Rubber composition for tire, and tire

Abstract

To provide a rubber composition for tires exhibiting excellent wet performance, rolling performance and dry performance, and to provide a tire produced by using the composition.SOLUTION: A rubber composition for a tire, comprising 100 parts by mass of rubber components including 30 parts by mass or more of SBR, 10 to 300 parts by mass of silica, C1, and C2, wherein C1 has an aromatic proton ratio of 20% or more and the following parameter S is 300 or more, C2 has an aromatic proton ratio of 1 to 15% and S is 200 or less, and a total content of C1 and C2 with respect to a content of SBR is 1 to 100% by mass: Kn represents the retention factor of the n-th peak from the smallest retention time in the total ion chromatogram obtained by pyrolysis gas chromatography-mass spectrometry of the resin, α represents the n of the peak of the maximum retention factor satisfying kn ≤ 6.0, and An represents the ratio (%) of the area of the n-th peak to the total area of the peaks satisfying kn ≤ 6.0.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a rubber composition for a tire and a tire. [Background technology]

[0002] BACKGROUND ART Conventionally, rubber compositions for tires that contain petroleum resins in order to control properties such as viscoelasticity have been known (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2024-002387 Summary of the Invention [Problem to be solved by the invention]

[0004] Recently, from the viewpoints of safety, environmental issues, etc., there has been a demand for wet performance, rolling performance, and dry performance to be all achieved at high levels. In this context, the present inventors have studied the rubber composition for tires described in Patent Document 1, and have found that the above-mentioned performances when used in tires may not always be sufficient.

[0005] In view of the above circumstances, an object of the present invention is to provide a rubber composition for tires that exhibits excellent wet performance, rolling performance, and dry performance when made into a tire, and a tire manufactured using the rubber composition for tires. [Means for solving the problem]

[0006] As a result of extensive research into the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using two specific types of resins in combination, and have arrived at the present invention. That is, the present inventors have found that the above problems can be solved by the following configuration.

[0007] (1) A rubber composition comprising 100 parts by mass of a rubber component (A) containing 30 parts by mass or more of a styrene-butadiene rubber, 10 to 300 parts by mass of silica (B), a resin (C1), and a resin (C2), The resin (C1) has a ratio of aromatic hydrocarbon-derived protons determined by an NMR method of 20% or more and the following parameter S is 300 or more, The resin (C2) is a resin having a ratio of aromatic hydrocarbon-derived protons determined by an NMR method of 1 to 15% and a parameter S described below of 200 or less, A rubber composition for tires, wherein the total content of the resin (C1) and the resin (C2) relative to the content of the styrene-butadiene rubber is 1 to 100% by mass. (2) The rubber composition for tires according to (1) above, wherein the parameter S of the resin (C1) is 330 or more. (3) A tire manufactured using the rubber composition for a tire according to (1) or (2) above. [Effects of the Invention]

[0008] As will be described below, according to the present invention, it is possible to provide a rubber composition for a tire that exhibits excellent wet performance, rolling performance, and dry performance when made into a tire, and a tire manufactured using the rubber composition for a tire. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a total ion chromatogram obtained by pyrolysis GC-MS of resin H. [Figure 2] 1 is a partial cross-sectional schematic view showing an example of an embodiment of a tire of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] The rubber composition for tires and the like of the present invention will be described below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. Each component may be used alone or in combination of two or more. When two or more components are used in combination, the content of the components refers to the total content unless otherwise specified. Furthermore, with regard to a rubber composition for tires, the wet performance, rolling performance, and dry performance when made into a tire are also simply referred to as "wet performance," "rolling characteristics," and "dry performance," respectively.

[0011] [I] Rubber composition for tires The rubber composition for tires of the present invention (hereinafter also referred to as "the composition of the present invention") is The rubber composition contains 100 parts by mass of a rubber component (A) containing 30 parts by mass or more of a styrene-butadiene rubber, 10 to 300 parts by mass of silica (B), a resin (C1), and a resin (C2), The resin (C1) is a resin having a ratio of aromatic hydrocarbon-derived protons determined by an NMR method of 20% or more and a parameter S described below of 300 or more, The resin (C2) has a ratio of aromatic hydrocarbon-derived protons determined by an NMR method of 1 to 15% and the following parameter S is 200 or less, In the rubber composition for tires, the total content of the resin (C1) and the resin (C2) relative to the content of the styrene-butadiene rubber is 1 to 100% by mass.

