KR101658634B1 - Rubber composition for tire bead filler and tire manufactured by using the same - Google Patents

Abstract

The present invention relates to a rubber composition for a tire bead filler comprising a thermoplastic elastomer (TPE). The rubber composition for a tire bead filler according to the present invention is a rubber composition for a tire bead filler, which has improved rigidity, A rubber composition for a bead filler and a tire using the same.

Description

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

The present invention relates to a rubber composition for a tire bead filler, which comprises a thermoplastic elastomer (TPE), which improves rigidity and improves the non-cloud resistance of the tire as a whole and the braking performance on a wet road surface, A rubber composition for a filler, and a tire manufactured using the same.

Recently, as the use of heavy-duty vehicles such as small trucks and SUVs increases, it is required to strengthen the high-load supporting performance of the tires.

The increase in vehicle load increases the deformation and severity of the tire, which has a great effect on tire wear (sepa).

For this reason, many tire companies in Korea and overseas are trying to acquire tire technology that has abrasion-resistant performance and maintain braking performance for heavy-duty vehicles.

In order to increase the filler content or increase the cure of the bead filler, which has a great effect on the abrasion and performance of the tire, the above-mentioned tire companies have developed a vulcanizer (accelerator) or sulfur vulcanizing agent sulfur) in the exhaust gas.

However, due to the increase in rigidity, the resistance of the tire to rain clouds and the braking performance on wet roads have declined, which is disadvantageous in terms of cost, which is a manufacturing cost of the tire.

An object of the present invention is to provide a rubber composition for a tire bead filler capable of improving rigidity of a tire and improving braking resistance and resistance to braking on a wet road surface.

Another object of the present invention is to provide a tire comprising the rubber composition.

In order to achieve the above object, according to one embodiment of the present invention, there is provided a tire bead filler rubber composition comprising 100 parts by weight of a raw rubber, 1 to 8 parts by weight of a TPE (thermoplastic elastomer), and 70 to 90 parts by weight of a reinforcing agent Lt; / RTI >

The TPE may be a styrene-ethylene-butadiene-styrene (SEBS) block copolymer, a styrene-ethylene-propylene-styrene (SEPS) block copolymer, a styrene- 100 parts by weight of at least one block copolymer selected from the group consisting of styrene (SEIS) block copolymer, styrene-ethylene-ethylene-propylene-styrene (SEEPS) block copolymer and mixtures thereof, magnesium stearate 0.1 to 1.0 part by weight of magnesium stearate, 1.0 to 1.5 parts by weight of ethylene bis stearamide as a second lubricant and 0.5 to 1.5 parts by weight of dispersible glass fiber having an average particle diameter of 40 to 60 μm By weight, followed by melting and extruding.

The TPE may have a weight average molecular weight of 140,000 to 180,000 g / mol and may be represented by the following formula (1).

≪ Formula 1 >

Wherein X is an integer of 1 to 3, Y is an integer of 1 to 3, and n is an integer of 1 to 10.

The raw material rubber may include 70 to 90 parts by weight of natural rubber and 10 to 30 parts by weight of gossypotyadiene rubber having a glass transition temperature of -110 to -100 DEG C, based on 100 parts by weight of the raw rubber.

The rubber composition for a tire bead filler may further comprise 0 to 15 parts by weight of a softening agent, 0.5 to 4 parts by weight of a vulcanizing agent and 0.5 to 4.0 parts by weight of a vulcanization accelerator based on 100 parts by weight of the raw rubber.

The tire according to another embodiment of the present invention is manufactured by using the rubber composition for the tire bead filler

The present invention can provide a tire in which TPE (thermoplastic elastomer) is manufactured and applied to a rubber composition for a tire bead filler to improve rigidity, rain resistivity performance, braking performance on a wet road surface, and wear prevention effect.

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

The rubber composition for a tire bead tiller according to an embodiment of the present invention comprises 100 parts by weight of a raw rubber, 1 to 8 parts by weight of a thermoplastic elastomer (TPE), and 70 to 90 parts by weight of a reinforcing agent.

The raw material rubber may be any one selected from the group consisting of natural rubber, synthetic rubber, and combinations thereof.

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

The above-mentioned general natural rubber may be used as long as it is known as natural rubber, and the country of 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. Examples of the modified natural rubber include epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber and the like.

