KR101140250B1 - Tread rubber composition and tire manufactured by using the same - Google Patents

Abstract

The present invention relates to a rubber composition for a tire tread and a tire manufactured using the same, comprising 10 to 30 parts by weight of natural rubber (NR), 30 to 50 parts by weight of styrene butadiene rubber (SBR) and 30 to 55 of butadiene rubber (BR). 100 parts by weight of raw rubber including parts by weight, 80 to 120 parts by weight of silica, and 5 to 10 parts by weight of an alkanoyl thio based silane coupling agent.

The rubber composition for tire treads has excellent braking performance on dry or wet roads while using eco-friendly materials, and also has excellent braking performance on snowy roads and excellent rolling resistance.

For all seasons, tread rubber composition, tread, rubber, styrene butadiene rubber, butadiene rubber, neodymium, Nd, silica, silane coupling agent, coupling agent, alkanoylthio, alkanoylthio silane coupling agent, softener, processing oil, braking performance

Description

Rubber composition for tire treads and tires manufactured using the same {TREAD RUBBER COMPOSITION AND TIRE MANUFACTURED BY USING THE SAME}

The present invention relates to a rubber composition for a tire tread and a tire manufactured using the same, which has excellent braking performance on dry or wet roads while using eco-friendly materials, and also has excellent braking performance on a snowy road surface, and also has a rolling resistance performance. It relates to an excellent rubber tread rubber composition and a tire produced using the same.

Recently, due to global warming, the amount of snow has decreased worldwide, and the temperature after snow has also increased relatively. Therefore, after the snow, ice roads may be formed, but as the snow melts to become a slush state or as it rains, there are many cases of forming a wet road surface state.

It is difficult to manufacture a tire having excellent braking performance in a general case that does not take into consideration snow and snow surface at the same time, because the characteristics of the composition are in conflict with each other, so if one performance is superior, another performance is disadvantageous. For losing.

In winter, consumers replace it with winter tires that have excellent braking performance on the snowy road surface, but when it is not on the snowy road surface or when the snow melts and gets wet, the braking performance becomes very disadvantageous. Is increasing. In particular, braking performance is directly related to driving stability, which is also a major concern of recent tire manufacturers, and research and development are actively being conducted to solve this problem.

In order to solve this problem, by using styrene butadiene rubber having a high styrene content in the tread rubber composition of the winter tire, the glass transition temperature of the rubber composition is raised to improve the braking performance on a general dry or wet road surface. However, in this case, as the styrene content is increased, the hardness and modulus of the rubber at a low temperature are increased, which has a problem of lowering the braking performance on the snow surface.

In addition, a method of using silica as a reinforcing agent is also used.Since silica has excellent reinforcement property compared to carbon black, it has excellent braking performance on dry or wet road surface in general case, and not on ice road surface, and temperature dependency at low temperature. Since the increase rate of hardness and modulus due to temperature decrease is low compared to carbon black, there is an advantage in braking performance on the ice road surface. However, simply changing the reinforcing agent from carbon black to silica in the formulation of the tread rubber composition of the winter tire does not effectively improve the braking performance on the wet road surface. Therefore, the improvement of braking performance on wet road surface of winter tires using silica has been very limited, and it remains a difficult technical task to balance the two contradictory performances to meet the needs of consumers.

On the other hand, although there are various kinds of softeners among the additives of the rubber composition for tire treads for passenger cars, aromatic oils are generally known to improve processability and optimum properties in refining and extrusion processes.

However, with the recent increase in environmental awareness, when the content of polycyclic aromatic hydrocarbons (PAHs) contained in aromatic oils of 3% by weight or more is known to cause cancer, the European Rubber Association (BRIC) accepts this result. In the EU, a specific use regulation plan was established, and in the EU, the benzopyrene content was 1 mg / kg or more, and the eight major PAHs contained more than 10 mg / kg or the total PAHs contained more than 3% by weight. By enforcing the prohibition system after January 1, 2010, all tire manufacturers consider it an urgent problem to solve.

It is an object of the present invention to provide a rubber composition for tire treads that is excellent in braking performance on a dry or wet road surface while also using environmentally friendly materials, and also excellent in braking performance on a snowy road surface.

Another object of the present invention is to provide a tire manufactured using the rubber tread rubber composition.

In order to achieve the above object, the rubber composition for a tire tread according to an embodiment of the present invention is 10 to 30 parts by weight of natural rubber (NR), 30 to 50 parts by weight of styrene butadiene rubber (SBR) and butadiene rubber (BR) 30 It includes 100 parts by weight of the raw material rubber including from 55 parts by weight, 80 to 120 parts by weight of silica, and 5 to 10 parts by weight of an alkanoyl thio-based silane coupling agent.

The styrene butadiene rubber is a solution-polymerized styrene butadiene rubber having a styrene content of 20 to 30% by weight, a vinyl content of butadiene is 60 to 70% by weight, a molecular weight distribution of 2 to 3, and the butadiene rubber is a neodyne butadiene It may be rubber.

