Rubber composition for tire, and tire

Abstract

To provide a rubber composition for a tire exhibiting excellent wet grip performance, rolling resistance characteristics and performance on an ice and snow road, and to provide a tire produced by using the rubber composition for a tire.SOLUTION: A rubber composition for a tire, comprising 100 parts by mass of a rubber component containing styrene-butadiene rubber, 20 to 90 parts by mass of a resin, 60 to 160 parts by mass of silica, and a plasticizer, wherein the resin has an aromatic hydrocarbon-derived proton ratio determined by NMR of 20% or more and a parameter S of 300 or more, the plasticizer has an aniline point lower than 23 °C, a content of the resin relative to a content of the styrene-butadiene rubber is 30% by mass or more, and a content of the plasticizer relative to the content of the resin is 5 to 50% by mass.SELECTED DRAWING: Figure 2

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, further improvements in wet grip performance, rolling resistance characteristics, and performance on snow have been required from the viewpoints of safety, environmental issues, etc. In this context, the present inventors have studied the rubber composition for tires described in Patent Document 1, and have found that the performance of the rubber composition 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 grip performance, rolling resistance characteristics, and performance on snow 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 intensive research into the above-mentioned problems, the inventors discovered that the above-mentioned problems can be solved by blending a specific resin in a predetermined ratio and a specific plasticizer in a predetermined ratio, and thus 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] The rubber composition contains 100 parts by mass of a rubber component containing styrene-butadiene rubber, 20 to 90 parts by mass of a thermoplastic resin, 60 to 160 parts by mass of silica, and a plasticizer, The thermoplastic resin contains a specific resin, The specific resin has 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 plasticizer has an aniline point below 23°C; the content of the specific resin relative to the content of the styrene-butadiene rubber is 30% by mass or more, A rubber composition for tires, wherein the content of the plasticizer relative to the content of the thermoplastic resin is 5 to 50% by mass. [2] The rubber composition for a tire according to [1], wherein the content of the styrene-butadiene rubber in the rubber component is 30% by mass or more. [3] The rubber composition for a tire according to [1] or [2], wherein the parameter S is 330 or more. [4] A tire manufactured using the rubber composition for a tire according to any one of [1] to [3]. [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 grip performance, rolling resistance characteristics, and performance on snow 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 A. [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 grip performance, rolling resistance characteristics, and performance on snow when made into a tire are also simply referred to as "wet grip performance," "rolling resistance characteristics," and "performance on snow," 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 containing styrene-butadiene rubber, 20 to 90 parts by mass of a thermoplastic resin, 60 to 160 parts by mass of silica, and a plasticizer, The thermoplastic resin contains a specific resin, The specific resin has 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 plasticizer has an aniline point below 23°C; the content of the specific resin relative to the content of the styrene-butadiene rubber is 30% by mass or more, In the rubber composition for tires, the content of the plasticizer relative to the content of the thermoplastic resin is 5 to 50% 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 contains a predetermined amount of a specific resin in which the ratio of aromatic hydrocarbon-derived protons determined by NMR (nuclear magnetic resonance) is 20% or more and the parameter S, which will be described later, is 300 or more relative to styrene-butadiene rubber (hereinafter also referred to as "SBR"). The specific resin has a structure similar to SBR because the ratio of protons derived from aromatic hydrocarbons (hereinafter also referred to as "aromatic proton ratio") is 20% or more. The specific resin has a parameter S (hereinafter also referred to as the "S value") described below 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 the "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. Since the specific resin 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 specific resin are compatible to an extremely high degree, which is thought to lead to excellent wet grip performance and rolling resistance characteristics.

[0015] As described above, the composition of the present invention contains a predetermined amount of a plasticizer having an aniline point lower than 23°C relative to the specific resin (hereinafter also referred to as "specific plasticizer"), and also contains a predetermined amount or more of a thermoplastic resin. The specific plasticizer has a low aniline point, which makes it easy for the rubber component to swell. This facilitates penetration of the thermoplastic resin into the rubber molecular chains, and when a sufficient amount of the thermoplastic resin is included, it is believed to be uniformly dispersed in the composition. This effect, combined with the effect of including a predetermined amount of the specific plasticizer, is believed to have resulted in a tire that exhibits good flexibility at low temperatures and exhibits excellent snow performance, wet grip performance, and rolling resistance characteristics.

[0016] Each component contained in the composition of the present invention will be described below.

[0017] [1] Rubber component 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, an amino group, or the like.

[0018] [SBR] SBR is a copolymer of styrene and butadiene.

