. Non-limiting examples of specific thiourea compounds include one or more of the following: thiourea, N,N'-diphenylthiourea, trimethylthiourea, N,N'-diethylthiourea (DEU), N,N'-dimethylthiourea, N,N'-dibutylthiourea, ethylenethiourea, N,N'-diisopropylthiourea, N,N'-dicyclohexylthiourea, 1,3-di(o-tolyl)thiourea, 1,3-di(p-tolyl)thiourea, 1,1-diphenyl-2-thiourea, 2,5-dithioviurea, guanylthiourea, 1-(1-naphthyl)-2-thiourea, 1-phenyl-2-thiourea, p-tolylthiourea, and o-tolylthiourea. In certain embodiments of the first to fourth embodiments, the activator comprises at least one thiourea compound selected from thiourea, N,N'-diethylthiourea, trimethylthiourea, N,N'-diphenylthiourea, and N-N'-dimethylthiourea.

[0114] Vulcanization inhibitors are generally used to control the vulcanization process, typically by delaying or inhibiting vulcanization until a desired time and / or temperature is reached. Common vulcanization inhibitors include, but are not limited to, PVI from Santogard and cyclohexylthiophthalmide. Generally, in certain embodiments of the first to fourth embodiments, the amount of vulcanization inhibitor is 0.1 to 3 phr (e.g., 0.1, 0.5, 1, 1.5, 2, 2.5, or 3 phr), preferably 0.5 to 2 phr (e.g., 0.5, 1, 1.5, or 2 phr).

[0115] Preparation of rubber composition The specific steps involved in the preparation of the tire tread rubber compositions of the first to fourth embodiments disclosed herein are generally steps of conventionally practiced methods, which include mixing the components in at least one non-production masterbatch step and a final production mixing step. In certain embodiments of the first to fourth embodiments, the tire tread rubber composition is prepared by mixing the components of the rubber composition (such as those disclosed above) by methods known in the art, such as kneading the components together in a Banbury mixer or milled roll. Such methods generally include at least one non-production masterbatch mixing step and a final production mixing step. The term non-production masterbatch step is known to those skilled in the art and is generally understood to be a mixing step (one or more) in which neither vulcanizing agents nor vulcanization accelerators are added. The term final production mixing step is also known to those skilled in the art and is generally understood to be a mixing step in which vulcanizing agents and vulcanization accelerators are added to the rubber composition. In certain embodiments of the first to fourth embodiments, the tire tread rubber composition is prepared by a process that includes two or more non-production masterbatch mixing steps.

[0116] In certain embodiments of the first to fourth embodiments, the tire tread rubber composition is prepared by a process in which the masterbatch mixing stage includes at least one of tandem mixing or intermeshing mixing. Tandem mixing can be understood as including the use of a mixer having two mixing chambers, each chamber having a pair of mixing rotors, and generally the two mixing chambers are stacked together with an upper mixer which is a primary mixer, and the lower mixer receives batches from the upper or primary mixer. In certain embodiments, the primary mixer utilizes intermeshing rotors, and in other embodiments, the primary mixer utilizes tangential rotors. Preferably, the lower mixer utilizes intermeshing rotors. Intermeshing mixing can be understood as including the use of a mixer having intermeshing rotors. Intermeshing rotors refer to a set of rotors in which the larger diameter of one rotor in the set interacts with the smaller diameter of an opposing rotor in the set so that the rotors intermesh each other. The intermeshing rotors must be driven at a uniform speed due to the interaction between the rotors. In contrast to meshing rotors, tangential rotors refer to a pair of rotors in which each rotor rotates independently of the others within a cavity that may be called a side. Generally, mixers with tangential rotors include a ram, which is not necessary for mixers with meshing rotors.

[0117] Generally, rubber (or polymer) and at least one reinforcing filler (and optional silane coupling agents and liquid plasticizers) are added during the non-production or masterbatch mixing stage. Generally, at least the vulcanizing agent and vulcanization accelerator components of the cured package will be added during the final or production mixing stage.

