KR101376986B1 - Rubber composition for tire tread and tire manufactured by using the same - Google Patents

Abstract

The present invention relates to a rubber composition for tire treads and a tire manufactured using the same.
10 to 30 parts by weight of natural rubber, 21 to 50% by weight of styrene, 30 to 70% by weight of vinyl in butadiene, styrene polymerized by a batch process with a glass transition temperature of -10 to -30 ° C. 100 parts by weight of raw rubber including 40 to 60 parts by weight of butadiene rubber, and 20 to 50 parts by weight of neodymium butadiene rubber (Nd-BR) containing 20 to 40% by weight of TDAE (treated distillate aromatic extract) oil, And it is provided as a rubber composition for tire tread comprising 75 to 95 parts by weight of silica.
The tire tread rubber composition may improve the braking property and the rolling resistance on the wet road surface and the snowy road surface, thereby maintaining low fuel efficiency.

Description

TECHNICAL FIELD [0001] The present invention relates to a rubber composition for a tire tread, and a tire manufactured using the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a rubber composition for a tire tread and a tire manufactured using the same, and more particularly, to a rubber composition for a tire tread having excellent low fuel efficiency and braking performance on a road surface, and a tire manufactured using the same.

Various characteristics are required for the tire, and the characteristics required for the tire are somewhat different depending on each part of the tire. In particular, since the tread of the tire is in direct contact with the road surface, most characteristics of the tire are required, and according to the trend of increasing performance of passenger cars, consumer demand for high performance tires is increasing day by day.

In particular, since 2012, the labeling system for tire performance has been implemented in Europe and Japan, and consumers' interest in tire performance, including low fuel consumption, has increased due to the implementation of energy efficiency rating system in Korea. This tire performance labeling system is leading the improvement of the efficiency of the wet road surface braking, low fuel consumption, low noise. In addition, snow tires, the most important performance of winter tires, cannot be excluded. Therefore, in the case of winter tires, it is an important task to simultaneously satisfy the braking performance, low fuel consumption and other performance.

In general, the use of low Tg (glass transition temperature) rubber can improve the wear performance and fuel economy of the tire. In this case, however, braking performance is generally lowered. This is because the braking property is excellent as the hysteresis heat loss caused by the deformation of the rubber is excellent, and on the contrary, the low fuel consumption performance is excellent when the hysteresis heat loss is small.

In addition, the braking performance of wet road surface can be improved by increasing the rubber content of rubber with high styrene or silica as a reinforcing agent, which increases rubber hardness and modulus. have.

Thus, each performance of a tire shows that when one performance is improved, the other performance is degraded. Therefore, the technical development has been improved by minimizing the performance degradation while minimizing the performance degradation of the other one, or at the same time, improving both performances. It's happening. Therefore, it is important to develop a rubber composition for a tire tread that has a balanced improvement in braking performance and low fuel consumption, which is a contradictory performance.

According to the prior art, Patent Document 1 (Registration No. KR 10-0749347, published date: August 14, 2007) is a tire tread rubber composition containing a reinforcing filler, silica, clay, carbonic acid with respect to 100phr of raw rubber Tire tread rubber composition characterized in that it comprises at least one reinforcing filler selected from magnesium 40 to 100 phr, crab shell powder 15 to 45 phr. This has the characteristics that can improve the braking properties while maintaining a low fuel consumption, the crab shell powder is difficult to be evenly dispersed with the rubber is not good workability, there is a problem of falling off the rubber of the finished tire due to the small affinity with the rubber. .

In addition, Patent Document 2 (Publication Number: KR 10-2003-0092669, Publication Date: December 6, 2003) is a tread using the carbon black, silica alone or a mixture thereof as a reinforcing filler In the rubber composition, although it is improved to wet road surface by including 7 to 50 parts by weight of barium sulfate with respect to 100 parts by weight of the raw material rubber, the use of carbon black and silica alone increases the hardness of the rubber, thus limiting the realization of low fuel consumption. There is a limit in not presenting the optimum mixing ratio even in the mixing thereof. In addition, the addition of barium sulfate also improves the braking performance, but there is a limit to the realization of low fuel consumption, there is a limit to simultaneously satisfy the aspects of low fuel consumption and improved braking performance.