[0019] [Styrene content] The styrene content of SBR is not particularly limited, but is preferably 5 to 50% by mass, more preferably 10 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.

[0020] [Vinyl unit content] The vinyl unit content of SBR is not particularly limited, but is preferably 5 to 60 mol %, more preferably 10 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.

[0021] [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 −85° C. to −40° 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.

[0022] [Content] The content of SBR in the rubber component is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, because the effects of the present invention are more excellent. The rubber component may be composed of only SBR. Multiple SBRs may be used in combination.

[0023] [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). Of these, NR and BR are preferred because they provide 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] Thermoplastic resin The thermoplastic resin includes the specific resin, and may further include a thermoplastic resin other than the specific resin (hereinafter referred to as "other resin").

[0027] In the composition of the present invention, the content of the thermoplastic resin is 20 to 90 parts by mass per 100 parts by mass of the rubber component. The content of the thermoplastic resin is preferably 20 to 80 parts by mass, more preferably 25 to 70 parts by mass, and even more preferably 30 to 60 parts by mass, per 100 parts by mass of the rubber component, because this provides better effects of the present invention.

[0028] [Specific resin] The composition of the present invention contains a resin (i.e., a specific resin) having a ratio of aromatic hydrocarbon-derived protons (aromatic proton ratio) of 20% or more as determined by an NMR method and a parameter S (S value) described below of 300 or more.

[0029] The specific resin is preferably a solid at 23°C. The aniline point of the specific resin is preferably 23° C. or higher. The aniline point will be explained later in the section on specific plasticizers.

[0030] [Aromatic proton ratio] The aromatic proton ratio of the specific resin 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 specific resin has a parameter S (S value) of 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 a specific 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 a specific resin, and kn 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 shows a total ion chromatogram (TIC) obtained by pyrolysis GC-MS of Resin A, which will be described later. The pyrolysis GC-MS conditions were as described above. As shown in Figure 1, the TIC of Resin A 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 A 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 specific resin 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 specific resin 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 C5 fractions, such as isoprene and cyclopentadiene.

[0043] When the monomer constituting the specific resin contains aliphatic hydrocarbons (e.g., C5 fractions) in addition to the aromatic hydrocarbons described above, the content of the aromatic hydrocarbons in the monomer 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 monomer constituting the specific resin contains aliphatic hydrocarbons (e.g., C5 fraction) in addition to the aromatic hydrocarbons described above, the content of the aliphatic hydrocarbons in the monomer 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 the specific resin is preferably 100 or more and less than 10,000, more preferably 200 to 5,000, and even more preferably 500 to 3,000, for reasons of better effects of the present invention.

[0045] [Content] In the composition of the present invention, the content of the specific resin relative to the content of the above-mentioned SBR (hereinafter also referred to as "specific resin / SBR") is 30% by mass or more. The lower limit of the specific resin / SBR is preferably 35% by mass or more, and more preferably 40% by mass or more, because the effects of the present invention are more excellent. Furthermore, the upper limit of the specific resin / SBR is preferably 200% by mass or less, more preferably 150% by mass or less, and even more preferably 100% by mass or less, for reasons of better effects of the present invention.

[0046] The content of the specific resin in the thermoplastic resin is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass, because this provides better effects of the present invention.

[0047] The content of the specific resin is preferably 20 to 90 parts by mass, more preferably 25 to 80 parts by mass, and even more preferably 30 to 70 parts by mass, per 100 parts by mass of the rubber component, because this provides better effects of the present invention.

[0048] [Other resins] The other resins are not particularly limited, but examples include thermoplastic resins having an aromatic hydrocarbon-derived proton ratio (aromatic proton ratio) of less than 20% as determined by the NMR method, and thermoplastic resins having an S value of less than 300.

[0049] The content of the other resin in the thermoplastic resin is preferably from 0 to 70% by mass, more preferably from 0 to 50% by mass, and even more preferably from 0 to 30% by mass.

[0050] The content of the other resin is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and further preferably 0 to 20 parts by mass, relative to 100 parts by mass of the rubber component.

[0051] [3] Silica 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.

[0052] [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.

[0053] [Content] In the composition of the present invention, the content of silica is 60 to 160 parts by mass relative to 100 parts by mass of the rubber component. The content is preferably 80 to 150 parts by mass, and more preferably 90 to 140 parts by mass, for the reason that the effects of the present invention are more excellent.

[0054] [4] Specific plasticizers The composition of the present invention contains a plasticizer having an aniline point lower than 23°C (specific plasticizer). The specific plasticizer is preferably a liquid at 23°C.