The silica may have a BET surface area of 160 to 180 m ² / g and a DBP oil absorption of 180 to 210 cc / 100 g.

The alkanoyl thio based silane coupling agent may be represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

N is an integer of 1 to 10,

R ₂ , R ₃ and R ₄ are each independently selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms, and R ₃ and R ₄ may be connected to each other to form a ring And

R ₅ and R ₆ are each independently selected from the group consisting of hydrogen and an alkyl group having 1 to 5 carbon atoms,

R ₁ is an alkyl group having 1 to 15 carbon atoms.

The alkanoyl thio based silane coupling agent may be represented by the following formula (2).

(2)

In Chemical Formula 2,

N is an integer of 1 to 10,

R ₂ is any one selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms,

R ₅ and R ₆ are each independently selected from the group consisting of hydrogen and an alkyl group having 1 to 5 carbon atoms,

R ₁ is an alkyl group having 1 to 15 carbon atoms.

Another object of the present invention is to provide a tire manufactured using the rubber composition for the tread.

Hereinafter, the present invention will be described in more detail.

Unless stated herein, an alkyl group may be linear or crushed, substituted or unsubstituted. Herein, "substituted" means that a hydrogen atom is a halogen atom, hydroxy group, carboxyl group, alkoxy group, nitrile group, aldehyde group, epoxy group, ether group, ester group, carbonyl group, acetal group, ketone group, alkyl group, heteroalkyl group, perfluor It means substituted by any one selected from the group consisting of a roalkyl group, cycloalkyl group, heterocycloalkyl group, allyl group, benzyl group, aryl group, heteroaryl group, derivatives thereof and combinations thereof.

Unless otherwise specified herein, the prefix "hetero" means that one to three heteroatoms selected from the group consisting of N, O, S and P are substituted for a carbon atom. For example, the heteroalkyl group means that the carbon atom in the alkyl group is substituted with 1 to 3 hetero atoms selected from the group consisting of N, O, S and P.

The tire tread rubber composition includes a raw material rubber, silica, and a silane coupling agent.

The raw rubber includes natural rubber (NR), styrene butadiene rubber (SBR) and butadiene rubber (BR).

The natural rubber is a rubber obtained in nature, and means a rubber mainly containing polyisoprene as a monomer. The natural rubber may further include dust and the like, and the RSS (ribbed smoked sheet) grade (grade) may be # 1, # 2, # 3, # 4, # 5, preferably RSS # 1, It may be # 2, # 3. The natural rubber may be a general natural rubber or modified natural rubber, the general natural rubber may be used as long as it is known as a natural rubber, may be produced in Malaysia, Cambodia, Indonesia, Sri Lanka, Brazil, etc. It is not limited.

The styrene butadiene rubber may include an emulsion-polymerized styrene-butadiene rubber (E-SBR), a solution-polymerized styrene-butadiene rubber (S-SBR), and a combination thereof. Any one selected from may be used, and preferably, solution polymerization styrene butadiene rubber (S-SBR) may be used.

In general, the solution-polymerized styrene butadiene rubber (S-SBR) is prepared by a continuous and batchwise manner. The styrene butadiene rubber produced by the continuous method contains a large amount of low molecular weight material, which is disadvantageous in terms of rotational resistance compared to the styrene butadiene rubber produced by the batch method, but has excellent processability and high hysteresis loss, so that dry roads or wet Excellent braking performance on road surface. Therefore, as the styrene butadiene rubber, it is more preferable to use a solution-polymerized styrene butadiene rubber prepared in a continuous manner.

The solution-polymerized styrene butadiene rubber prepared by the continuous method has a molecular weight distribution of 2 to 3, and has a broader molecular weight distribution than the styrene butadiene rubber prepared by a batch method. The solution-polymerized styrene butadiene rubber prepared by the continuous method having such a molecular weight distribution has excellent workability and high hysteresis loss, which is characterized by excellent braking performance on dry or wet roads.

The styrene butadiene rubber may be a solution-polymerized styrene butadiene rubber having a styrene content of 20 to 30% by weight and a vinyl content of butadiene to 60 to 70% by weight. The styrene butadiene rubber is excellent in braking performance due to high hysteresis loss due to the high vinyl content when using styrene butadiene rubber having a styrene content of 20 to 30% by weight and a vinyl content of butadiene is 60 to 70% by weight. There is an advantageous effect in that.

The styrene butadiene rubber may also contain no oil, and may contain oil. In the case of containing the oil, the amount of the extended oil may be used in a range that can be generally used in consideration of the processability and the effect on the rubber composition.