[0118] In certain embodiments of the first to fourth embodiments, the tire tread rubber composition is prepared using a process in which at least one non-production masterbatch mixing step is carried out at a temperature of about 130°C to about 200°C. In certain embodiments of the first to fourth embodiments, the tire tread rubber composition is prepared using a final production mixing step carried out at a temperature below the vulcanization temperature to avoid undesirable pre-curing of the rubber composition. Thus, the temperature of the production or final mixing step should generally not exceed about 120°C, and is typically about 40°C to about 120°C, or about 60°C to about 110°C, particularly about 75°C to about 100°C. In certain embodiments of the first to fourth embodiments, the tire tread rubber composition is prepared according to a process comprising at least one non-production mixing step and at least one production mixing step. The use of silica fillers may optionally require a separate re-grinding step to separately add some or all of such fillers. This stage is often performed at temperatures similar to those used in the masterbatch stage, but frequently slightly lower, typically between approximately 90°C and 150°C, which is the drop temperature.

[0119] Tire tread characteristics The use of the tire tread rubber compositions of the first to fourth embodiments disclosed herein preferably results in a tire having improved or desirable tread characteristics. These improved or desirable characteristics may include one or more of the following: rolling resistance, snow or ice traction friction, wet traction friction, dry handling, or abrasion, preferably improved rolling resistance and abrasion. Additional improved or desirable characteristics may include elongation at break (Eb), tensile strength at break (Tb), and Tb × Eb. These characteristics can be measured by various methods, but the values ​​referred to herein for rolling resistance, snow or ice traction friction, wet traction friction, and dry handling refer to tanδ values ​​measured at the following temperatures and according to the following procedure. The tanδ value can generally be measured using a dynamic mechanical thermal spectrometer (Gabo Qualimeter Testanlagen GmbH (Ahiden, Germany) Eplexor® 500N) under the following conditions, in accordance with the guidelines of ASTM D5992-96 (2011): Measurement mode: tensile test mode, Measurement frequency: 52 Hz, 0.2% strain at -50 to -5°C and 1% strain at -5 to 65°C are applied, data is collected at approximately 1°C intervals to provide measurements at temperatures of -30°C, 0°C, 30°C, and 60°C, Sample shape: 4.75 mm wide × 29 mm long × 2.0 mm thick. The measurement is performed on a cured rubber sample (cured at 170°C for 15 minutes). The tanδ of a rubber composition at -30°C indicates its snow or ice traction friction (also known as winter performance) when incorporated into a tire tread; the tanδ at 0°C indicates its wet traction friction when incorporated into a tire tread; the tanδ at 30°C indicates its dry handling when incorporated into a tire tread; and the tanδ at 60°C indicates its rolling resistance when incorporated into a tire tread.