[0055] [Aniline point] The aniline point of certain plasticizers is below 23°C. The aniline point of a specific plasticizer refers to the lowest temperature at which a mixture (volume ratio 1:1) of aniline and a sample (specific plasticizer) exists as a homogeneous solution, and can be measured in accordance with JIS K 2256:2013.

[0056] [Preferred embodiment] Examples of the specific plasticizer include phosphate esters, phthalate esters, aliphatic polybasic acid esters (for example, bis(2-ethylhexyl) adipate), trimellitate esters, acetate esters, ricinoleate esters, and seed oils, all of which have an aniline point lower than 23° C. Among these, phosphate esters, aliphatic polybasic acid esters, and seed oils are preferred, and phosphate esters and aliphatic polybasic acid esters are more preferred, as they provide better effects of the present invention.

[0057] The phosphate ester as the specific plasticizer is not particularly limited as long as it is an ester of phosphoric acid (H3PO5) and has an aniline point lower than 23° C. The phosphate ester may be any of a monoester, a diester, or a trisester. In the above phosphate ester, the hydrocarbon group constituting the ester is not particularly limited, and examples thereof include an aliphatic hydrocarbon group (linear, branched, or cyclic), an aromatic hydrocarbon group, or a combination thereof. The hydrocarbon group may have, for example, a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom; or a halogen atom such as a chlorine atom. Specific examples of phosphate esters as the specific plasticizer include trisphosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate (particularly tris(2-ethylhexyl)phosphate), tris(2-butoxyethyl)phosphate, tris(2-chloroethyl)phosphate, and 2-ethylhexyldiphenyl phosphate. Among these, tris(2-ethylhexyl)phosphate and tris(2-butoxyethyl)phosphate are preferred, tris(2-ethylhexyl)phosphate and tris(2-butoxyethyl)phosphate are more preferred, and tris(2-butoxyethyl)phosphate is even more preferred, in terms of achieving better effects of the present invention.

[0058] The seed oil as the specific plasticizer is a seed oil having an aniline point lower than 23°C. Specific examples of the seed oil include sunflower oil, rapeseed oil, palm oil, soybean oil, rice bran oil, sesame oil, corn oil, cottonseed oil, olive oil, safflower oil, perilla oil, linseed oil, castor oil, etc. Among these, sunflower oil is preferred because it provides better effects of the present invention.

[0059] The specific plasticizer may be used alone or in combination of two or more types.

[0060] [Content] In the composition of the present invention, the content of the specific plasticizer relative to the content of the thermoplastic resin (hereinafter also referred to as "specific plasticizer / thermoplastic resin") is 5 to 50% by mass. The specific plasticizer / thermoplastic resin content is preferably 5 to 40% by mass, more preferably 10 to 40% by mass, and even more preferably 10 to 35% by mass, in order to achieve better effects of the present invention.

[0061] In the composition of the present invention, the content of the specific plasticizer is preferably 3 to 35 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 5 to 25 parts by mass, per 100 parts by mass of the rubber component.

[0062] [5] 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 various additives commonly used in rubber compositions, such as resins other than thermoplastic resins (e.g., thermosetting resins), plasticizers other than the specific plasticizer, 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, vulcanizing agents (e.g., sulfur), vulcanization accelerators (accelerators), and vulcanization activators.

[0063] [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.

[0064] [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."

[0065] [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, it is preferably 1 to 130 parts by mass, and more preferably 2 to 100 parts by mass, per 100 parts by mass of the rubber component described above.

[0066] [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.

[0067] 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.

[0068] 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.

[0069] The silane coupling agent is preferably a sulfur-containing silane coupling agent, since this provides a better effect of the present invention.

[0070] 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.

[0071] [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.

[0072] 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.

[0073] [6] 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.

[0074] [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.

[0075] 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.

[0076] 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.

[0077] 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]

[0078] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0079] [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 the 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 the vulcanization accelerator were kneaded into the obtained master batch using an open roll to obtain a rubber composition for tires.

[0080] [Wet grip performance and rolling resistance characteristics] 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. The vulcanized rubber sheets were measured for tan δ at temperatures of 0°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 grip performance was evaluated from tan δ at 0°C, and rolling resistance characteristics were evaluated from tan δ at 60°C. The wet grip performance is shown in Tables 1 and 2 as an index (tan δ(0°C)) with the value of Comparative Example 1 being 100. A larger index means better wet grip performance. In practice, an index of 110 or more is preferred. The rolling resistance properties are shown in Tables 1 and 2 as an index (tan δ(60°C)) with the value of Comparative Example 1 being 100. A smaller index means better rolling resistance properties (smaller rolling resistance). In practice, an index of 85 or less is preferable.