The butadiene rubber may be any one selected from the group consisting of cobalt butadiene rubber (Co-BR), nickel butadiene rubber (Ni-BR), neodymium butadiene rubber (Nd-BR), and a combination thereof, preferably neodymium Butadiene rubber (Nd-BR) can be used. Compared to cobalt butadiene rubber (Co-BR) or nickel butadiene rubber (Ni-BR), the neodymium butadiene rubber (Nd-BR) has a narrow molecular weight distribution and linear molecular structure, and thus has low hysteresis of the rubber, thereby reducing rolling resistance. Excellent and excellent wear performance.

The butadiene rubber may also contain no oil and may contain oil. In the case of containing the oil, the amount of the extended oil may be used in a range that can be generally used in consideration of processability and the effect on the rubber composition.

The raw rubber may include 10 to 30 parts by weight of natural rubber (NR), 30 to 50 parts by weight of styrene butadiene rubber (SBR), and 30 to 55 parts by weight of butadiene rubber (BR), preferably natural rubber (NR) 10 to 30 parts by weight, styrene butadiene rubber (SBR) may include 30 to 40 parts by weight, and butadiene rubber (BR) 30 to 40 parts by weight.

Including less than 10 parts by weight of the natural rubber as the raw material rubber may be disadvantageous to the durability of the tire tread, when containing more than 30 parts by weight of the natural rubber may be disadvantageous braking performance on wet or dry road surface have. When the styrene butadiene rubber is included as less than 30 parts by weight of the raw material rubber, braking performance may be disadvantageous on dry or wet road surfaces, and when it contains more than 50 parts by weight, braking performance and fuel economy performance on ice and snow road surfaces. This can be disadvantageous. When the butadiene rubber is included as less than 30 parts by weight of the raw material rubber, braking performance and fuel efficiency may be deteriorated on ice and snow surfaces, and when it is included in more than 55 parts by weight, braking performance on wet or dry road surfaces may be detrimental. have.

The raw material rubber may further include any one selected from the group consisting of natural rubber, synthetic rubber and combinations thereof that are generally used as raw rubber.

The natural rubber may be a general natural rubber or modified natural rubber.

The general natural rubber may be used as long as it is known as a natural rubber, the country of origin and the like are not limited. The natural rubber contains cis-1,4-polyisoprene as a main agent, but may also include trans-1,4-polyisoprene depending on the required properties. Accordingly, the natural rubber includes, in addition to natural rubber containing cis-1,4-polyisoprene as a main agent, for example, natural containing trans-1,4-isoprene as a main agent such as balata, which is a kind of rubber of South American sapotaceae. Rubber may also be included.

The modified natural rubber means a modified or refined general natural rubber. For example, the modified natural rubber may include epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, and the like.

The synthetic rubber is styrene butadiene rubber (SBR), modified styrene butadiene rubber, butadiene rubber (BR), modified butadiene rubber, chloro sulfonated polyethylene rubber, epichlorohydrin rubber, fluorine rubber, silicone rubber, nitrile rubber, hydrogenated Nitrile Rubber, Nitrile Butadiene Rubber (NBR), Modified Nitrile Butadiene Rubber, Chlorinated Polyethylene Rubber, Styrene Ethylene Butylene Styrene (SEBS) Rubber, Ethylene Propylene Rubber, Ethylene Propylene Diene (EPDM) Rubber, Hypalon Rubber, Chloroprene Rubber, Ethylene vinyl acetate rubber, acrylic rubber, hydrin rubber, vinyl benzyl chloride styrene butadiene rubber, bromo methyl styrene butyl rubber, maleic acid styrene butadiene rubber, carboxylic acid styrene butadiene rubber, epoxy isoprene rubber, maleic acid ethylene propylene rubber, carboxylic acid Nitrile Butadiene High Radish, brominated polyisobutyl isoprene-co-paramethyl styrene (brominated polyisobutyl isoprene-co-paramethyl styrene, BIMS) and combinations thereof may be any one selected from the group.

The silica may be any silica that is used as a reinforcing filler in rubber for tires. Preferably, precipitated silica can be used. The silica may have a BET surface area of 160 to 180 m ² / g and a DBP (n-dibutyl phthalate) oil absorption of 180 to 210 cc / 100 g. In the case of using the silica, it is advantageous to improve the abrasion resistance because the dispersion is advantageous, and in particular, the braking performance on the wet road surface.

The silica may be used both wet or dry methods, and commercially available products include Ultrasyl 7000 (manufactured by Evonik Degussa), Ultrasyl VN2 (manufactured by Evonik Degussa), Ultrasyl VN3 (manufactured by Evonik Degussa) , Zeil 1165MP (Rhodia) can be used

The content of the silica may be included in an amount of 80 to 120 parts by weight, preferably 80 to 110 parts by weight, and more preferably 100 to 110 parts by weight, based on 100 parts by weight of the raw material rubber.

When the content of the silica is less than 80 parts by weight, the strength improvement of the rubber may be insufficient and the braking performance of the tire may be reduced, and when the content of the silica exceeds 120 parts by weight, wear performance may be reduced.