[0120] In certain embodiments of the first to fourth embodiments, the rubber composition has a tanδ value at 60°C of 0.18 to 0.26 (e.g., 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, or 0.26), preferably 0.19 to 0.24 (e.g., 0.19, 0.2, 0.21, 0.22, 0.23, or 0.24). A tanδ at 60°C of one or less of the aforementioned ranges can be understood as indicating a tire (or more specifically, a tire tread) with moderate rolling resistance (in contrast to a tire with low rolling resistance, which may generally be indicated by a tanδ of less than 0.2 at 60°C).In certain embodiments of the first to fourth embodiments, the value of tanδ at 60°C is as follows: (a) 3 times or less the value of tanδ at 60°C (e.g., 3, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2, 1.9, 1.8, 1.7, 1.6 times, etc.), preferably 3 to 1.8 times the value of tanδ at 60°C (e.g., 3, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2 (b) the value of tanδ at -30°C which is at least 1.3 times the value of tanδ at 60°C (e.g., 1.9, 1.8 times), more preferably 2.9 to 2 times the value of tanδ at 60°C (e.g., 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, or 2 times); (b) the value of tanδ at -30°C which is at least 1.3 times the value of tanδ at 60°C (e.g., 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2 times, etc.), preferably 1.3 to 1.8 times the value of tanδ at 60°C (e.g., (c) The value of tanδ at 30°C that is 1.3, 1.4, 1.5, 1.6, 1.7, or 1.8 times the value of tanδ at 60°C (for example, 1.4, 1.5, 1.6, or 1.7 times); or (c) At least 1.9 times the value of tanδ at 60°C (for example, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 times, etc.), preferably 1.9 times the value of tanδ at 60°C It is combined with at least one of the values ​​of tanδ at 0°C, which are 2 to 2.7 times (e.g., 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, or 2.7 times), more preferably 2 to 2.5 times the value of tanδ at 60°C (e.g., 2, 2.1, 2.2, 2.3, 2.4, or 2.5 times), and in a particular such embodiment, the value of tanδ at 60°C is combined with each of (a), (b), and (c). In certain embodiments of the first to fourth embodiments, one of the aforementioned values ​​of tanδ at 60°C (e.g., 0.18 to 0.26 or 0.19 to 0.24) is combined with (a) a value for δ at -30°C that is 3 to 1.8 times the tanδ value at 60°C (e.g., 3, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2, 1.9, 1.8 times).In certain embodiments of the first to fourth embodiments, one of the aforementioned values ​​of tanδ at 60°C (e.g., 0.18 to 0.26 or 0.19 to 0.24) is combined with (b) a value for δ at 0°C that is 1.9 to 2.7 times the value of tanδ at 60°C (e.g., 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, or 2.7). In certain embodiments of the first to fourth embodiments, one of the aforementioned values ​​of tanδ at 60°C (e.g., 0.18 to 0.26 or 0.19 to 0.24) is combined with (c) a value for δ at 30°C that is 1.3 to 1.8 times the value of tanδ at 60°C (e.g., 1.3, 1.4, 1.5, 1.6, 1.7, or 1.8). In certain embodiments of the first to fourth embodiments, one of the aforementioned values ​​of tanδ at 60°C (e.g., 0.18 to 0.26 or 0.19 to 0.24) is combined with a more preferred value of tanδ at -30°C, a more preferred value of tanδ at 30°C, and a more preferred value of tanδ at 30°C.

[0121] In certain embodiments of the first and second embodiments, and according to the third and fourth embodiments disclosed herein, the tire tread rubber composition has a tanδ value at 60°C of 0.18 to 0.26, preferably 0.19 to 0.24, and is less than or equal to (i.e., (a) to (c)): (a) has a tanδ value at -30°C of 3 times or less the tanδ value at 60°C, preferably 3 to 1.8 times the tanδ value at 60°C, more preferably 2.9 to 2 times the tanδ value at 60°C, (b) at 60°C (c) The tanδ value at 30°C is at least 1.3 times the tanδ value at 60°C, preferably 1.3 to 1.8 times the tanδ value at 60°C, more preferably 1.4 to 1.7 times the tanδ value at 60°C, or (c) the tanδ value at 0°C is at least 1.9 times the tanδ value at 60°C, preferably 1.9 to 2.7 times the tanδ value at 60°C, more preferably 2 to 2.5 times the tanδ value at 60°C, at least one of these, preferably each of them, is satisfied.