Accordingly, there is a need for development of a tire tread composition that simultaneously realizes low fuel efficiency and simultaneously meets the opposite performance of improving braking performance on ice or wet road surfaces.

KR 10-0749347 B1 KR 10-2003-0092669 A

SUMMARY OF THE INVENTION An object of the present invention is to provide a rubber tread rubber composition which shows excellent braking property even on wet roads and snowy roads and improves rolling resistance on ice roads, and at the same time the rubber tread rubber composition has excellent low fuel efficiency. To have.

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

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, 21 to 50% by weight of styrene, 30 to 70% by weight of vinyl in butadiene A glass transition temperature of -10 to -30 ° C, neodymium containing 40 to 60 parts by weight of styrene-butadiene rubber polymerized by a batch process, and 20 to 40% by weight of treated distillate aromatic extract (TDAE) oil. ) Butadiene rubber (Nd-BR) may be 100 parts by weight of the raw material rubber containing 20 to 50 parts by weight, and may include 75 to 95 parts by weight of silica.

The neodymium-butadiene rubber may have a glass transition temperature of −110 to −100 ° C. and a cis 1,4-butadiene content of 94 to 98 wt%.

In addition, the silica is IDS (Intermediate DisperSibility) silica, nitrogen adsorption specific surface area of 140 to 160m ² / g, CTAB (cetyltrimethyl ammonium bromide) adsorption specific surface area of 140 to 160m ² / g, DBP oil absorption 120 to 140cc It may be / 100g.

Tire tread according to another embodiment of the present invention is prepared by using the rubber composition for the tire tread.

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

Rubber tread composition according to an embodiment of the present invention 10 to 30 parts by weight of natural rubber, styrene content of 21 to 50% by weight, vinyl content of butadiene 30 to 70% by weight and a glass transition temperature of -10 to Neodymium butadiene rubber (Nd-BR) containing from 40 to 60 parts by weight of styrene-butadiene rubber polymerized in a batch process and 20 to 40% by weight of treated distillate aromatic extract (TDAE) oil. ) May include 100 parts by weight of raw material rubber including 20 to 50 parts by weight, and 75 to 95 parts by weight of silica.

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

The general natural rubber may be used as long as it is known as natural rubber, and the origin and the like are not limited. The natural rubber includes cis-1,4-polyisoprene as a main component, but may also include trans-1,4-polyisoprene depending on required characteristics. Therefore, in addition to natural rubber containing cis-1,4-polyisoprene as a main component, natural rubber including trans-1,4-isoprene as a main component, such as balata, Rubber may also be included.

The modified natural rubber means that the general natural rubber is modified or purified. For example, examples of the modified natural rubber include epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber.

When the natural rubber is included in less than 10 parts by weight based on 100 parts by weight of the raw rubber, there is a problem that the elastic force is lowered, and when included in more than 30 parts by weight may be abrasion resistance and aging resistance of the tire.

Generally, solution-polymerized styrene butadiene rubber (hereinafter referred to as "S-SBR") is prepared by continuous and batchwise processes. 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 low hysteresis loss, which is suitable for low fuel efficiency performance. can do.

The S-SBR may have a styrene content of 21 to 50% by weight, a vinyl content in butadiene of 30 to 70% by weight, and a glass transition temperature (Tg) of -10 to -30 ° C. In the case of using the S-SBR having the above characteristics, since the hysteresis of the tire tread is increased, the braking performance may be improved on the road surface, and the braking property on the wet road surface may be more advantageous because the glass transition temperature is relatively higher. In addition, since it has a vinyl content in the butadiene relatively high compared to the styrene content, it has an advantageous feature in low fuel consumption.

The content of the styrene butadiene rubber may be included in an amount of 40 to 60 parts by weight based on 100 parts by weight of the raw material rubber. When the content of the styrene butadiene rubber is less than 40 parts by weight, the braking performance may be low. This can be disadvantageous.

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 has low hysteresis of the rubber, thus excellent rotation resistance. In particular, the neodymium butadiene rubber having a glass transition temperature of −110 to −100 ° C. and a cis 1,4-butadiene content of 94 to 98 wt% has excellent rotational resistance and excellent wear performance.