Alkanoyl thio based silane coupling agent means a silane coupling agent comprising an R'COS- group.

The alkanoyl thio-based silane coupling agent may be preferably represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

N is an integer of 1-10, Preferably it is an integer of 1-6.

R ₂ , R ₃ and R ₄ are each independently selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms, preferably an alkyl group having 2 to 4 carbon atoms and alkoxy having 1 to 4 carbon atoms Any one selected from the group consisting of groups, wherein R ₃ and R ₄ may be connected to each other to form a ring.

R ₅ and R ₆ are each independently selected from hydrogen and an alkyl group having 1 to 5 carbon atoms.

R ₁ is an alkyl group having 1 to 15 carbon atoms, preferably an alkyl group having 3 to 10 carbon atoms.

The alkanoyl thio based silane coupling agent may be more preferably represented by the following formula (2).

(2)

In Chemical Formula 2,

N is an integer of 1-10, Preferably it is an integer of 1-6.

R ₂ is any one selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms, and preferably may be any one selected from the group consisting of an alkyl group having 2 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. have.

R ₅ and R ₆ are each independently selected from hydrogen and an alkyl group having 1 to 5 carbon atoms.

R ₁ is an alkyl group having 1 to 15 carbon atoms, preferably an alkyl group having 3 to 10 carbon atoms.

The alkanoyl thio-based silane coupling agent may be specifically represented by the following formula (3).

[Formula 3]

The alkanoyl thio-based silane coupling agent, unlike the sulfide-based silane coupling agent commonly used in rubber compositions for tires, does not provide free sulfur that can participate in vulcanization in the molecule, so that the scorch in the compounding process of the rubber composition The phenomenon is very stable. In addition, since high scorch stability enables rubber compounding at high temperatures, the coupling reaction rate between the polymer and silica is high, which is very advantageous for the rotational resistance of the compounded rubber.

In addition, when a large amount of practice car is used as a reinforcing filler, the braking performance on dry or wet roads is improved, but the rubber itself tends to become hard, so that braking performance is particularly disadvantageous on ice and snow roads. In case the reaction is not sufficiently achieved, there is a disadvantage in that the wear performance is disadvantageous. In the case of using the alkanoyl thio-based silane coupling agent, even if a large amount of silica is used, the wear performance does not decrease due to the high coupling reaction rate. No, the rubber is less hard. For this reason, in the case of the rubber composition using the alkanoyl thio-based silane coupling agent, the braking performance on the ice-snow road surface is also not reduced.

The alkanoyl thio based silane coupling agent may be used in an amount of 5 to 10 parts by weight based on 100 parts by weight of the raw material rubber. When the alkanoyl thio-based silane coupling agent is used in less than 5 parts by weight, the wear resistance and fuel efficiency of the rubber may be lowered, and when used in excess of 10 parts by weight, the hardness increases and the snow surface This can adversely affect the braking performance at.

Examples of the silane coupling agent include a sulfide silane compound, a mercapto silane compound, a vinyl silane compound, an amino silane compound, a glycidoxy silane compound, a nitro silane compound, a chloro silane compound, a methacryl silane compound, and these Any one selected from the group consisting of combinations may be further used.

The sulfide silane compound may include bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (4-triethoxysilylbutyl) tetrasulfide, bis (3- Trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, bis (4-trimethoxysilylbutyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis ( 2-triethoxysilylethyl) trisulfide, bis (4-triethoxysilylbutyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide, bis (2-trimethoxysilylethyl) trisulfide, Bis (4-trimethoxysilylbutyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) disulfide, bis (4-triethoxysilylbutyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, bis (2-trimeth Sisylethyl) disulfide, bis (4-trimethoxysilylbutyl) disulfide, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethyl Thiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide and combinations thereof It may be any one selected from the group consisting of.

The mercapto-based silane compound is 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and combinations thereof It may be any one selected from the group consisting of. The vinyl silane compound may be any one selected from the group consisting of ethoxysilane, vinyltrimethoxysilane and combinations thereof. The amino silane compound is 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltri It may be any one selected from the group consisting of methoxysilane and combinations thereof.

The glycidoxy silane compounds include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane And combinations thereof may be any one selected from the group consisting of. The nitro silane compound may be any one selected from the group consisting of 3-nitropropyltrimethoxysilane, 3-nitropropyltriethoxysilane, and combinations thereof. The chloro-based silane compound is selected from the group consisting of 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, and combinations thereof. It can be any one.

The methacrylic silane compound is any one selected from the group consisting of γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl methyldimethoxysilane, γ-methacryloxypropyl dimethyl methoxysilane, and combinations thereof Can be.

The rubber composition for tire treads may further include a softener to impart plasticity to the rubber to facilitate processing or to lower the hardness of the vulcanized rubber. The softener may be any one selected from the group consisting of process oil, vegetable oil, and combinations thereof, but the present invention is not limited thereto.