[0122] The wear performance of tire tread rubber compositions can be evaluated by various methods. However, the absolute wear values ​​provided herein refer to DIN wear values ​​that can be measured using standard methods including DIN ISO 4649, 2017 edition, or more preferably DIN ISO 53516. According to such methods, the value is the amount of material loss (mm) during the wear test. 3 (in units) is expressed. Comparing two DIN wear values, it is shown that a lower number corresponds to less material loss and improved wear. Improved wear can also be described as improved wear resistance and is desirable in tire treads because it generally leads to tires with a longer lifespan (e.g., a higher predicted mileage rating). In certain preferred embodiments of the first to fourth embodiments, the tire tread rubber composition is 100 mm 3 The following (for example, 100, 99, 98, 97, 96, 95, 94, 93, 92, 91, 90, 89, 88, 87, 86, 85, 84, 83, 82, 81, 80, 79, 78, 77, 76, 75, 74, 73, 72, 71, 70, 69, 68, 67, 66, 65, 64, 63, 62, 61, 60 mm) 3 (The following), preferably 95 mm 3 The following (for example, 95, 94, 93, 92, 91, 90, 89, 88, 87, 86, 85, 84, 83, 82, 81, 80, 79, 78, 77, 76, 75, 74, 73, 72, 71, 70, 69, 68, 67, 66, 65, 64, 63, 62, 61, 60 mm) 3 (More preferably 90 mm) 3 The following (for example, 90, 89, 88, 87, 86, 85, 84, 83, 82, 81, 80, 79, 78, 77, 76, 75, 74, 73, 72, 71, 70, 69, 68, 67, 66, 65, 64, 63, 62, 61, 60 mm) 3 The following), and more preferably 85 mm 3 The following (for example, 85, 84, 83, 82, 81, 80, 79, 78, 77, 76, 75, 74, 73, 72, 71, 70, 69, 68, 67, 66, 65, 64, 63, 62, 61, 60 mm) 3 Below), or 100-80mm 3(For example, 100, 99, 98, 97, 96, 95, 94, 93, 92, 91, 90, 89, 88, 87, 86, 85, 84, 83, 82, 81, or 80 mm) 3 ), 95~80mm 3 (For example, 95, 94, 93, 92, 91, 90, 89, 88, 87, 86, 85, 84, 83, 82, 81, or 80 mm) 3 ), 90~80mm 3 (For example, 90, 89, 88, 87, 86, 85, 84, 83, 82, 81, or 80 mm) 3 ), 85~80mm 3 (For example, 85, 84, 83, 82, 81, or 80 mm) 3 ), 100~85mm 3 (For example, 100, 99, 98, 97, 96, 95, 94, 93, 92, 91, 90, 89, 88, 87, 86, 85 mm) 3 ), 95~85mm 3 (For example, 95, 94, 93, 92, 91, 90, 89, 88, 87, 86, or 85 mm) 3 ), or 90-85mm 3 (For example, 90, 89, 88, 87, 86, or 85 mm) 3 It has DIN wear (according to DIN ISO 4649, 2017 edition, more preferably DIN ISO 53516).

[0123] The tire tread rubber compositions of the first to fourth embodiments can be considered particularly useful in that they provide improved rolling resistance and wear performance to the tire tread. To refer to a balanced rolling resistance and wear performance means that both rolling resistance and wear performance are improved by at least 5% compared to the control, while maintaining wear performance, where the control refers to a tread rubber composition in which silica-reactive functionalized polybutadiene(ii) is replaced with an equivalent amount of non-functionalized high-cis polybutadiene. When we mention improved wear performance, we mean that the wear performance (measured by ISO 23337:2016) is at least 101% of the control (e.g., 101%, 102%, 103%, 104%, 105%, etc.), and in certain specific examples, it should be understood to include an improvement in wear of, for example, at least 5% (e.g., 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or more, including ranges such as 5-15% and 5-10% as mentioned above), or even at least 10% (e.g., 10%, 11%, 12%, 13%, 14%, 15% or more, including ranges such as 10-15% as mentioned above). Alternatively, the aforementioned improvements can be described as being at least 105% (105% is 5% higher than 100%) and at least 110% (110% is 10% higher than 100%) compared to the control. As a non-limiting example, if a sample exhibits a wear loss of 0.0055 mg and its control exhibits a wear loss of 0.0050 mg, the sample may be described as having 95% of the wear performance of its control. If a sample exhibits a wear loss of 0.0054 mg and its control exhibits a wear loss of 0.0060 mg, the sample may be described as having 10% improved wear performance compared to its control. According to the above description, a wear performance of 100% of the control should be understood as having equal wear performance to the control, and the comparison with the control is calculated by dividing the control value by the sample value and multiplying by 100%.When we refer to an improvement in rolling resistance, we mean that the rolling resistance (as reflected by the tanδ measurement at 60°C, as further described herein) is at least 101% of the control (e.g., 101%, 102%, 103%, 104%, 105%, etc.), and in certain specific examples, it should be understood to include an improvement in rolling resistance of, for example, at least 5% (e.g., 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or more, including ranges such as 5-15% and 5-10% as described above), or even at least 10% (e.g., 10%, 11%, 12%, 13%, 14%, 15% or more, including ranges such as 10-15% as described above). Alternatively, the aforementioned improvements could be described as being at least 105% (105% is 5% higher than 100%) and at least 110% (110% is 10% higher than 100%) compared to the control. Mentioning that rolling resistance and wear performance are each improved by at least 5% compared to the control means encompassing improvements of 5%, 6%, 7%, 8%, 9%, 10%, 11%, etc. (as discussed above), or even further improvements of at least 10%.