In addition, the neodymium-butadiene rubber contains 20 to 40% by weight of treated distillate aromatic extract (TDAE) oil, when the TDAE oil content is less than 20% by weight, the effect of improving the wear resistance and low fuel consumption is insignificant, exceeding 40% by weight. In this case, since the amount of processing oil used because the oil contained in the rubber is excessively reduced, workability is disadvantageous.

The tire tread rubber composition includes 75 to 95 parts by weight of silica as a reinforcing agent.

The silica may be included in an amount of 75 to 95 parts by weight, and preferably 80 to 90 parts by weight, based on 100 parts by weight of the raw material rubber. When the content of silica is less than 75 parts by weight, the strength improvement of the rubber may be insufficient and the braking performance of the tire may be reduced. When the content of the silica is more than 95 parts by weight, wear resistance may be deteriorated and fuel efficiency may be adversely affected. Because it can.

The silica may be HDS (High DisperSibility) silica or IDS (Intermediate DisperSibility) silica.

HDS silica has a nitrogen adsorption specific surface area (N ₂ SA) of 160 to 180 m ₂ / g and a CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area Refers to a silica of 150 to 170 m 2 / g. In addition, the IDS silica refers to silica having a nitrogen adsorption specific surface area of 140 to 160 m 2 / g and a CTAB adsorption specific surface area of 140 to 160 m 2 / g.

When the nitrogen adsorption specific surface area of the silica is less than 140 m 2 / g, reinforcing performance by silica as a filler may be disadvantageous, and when it exceeds 160 m 2 / g, the workability of the rubber composition may be detrimental. In addition, when the CTAB adsorption specific surface area of the silica is less than 140 m 2 / g, the reinforcing performance by the filler silica may be detrimental, and when it exceeds 160 m 2 / g, the workability of the rubber composition may be detrimental. Therefore, the present invention is not limited thereto, but the silica may be IDS silica (Intermediate DisperSibility).

In addition, the HDS silica has a small dispersiveness compared to the IDS silica, but has a high dispersibility, but there is a problem that the reinforcement is lowered, but because the IDS silica is superior in reinforcement compared to the HDS silica, tires for wet road surface This has the advantage of improving braking performance.

As the reinforcing agent other than the silica, any one selected from the group consisting of carbon black, calcium carbonate, clay (aluminum hydrated silica), aluminum hydroxide, lignin, silicate, talc and combinations thereof may be used together. Preferably, silica and carbon black can be used together, since the silica and carbon black can be used together to improve braking performance on wet roads and exhibit good abrasion resistance.

The carbon black may have a nitrogen surface area per gram (N ₂ SA) of 30 to 300 m ² / g and an oil absorption amount of DBP (n-dibutyl phthalate) of 60 to 180 cc / 100 g, But is not limited thereto.

If the nitrogen adsorption specific surface area of the carbon black exceeds 300 m ² / g, the workability of the rubber composition for a tire may be deteriorated. If it is less than 30 m ² / g, the reinforcing performance by carbon black as a filler may be deteriorated. If the DBP oil absorption of the carbon black exceeds 180 cc / 100 g, the workability of the rubber composition may be deteriorated. If it is less than 60 cc / 100 g, the reinforcing performance by carbon black as a filler may be deteriorated.

Examples of the carbon black include N110, N121, N134, N220, N231, N234, N242, N293, N299, S315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 or N991.

The rubber composition for a tire tread may further include various additives such as an additional vulcanizing agent, a vulcanization accelerator, a vulcanization accelerator, a coupling agent, an anti-aging agent, and a softening agent. The various additives can be used as long as they are commonly used in the field to which the present invention belongs. The content thereof is not particularly limited as long as it depends on a compounding ratio used in a rubber composition for a tire tread.

As the vulcanizing agent, a sulfur vulcanizing agent can be preferably used. The sulfur vulcanizing agent may be an inorganic vulcanizing agent such as powdered sulfur (S), insoluble sulfur (S), precipitated sulfur (S), or colloid sulfur. As the sulfur vulcanizing agent, a vulcanizing agent which produces elemental sulfur or sulfur, for example, amine disulfide, polymer sulfur and the like can be used.