As the processing oil, any one selected from the group consisting of paraffin processing oil, naphthenic processing oil, aromatic processing oil, and combinations thereof may be used.

However, with the recent increase in environmental awareness, when the content of polycyclic aromatic hydrocarbons (PAHs) contained in the aromatic process oil is more than 3% by weight, it is known that cancer is likely to be caused.TDAE (treated distillate) Aromatic extract oil, mild extraction solvate (MES) oil, residual aromatic extract (RAE) oil or heavy naphthenic oil can be preferably used.

In particular, the oil used as the softener has a total content of PAHs component of 3% by weight or less, a kinematic viscosity of 95 ° C or more (210 ° F SUS), an aromatic component in the softener of 15 to 25% by weight, naphthenic TDAE oils with 27 to 37% by weight and 38 to 58% by weight of paraffinic components can be preferably used.

The TDAE oil is advantageous in terms of environmental factors such as the low temperature characteristics of the tire tread including the TDAE oil, fuel efficiency, and the likelihood of causing cancer of PAHs.

The plant oils include castor oil, cottonseed oil, linseed oil, canola oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, pine tar, tall oil, corn oil, rice bran oil, safflower oil, sesame oil, olive oil, sunflower oil, palm kernel oil, camellia oil It may be used any one selected from the group consisting of jojoba oil, macadamia nut oil, saflower flower oil, tung oil and combinations thereof.

The softener may be used in 20 to 40 parts by weight with respect to 100 parts by weight of the raw rubber, preferably 20 to 30 parts by weight. If the content of the softener is less than 20 parts by weight, the workability and braking performance may be low. If the content of the softener exceeds 40 parts by weight, the workability and wear performance may be disadvantageous.

The tire tread rubber composition may optionally further include various additives such as additional vulcanizing agents, vulcanization accelerators, vulcanization accelerators, anti-aging agents and the like. The various additives can be used as long as it is commonly used in the field of the present invention, the content thereof is not particularly limited, depending on the compounding ratio used in the conventional tire tread rubber composition.

As the vulcanizing agent, metal oxides such as sulfur vulcanizing agents, organic peroxides, resin vulcanizing agents, and magnesium oxide can be used.

The sulfur-based vulcanizing agents include inorganic vulcanizing agents such as powdered sulfur (S), insoluble sulfur (S), precipitated sulfur (S) and colloidal sulfur, tetramethylthiuram disulfide (TMTD) and tetraethyl. Organic vulcanizing agents such as tetraethyltriuram disulfide (TETD) and dithiodimorpholine can be used. Specifically, as the sulfur vulcanizing agent, a vulcanizing agent which produces elemental sulfur or sulfur, for example, amine disulfide, polymer sulfur, or the like can be used.

The organic peroxide may be benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3 -Bis (t-butylperoxypropyl) benzene, di-t-butylperoxy-diisopropylbenzene, t-butylperoxybenzene, 2,4-dichlorobenzoyl peroxide, 1,1-dibutylperoxy- Any one selected from the group consisting of 3,3,5-trimethylsiloxane, n-butyl-4,4-di-t-butylperoxyvalerate and combinations thereof can be used.

As the vulcanizing agent, sulfur vulcanizing agents can be preferably used. Specifically, amine disulfide, polymer sulfur, or the like, which is a vulcanizing agent for producing elemental sulfur or sulfur, may be used. Particularly preferably elemental sulfur can be used.

The vulcanizing agent is preferably included in an amount of 1 to 3 parts by weight based on 100 parts by weight of the raw rubber, which is preferable in that the raw rubber is less sensitive to heat and chemically stable.

The vulcanization accelerator refers to an accelerator that promotes the rate of vulcanization or promotes delay in the initial vulcanization stage.

The vulcanization accelerators include sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamic acid, aldehyde-amine, aldehyde-ammonia, imidazoline, xanthate and their Any one selected from the group consisting of a combination can be used.

Examples of the sulfenamide vulcanization accelerators include N-cyclohexyl-2-benzothiazylsulfenamide (CBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS), and N, N-dicyclohexyl. Any one selected from the group consisting of 2-benzothiazylsulfenamide, N-oxydiethylene-2-benzothiazylsulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide and combinations thereof The sulfenamide type compound of can be used.

Examples of the thiazole vulcanization accelerators include 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), sodium salt of 2-mercaptobenzothiazole and zinc salt of 2-mercaptobenzothiazole. , Copper salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-di Any thiazole compound selected from the group consisting of ethyl 4-morpholinothio) benzothiazole and combinations thereof can be used.

Examples of the thiuram-based vulcanization accelerators include tetramethyl thiuram disulfide (TMTD), tetraethyl thiuram disulfide, tetramethyl thiuram monosulfide, dipentamethylene thiuram disulfide, dipentamethylene thiuram monosulfide and dipentamethylene. Any thiuram-based compound selected from the group consisting of thiuram tetrasulfide, dipentamethylene thiuram hexasulfide, tetrabutyl thiuram disulfide, pentamethylene thiuram tetrasulfide, and combinations thereof can be used.