[0124] In certain embodiments of the first to fourth embodiments, the rubber composition contains at least 425% (for example, 425%, 430%, 435%, 440%, 445%, 450%, 455%, 460%, 465%, 470%, 475%, 480%, 485%, 490%, 495%, 500%, 505%, 510%, 515%, 520%, 525%, 530%, 535%, 540%, 545%, 550%). 555%, 560%, 565%, 570%, 575%, 580%, 585%, 590%, 595%, 600%, 605%, 610%, 615%, 620%, 625%, or more), or within the range of 425-625%, or a partial range within that range, preferably at least 475% (e.g., 475%, 480%, 485%, 490%, 495%, 500%, 505%, 510%, 51%). 5%, 520%, 525%, 530%, 535%, 540%, 545%, 550%, 555%, 560%, 565%, 570%, 575%, 580%, 585%, 590%, 595%, 600%, 605%, 610%, 615%, 620%, 625%, or more), or within the range of 475-625%, or a portion of that range, more preferably at least 500% (for example, 50%). The room temperature Eb is 0%, 505%, 510%, 515%, 520%, 525%, 530%, 535%, 540%, 545%, 550%, 555%, 560%, 565%, 570%, 575%, 580%, 585%, 590%, 595%, 600%, 605%, 610%, 615%, 620%, 625%, or higher, or within the range of 500-625%, or a sub-range within that range. The above room temperature Eb values ​​refer to measurements taken at 23°C. Eb can be measured using a dumbbell-shaped sample with a cross-sectional width of 4 mm and a center thickness of 1.9 mm, following the standard procedure described in ASTM D-412, but not limited to the guidelines thereto. During measurement, the test specimen is deformed at a constant rate (20% per second), and the resulting force can be recorded as a function of extension (strain).

[0125] In certain embodiments of the first to fourth embodiments, the rubber composition is at least 375% (e.g., 375%, 380%, 385%, 390%, 395%, 400%, 405%, 410%, 415%, 420%, 425%, 430%, 435%, 440%, 445%, 450%, 455%, 460%, 465%, 470%, 475%, 480%, 485%, 490%, 495%, 499%, or more), or 375-49%. The high-temperature Eb is within the range of 9%, or a partial range within that range, preferably at least 400% (e.g., 400%, 405%, 410%, 415%, 420%, 425%, 430%, 435%, 440%, 445%, 450%, 455%, 460%, 465%, 470%, 475%, 480%, 485%, 490%, 495%, 499%, or higher), or within the range of 400-499%, or a partial range within that range. The above high-temperature Eb values ​​refer to measurements taken at 100°C. Eb can be measured using a dumbbell-shaped specimen having a cross-sectional width of 4 mm and a center thickness of 1.9 mm, following the standard procedure described in ASTM D-412, but not limited to the guidelines thereto. During measurement, the specimen is deformed at a constant rate (20% per second), and the resulting force can be recorded as a function of extension (strain). Generally, the high-temperature Eb value of a given tread rubber composition is lower (i.e., less than) the room-temperature Eb value of that tread rubber composition.

[0126] In certain embodiments of the first to fourth embodiments, the rubber composition has at least 3500 (e.g., 3500, 3550, 3600, 3650, 3700, 3750, 3800, 3850, 3900, 3950, 4000, 4050, 4100, 4150) The high-temperature EbxTb (both values ​​determined at 100°C) is calculated by multiplying the high-temperature Tb value by the high-temperature Eb value and refers to a measurement taken at 100°C. Tb can be measured using a dumbbell-shaped specimen with a cross-sectional width of 4 mm and a central thickness of 1.9 mm, following the standard procedure described in ASTM D-412, but not limited to the guidelines thereto. During measurement, the specimen is deformed at a constant rate (20% per second), and the resulting force can be recorded as a function of extension (strain).

[0127] tire As disclosed herein, the tire tread rubber compositions according to the first to fourth embodiments are specifically intended for use in tire treads. Accordingly, tire treads comprising (or made from) the tire tread rubber compositions according to the first to fourth embodiments are also disclosed herein, as considered herein. Similarly, such tire treads can be used in tires (together with other components). Accordingly, tires having treads comprising (or made from) the tire tread rubber compositions according to the first to fourth embodiments are also disclosed herein, as considered herein.