The synthetic rubber may be at least one selected from the group consisting of styrene butadiene rubber (SBR), modified styrene butadiene rubber, butadiene rubber (BR), modified butadiene rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, fluorine rubber, silicone rubber, Butadiene rubber, 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, Ethylene vinyl acetate rubber, acrylic rubber, hydrin rubber, vinyl benzyl chloride styrene butadiene rubber, bromomethyl styrene butyl rubber, maleic styrene butadiene rubber, carboxylic styrene butadiene rubber, epoxy isoprene rubber, ethylene propylene rubber maleic acid, Nitrile butadiene rubber It may be a p-methyl styrene (brominated polyisobutyl isoprene-co-paramethyl styrene, BIMS), and one selected from the group consisting of -, bromo mineyi suited polyisobutyl isoprene-co.

The butadiene rubber may be preferably used as the synthetic rubber, and more preferably, a high cis-butadiene rubber may be used.

The gossybutadiene rubber may have a content of cis-1,4 butadiene of 96% by weight or more, a glass transition temperature of -110 to -100 캜, and preferably -104 to -107 캜. The gossybutadiene rubber may have a Mooney viscosity of 43 to 47 at 100 占 폚. When the gossybutadiene rubber is used, there is an advantageous effect in terms of wear resistance and heat build up under dynamic stress.

When a mixture of natural rubber and gossybutadiene rubber is used as the raw rubber, 70 to 90 parts by weight of natural rubber and 10 to 30 parts by weight of gossypotadiene rubber may be used relative to 100 parts by weight of the raw rubber. 80 to 90 parts by weight of natural rubber and 10 to 20 parts by weight of gossypotadiene rubber can be preferably used.

The TPE contained in the rubber composition for continuous tire bead filler may be prepared by mixing the block copolymer, the lubricant and the glass fiber, followed by melting and extruding.

The block copolymer may be any one selected from the group consisting of polystyrene series (SBS, SIS), polyolefin series (TPO, TPV), polydiolipine series, chlorine series, engineering plastic series (TPU, TPEE) thermoplastic elastomers (SEBS) block copolymers, styrene-isoprene-styrene (SIS) block copolymers, styrene-ethylene-butadiene-styrene (SEBS) block copolymers, ) Block copolymers, styrene-ethylene-ethylene-propylene-styrene (SEEPS) block copolymers, and mixtures thereof.

For the production of the TPE, a lubricant which facilitates flowability and releasability during thermoforming of the thermoplastic resin may be added.

Examples of the activator include hydrocarbons, carboxylic acids, alcohols, amides, esters, and carboxylate salts.

Preferably, at least one selected from ester-based Butyl Stearate, GMS (Glycerol Mono Stearate), GMO (Glycerine Mono Oleate) and stearyl stearate may be used as the first lubricant, As the second lubricant, at least one selected from amide-based stearamide, oleamide, and erucamide may be used. Particularly, when ethylene bisstearamide is used, it has a hydrogen bond internally due to the polarity of the lubricant and functions as an external lubricant, thereby enhancing the strength of TPE.

0.1 to 1.0 part by weight of the first lubricant and 1.0 to 1.5 parts by weight of the second lubricant, based on the total weight of the TPE. When the amount of the first lubricant is less than 0.1 part by weight, there is a problem that the TPE stress is low and the stiffness is lowered. When the amount of the first lubricant is more than 1.0 part by weight, the stiffness is not improved. If the amount of the second lubricant is less than 1.0 part by weight, crosslinking with the first lubricant may be deteriorated. If the amount of the second lubricant is more than 1.5 parts by weight, the crosslinking effect may not be improved.

And, glass fiber is used as an additive constituting the composition of the present invention, which provides excellent productivity in extrusion and injection molding, eliminates the aggregation phenomenon, and has a surface improving effect.

The average particle diameter of the glass fiber is preferably 40 to 60 占 퐉, and the uniformly dispersed material can be uniformly mixed in the TPE composition.

As to the total weight of the TPE, the glass fiber preferably includes 0.5 to 1.5 parts by weight. If the amount of the glass fiber is less than 0.5 parts by weight, the effect is insignificant. When the amount of the glass fiber exceeds 1.5 parts by weight, the viscosity of the TPE increases and the melting point index of the TPE becomes weak.

The above-mentioned raw materials and additives may have an appropriate blending ratio as described above with respect to the total weight of the TPE, and the TPE may be prepared by mixing the main raw materials and the auxiliary raw materials and then melting and extruding them.