As the thiourea vulcanization accelerator, for example, thiocarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea, and any combination thereof is selected from the group of thiourea Compounds can be used.

As the guanidine-based vulcanization accelerator, for example, any one guanidine-based compound selected from the group consisting of diphenylguanidine, diorthotolylguanidine, triphenylguanidine, orthotolylbiguanide, diphenylguanidine phthalate, and combinations thereof can be used. Can be.

Examples of the dithiocarbamic acid-based vulcanization accelerators include ethylphenyldithiocarbamate zinc, butylphenyldithiocarbamate zinc, sodium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, Zinc dibutyldithiocarbamate, zinc diamyldithiocarbamate, zinc dipropyldithiocarbamate, zinc salt of pentamethylenedithiocarbamate and piperidine, hexadecylisopropyldithiocarbamate zinc, octadecyl Isopropyldithiocarbamate zinc dibenzyldithiocarbamate zinc, sodium diethyldithiocarbamate, pentamethylenedithiocarbamate piperidine, dimethyldithiocarbamate selenium, diethyldithiocarbamate tellurium, dia One dithiocarbamic acid compound selected from the group consisting of cadmium didicarbamate and combinations thereof can be used.

The aldehyde-amine-based or aldehyde-ammonia based vulcanization accelerator, for example, acetaldehyde-aniline reactant, butylaldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde-ammonia reactant and combinations thereof -Amine based or aldehyde-ammonia based compounds can be used.

As said imidazoline type vulcanization accelerator, imidazoline type compounds, such as 2-mercaptoimidazoline, can be used, for example, As said xanthate type vulcanization accelerator, xanthate type, such as zinc dibutyl xanthogenate Compounds can be used.

The vulcanization accelerator may be included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the raw rubber in order to maximize productivity and rubber properties by promoting the vulcanization rate.

The vulcanization accelerator is a compounding agent used in combination with the vulcanization accelerator to complete its promoting effect. Any one selected from the group consisting of inorganic vulcanization accelerators, organic vulcanization accelerators and combinations thereof can be used. .

As the inorganic vulcanization accelerating aid, any one selected from the group consisting of zinc oxide (ZnO), zinc carbonate, magnesium oxide (MgO), lead oxide, potassium hydroxide and combinations thereof may be used have. The organic vulcanization accelerator is selected from the group consisting of stearic acid, zinc stearate, palmitic acid, linoleic acid, oleic acid, lauric acid, dibutyl ammonium oleate, derivatives thereof, and combinations thereof. You can use either one.

In particular, the zinc oxide and the stearic acid may be used together as the vulcanization accelerator, in which case the zinc oxide is dissolved in the stearic acid to form an effective complex with the vulcanization accelerator, thereby releasing advantageous sulfur during the vulcanization reaction. It facilitates the crosslinking reaction of the rubber.

When using the zinc oxide and the stearic acid together may be used in 1 to 5 parts by weight and 0.5 to 3 parts by weight with respect to 100 parts by weight of the raw rubber, respectively, to serve as a suitable vulcanization accelerator.

The anti-aging agent is an additive used to stop the chain reaction in which the tire is automatically oxidized by oxygen. As the anti-aging agent, any one selected from the group consisting of amine-based, phenol-based, quinoline-based, imidazole-based, carbamic acid metal salts, waxes, and combinations thereof may be appropriately selected.

Examples of the amine antioxidant include N-phenyl-N '-(1,3-dimethyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-diaryl-p-phenylenediamine, N-phenyl-N ' Any one selected from the group consisting of -cyclohexyl p-phenylenediamine, N-phenyl-N'-octyl-p-phenylenediamine, and combinations thereof can be used.

The phenolic anti-aging agent is phenolic 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-isobutylidene-bis (4,6-dimethylphenol), 2 Any one selected from the group consisting of, 6-di-t-butyl-p-cresol and combinations thereof can be used.

As the quinoline anti-aging agent, 2,2,4-trimethyl-1,2-dihydroquinoline and derivatives thereof may be used, and specifically 6-ethoxy-2,2,4-trimethyl-1,2-di Hydroquinoline, 6-anilino-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline and combinations thereof Any one selected from the group can be used. Wax hydrocarbon may be preferably used as the wax.

The anti-aging agent is preferably N- (1,3-dimethylbutyl) -N-phenyl-p-phenylenediamine (N- (1,3-Dimethybutyl) -N-phenyl-p-phenylenediamine, 6PPD), N N-phenyl-n-isopropyl-p-phenylenediamine (3PPD), poly (2,2,4-trimethyl-1,2-dihydroquinoline (Poly (2 , 2,4-trimethyl-1,2-dihydroquinoline, RD) and combinations thereof may be used.