[0128] method Furthermore, a method for providing a tire tread is disclosed herein. More specifically, the method provides a tire tread having improved wear and / or rolling resistance performance (preferably both improved wear and improved rolling resistance) by utilizing a tire tread rubber composition according to the first to third embodiments disclosed herein. As discussed in detail above, the improvement in wear and / or rolling resistance can be measured according to the method described herein. [Examples]

[0129] The following examples are provided to illustrate specific and exemplary embodiments of the Disclosure, and / or features of those embodiments. The examples are provided for illustrative purposes only and should not be construed as limiting the Disclosure. Many modifications to these specific examples are possible without departing from the spirit and scope of the embodiments of the Disclosure. It should be specifically understood that the tire tread rubber compositions according to the Disclosure may be made using different SBRs, different polybutadienes, different reinforcing silica fillers, different (or non)carbon blacks, different hydrocarbon resins, and different liquid plasticizers, generally with respect to the teachings provided herein and fully disclosed in the preceding paragraphs. It should also be understood that the aforementioned components may differ (i.e., completely, as disclosed in the preceding paragraphs) in relative amounts, composition, or both of those used in the examples.

[0130] Table 1 contains a summary of information regarding exemplary tire tread rubber compositions of the present invention and exemplary control tire tread rubber compositions. As is evident from a detailed examination of Table 1, the control compositions differ from the compounds of the present invention with respect to some of the listed components and the resulting properties (i.e., tanδ values), as described below. The use of components according to the first to fourth embodiments described in detail in the above paragraphs results in a tire tread rubber composition having a tanδ at 60°C in the range of 0.18 to 0.26, a tanδ at -30°C no more than three times the tanδ at 60°C, a tanδ at 0°C at least 1.9 times greater than the tanδ at 60°C, and a tanδ at 30°C at 1.4 to 1.7 times the tanδ at 60°C. In contrast, the control compositions do not have a tanδ at 0°C at at least 1.9 times greater than the tanδ at 60°C, or a tanδ at 30°C at 1.4 to 1.7 times the tanδ at 60°C.

[0131] [Table 1]

[0132] This application discloses several numerical range limits that support any range within the disclosed numerical range, even if explicit range limits are not explicitly mentioned in the specification, because embodiments of the compositions and methods disclosed herein can be performed across the entire numerical range disclosed. With regard to the use of substantially any plural or singular term herein, those skilled in the art can substitute plurals for singulars or singulars for plurals as appropriate to the context or application. Various singular or plural substitutions may be explicitly described herein for brevity.

[0133] In general, those skilled in the art will understand that the terms used herein and in particular in the appended claims are generally intended to be “open” terms. For example, the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” and the term “listed” should be interpreted as “listed but not limited to.” Furthermore, those skilled in the art will understand that if a particular number is intended in the description of a preceding claim, such intention will be explicitly stated in that claim, and if there is no such statement, such intention does not exist. For example, to aid understanding, the following appended claims may include the use of the prefix phrases “at least one” and “one or more” to prefix the description of the claims. However, the use of such phrases should not be interpreted as meaning that the indefinite article "a" or "an" preamble to a claim is limited to an invention containing only one such claim, even if the same claim contains the preamble "one or more" or "at least one" and an indefinite article such as "a" or "an" (for example, "a" or "an" should typically be interpreted as meaning "at least one" or "one or more"), and the same applies to the use of definite articles used to preamble claims. In addition, even if a specific number is explicitly stated in the preamble of a claim, a person skilled in the art will understand that such a statement should typically be interpreted as meaning at least the number stated (for example, "two statements," which is an obvious statement without other modifiers, typically means at least two statements or two or more statements).Furthermore, when using conventional expressions similar to "at least one of A, B, and C, etc.," such expressions are generally intended to be understood by those skilled in the art (for example, "a system having at least one of A, B, and C" may include, but is not limited to, A only, B only, C only, A and B together, A and C together, B and C together, and / or a system having A, B, and C together). Furthermore, those skilled in the art will understand that any disjunct word or phrase that effectively indicates two or more alternative terms should be understood, whether in the specification, claims, or drawings, as intended to include the possibility of including one of these terms, any of these terms, or both of these terms. For example, the phrase "A or B" will be understood to include the possibilities of "A" or "B" or "A and B."