[0012] It is believed that the composition of the present invention can solve the above-mentioned problems because of its structure. The reason for this is not clear, but is presumed to be as follows. As described above, the composition of the present invention uses, in combination with styrene-butadiene rubber (hereinafter also referred to as "SBR"), predetermined amounts of a resin (C1) (hereinafter also referred to as "resin C1") having an aromatic hydrocarbon-derived proton ratio (hereinafter also referred to as "aromatic proton ratio") of 20% or more as determined by NMR (nuclear magnetic resonance) and a parameter S (hereinafter also referred to as "S value") described below of 300 or more, and a resin (C2) (hereinafter also referred to as "resin C2") having an aromatic proton ratio of 1 to 15% and an S value of 200 or less. As described above, resin C1 has an aromatic proton ratio of 20% or more, and therefore has a structure similar to SBR. Furthermore, as mentioned above, Resin C1 has an S value of 300 or more. Here, the S value is a parameter related to the retention coefficient (for peaks with a retention coefficient of 6 or less) and area ratio in a total ion chromatogram (hereinafter also referred to as "TIC") obtained by pyrolysis gas chromatography mass spectrometry (hereinafter also referred to as "pyrolysis GC-MS") using a packing material (structure shown below) similar in structure to SBR, and represents the retention of the monomers that make up the resin to the packing material. Because Resin C1 has an S value equal to or greater than a specific value, it is considered to have extremely high compatibility with SBR.

[0013] [ka]

[0014] As a result, in the composition of the present invention, the rubber component containing SBR and the resin C1 are compatible to an extremely high degree, which is thought to lead to excellent wet performance and rolling performance. Furthermore, since the composition of the present invention also uses resin C2, the tan δ (loss coefficient) at each temperature is broadened, and it is believed that in addition to the excellent wet performance and rolling performance described above, dry performance can also be achieved.

[0015] Each component contained in the composition of the present invention will be described below.

[0016] [1] Rubber component (A) The composition of the present invention contains a rubber component comprising styrene butadiene rubber (SBR). The rubber component may contain a rubber component other than SBR. The rubber component may be modified with an alkoxy group, an alkoxysilyl group, or the like.

[0017] [SBR] SBR is a copolymer of styrene and butadiene.

[0018] [Styrene content] The styrene content of SBR is not particularly limited, but is preferably 10 to 50% by mass, more preferably 20 to 45% by mass, for reasons of better effects of the present invention. Here, the styrene content refers to the proportion (% by mass) of repeating units derived from styrene relative to the total SBR.

[0019] [Vinyl unit content] The vinyl unit content of SBR is not particularly limited, but is preferably 20 to 60 mol %, more preferably 20 to 50 mol %, for reasons of better effects of the present invention. Here, the vinyl unit content refers to the proportion (mol %) of repeating units of 1,2-vinyl unit bonds among repeating units derived from butadiene in SBR.

[0020] [Glass transition temperature] The glass transition temperature (Tg) of SBR is not particularly limited, but in order to achieve better effects of the present invention, it is preferably −85° C. to −10° C., and more preferably −50° C. to −20° C. The glass transition temperature can be adjusted, for example, by the styrene content or the vinyl unit content. In this specification, the glass transition temperature (Tg) is measured using a differential scanning calorimeter (DSC) at a temperature rise rate of 10° C. / min and calculated by the midpoint method.

[0021] [Content] The content of SBR in the rubber component is 30 parts by mass or more per 100 parts by mass of the rubber component. In particular, 50 parts by mass or more is preferred for the reason that the effects of the present invention are more excellent. The rubber component may be composed solely of SBR. Multiple SBRs may also be used in combination.

[0022] [Other rubber components] The rubber component may contain rubber components other than SBR (other rubber components). Examples of such other rubber components include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), acrylonitrile-butadiene copolymer rubber (NBR), butyl rubber (IIR), halogenated butyl rubber (Br-IIR, Cl-IIR), and chloroprene rubber (CR). Among these, NR and BR are preferred, and BR is more preferred, because they provide better effects of the present invention.

[0023] When the rubber component contains other rubber components, the content of the other rubber components in the rubber component is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less, per 100 parts by mass of the rubber component, for reasons of better effects of the present invention.

[0024] [Average Tg] The glass transition temperature of the rubber component as a whole (hereinafter also referred to as "average Tg") is not particularly limited, but for reasons of superior effects of the present invention, it is preferably from -100°C to -20°C, and more preferably from -80°C to -20°C. Here, the average Tg of the rubber component is the sum (weighted average value of glass transition temperatures) obtained by multiplying the glass transition temperature (Tg) of each rubber component by the mass fraction of each rubber component.

[0025] [Molecular weight] The weight average molecular weight (Mw) of the rubber component is preferably 100,000 to 10,000,000, and more preferably 300,000 to 3,000,000, for the reason that the effects of the present invention are more excellent. The number average molecular weight (Mn) of the rubber component contained in the composition of the present invention is preferably 50,000 to 5,000,000, and more preferably 150,000 to 1,500,000, for reasons of better effects of the present invention. It is preferable that the Mw and / or Mn of at least one rubber component contained in the rubber component falls within the above range, and it is more preferable that the Mw and / or Mn of all rubber components contained in the rubber component fall within the above range. In this specification, Mw and Mn are values ​​calculated as standard polystyrene obtained by gel permeation chromatography (GPC) measurement under the following conditions. Solvent: Tetrahydrofuran Detector: RI detector

[0026] [2] Silica (B) The composition of the present invention contains silica. The silica is not particularly limited, and any conventionally known silica can be used. Examples of silica include wet silica, dry silica, fumed silica, and diatomaceous earth. Biomass-derived silica such as rice husks may also be used. The silica may be used alone or in combination of two or more types.