The vulcanizing agent is preferably included in an amount of 1.5 to 25 parts by weight based on 100 parts by weight of the raw material rubber, in that the raw material rubber is less sensitive to heat and chemically stable.

The vulcanization accelerator refers to an accelerator that promotes the vulcanization rate or accelerates the retardation in the initial vulcanization step.

Examples of the vulcanization accelerator include sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamate, aldehyde-amine, aldehyde-ammonia, imidazoline, Or a combination thereof.

Examples of the sulfenamide type vulcanization accelerator include N-cyclohexyl-2-benzothiazyl sulfenamide (CBS), N-tert-butyl-2-benzothiazyl sulfenamide (TBBS), N, N-dicyclohexyl -2-benzothiazyl sulfenamide, N-oxydiethylene-2-benzothiazyl sulfenamide, N, N-diisopropyl-2-benzothiazole sulfenamide, and combinations thereof Based compound can be used.

Examples of the thiol-based vulcanization accelerator include 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), sodium salt of 2-mercaptobenzothiazole, zinc salt of 2-mercaptobenzothiazole , A copper salt of 2-mercaptobenzothiazole, a cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- Ethyl 4-morpholinothio) benzothiazole, and combinations thereof. The thiazole-based compound may be used alone or in combination of two or more thereof.

Examples of the thiuram-based vulcanization accelerator include tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylthiuram disulfide, dipentamethylthiuram monosulfide, dipentamethylene Any one of thiuram-based compounds selected from the group consisting of thiuram tetrasulfide, dipentamethylenethiuram hexasulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, and combinations thereof can be used.

Examples of the thiourea vulcanization accelerator include thiourea compounds selected from the group consisting of thiacarbamide, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, diorthotolyl thiourea, and combinations thereof. Compounds may be used.

Examples of the guanidine-based vulcanization accelerator include guanidine-based compounds selected from the group consisting of diphenyl guanidine, diorthotolyl guanidine, triphenyl guanidine, orthotolyl biguanide, diphenyl guanidine phthalate, and combinations thereof .

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.

Examples of the aldehyde-amine type or aldehyde-ammonia type vulcanization accelerator include aldehyde selected from the group consisting of acetaldehyde-aniline reactant, butylaldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde-ammonia reactant, -Amine-based or aldehyde-ammonia-based compounds may be used.

As the imidazoline-based vulcanization accelerator, for example, an imidazoline-based compound such as 2-mercaptoimidazoline can be used. Examples of the xanthate vulcanization accelerator include xanthates such as zinc dibutylxanthogenate Compounds may be used.

The vulcanization accelerator may be included in an amount of 0.5 to 4.0 parts by weight based on 100 parts by weight of the raw material rubber in order to maximize productivity improvement and rubber property enhancement through vulcanization speed promotion.

The vulcanization accelerating assistant may be any one selected from the group consisting of an inorganic vulcanization accelerator aid, an organic vulcanization accelerator aid, and a combination thereof, which is used in combination with the vulcanization accelerator to complete the promoting effect thereof .

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. As the organic vulcanization accelerating auxiliary, there may be selected from the group consisting of stearic acid, zinc stearate, palmitic acid, linoleic acid, oleic acid, lauric acid, dibutyl ammonium oleate, derivatives thereof, Can be used.

In particular, the zinc oxide and the stearic acid may be used together as the vulcanization accelerating assistant. In this case, the zinc oxide is dissolved in the stearic acid to form an effective complex with the vulcanization accelerator, Thereby facilitating the crosslinking reaction of the rubber.

When the zinc oxide and the stearic acid are used together, they may be used in an amount of 1 to 5 parts by weight and 0.5 to 3 parts by weight, respectively, based on 100 parts by weight of the raw rubber to serve as a proper vulcanization accelerator. If the content of the zinc oxide and the stearic acid is less than the above range, the vulcanization rate may be slow and the productivity may be deteriorated. If the content exceeds the above range, the scorch phenomenon may occur and the physical properties may be deteriorated.

Examples of the 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 a combination thereof. Any one selected from the group consisting of may be used, and preferably a sulfide-based silane compound may be used.