The anti-aging agent has a high solubility in rubber in addition to the anti-aging action, is low in volatility, inert to rubber, and does not inhibit vulcanization. It may be included in parts by weight.

The rubber composition for a tire tread can be produced through a conventional two-step continuous manufacturing process. That is, during the finishing step in which the first step of thermomechanical treatment or kneading at a maximum temperature ranging from 110 to 190 ° C., preferably from 130 to 180 ° C. (called “non-production” step) and the crosslinking system are mixed, Typically can be prepared in a suitable mixer using a second step (called "production" step) of mechanical treatment at a low temperature of less than 110 ° C, for example 40 to 100 ° C, but the invention is not limited thereto. .

The rubber composition for the tire tread is not limited to the tread (tread cap and tread base), and may be included in various rubber components constituting the tire. Such rubber components include sidewalls, sidewall inserts, apex, chafers, wire coats or innerliners, and the like.

A tire according to another embodiment of the present invention is manufactured using the rubber tread rubber composition. The method of manufacturing a tire using the tire tread rubber composition may be applied to any method conventionally used for the production of tires, and thus, detailed description thereof will be omitted.

The tire may be a passenger car tire, a racing tire, an airplane tire, a farm tire, an off-the-road tire, a truck tire or a bus tire. In addition, the tire may be a radial tire or a bias tire, and is preferably a radial tire.

The rubber composition for tire treads of the present invention is excellent in braking performance on dry or wet roads while also using environmentally friendly materials, and also excellent in braking performance on ice roads, and excellent in rolling resistance.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[ Manufacturing example : Preparation of Rubber Composition]

To prepare a tire tread rubber composition according to the following Examples and Comparative Examples using the composition shown in Table 1. The preparation of the tire tread rubber composition was in accordance with a conventional method for producing tire tread rubber.

Table 1

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Example 1 Example 2 Example 3 Natural rubber 20 20 20 20 20 20 20 20 S-SBR 1 ⁽¹⁾ 40 (55) - - - - - - - S-SBR 2 ⁽²⁾ - 40 (55) 40 (55) 40 (55) 40 (55) 40 (55) 40 (55) 40 (55) BR 1 ⁽³⁾ 40 40 - - - - - - BR 2 ⁽⁴⁾ - - 40 (55) 40 (55) 40 (55) 40 (55) 40 (55) 40 (55) Silica ⁽⁵⁾ 100 100 100 100 100 100 100 100 Coupling Agents 1 ⁽⁶⁾ 7 7 7 - - - - - Coupling Agents 2 ⁽⁷⁾ - - - 3 12 5 7 9 Oil Processed ⁽⁸⁾ 40.6 40.6 25.6 25.6 25.6 25.6 25.6 25.6 Zinc oxide 3 3 3 3 3 3 3 3 Stearic acid One One One One One One One One Antioxidant ⁽⁹⁾ 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 Vulcanizer ⁽¹⁰⁾ 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Accelerators ⁽¹¹⁾ 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Accelerators ⁽¹²⁾ 2 2 2 2 2 2 2 2

(Unit: parts by weight)

The numerical values in parentheses listed in Table 1 above represent the weight parts of raw rubber including oil when each rubber used as raw rubber contains oil.

(1) S-SBR 1: solution-polymerized styrene-butadiene rubber (SBR) prepared by a batch method having a styrene content of 24% by weight and a vinyl content of 66% by weight of butadiene, including 37.5 parts by weight of TDAE Oil.

(2) S-SBR 2: solution-polymerized styrene-butadiene rubber (SBR), TDAE Oil having a molecular weight distribution of 2 to 3, prepared by a continuous process having a styrene content of 24% by weight and a vinyl content of 66% by weight of butadiene. 37.5 parts by weight.

(3) BR 1: Nickel butadiene (BR) rubber made by Kumho Petrochemical Co., Ltd.

(2) BR 2: Neodyne butadiene rubber (BR) manufactured by Lanxess, which includes 37.5 parts by weight of CB29MES and MES Oil.

(5) Silica: Precipitated silica having a BET surface area of 160 to 180 m ² / g and a DBP oil absorption of 180 to 210 cc / 100 g

(6) Coupling Agent 1: Degussa trade name is Si69

(7) Coupling agent 2: Alkanoyl Thio silane made by Momentive, trade name is Low V NXT

(8) Processed oil: As a softener, the total content of Polycyclic Aromatic Hydocarbons (PAHs) is 3% by weight or less. % And 47.5% by weight paraffinic component as trade name Vivatec500

(9) Antioxidant: N- (1,3-dimethylbutyl) -N-phenyl-p-phenylenediamine (N- (1,3-Dimethybytyl) -N'-Phenyl-p-Phenlenediamine) manufactured by Unibond. Silver 6PPD

(10) Vulcanizer: Elemental Sulfur

(11) Accelerator: N-Cyclohexyl-2-Benzothiazolesulfonamide, which is a DUSLO brand name Sulfenax CBS.