[0027] [CTAB] The cetyltrimethylammonium bromide (CTAB) adsorption specific surface area of ​​silica (hereinafter, "CTAB adsorption specific surface area" may be simply referred to as "CTAB") is not particularly limited, but for the reason that the effect of the present invention is superior, it is preferred that the specific surface area be 70 to 300 m 2 / g, and 110 to 250m 2 / g is more preferred. Here, the CTAB adsorption specific surface area is a value measured in accordance with JIS K6430:2008, Appendix G.

[0028] [Content] In the composition of the present invention, the content of silica is 10 to 300 parts by mass relative to 100 parts by mass of the rubber component. The content is preferably 30 to 200 parts by mass, and more preferably 50 to 150 parts by mass, for the reason that the effects of the present invention are more excellent.

[0029] [3] Resin (C1) The composition of the present invention contains a resin (resin C1) having a ratio of aromatic hydrocarbon-derived protons (aromatic proton ratio) of 20% or more as determined by NMR and a parameter S (S value) described below of 300 or more.

[0030] [Aromatic proton ratio] The aromatic proton ratio of resin C1 is 20% or more. The aromatic proton ratio is preferably 22% or more, more preferably 24% or more, even more preferably 26% or more, and particularly preferably 28% or more, because the effects of the present invention are more excellent. There is no particular upper limit to the ratio, but because the effects of the present invention are more excellent, it is preferably 80% or less, and more preferably 50% or less.

[0031] The aromatic proton ratio is determined as follows. Resin is dissolved in a solvent 1 The H-NMR spectrum is measured. In the spectrum, the ratio of the area of ​​the peaks of protons derived from aromatic hydrocarbons (aromatic rings) to the total area of ​​the peaks of protons derived from the resin is calculated, and this is taken as the aromatic proton ratio. For example, when the resin is a styrene polymer (polystyrene), the aromatic proton ratio is the ratio of the peak area of ​​protons derived from benzene rings to the sum of the peak areas of protons derived from polystyrene.

[0032] [S value] The following parameter S (S value) of resin C1 is 300 or more.

[0033]

number

[0034] where k n represents the retention coefficient of the nth peak from the smallest retention time in the total ion chromatogram obtained by pyrolysis gas chromatography mass spectrometry of the resin, and α represents the retention coefficient of the nth peak from the smallest retention time in the total ion chromatogram obtained by pyrolysis gas chromatography mass spectrometry of the resin, and k n represents the n above of the peak with the maximum retention factor of ≦6.0, and A n is k n It represents the ratio (%) of the area of ​​the nth peak to the total area of ​​peaks that satisfy the condition ≦6.0.

[0035] The S value is preferably 330 or more, and more preferably 350 or more, because the effects of the present invention are more excellent. There is no particular upper limit to the S value, but the S value is preferably 500 or less, and more preferably 400 or less, because the effects of the present invention are more excellent.

[0036] The pyrolysis gas chromatography mass spectrometry (pyrolysis GC-MS) is carried out under the following conditions.

[0037] (conditions) - Instrument name: Shimadzu GCMS-QP2020 Pyrolysis equipment name: Frontier Labs Double Shot Pyrolyzer PY-2020iD ·Thermal decomposition temperature: 550℃ ·Inlet temperature: 320℃ Column used: 5% diphenyldimethl polysiloxane (GL Sciences UA-5) Column size: Length 30m, inner diameter 0.25mm, film thickness 0.25μm Method (column temperature conditions): 70°C (3 min) → Heat at 10°C / min (25 min) → Final temperature 320°C Carrier gas: Ultra-high purity helium gas (total flow rate: 104 mL / min, column flow rate: 1 mL / min) ·Injection volume: 1μL

[0038] A specific example of how to calculate the S value is shown below. 1 is a total ion chromatogram (TIC) obtained by pyrolysis GC-MS of Resin H, which will be described later. The pyrolysis GC-MS conditions are as described above. As shown in Figure 1, the TIC of Resin H has two peaks. The retention factor k1 of the peak with the shortest retention time (the left peak) is 1.7, and the retention factor k2 of the peak with the second shortest retention time (the right peak) is 2.8. Since the retention factors of both peaks are 6.0 or less, k n The peak with the largest retention factor that satisfies ≦6.0 is the right peak. Because the right peak is the second peak from the shortest retention time, α in the parameter S is 2. Furthermore, the ratio A1 of the area of ​​the left peak to the sum of the areas of the two peaks is 40(%), and the ratio A2 of the area of ​​the right peak to the sum of the areas of the two peaks is 60(%). Therefore, the S value of resin H is calculated as 1.7×40+2.8×60=236.