[0081] [Snow 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. The storage modulus E'(-20°C) of the obtained vulcanized rubber sheet was measured in accordance with JIS K6394:2007 using a viscoelasticity spectrometer (manufactured by Toyo Seiki Seisakusho, Ltd.) under conditions of an elongation deformation strain rate of 10%±0.5%, a vibration frequency of 20 Hz, and a temperature of -20°C. "On-snow performance" was evaluated as the reciprocal of the storage modulus E' (-20°C), and is shown in Tables 1 and 2 as an index (E' (-20°C)) with the value of Comparative Example 1 being 100. A higher index indicates better "on-snow performance." In practice, an index of 115 or higher is preferred.

[0082] [Table 1]

[0083] [Table 2]

[0084] In Tables 1 and 2, the columns "aromatic proton ratio" and "S value" respectively show the aromatic proton ratio and S value of the resin (resins A to E) used in each example. In Tables 1 and 2, the column "specific resin / SBR" indicates the content (mass %) of the specific resin (resins A to C) relative to the content of SBR in each example. In addition, in Tables 1 and 2, the column "Specific plasticizer / thermoplastic resin" indicates the content (mass %) of the specific plasticizer (plasticizers 1 to 4) relative to the content of the thermoplastic resin (resins A to E) in each example.

[0085] [Thermoplastic resin] In Tables 1 and 2, resins A to E, which are thermoplastic resins, are as follows. Note that 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 specific resins. On the other hand, resin D does not fall under the above-mentioned specific resins, as its aromatic proton ratio is less than 20%. Furthermore, resin E does not fall under the above-mentioned specific resins, as its S value is less than 300. Furthermore, the Mw of resins A to E is all less than 100,000. Furthermore, resins A to E are all solid at 23°C. 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: A resin obtained by thermal polymerization of C5 fraction and indene in a 4 / 1 (mass ratio) ratio (aromatic proton ratio: 12%, S value: 355) Resin E: A resin obtained by thermally polymerizing α-methylstyrene and styrene in a 6 / 5 (mass ratio) ratio (aromatic proton ratio: 54%, S value: 236)

[0086] [Plasticizer] The plasticizers in Tables 1 and 2 are as follows. Plasticizers 1 to 4 have aniline points below 23°C, so they all fall under the above-mentioned specific plasticizers. On the other hand, plasticizers 5 and 6 have aniline points above 23°C, so they do not fall under the above-mentioned specific plasticizers. Furthermore, all of plasticizers 1 to 6 are liquid at 23°C. Plasticizer 1: Tris(2-ethylhexyl) phosphate, Aniline point: Room temperature (23°C) or below Plasticizer 2: Tris(2-butoxyethyl) phosphate, Aniline point: Room temperature (23°C) or below Plasticizer 3: bis(2-ethylhexyl) adipate, aniline point: room temperature (23°C) or below Plasticizer 4: Sunflower oil, Aniline point: Room temperature (23°C) or below Plasticizer 5: Shell TDAE oil, aniline point: 88°C Plasticizer 6: Sankyo Yuka Co., Ltd., naphthenic oil, aniline point: 83°C

[0087] [Components other than resin] In Tables 1 and 2, the components other than the resin and plasticizer are as follows. SBR HPR840: SBR, manufactured by ENEOS Materials, with a glass transition temperature of -60°C NR: Natural rubber, SIR-20, glass transition temperature -62℃ Li-BR BR1261: NIPOL BR 1261 manufactured by Nippon Zeon Co., Ltd. CB: Cabot Japan Show Black N339 ·Silica: Solvay ZEOSIL 1165MP (CTAB adsorption specific surface area: 160m 2 / g) Silane coupling agent: Evonik Si69 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 1: Noccela CZ-G (CZ) manufactured by Ouchi Shinko Chemical Industry Co., Ltd. Vulcanization accelerator 2: Sumitomo Chemical Co., Ltd., Soxinol DG (DPG)