The sulfide-based silane compound is preferably selected from the group consisting of bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, bis (4-trimethoxysilylbutyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis Bis (3-trimethoxysilylethyl) trisulfide, bis (4-triethoxysilylethyl) trisulfide, bis (4-trimethoxysilylbutyl) trisulfide, bis (3-triethoxysilylbutyl) disulfide, bis (4-triethoxysilylbutyl) disulfide, bis 3-trimethoxysilylpropyl) disulfide, bis (2-trimethoxy Triethoxysilylbutyl) disulfide, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethyl 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 2-trimethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl 3-trimethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, and combinations thereof may be used in combination with at least one compound selected from the group consisting of benzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, And the like.

The mercaptosilane compound may be at least one selected from the group consisting of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, May be any one selected from the group consisting of The vinyl-based silane compound may be any one selected from the group consisting of ethoxysilane, vinyltrimethoxysilane, and combinations thereof. The amino-based silane compound is preferably selected from the group consisting of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- Methoxysilane, and a combination thereof.

The glycidoxime silane compound is preferably selected from the group consisting of? -Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropylmethyldimethoxysilane And a combination thereof. The nitro-based 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 Lt; / RTI >

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 coupling agent may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the raw rubber for improving dispersibility of the silica. If the content of the coupling agent is less than 1 part by weight, improvement in dispersibility of silica may be insufficient, resulting in deterioration of rubber workability and lowering of fuel consumption performance. When the amount exceeds 20 parts by weight, interaction between silica and rubber is too strong, May be excellent, but the braking performance may be very poor.

The sulfide-based silane compound is preferably selected from the group consisting of bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, bis (4-trimethoxysilylbutyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis Bis (3-trimethoxysilylethyl) trisulfide, bis (4-triethoxysilylethyl) trisulfide, bis (4-trimethoxysilylbutyl) trisulfide, bis (3-triethoxysilylbutyl) disulfide, bis (4-triethoxysilylbutyl) disulfide, bis 3-trimethoxysilylpropyl) disulfide, bis (2-trimethoxy Triethoxysilylbutyl) disulfide, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethyl 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 2-trimethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl 3-trimethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, and combinations thereof may be used in combination with at least one compound selected from the group consisting of benzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, And the like.

The mercaptosilane compound may be at least one selected from the group consisting of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, May be any one selected from the group consisting of The vinyl-based silane compound may be any one selected from the group consisting of ethoxysilane, vinyltrimethoxysilane, and combinations thereof. The amino-based silane compound is preferably selected from the group consisting of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- Methoxysilane, and a combination thereof.

The glycidoxime silane compound is preferably selected from the group consisting of? -Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropylmethyldimethoxysilane And a combination thereof. The nitro-based 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 Lt; / RTI >

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 coupling agent may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the raw rubber for improving dispersibility of the silica. If the content of the coupling agent is less than 1 part by weight, improvement in dispersibility of silica may be insufficient, resulting in deterioration of rubber workability and lowering of fuel consumption performance. When the amount exceeds 20 parts by weight, interaction between silica and rubber is too strong, May be excellent, but the braking performance may be very poor.

The softening agent is added to the rubber composition in order to impart plasticity to the rubber to facilitate processing or to decrease the hardness of the vulcanized rubber, and means an oil or other material used in rubber compounding or rubber production. The softening agent means an oil contained in a process oil or other rubber composition. The softener may be selected from the group consisting of petroleum oils, vegetable oils, and combinations thereof, but the present invention is not limited thereto.

The petroleum-based oil may be selected from the group consisting of paraffinic oil, naphthenic oil, aromatic oil, and combinations thereof.

Examples of the paraffin oil include P-1, P-2, P-3, P-4, P-5 and P-6 of Mychang Oil Co., N-1, N-2 and N-3 of Kokai Co., Ltd., and representative examples of the aromatic oils include A-2 and A-3 of Mingchang Oil Co.,

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

Particularly, the oil used as the softening agent preferably has a total content of PAHs components of not more than 3 wt%, a kinematic viscosity of not less than 95 (210 S SUS), an aromatic component of 15 to 25 wt%, a naphthene component Of 27 to 37% by weight and a paraffinic component of 38 to 58% by weight can be preferably used.