[0134] All references, including but not limited to patents, patent applications, and non-patent literature, are incorporated herein by reference in their entirety.

[0135] While various aspects and embodiments of compositions and methods have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for illustrative purposes only and are not intended to limit the true scope and spirit set forth in the claims.

Claims

1. A tire tread rubber composition, a. 100 parts of elastomer components, i. 30 to 45 parts, preferably 30 to 40 parts, of at least one styrene-butadiene rubber having a Tg of at least about -20°C, preferably about -10 to about -20°C, and ii. An elastomer component comprising 55 to 70 parts, preferably 60 to 70 parts, of polybutadiene rubber having a cis bond content of at least 95%, a Tg of less than -101°C, preferably -101 to -110°C, and silica-reactive functional groups, b. Approximately 100 to approximately 300m ２ / g, preferably about 150 to about 300m ２ A reinforcing silica filler having a surface area of ​​80 to 120 phr and having a surface area of ​​1 / g, c. Carbon black with a density of 15 phr or less, preferably carbon black with a density of 10 phr or less, d. At least one hydrocarbon resin having a Tg of about 30 to about 50°C and a ferrous resin of 30 to 40 phr, preferably 30 to 35 phr, e. At least one liquid plasticizer, preferably consisting of at least one oil, in an amount of 15 to 30 phr, preferably 15 to 25 phr, f. Includes a cured package, A tire tread rubber composition in which the total amount of (d) and (e) is 45 to 60 phr, preferably 45 to 55 phr.

2. below: a. The at least one styrene-butadiene rubber in (a)(i) is non-functionalized. b. The at least one styrene-butadiene rubber of (a)(i) is oil-distributed, or c. The tire tread rubber composition according to claim 1, wherein at least one of the following is satisfied: the at least one of the styrene-butadiene rubbers of (a) and (i) has an Mw of at least 600,000 grams / mol, preferably 600,000 to 1,200,000 grams / mol, and more preferably 700,000 to 950,000 grams / mol.

3. The tire tread rubber composition according to claim 2, wherein each of (a) to (c) is satisfied.

4. The tire tread rubber composition according to any one of claims 1 to 3, wherein the at least one hydrocarbon resin in (d) is an aromatic hydrocarbon resin.

5. The tire tread rubber composition according to any one of claims 1 to 4, wherein the at least one styrene-butadiene rubber of (a)(i) has an Mw of about 600,000 grams / mol, preferably 600,000 to 1,200,000 grams / mol, and more preferably about 350,000 to about 450,000 grams / mol.

6. A tire tread rubber composition, a. 100 parts of elastomer components, i. 30 to 45 parts, preferably 30 to 40 parts, of at least one oil-spreadable non-functionalized styrene-butadiene rubber having a Tg of at least about -20°C, preferably about -20 to about -10°C, and Mw of at least 600,000 grams / mol, preferably 600,000 to 1,200,000 grams / mol, and ii. An elastomer component comprising 55 to 70 parts, preferably 60 to 70 parts, of polybutadiene rubber having a cis bond content of at least 95%, a Tg of less than -101°C, preferably -101 to -110°C, and silica-reactive functional groups, b. Approximately 100 to approximately 300m ２ / g, preferably about 150 to about 300m ２ A reinforcing silica filler having a surface area of ​​80 to 120 phr and having a surface area of ​​1 / g, c. Carbon black with a density of 15 phr or less, preferably carbon black with a density of 10 phr or less, d. At least one aromatic hydrocarbon resin having a Tg of about 30 to about 50°C and a ferrous resin of 30 to 40 phr, preferably 30 to 35 phr, e. A liquid plasticizer comprising 15 to 30 phr, preferably 15 to 25 phr, wherein the 15 to 30 phr liquid plasticizer comprises an oil from the oil-spreadable non-functionalized styrene-butadiene rubber of (a)(i), f. Includes a cured package, A tire tread rubber composition in which the total amount of (d) and (e) is 45 to 60 phr, preferably 45 to 55 phr.