[0088] [Summary of Tables 1 and 2] As can be seen from Tables 1 and 2, Examples 1 to 12, which contain a specific resin in a predetermined ratio relative to the SBR content, a specific plasticizer in a predetermined ratio relative to the thermoplastic resin content, a predetermined amount of thermoplastic resin, and a predetermined amount of silica, showed excellent wet grip performance, rolling resistance characteristics, and performance on snow. Comparing Examples 1 to 3 (comparison of embodiments differing only in the type of specific resin), Examples 1 and 2, in which the specific resin had an S value of 330 or more, exhibited better wet grip performance, rolling resistance characteristics, and performance on snow. Among them, Example 1, in which the specific resin had an S value of 350 or more, exhibited even better wet grip performance, rolling resistance characteristics, and performance on snow. Furthermore, a comparison between Example 1 and Example 5 (comparison between embodiments with different SBR contents) showed that Example 1, in which the SBR content in the rubber component was 30% by mass or more, exhibited better rolling resistance properties and snow performance. Furthermore, a comparison between Example 1 and Example 6 (comparison between embodiments with different silica contents, carbon black contents, and silane coupling agent contents) showed that Example 1, which had a silica content of 80% by mass or more, exhibited better wet grip performance, rolling resistance characteristics, and performance on snow. Furthermore, a comparison between Example 1 and Example 7 (comparison between embodiments with different thermoplastic resin content, specific plasticizer content, and plasticizer type) showed that Example 1, which has a thermoplastic resin content of 40 parts by mass or more, exhibited better wet grip performance, rolling resistance characteristics, and performance on snow. Furthermore, a comparison of Example 1, Example 8, Example 9, and Example 10 (comparison between embodiments that differ only in the type of specific plasticizer) revealed that Examples 1 and 8, in which the specific plasticizer is a phosphate ester, and Example 9, in which the specific plasticizer is an aliphatic polybasic acid ester, exhibited better wet grip performance, rolling resistance characteristics, and performance on snow. Furthermore, a comparison between Example 1 and Example 11 (comparison between examples in which the content of the specific plasticizer and the type of plasticizer differ in part) showed that Example 1, in which the content of the specific plasticizer was 10 parts by mass or more, exhibited better wet grip performance, rolling resistance characteristics, and performance on snow. Furthermore, comparing Example 1 and Example 12 (comparison between embodiments with different specific plasticizer contents, carbon black contents, and silica contents), Example 1, in which the specific plasticizer content was 30 parts by mass or less, showed better wet grip performance.

[0089] On the other hand, Comparative Example 1, which contained a resin other than the specified resin instead of the specified resin and a plasticizer other than the specified plasticizer instead of the specified plasticizer, had insufficient wet grip performance, rolling resistance characteristics, and performance on snow. Furthermore, Comparative Examples 2 to 4, which contained a plasticizer other than the specified plasticizer instead of the specified plasticizer, were insufficient in wet grip performance, rolling resistance characteristics, and performance on snow. Furthermore, Comparative Examples 5 and 9, in which the specific plasticizer / thermoplastic resin content was outside the range of 5 to 50% by mass, were insufficient in wet grip performance, rolling resistance characteristics, and performance on snow. Furthermore, Comparative Examples 6 and 7, which contained a resin other than the specific resin instead of the specific resin, were insufficient in wet grip performance, rolling resistance characteristics, and performance on snow. Furthermore, Comparative Example 8, in which the specific resin / SBR content was less than 30% by mass, was insufficient in wet grip performance, rolling resistance characteristics, and performance on snow. Furthermore, Comparative Example 10, which did not contain SBR, was insufficient in wet grip performance, rolling resistance characteristics and performance on snow. Furthermore, Comparative Example 11, in which the content of the thermoplastic resin was less than 20 parts by mass, had insufficient wet grip performance. Furthermore, Comparative Example 12, in which the content of the thermoplastic resin was more than 90 parts by mass, had insufficient rolling resistance characteristics and performance on snow. Furthermore, Comparative Example 13, in which the silica content was less than 60 parts by mass, was insufficient in wet grip performance, rolling resistance characteristics, and performance on snow. [Explanation of symbols]

[0090] 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 containing styrene-butadiene rubber, 20 to 90 parts by mass of a thermoplastic resin, 60 to 160 parts by mass of silica, and a plasticizer, The thermoplastic resin contains a specific resin, The specific resin has 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 plasticizer has an aniline point below 23°C; the content of the specific resin relative to the content of the styrene-butadiene rubber is 30% by mass or more, A rubber composition for tires, wherein the content of the plasticizer relative to the content of the thermoplastic resin is 5 to 50 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 content of the styrene-butadiene rubber in the rubber component is 30% by mass or more.

3. The rubber composition for a tire according to claim 1, wherein the parameter S is 330 or more.

4. A tire manufactured using the rubber composition for tires according to any one of claims 1 to 3.

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