[0039] One example of a method for achieving an S value of 300 or greater is to polymerize a resin using a monomer containing an aromatic hydrocarbon having a polymerizable group, and increase the proportion of components in the aromatic hydrocarbons that have a high retention coefficient (the aforementioned retention coefficient) (preferably components with a retention coefficient of 2 or greater, more preferably components with a retention coefficient of 3 or greater). To enhance the effects of the present invention, the proportion is preferably 50% by mass or greater, more preferably 70% by mass or greater, and even more preferably 90% by mass or greater. The upper limit of the proportion is not particularly limited, and is 100% by mass. Since aliphatic hydrocarbons are likely to decompose at the decomposition temperature (550°C) of the pyrolysis GC-MS described above, the presence of aliphatic hydrocarbons in the monomers that make up the resin is thought to have little effect on the S value.

[0040] [Preferred embodiment] The monomer constituting the resin C1 preferably contains an aromatic hydrocarbon having a polymerizable group (for example, a vinyl group, an isopropenyl group, etc.) because this provides a better effect of the present invention. Specific examples of the aromatic hydrocarbon include styrene, α-methylstyrene, vinyltoluene, isopropenyltoluene, indene, and methylindene. Among these, vinyltoluene, isopropenyltoluene, indene, and methylindene are preferred, and isopropenyltoluene, indene, and methylindene are more preferred, because they provide better effects of the present invention.

[0041] For reasons of better effects of the present invention, the retention coefficient of the aromatic hydrocarbons (the retention coefficient described above) is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. There is no particular upper limit to the retention coefficient, but for reasons of better effects of the present invention, it is preferably 6 or less, and more preferably 5 or less.

[0042] The monomers constituting the resin C1 preferably contain aliphatic hydrocarbons (preferably aliphatic hydrocarbons containing unsaturated double bonds) in addition to the above-mentioned aromatic hydrocarbons. The aliphatic hydrocarbon may be linear, branched, or cyclic. Specific examples of the aliphatic hydrocarbons include aliphatic hydrocarbons that constitute the C5 fraction, such as isoprene, cyclopentadiene, pentane, and dicyclopentadiene (DCPD).

[0043] When the monomers constituting the resin C1 contain aliphatic hydrocarbons (e.g., C5 fractions) in addition to the aromatic hydrocarbons described above, the content of the aromatic hydrocarbons in the monomers is preferably 30 to 99 mass%, more preferably 50 to 97 mass%, and even more preferably 70 to 95 mass%, for reasons of better effects of the present invention. When the monomers constituting the resin C1 contain aliphatic hydrocarbons (e.g., C5 fractions) in addition to the aromatic hydrocarbons described above, the content of the aliphatic hydrocarbons in the monomers is preferably 1 to 70 mass%, more preferably 3 to 50 mass%, and even more preferably 5 to 30 mass%, for reasons of better effects of the present invention.

[0044] [Molecular weight] The weight average molecular weight (Mw) of resin C1 is preferably 100 or more and less than 100,000, more preferably 200 to 50,000, and even more preferably 500 to 10,000, for reasons of better effects of the present invention.

[0045] [Content] In the composition of the present invention, the content of resin C1 relative to the content of the above-mentioned SBR is preferably 0.5 to 50 mass%, more preferably 1 to 40 mass%, even more preferably 2 to 30 mass%, and particularly preferably 5 to 20 mass%, because this provides better effects of the present invention.

[0046] In the composition of the present invention, the content of resin C1 is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, even more preferably 2 to 30 parts by mass, and particularly preferably 5 to 20 parts by mass, relative to 100 parts by mass of the rubber component, for reasons of better effects of the present invention.

[0047] [4] Resin (C2) The composition of the present invention contains, in addition to the above-mentioned resin C1, a resin (resin C2) having an aromatic proton ratio of 1 to 15% and the above-mentioned S value of 200 or less.

[0048] [Aromatic proton ratio] The aromatic proton ratio of resin C2 is 1 to 15%. The aromatic proton ratio is preferably 3% or more, more preferably 5% or more, and even more preferably 7% or more, for reasons of superior effects of the present invention. The method for determining the aromatic proton ratio is as described above.

[0049] [S value] The S value of resin C2 is not more than 200. In particular, the S value is preferably 100 to 190, more preferably 120 to 170, and even more preferably 130 to 150, for reasons of better effects of the present invention. The method for determining the S value is as described above.

[0050] One example of a method for setting the S value to 200 or less is to polymerize a resin using a monomer containing an aromatic hydrocarbon having a polymerizable group, and increase the proportion of components in the aromatic hydrocarbons that have a low retention coefficient (the retention coefficient described above) (preferably components with a retention coefficient of 3 or less, more preferably components with a retention coefficient of 2 or less). To enhance the effects of the present invention, the proportion is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. The upper limit of the proportion is not particularly limited, and is 100% by mass. Since aliphatic hydrocarbons are likely to decompose at the decomposition temperature (550°C) of the pyrolysis GC-MS described above, the presence of aliphatic hydrocarbons in the monomers that make up the resin is thought to have little effect on the S value.