The TDAE oil is advantageous for environmental factors such as the low temperature characteristics of the tire tread including the TDAE oil and the possibility of the cancer induction of PAHs while improving the fuel consumption performance.

Examples of the vegetable oils include vegetable oils such as castor oil, cottonseed oil, linseed oil, canola oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, pine tar, tall oil, cone oil, rice bran oil, safflower oil, sesame oil, , Jojoba oil, macadamia nut oil, four flower oil, tung oil, and combinations thereof.

It is preferable that the softening agent is used in an amount of 0 to 150 parts by weight based on 100 parts by weight of the raw material rubber in order to improve workability of the raw material rubber.

The antioxidant is an additive used to stop the chain reaction in which the tire is autoxidized by oxygen. As the anti-aging agent, any one selected from the group consisting of an amine type, a phenol type, a quinoline type, an imidazole type, a carbamic acid metal salt, a wax and a combination thereof can be appropriately selected and used.

Examples of the amine type antioxidant include N-phenyl-N '- (1,3-dimethyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N'- Phenyl-N'-isopropyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, -Cyclohexyl p-phenylenediamine, N-phenyl-N'-octyl-p-phenylenediamine, and combinations thereof. Examples of the phenolic antioxidant include phenol-based 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'- isobutylidene- Di-t-butyl-p-cresol, and combinations thereof. As the quinoline antioxidant, 2,2,4-trimethyl-1,2-dihydroquinoline and its derivatives can be used. Specifically, 6-ethoxy-2,2,4-trimethyl- Dihydroquinoline, 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. As the wax, waxy hydrocarbons can be preferably used.

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

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

The tires may be automobile tires, racing tires, airplane tires, agricultural tires, off-the-road tires, truck tires or bus tires. Further, the tire may be a radial tire or a bias tire, and preferably a radial tire.

The rubber composition for tire treads according to the present invention exhibits excellent braking property even on wet roads and snow roads, and can improve rotational resistance to ice roads. At the same time, it is possible to improve low fuel efficiency.

Therefore, it is possible to have more stable running and economical efficiency by being applied as a tire for winter by improving braking property and low fuel consumption.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out 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 rubber tread rubber composition according to Examples 1 and 2 and Comparative Examples 1 to 6 using the composition shown in Table 1 below. The production of the rubber composition was in accordance with the usual production method of the rubber composition.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Example 1 Example 2 Natural Rubber ⁽¹⁾ 20 20 20 20 20 20 20 20 S-SBR 1 ⁽²⁾ 68.75
(50) - - - - - - - S-SBR 2 ⁽³⁾ - 36
(30) 84
(70) - - - 48
(40) 72
(60) S-SBR 3 ⁽⁴⁾ - - - 48
(40) - - - - S-SBR 4 ⁽⁵⁾ - - - - 48
(40) - - - S-SBR 5 ⁽⁶⁾ - - - - - 48
(40) - - BR ⁽⁷⁾ 41.25
(30) 68.75
(50) 13.75
(10) 55
(40) 55
(40) 55
(40) 55
(40) 27.5
(20) Carbon Black ⁽⁸⁾ 10 10 10 10 10 10 10 10 Silica ⁽⁹⁾ 85 85 85 85 85 85 85 85 Coupling Agents ⁽¹⁰⁾ 14 14 14 14 14 14 14 14 Oil Processed ⁽¹¹⁾ 33.8 52.6 46.92 41.3 41.3 41.3 41.3 33.8 Zinc oxide 3 3 3 3 3 3 3 3 Stearic acid One One One One One One One One Antioxidant 6 6 6 6 6 6 6 6 Vulcanizing agent 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 accelerant 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Accelerator (DPG) 2 2 2 2 2 2 2 2

(Unit: parts by weight)

(1) Natural rubber: As the rubber obtained in nature, the chemical name is polyisoprene.

(2) S-SBR 1: solution-polymerized styrene-butadiene rubber (SBR) prepared by a continuous process having a styrene content of 40% by weight and a vinyl content of 25% by weight of butadiene, Tg −35 ° C., 37.5 weight of TDAE oil (The figures in parentheses refer to the content of S-SBR 1 rubber, excluding oil).