The TPE may contain from 1 to 8 parts by weight based on 100 parts by weight of the starting rubber. If the TPE is contained in an amount of less than 1 part by weight, the effect is insignificant. When the amount exceeds 8 parts by weight, The elongation and viscoelastic performance that it possesses greatly decreases, and the rotational resistance performance is deteriorated.

The TPE may have a weight average molecular weight of 140,000 to 180,000 g / mol and may be represented by the following formula (1).

≪ Formula 1 >

Wherein X is an integer of 1 to 3, Y is an integer of 1 to 3, and n is an integer of 1 to 10.

The reinforcing agent may be any one selected from carbon black and silica, but is not limited thereto.

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 the DBP oil absorption is less than 60 cc / 100 g, the reinforcing performance of the 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 carbon black may be contained in an amount of 30 to 80 parts by weight based on 100 parts by weight of the raw rubber, more preferably 45 to 65 parts by weight, and still more preferably 53 to 57 parts by weight. When the content of the carbon black is less than 30 parts by weight, the reinforcing performance by the carbon black as the filler may be deteriorated. If the content is more than 80 parts by weight, the workability of the rubber composition may be deteriorated.

The silica may have a nitrogen surface area per gram (N ₂ SA) of 100 to 180 m ₂ / g and a cetyl trimethyl ammonium bromide (CTAB) adsorption specific surface area of 110 to 170 m 2 / g. But is not limited thereto.

If the nitrogen adsorption specific surface area of the silica is less than 100 m < 2 > / g, the reinforcing performance by the silica as the filler may be deteriorated. If it exceeds 180 m2 / g, the workability of the rubber composition may be deteriorated. If the CTAB adsorption specific surface area of the silica is less than 110 m < 2 > / g, the reinforcing performance by silica as a filler may be deteriorated.

Ultrasil VN2 (manufactured by Degussa AG), Ultrasil VN3 (manufactured by Degussa AG), Z1165MP (manufactured by Rhodia) or Z165GR (manufactured by Rhodia) can be used as the commercially available products. .

The silica may be contained in an amount of 20 to 90 parts by weight based on 100 parts by weight of the raw rubber, more preferably 30 to 70 parts by weight, and further preferably 40 to 60 parts by weight. When the content of the silica is less than 20 parts by weight, the strength of the rubber is not improved and the braking performance of the tire may be deteriorated. When the content of the silica exceeds 90 parts by weight, the wear performance may be deteriorated.

The rubber composition for a tire bead filler may further include various additives such as additional vulcanizing agents, vulcanization accelerators, vulcanization accelerators, fillers, coupling agents, anti-aging agents, softening agents or pressure-sensitive adhesives. The rubber composition for a tire bead filler may comprise 0 to 15 parts by weight of a softening agent, 0.5 to 5 parts by weight of a vulcanizing agent, And 0.5 to 4.0 parts by weight of a vulcanization accelerator.

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.,

It is preferable that the softening agent is used in an amount of 0 to 15 parts by weight based on 100 parts by weight of the raw material rubber, because it improves the workability of the raw material rubber.

The total amount of the petroleum-based oil may be replaced by the liquid rubber, and if the content of the petroleum-based oil exceeds 15 parts by weight, the problem of lowering the hardness may occur.

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

The sulfur vulcanizing agent is an inorganic vulcanizing agent such as powder sulfur (S), insoluble sulfur (S), precipitated sulfur (S), colloid sulfur, etc., tetramethylthiuram disulfide (TMTD) Organic vulcanizing agents such as tetraethyltriuram disulfide (TETD) and dithiodimorpholine can be used. 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 organic peroxide is selected from the group consisting of benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, 2,5- butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5- Bis (t-butylperoxypropyl) benzene, di-t-butylperoxy-diisopropylbenzene, t-butylperoxybenzene, 2,4-dichlorobenzoylperoxide, 1,1- , 3,5-trimethylsiloxane, n-butyl-4,4-di-t-butylperoxyvalerate, and combinations thereof.