[0051] [Preferred embodiment] The monomer constituting the resin C2 preferably contains an aromatic hydrocarbon having a polymerizable group (for example, a vinyl group, an isopropenyl group, etc.) because this provides a better effect of the present invention. Specific examples of the aromatic hydrocarbon include styrene, α-methylstyrene, vinyltoluene, isopropenyltoluene, indene, and methylindene. Among these, styrene and α-methylstyrene are preferred, and styrene is more preferred, because they provide better effects of the present invention.

[0052] For reasons of better effects of the present invention, the retention coefficient of the aromatic hydrocarbons (the retention coefficient described above) is preferably 3 or less, and more preferably 2 or less. There is no particular lower limit to the retention coefficient, but for reasons of better effects of the present invention, it is preferably 1 or more.

[0053] The monomers constituting the resin C2 preferably contain aliphatic hydrocarbons (preferably aliphatic hydrocarbons containing unsaturated double bonds) in addition to the aromatic hydrocarbons described above, for the reason that the effects of the present invention are more excellent. The aliphatic hydrocarbon may be linear, branched, or cyclic. Specific examples of the aliphatic hydrocarbons include aliphatic hydrocarbons that constitute the C5 fraction, such as isoprene, cyclopentadiene, pentane, and dicyclopentadiene (DCPD).

[0054] The content of the aromatic hydrocarbon in the monomer is preferably 1 to 70 mass%, more preferably 5 to 50 mass%, and even more preferably 20 to 40 mass%, because this provides better effects of the present invention. The content of the aliphatic hydrocarbon in the monomer is preferably 30 to 99% by mass, more preferably 50 to 95% by mass, and even more preferably 60 to 80% by mass, because this provides better effects of the present invention.

[0055] Resin C2 is preferably an aromatic modified terpene resin, since this provides better effects of the present invention.

[0056] [Molecular weight] The preferred range of Mw for resin C2 is the same as that for resin C1 described above.

[0057] [Content] In the composition of the present invention, the content of resin C2 relative to the content of the above-mentioned SBR is preferably 0.5 to 50 mass%, more preferably 1 to 40 mass%, even more preferably 2 to 30 mass%, and particularly preferably 5 to 20 mass%, because this provides better effects of the present invention.

[0058] In the composition of the present invention, the content of resin C2 is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, even more preferably 2 to 30 parts by mass, and particularly preferably 5 to 20 parts by mass, per 100 parts by mass of the rubber component, because this provides better effects of the present invention.

[0059] [5]Resin content In the composition of the present invention, the total content of the resin (C1) and the resin (C2) relative to the content of the styrene-butadiene rubber (SBR) (hereinafter also referred to as "resin content") is 1 to 100 mass %. In particular, for reasons of better effects of the present invention, it is preferably 5 to 70 mass %, more preferably 10 to 50 mass %, and even more preferably 20 to 40 mass %.

[0060] [6] C2 / C1 In the composition of the present invention, the content of the above-mentioned resin C2 relative to the content of the above-mentioned resin C1 (hereinafter also referred to as "C2 / C1") is preferably 0.1 to 10, more preferably 0.2 to 5, and even more preferably 0.5 to 2, for reasons of better effects of the present invention.

[0061] [7] Optional component The composition of the present invention may contain components (optional components) other than the above-mentioned components, if necessary. Examples of such components include resins other than Resin C1 and Resin C2, fillers other than silica (preferably carbon black or aluminum hydroxide), silane coupling agents, thermally expandable microcapsules, zinc oxide (zinc white), stearic acid, antioxidants, waxes, processing aids, liquid polymers, thermosetting resins, vulcanizing agents (e.g., sulfur), vulcanization accelerators (accelerators), vulcanization activators, and other various additives commonly used in rubber compositions.

[0062] [Carbon black] The composition of the present invention preferably contains carbon black because the effects of the present invention are more excellent. The carbon black may be used alone or in combination of two or more types. The carbon black is not particularly limited, and various grades such as SAF-HS, SAF, ISAF-HS, ISAF, ISAF-LS, IISAF-HS, HAF-HS, HAF, HAF-LS, FEF, GPF, and SRF can be used.

[0063] [N2SA] The nitrogen adsorption specific surface area (N2SA) of the carbon black is not particularly limited, but is preferably 50 to 200 m for the reason that the effect of the present invention is more excellent. 2 / g, and 70 to 150m 2 / g is more preferred. Here, the nitrogen adsorption specific surface area (N2SA) is the amount of nitrogen adsorbed onto the surface of carbon black measured according to JIS K6217-2:2001 "Part 2: Determination of specific surface area - Nitrogen adsorption method - Single point method."

[0064] [Content] In the composition of the present invention, the content of carbon black is not particularly limited, but in order to achieve better effects of the present invention, the content is preferably 1 to 130 parts by mass, more preferably 2 to 100 parts by mass, and even more preferably 5 to 50 parts by mass, per 100 parts by mass of the rubber component described above.