(3) S-SBR 2: solution-polymerized styrene-butadiene rubber (SBR) prepared by a batch method of 35% by weight of styrene and 55% by weight of vinyl in butadiene, Tg -27 ° C, 20 parts by weight of TDAE oil (The figures in parentheses refer to the content of S-SBR 2 rubber excluding oil).

(4) S-SBR 3: 20 parts by weight of a solution-polymerized styrene-butadiene rubber (SBR) prepared by a batch method having a styrene content of 20% by weight and a vinyl content of 50% by weight of butadiene, Tg-27 ° C, and TDAE oil. It was included. (The figures in parentheses refer to the S-SBR 3 rubber content excluding the oil content.)

(5) S-SBR 4: solution-polymerized styrene-butadiene rubber (SBR) prepared by a batch method of 35% by weight of styrene and 55% by weight of vinyl in butadiene, Tg-40 ° C, 20 parts by weight of TDAE oil It was included. (The figures in parentheses refer to the content of S-SBR 4 rubber except oil)

(6) S-SBR 5: solution-polymerized styrene-butadiene rubber (SBR) prepared by a continuous process having a styrene content of 35% by weight and a vinyl content of 55% by weight of butadiene, Tg -27 ° C, 20 weights of TDAE oil Wealth included. (The figures in parentheses refer to the S-SBR 5 rubber content excluding the oil content.)

(7) BR: Neodymium butadiene rubber containing 27.3 wt% of TDAE oil and having a glass transition temperature of -100 ° C. (values in parentheses are the contents of BR rubber except the oil content).

(8) Carbon Black: Carbon black having a nitrogen adsorption specific surface area of 80 to 100 m ² / g, a DBP oil absorption of 90 to 110 cc / 100 g, and a tint value of 100 to 120%.

(9) Silica: Precipitated IDS silica having a nitrogen adsorption value of 150 m 2 / g, a CTAB value of 155 m 2 / g, and a DBP value of 120 ml / 100 g.

(10) Coupling agent: As bis-trialkoxy silylpropyl polysulfide (TESPD) in the alkoxy polysulfide silane compound, X50S (Degussa) in which a coupling agent and carbon black were mixed in a 1: 1 weight ratio was used.

(11) Processed oil: Total content of Poly Cyclic Aromatic Hydocarbo (PAH) component is 3 wt% or less, kinematic viscosity 95 (210 ℉), 25 wt% aromatic component in softener, 32.5 wt% naphthenic component and paraffinic The component used was 47.5 weight%.

* TDAE Oil: The content of benzo (a) pyrene is less than 0.000001% by weight, the total amount of the eight PAHs materials is less than 0.00001% by weight, the kinematic viscosity is 98, the content of the aromatic component is 20% by weight, naphthenic The content of the component is 32% by weight and the content of the paraffinic component is 48% by weight.

[ Experimental Example : Measurement of physical properties of the prepared rubber composition]

The rubber samples prepared according to Examples 1 and 2 and Comparative Examples 1 to 6 were measured for physical properties such as Mooney viscosity, hardness, 300% modulus, viscoelasticity, and the results are shown in Table 2 below.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Example 1 Example 2 Mooney viscosity (ML _{1 +4} (125 ℃)) 55 49 56 53 54 55 52 54 Hardness (ShoreA) 64 62 67 64 64 65 64 65 300% modulus (MPa) 78 58 89 79 76 80 77 84 -40 ℃ G (dyne / ㎠) 2.18E + 09 1.05E + 09 2.28E + 09 2.03E + 09 2.18E + 09 2.30E + 09 1.94E + 09 2.15E + 09 0 ℃ tanδ 0.241 0.107 0.397 0.285 0.218 0.298 0.294 0.315 60 ℃ tanδ 0.157 0.125 0.163 0.153 0.147 0.150 0.137 0.145

(1) Pattern viscosity (ML _{1 +4} (125 degreeC)) was measured by ASTM specification D1646.

(2) The hardness was measured according to DIN 53505.

(3) 300% modulus was measured by ISO 37 standard.