It is preferable that the vulcanizing agent is included in an amount of 0.5 to 4.0 parts by weight based on 100 parts by weight of the raw rubber, in view of a suitable vulcanizing effect because the raw 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 dithiocarbamate-based vulcanization accelerator include zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, Zinc dibutyldithiocarbamate, zinc diamidithiocarbamate, zinc dipropyldithiocarbamate, complexation of zinc with piperidinedithiocarbamate and piperidine, zinc hexadecylisopropyldithiocarbamate, octadecyl Isopropyl dithiocarbamic acid zinc zinc dibenzyldithiocarbamate, sodium diethyldithiocarbamate, penta methylenedithiocarbamate, sodium selenium dimethyldithiocarbamate, diethyldithiocarbamate, sodium diethyldithiocarbamate, Cadmium dithiocarbamate, and combinations thereof. The dithiocarbamic acid-based compound may be used alone or in combination of two or more thereof.

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

In the case where silica is used as the reinforcing agent, a coupling agent may be further included.

Examples of the coupling agent include a sulfide-based silane compound, a mercapto-based silane compound, a vinyl-based silane compound, an amino-based silane compound, a glycidoxine clock silane compound, a nitro- based silane compound, a chlorosilicate compound, a methacrylic silane compound, May be used, and a sulfide-based silane compound may be preferably 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 may be any one selected from the group consisting of? -Methacryloxypropyltrimethoxysilane,? -Methacryloxypropylmethyldimethoxysilane,? -Methacryloxypropyldimethylmethoxysilane, and combinations thereof Lt; / RTI >

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 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.

Considering the conditions that the solubility of the antioxidant in addition to the anti-aging action is high, the solubility in the rubber is small, the volatility is small, the solubility should be inactive to the rubber, and the vulcanization should not be inhibited, By weight.

The rubber composition for a tire bead filler can be produced through a conventional two-step continuous manufacturing process. That is, during the finishing step in which a first step (referred to as a "non-production" step) of thermomechanical treatment or kneading at a maximum temperature of 110-190 ° C, preferably 130-180 ° C, and a crosslinking system are mixed, Can be prepared in a suitable mixer using a second stage (referred to as the "production" step) of mechanically treating at a low temperature, typically below 110 ° C, for example 40-100 ° C, but the invention is not so limited .

The rubber composition for a tire bead filler is not limited to a bead filler and may be included in various rubber components constituting the tire. Said rubber components include treads (tread caps and tread bases), sidewalls, sidewall inserts, apex, chafer, wire coat or inner liner.

The tire according to another embodiment of the present invention is manufactured using the rubber composition for the tire bead filler. The method of manufacturing a tire using the rubber composition for a tire bead filler 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.

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]

Rubber compositions for tire bead fillers according to the following Examples and Comparative Examples were prepared using the compositions 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 Example 1 Example 2 Comparative Example 2 Comparative Example 3 Example 3 Comparative Example 4 Natural rubber ^{1 )} 85 85 85 85 85 85 85 Butadiene rubber ^{2 )} 15 15 15 15 15 15 15 Silaka 70 70 70 70 - - - Silane 10 10 10 10 - - - Carbon black - - - - 80 80 80 zinc oxide 2 2 2 2 2 2 2 Stearic acid One One One One One One One Petroleum oil 15 15 15 15 15 15 15 TPE - 5 8 10 - 8 10

(Unit: parts by weight)

1) Natural rubber: TSR 20 Grade

2) Butadiene rubber: Gossybutadiene rubber having a glass transition temperature of -106 ° C

< TPE Gt;

100 parts by weight of a styrene-ethylene-butadiene-styrene (SEBS) block copolymer, 0.4 parts by weight of a first lubricant magnesium stearate, 1.2 parts by weight of a second lubricant ethylene bis-stearamide and 100 parts by weight of a dispersive glass fiber glass fiber) were mixed and stirred for 1 hour and 30 minutes, followed by melting, kneading and extruding to produce pellets. At this time, a twin-screw extruder having an L / D of 29 and a diameter of 45 mm was used, and the cylinder temperature was set at 200 to 230 ° C.

< Comparative Example  1>

As the compounding ratio disclosed in the following Table 1, it is preferable to use a solution-polymerized natural rubber or butadiene rubber as raw material rubber, silica as a reinforcing agent, petroleum oil, coupling agent, zinc oxide, stearic acid, an antioxidant, a vulcanizing agent, To prepare a rubber composition for a tire bead filler. An aromatic oil was used as the petroleum oil.

< Example  1 and 2>

A rubber composition for a tire bead filler was prepared in the same manner as in Comparative Example 1, except that TPE was used in an amount of 5 parts by weight and 8 parts by weight, respectively.

< Comparative Example  2>

A rubber composition for tire bead filler was prepared in the same manner as in Comparative Example 1, except that 10 parts by weight of TPE was used in Comparative Example 1.