[0065] [Silane coupling agents] The composition of the present invention preferably contains a silane coupling agent, since this will provide better effects of the present invention.

[0066] The silane coupling agent is not particularly limited as long as it is a silane compound having a hydrolyzable group and an organic functional group. The hydrolyzable group is not particularly limited, and examples thereof include an alkoxy group, a phenoxy group, a carboxyl group, and an alkenyloxy group. Of these, an alkoxy group is preferred because the effects of the present invention are more excellent. When the hydrolyzable group is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 to 16, and more preferably 1 to 4, because the effects of the present invention are more excellent. Examples of alkoxy groups having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

[0067] The organic functional group is not particularly limited, but is preferably a group capable of forming a chemical bond with an organic compound, and examples thereof include an epoxy group, a vinyl group, an acryloyl group, a methacryloyl group, an amino group, a sulfide group, a mercapto group, and a blocked mercapto group (protected mercapto group) (for example, an octanoylthio group). Of these, a sulfide group (particularly a disulfide group or a tetrasulfide group), a mercapto group, and a blocked mercapto group are preferred because they provide better effects of the present invention. The silane coupling agents may be used alone or in combination of two or more.

[0068] The silane coupling agent is preferably a sulfur-containing silane coupling agent, since this provides a better effect of the present invention.

[0069] Specific examples of the silane coupling agent include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)disulfide, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl-tetrasulfide, trimethoxysilylpropyl-mercaptobenzothiazole tetrasulfide, triethoxysilylpropyl-methacrylate-monosulfide, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl-tetrasulfide, 3-octanoylthio-1-propyltriethoxysilane, and the like. One of these may be used alone, or two or more may be used in combination.

[0070] [Content] In the composition of the present invention, the content of the silane coupling agent is not particularly limited, but is preferably 2 to 20 parts by mass per 100 parts by mass of the rubber component, because this provides better effects of the present invention.

[0071] In addition, in the composition of the present invention, the content of the silane coupling agent relative to the content of silica described above is preferably 1 to 20 mass %, and more preferably 5 to 15 mass %, because this provides better effects of the present invention.

[0072] [8] Method for preparing rubber composition for tires The method for producing the composition of the present invention is not particularly limited, and specific examples thereof include a method of kneading the above-mentioned components using a known method or apparatus (e.g., a Banbury mixer, a kneader, a roll, etc.) When the composition of the present invention contains sulfur or a vulcanization accelerator, it is preferable to first mix the components other than the sulfur and the vulcanization accelerator at a high temperature (preferably 100 to 160°C), cool the mixture, and then mix the sulfur or the vulcanization accelerator. The composition of the present invention can be vulcanized or crosslinked under conventionally known vulcanization or crosslinking conditions.

[0073] [II] Tires The tire of the present invention is a tire manufactured using the composition of the present invention described above. The tire of the present invention is preferably a pneumatic tire, and can be filled with air, an inert gas such as nitrogen, or other gases.

[0074] 2 is a partial cross-sectional schematic view of a tire showing one example of an embodiment of the tire of the present invention, although the tire of the present invention is not limited to the embodiment shown in FIG.

[0075] In FIG. 2, reference numeral 1 denotes a bead portion, reference numeral 2 denotes a sidewall portion, and reference numeral 3 denotes a tire tread portion. Between the pair of left and right bead portions 1, a carcass layer 4 with fiber cords embedded therein is mounted, and the ends of this carcass layer 4 are folded back and wrapped around the bead core 5 and bead filler 6 from the inside to the outside of the tire. In the tire tread portion 3, a belt layer 7 is disposed on the outer side of the carcass layer 4 around the entire circumference of the tire. In addition, a rim cushion 8 is disposed in the bead portion 1 at the portion that comes into contact with the rim. At least one of the reference numerals 2 to 3, 5 to 6, and 8 (preferably reference numeral 3) is formed from the composition of the present invention described above.

[0076] The tire of the present invention can be manufactured, for example, by a conventionally known method. The gas to be filled into the tire can be normal air or air with an adjusted oxygen partial pressure, or an inert gas such as nitrogen, argon, or helium. [Example]

[0077] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0078] [Production of rubber composition for tires] The components shown in Tables 1 and 2 below were blended in the proportions (parts by mass) shown in the tables. Specifically, first, the components except for sulfur and vulcanization accelerator were kneaded in a 1.7-liter internal mixer for 5 minutes, and then released when the temperature reached 150°C to obtain a master batch. Next, sulfur and vulcanization accelerator were kneaded into the obtained master batch using an open roll to obtain a rubber composition for tires. Note that the parts by mass in the SBR column indicate the net parts by mass of rubber in the SBR (parts by mass excluding extender oil).