(4) Viscoelasticity was measured G ', G ”, tan δ from -60 ℃ to 60 ℃ under 10Hz frequency at 0.5% strain using an RDS meter.

In Table 2, ML _{1 +4} is a value representing the viscosity of the unvulcanized rubber, and the lower the value, the better the processability of the unvulcanized rubber. In addition, the hardness of Table 2 indicates the steering stability, the higher the value is, the better the steering stability, -40 ℃ G 'represents the braking characteristics on the ice snow road surface, the lower the value shows the excellent braking performance. In addition, 0 ° C tanδ of Table 2 shows braking characteristics on dry or wet road surface. The higher the value, the better the braking performance, and 60 ° C tanδ shows the rolling resistance. .

Referring to Table 2, in the case of Examples 1 and 2, while 0 ° C tanδ is 294 or more and 60 ° C tanδ is 145 or less, the braking performance and the low fuel consumption performance are not the only ones. It was confirmed that the non-combustible performance was improved evenly. Accordingly, it can be seen that the braking performance is excellent while the rolling resistance and the low fuel consumption performance are excellent.

On the other hand, in Comparative Examples 1 and 4 to 6, the effects of improving braking performance, rotational resistance and low non-combustibility were relatively insufficient compared to the examples. In addition, in the case of Comparative Example 2, the braking performance was reduced, and in Comparative Example 3, there was a problem in that the rotational resistance and the low non-combustibility performance were reduced.

[ Experimental Example : Determination of braking property and rolling resistance of manufactured rubber composition]

According to Comparative Examples 1 to 6 and Examples 1 and 2, a tire of 225 / 45R17 standard is prepared, which manufactures tread rubber and includes the tread rubber as a semi-finished product. The relative ratios of braking distance and rolling resistance were measured. The measured value for Comparative Example 1 was set to 100, and the measured values for each of Comparative Examples 2 and 6 and Examples 1 and 2 were indexed based on Comparative Example 1, and are shown in Table 3 below.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example
6 Example 1 Example 2 Wet road braking distance 100 96 105 99 95 100 101 103 Braking distance 100 102 99 98 101 98 101 101 Rotation resistance 100 104 97 99 101 95 103 102

Referring to Table 3, Examples 1 and 2 was confirmed that the braking performance is improved on the wet road surface and the snowy road surface, the braking performance is improved and the rotational resistance is also improved. Therefore, according to the first and second embodiments, it is possible to manufacture a rubber tread rubber composition having excellent braking performance and excellent rolling resistance and low fuel efficiency.

On the other hand, in the case of Comparative Examples 1, 4 and 6 it was confirmed that the braking performance and the rolling resistance is relatively reduced compared to Examples 1 and 2. In addition, in the case of Comparative Examples 2 and 5, it was confirmed that the braking performance on the wet road surface, and in the case of Comparative Example 3, the braking performance and the rotational resistance on the ice road surface were lowered.

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 (4)

10 to 30 parts by weight of natural rubber,
Styrene content is 21 to 50% by weight, vinyl content in butadiene is 30 to 70% by weight, glass transition temperature is -10 to -30 ° C, and 40 to 60 parts by weight of styrene-butadiene rubber polymerized in a batch process. , And
Neodymium butadiene rubber containing 20 to 40% by weight of TDAE (treated distillate aromatic extract) oil, glass transition temperature from -110 to -100 ° C, and 94 to 98% by weight of cis 1,4-butadiene (Nd-BR) 100 parts by weight of the raw material rubber, including 20 to 50 parts by weight, and
Intermediate DisperSibility (IDS) silica, nitrogen surface area per gram (N2SA) of 140 to 160 m ² / g, cetyltrimethyl ammonium bromide (CTAB) adsorption specific surface area of 140 to 160 m ^{2 /} g, DBP oil absorption 75 to 95 parts by weight of silica which is 120 to 140cc / 100g
10 parts by weight of carbon black having a nitrogen adsorption specific surface area of 80 to 100 m ² / g, a DBP oil absorption of 90 to 110 cc / 100 g, and a tint value of 100 to 120%
And a rubber composition for a tire tread. delete delete A tire manufactured using the rubber composition for tire tread according to claim 1.