(12) Accelerator: Diphenylguanidine (DPG)

KBR01, BR1 in Table 1, does not contain oil, and BR2 is an oil containing butadiene rubber, in the case of Comparative Examples 1 and 2 including BR1. It was used compared to the increase.

[ Experimental Example : Manufactured tire For tread  Measurement of physical properties of rubber composition]

Mooney viscosity, hardness, 300% modulus, viscoelasticity, and the like were measured using the rubber composition for tire treads obtained in Examples 1 to 3 and Comparative Examples 1 to 5 according to ASTM-related regulations. Table 2 shows.

TABLE 2

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Example 1 Example 2 Example 3 Mooney viscosity 70 66 69 55 45 52 50 48 Hardness (ShoreA) 66 66 66 65 70 66 67 68 300% Modulus (Mpa) 8.0 7.9 8.0 7.9 9.0 8.2 8.4 8.6 -40 ℃ G '(dyne / ㎠) 8.9E + 08 9.3E + 08 9.0E + 08 1.24E + 09 9.1E + 08 9.5E + 08 9.7E + 08 1.04E + 09 0 ℃ tan δ 0.221 0.219 0.218 0.219 0.341 0.233 0.243 0.281 60 ℃ tan δ 0.150 0.153 0.145 0.169 0.107 0.126 0.122 0.111

Pattern viscosity (ML1 + 4 (125 degreeC)) was measured by ASTM specification D1646. ML1 + 4 represents the viscosity of the unvulcanized rubber, and the lower the value, the better the workability of the unvulcanized rubber.

Hardness was measured according to DIN 53505. The higher the value, the better the steering stability.

300% modulus was measured by ISO 37 standard. Higher values indicate better strength.

Viscoelasticity was measured G ′, G ”, tan δ from −60 ° C. to 60 ° C. at 10 Hz frequency at 0.5% strain using an RDS meter. -40 ℃ G 'represents the braking characteristics on ice and snow surface. The lower the value, the better the braking performance. The 0 ℃ tanδ shows the braking characteristics on the dry or wet road surface. Excellent. 60 ° C tan δ represents rotation resistance, and the lower the value, the better the fuel efficiency.

Examples 1 to 3 showed excellent results in overall workability, hardness, 300% modulus, and viscoelasticity compared to Comparative Examples 1 to 4. Comparative Example 5 showed more excellent physical properties than the example, but it was found that the braking performance on the ice snow surface was remarkably inferior.

By using the rubber composition of the comparative examples and examples, a tire of 205 / 55R16 standard including a tread rubber manufactured as a semi-finished product was manufactured, and a braking performance and a fuel efficiency performance on a dry road surface, a wet road surface, and a snow road surface were manufactured. Was measured and the relative ratio is shown in Table 3.

[Table 3]

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Example 1 Example 2 Example 3 Dry road braking performance 100 100 99 100 107 102 104 106 Wet road
Braking performance 100 102 102 102 112 105 108 110 Snow surface
Braking performance 100 98 100 100 92 99 98 97 Fuel efficiency 100 98 102 95 110 105 107 109

As can be seen from the results of Tables 2 and 3, compared with Comparative Examples 1 and 3, Examples 1 to 3 improved the braking performance on the wet road surface without deteriorating the braking performance on the ice road surface, and Comparative Example 4 Compared with Comparative Example 5 and Examples 1 to 3 it can be seen that the braking performance on the dry and wet road surface is greatly improved and the rotational resistance is also significantly lowered and the fuel economy performance is excellent without a great decrease in the braking performance on the ice snow road surface. .

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims (6)

100 parts by weight of raw rubber including 10 to 30 parts by weight of natural rubber (NR), 30 to 50 parts by weight of styrene butadiene rubber (SBR), and 30 to 55 parts by weight of butadiene rubber (BR), 100 to 120 parts by weight of silica, and Alkanoyl thio based silane coupling agent 5 to 10 parts by weight Including; The alkanoyl thio-based silane coupling agent is a rubber composition for tire treads represented by the following formula (2). (2)

(In Formula 2, N is an integer of 1 to 10, R ₂ is any one selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms, R ₅ and R ₆ are each independently selected from the group consisting of hydrogen and an alkyl group having 1 to 5 carbon atoms, R ₁ is an alkyl group having 1 to 15 carbon atoms) The method of claim 1, The styrene butadiene rubber is a solution-polymerized styrene butadiene rubber having a styrene content of 20 to 30% by weight, butadiene content of 60 to 70% by weight, a molecular weight distribution of 2 to 3, The butadiene rubber is a rubber composition for tire tread that is neodyne butadiene rubber. The method of claim 1, The silica has a BET surface area of 160 to 180m ² / g, DBP oil absorption of 180 to 210cc / 100g rubber composition for a tire tread. delete delete A tire manufactured using the rubber composition for tire tread according to any one of claims 1 to 3.