[0079] [Wet performance, rolling performance, and dry performance] The obtained rubber composition for tires was vulcanized at 170°C for 15 minutes using a mold of a predetermined shape (inner dimensions: length 150 mm, width 150 mm, thickness 2 mm) to prepare a vulcanized rubber sheet. For the obtained vulcanized rubber sheet, tan δ was measured at temperatures of 0°C, 20°C, and 60°C under conditions of an elongation deformation strain rate of 10%±2% and a vibration frequency of 20 Hz using a viscoelasticity spectrometer (manufactured by Toyo Seiki Seisakusho, Ltd.) in accordance with JIS K6394:2007. Wet performance (braking performance on a wet road surface) was evaluated from tan δ at 0°C, rolling resistance (RRC) from tan δ at 20°C, and dry performance (braking performance on a dry road surface) from tan δ at 60°C. The wet performance is shown in Tables 1 and 2 as an index with the standard example value being 100 (Wet performance). A higher index means better wet performance. In practice, an index of 100 or more is preferable. The rolling performance is shown in Tables 1 and 2 as an index (RRC), with the standard example value being 100. The smaller the index, the better the rolling performance (the smaller the rolling resistance). In practice, an index smaller than 100 is preferable. The dry performance is shown in Tables 1 and 2 as an index with the standard example value being 100 (Dry Performance). A higher index means better dry performance. In practice, an index of 100 or more is preferable.

[0080] [Table 1]

[0081] [Table 2]

[0082] In Tables 1 and 2, the left-hand number in parentheses in the resin column indicates the aromatic proton ratio (%) of the resin, and the right-hand number indicates the S value of the resin. The resin content column indicates the total resin content (mass%) relative to the styrene-butadiene rubber content.

[0083] 〔resin〕 The resins in Tables 1 and 2 are as follows. Resins A to C have an aromatic proton ratio of 20% or more and an S value of 300 or more, and therefore all fall under the above-mentioned resin C1. Resins D to F have an aromatic proton ratio of 1 to 15% and an S value of 200 or less, and therefore all fall under the above-mentioned resin C2. On the other hand, resins G to J do not fall under the above-mentioned resin C1 or resin C2. Furthermore, the Mw of resins A to J is all less than 100,000. Resin A: A resin obtained by thermal polymerization of C5 fraction, indene, and methylindene in a mass ratio of 10 / 63 / 27 (aromatic proton ratio: 41%, S value: 390, Mw: 1037) Resin B: A resin obtained by thermal polymerization of C5 fraction, styrene, α-methylstyrene, vinyltoluene, indene, isopropenyltoluene, and methylindene in a mass ratio of 100 / 3 / 4 / 24 / 28 / 9 / 32 (aromatic proton ratio: 25%, S value: 336, Mw: 1936). Resin C: A resin obtained by thermal polymerization of styrene, α-methylstyrene, vinyltoluene, indene, and isopropenyltoluene in a mass ratio of 3 / 14 / 68 / 13 / 2 (aromatic proton ratio: 37%, S value: 308, Mw: 1522). Resin D: ENEOS T-REZ PR803 (DCPD / C9 resin) (aromatic proton ratio: 10%, S value: 172, Mw: 863) Resin E: Yasuhara Chemical YS Resin TO-85 (aromatic modified terpene resin) (aromatic proton ratio: 10%, S value: 164, Mw: 1408) Resin F: Yasuhara Chemical YS Resin TO-125 (aromatic modified terpene resin) (aromatic proton ratio: 12%, S value: 122, Mw: 1487) Resin G: Resin obtained by thermal polymerization of C5 fraction and indene in a 4 / 1 (mass ratio) (aromatic proton ratio: 12%, S value: 355) Resin H: A resin obtained by thermal polymerization of α-methylstyrene and styrene in a 6 / 5 (mass ratio) ratio (aromatic proton ratio: 54%, S value: 236) Resin I: A resin obtained by thermally polymerizing styrene and then hydrogenating it (aromatic proton ratio: 20%, S value: 189) Resin J: Tosoh Petrotack 90 (C5 / C9 resin) (aromatic proton ratio: 29%, S value: 272, Mw: 2000)

[0084] [Components other than resin] In Tables 1 and 2, the components other than the resin are as follows. SBR: TUFDENE F3420 manufactured by Asahi Kasei Corporation (styrene content: 36% by mass, vinyl unit content: 41 mol%, Tg: -27°C, contains 25 parts by mass of oil extender oil per 100 parts by mass of SBR) BR: Nipol BR1220 manufactured by Nippon Zeon Co., Ltd. Carbon black: Seast N manufactured by Tokai Carbon Co., Ltd. ·Silica: Solvay ZEOSIL 1165MP (CTAB adsorption specific surface area: 160m 2 / g) Silane coupling agent: Evonik Si69 Oil: Shell Lubricants Japan Extract No. 4 S Zinc oxide: Three types of zinc oxide manufactured by Seido Chemical Industry Co., Ltd. Stearic acid: NOF Corporation Beads Stearic Acid YR Anti-aging agent: Flexis 6PPD Sulfur: Tsurumi Chemical Industry Co., Ltd. Kinka-in oil-filled fine powder sulfur Vulcanization accelerator (CZ): Noccela CZ-G (CZ) manufactured by Ouchi Shinko Chemical Industry Co., Ltd. Vulcanization accelerator (DPG): Sumitomo Chemical's Soxinol DG (DPG)