7. The tire tread rubber composition according to any one of claims 1 to 4, wherein the polybutadiene rubber of (a)(ii) has an Mw of about 450,000 to about 700,000 grams / mol, preferably about 500,000 to about 650,000 grams / mol.

8. The tire tread rubber composition according to any one of claims 1 to 7, wherein the at least one reinforcing silica filler of (b) is present in an amount of 85 to 95 phr.

9. The tire tread rubber composition according to any one of claims 1 to 7, wherein the at least one reinforcing silica filler of (b) is present in an amount of 100 to 120 phr.

10. The tire tread rubber composition according to any one of claims 1 to 9, wherein the total amount of natural rubber, polyisoprene, or a combination thereof in the elastomer components is 9 phr or less, preferably 5 phr or less, and more preferably 0 phr.

11. The tire tread rubber composition according to any one of claims 1 to 10, wherein the polybutadiene in (ii) comprises less than 3% by weight, preferably 0%, of syndiotactic 1,2-polybutadiene.

12. The polybutadiene in (ii) has a silica-reactive functional group derived from a functional compound having the following formula (II) and / or a partial condensation product thereof, 【Chemistry 1】 In the formula, A １ is preferably a glycidoxy group, a 3,4-epoxycyclohexyl group, or has 3 to 8 carbon atoms in total, preferably 3 to 6 carbon atoms, and two terminal carbons are within the epoxy ring, and the other end of the carbon chain is R ｃ represents a monovalent epoxy group selected from glycidyl groups bonded to R ｃ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), and R ｄ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms (for example, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms), or a reactive group, and R ｅ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms (for example, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms), b is an integer of 0 to 2, and when two or more R ｄ or OR ｅ exist, each R ｄ and / or OR ｅ may be the same as or different from each other, and no active proton is contained in the molecule), the tire tread rubber composition according to any one of claims 1 to 11.

13. The monovalent epoxy group A １ The tire tread rubber composition according to claim 12, wherein the group is selected from glycidoxy groups.

14. The monovalent epoxy group A １ The tire tread rubber composition according to claim 12, wherein the group is selected from 3,4-epoxycyclohexyl groups.

15. The monovalent epoxy group has a total of 3 to 8 carbon atoms, preferably 3 to 6, with two terminal carbon atoms located within the epoxy ring, and the other end of the carbon chain being R ｃ The tire tread rubber composition according to claim 12, selected from glycidyl groups bonded to the glycidyl group.

16. The tire tread rubber composition according to any one of claims 1 to 15, wherein the at least one hydrocarbon resin in (d) comprises a terpene resin with less than 5 phr, preferably a terpene resin with 0 phr.

17. The tire tread rubber composition according to any one of claims 1 to 16, wherein the at least one liquid plasticizer in (e) comprises a vegetable oil.

18. The rubber composition has a tanδ value at 60°C of 0.18 to 0.26, preferably 0.19 to 0.24, and the following: a. The tanδ value at -30°C is 3 times or less the tanδ value at 60°C, preferably 3 to 1.8 times the tanδ value at 60°C, and more preferably 2.9 to 2 times the tanδ value at 60°C. b. Having a tanδ value at 30°C that is at least 1.3 times, preferably 1.3 to 1.8 times, and more preferably 1.4 to 1.7 times, the tanδ value at 60°C, or c. Having a tanδ value at 0°C that is at least 1.9 times, preferably 1.9 to 2.7 times, and more preferably 2 to 2.5 times, the tanδ value at 60°C, which is at least one of the above, preferably each of them, is satisfied, the tire tread rubber composition according to any one of claims 1 to 17.

19. The rubber composition is as follows: a. Having room temperature Eb of at least 425%, preferably at least 475%, and more preferably at least 500%. b. Having at least 375%, preferably at least 400%, of Eb at 100°C, or c. A tire tread rubber composition according to any one of claims 1 to 18, wherein at least one of the following is satisfied, preferably each of them: having at least 3500, preferably at least 3700, both Tb × Eb at 100°C.

20. The rubber composition is 95 mm ３ Preferably 90 mm ３ More preferably, 85 mm ３ A tire tread rubber composition according to any one of claims 1 to 19, having the following DIN wear.

21. A tire having a tread comprising the tire tread rubber composition according to any one of claims 1 to 20.

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