< Comparative Example  3>

A rubber composition for a tire bead filler was prepared in the same manner as in Comparative Example 1, except that the silica and silane were replaced with 80 parts by weight of carbon black in Comparative Example 1.

< Example 3 >

A rubber composition for tire bead filler was prepared in the same manner as in Comparative Example 3, except that 8 parts by weight of TPE was used in Comparative Example 3.

< Comparative Example  4>

A rubber composition for a tire bead filler was prepared in the same manner as in Comparative Example 3 except that 10 parts by weight of TPE was used in Comparative Example 3.

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

The physical properties of the rubber specimens prepared in Examples and Comparative Examples were measured and the results are shown in Table 2 below.

division Comparative Example 1 Example
One Example 2 Comparative Example 2 Comparative Example 3 Example 3 Comparative Example 4 t5 ^{1 )} 14 14 14 14 11 15 12 Hardness ^{2 )} 66 70 72 79 67 71 80 300% modulus ^{2 )} 69 82 88 94 71 86 96 Elongation ^{2 )} 150 145 143 135 152 145 131 60 deg. C tan? (Index) ³⁾ 100 103 105 98 101 104 96

1) Scorch time (t5, 138 ° C): Measured using a Mooney MV2000 (Alpha Technology) instrument at a large rotor, preheating 1 min, rotor operating time 4 min, and temperature 138 ° C.

2) Tensile Properties: The hardness was measured using a Shore A hardness tester and the tensile properties were measured using an Instron tester according to ASTM D412.

3) Viscoelastic properties: Dynamic swing test was performed at 10Hz, static strain 5% and dynamic strain 0.5% using DMTS (Dynamic Material Testing System) tester from -60 ℃ to 80 ℃. In this case, the higher the 0 ° C tan δ value, the better the braking performance on the wet road surface, and the lower the tan δ value of 60 ° C, the lower the rotational resistance performance. The value of tan? Of 60 占 폚 of Comparative Example 1 was indexed based on the standard (100).

Referring to Table 2, it was confirmed that the t5, the hardness and the modulus of Examples 1 to 3 were improved as compared with Comparative Examples 1 and 3. It was expected that the rubber composition according to the present invention could be supported without being stretched even under the high load of the automobile. It was confirmed that Examples 1 to 3, in which the TPE was used in the range of 1 to 8 parts by weight, were remarkably improved as compared with Comparative Examples 1 to 4.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

Claims (6)

100 parts by weight of the raw rubber,
1 to 8 parts by weight of a thermoplastic elastomer (TPE), and
70 to 90 parts by weight of a reinforcing agent,
The TPE may be added to the total weight of the TPE,
Styrene (SEBS) block copolymers, styrene-ethylene-butadiene-styrene (SEBS) block copolymers, styrene-ethylene-propylene- 100 parts by weight of a block copolymer selected from the group consisting of block copolymers, styrene-ethylene-ethylene-propylene-styrene (SEEPS) block copolymers and mixtures thereof,
0.1 to 1.0 part by weight of magnesium stearate as the first lubricant,
1.0 to 1.5 parts by weight of ethylene bisstearamide as the second lubricant, and
And 0.5 to 1.5 parts by weight of dispersible glass fiber (glass fiber) having an average particle diameter of 40 to 60 탆 are mixed and then melted and extruded,
Rubber composition for tire bead filler. delete The method according to claim 1,
Wherein the TPE has a weight average molecular weight of 140,000 to 180,000 g / mol, and the rubber composition for a tire bead filler represented by the following formula (1)
&Lt; Formula 1 >

Wherein X is an integer of 1 to 3, Y is an integer of 1 to 3, and n is an integer of 1 to 10. The method according to claim 1,
Wherein the raw material rubber comprises, relative to 100 parts by weight of the raw material rubber,
70 to 90 parts by weight of natural rubber, and
And 10 to 30 parts by weight of a gossybutadiene rubber having a glass transition temperature of -110 to -100 캜. The method according to claim 1,
Wherein the rubber composition for a tire bead filler further comprises 0 to 15 parts by weight of a softening agent, 0.5 to 4 parts by weight of a vulcanizing agent, and 0.5 to 4.0 parts by weight of a vulcanization accelerator, based on 100 parts by weight of the raw rubber . A tire made from the rubber composition for a tire bead filler according to claim 1.