[0085] [Summary of Tables 1 and 2] As can be seen from Tables 1 and 2, Examples 1 to 8, which used a combination of Resin C1 and Resin C2, exhibited excellent wet performance, rolling performance, and dry performance. Furthermore, comparing Examples 1 to 3 (comparison of embodiments differing only in the type of resin C1), Examples 1 and 2, in which the S value of resin C1 was 330 or greater, exhibited better wet performance, rolling performance, and dry performance. In particular, Example 3, in which the S value of resin C1 was 350 or greater, exhibited even better wet performance, rolling performance, and dry performance. Furthermore, comparing Example 1 with Examples 4 and 5 (comparison of embodiments differing only in the type of resin C2), Examples 4 and 5, in which the S value of resin C2 was 170 or less, exhibited better wet performance, rolling performance, and dry performance. In particular, Example 5, in which the S value of resin C2 was 150 or less, exhibited even better wet performance, rolling performance, and dry performance. Furthermore, comparing Examples 1 to 6 (comparison between embodiments in which the total parts by mass of resin C1 and resin C2 is 20 parts by mass), Examples 1 to 5 in which C2 / C1 is 0.5 or more exhibited better dry performance. Furthermore, comparing Examples 1 to 6 (comparison between embodiments in which the total mass parts of resin C1 and resin C2 is 20 mass parts), Example 6, in which C2 / C1 is 0.5 or less, exhibited better wet performance and rolling performance. Furthermore, comparing Example 1 and Example 7 (comparison between embodiments differing only in the content of resin C1 and resin C2), Example 1, in which the total content of resin C1 and resin C2 relative to the content of styrene-butadiene rubber was 10 mass% or more, showed better wet performance and dry performance. Furthermore, comparing Example 1 and Example 8 (comparison between embodiments differing only in the content of resin C1 and resin C2), Example 1, in which the total content of resin C1 and resin C2 relative to the content of styrene-butadiene rubber was 50 mass% or less, showed better rolling performance. Furthermore, comparing Example 1 and Example 8 (comparison between embodiments differing only in the content of resin C1 and resin C2), Example 1, in which the total content of resin C1 and resin C2 relative to the content of styrene-butadiene rubber is 50 mass% or more, exhibited better wet performance and dry performance.

[0086] On the other hand, the following tires were insufficient in at least one of wet performance, rolling performance, and dry performance: the standard example which did not contain resin C1 and resin C2 (contained resins other than resin C1 and resin C2), comparative example 1 which contained resin C1 but not resin C2, comparative example 2 which contained resin C2 but not resin C1, comparative examples 3 and 4 which contained resin C1 but not resin C2 (contained resins other than resin C2), comparative examples 5 and 6 and comparative example 9 which contained resin C2 but not resin C1 (contained resins other than resin C1), comparative example 7 which contained resin C1 and resin C2 but had an SBR content of less than 30 parts by mass per 100 parts by mass of the rubber component, and comparative example 8 which contained resin C1 and resin C2 but not silica. [Explanation of symbols]

[0087] 1 Bead section 2 Sidewall 3 Tire tread 4 carcass layers 5 bead core 6 Bead filler 7 Belt Layer 8 Rim Cushion

Claims

1. The rubber composition contains 100 parts by mass of a rubber component (A) containing 30 parts by mass or more of a styrene-butadiene rubber, 10 to 300 parts by mass of silica (B), a resin (C1), and a resin (C2), The resin (C1) is a resin having a ratio of aromatic hydrocarbon-derived protons determined by an NMR method of 20% or more and a parameter S of 300 or more: The resin (C2) is a resin having a ratio of aromatic hydrocarbon-derived protons determined by an NMR method of 1 to 15% and a parameter S below of 200 or less, a total content of the resin (C1) and the resin (C2) relative to the content of the styrene-butadiene rubber is 1 to 100 mass%. [Equation 1] Here, k ｎ represents the retention coefficient of the n-th peak from the shortest retention time in the total ion chromatogram obtained by pyrolysis gas chromatography mass spectrometry of the resin, and α represents the retention coefficient of the n-th peak from the shortest retention time in the total ion chromatogram obtained by pyrolysis gas chromatography mass spectrometry of the resin, and k ｎ represents the n of the peak having the maximum retention factor of ≦6.0, and A ｎ is k ｎ It represents the ratio (%) of the area of ​​the nth peak to the total area of ​​peaks that satisfy the condition ≦6.

0.

2. The rubber composition for a tire according to claim 1, wherein the parameter S of the resin (C1) is 330 or more.

3. A tire manufactured using the rubber composition for tires according to claim 1 or 2.

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