KR101315114B1 - Rubber composition for tire tread, method for manufacturing the same and tire manufactured by the method - Google Patents

Abstract

The present invention relates to a rubber composition for a tire tread, a manufacturing method thereof, and a tire manufactured using the manufacturing method, wherein 100 parts by weight of raw material rubber, 10 to 100 parts by weight of reinforcing filler, 1 to 8 parts by weight of foaming agent, and coconut 5 to 40 parts by weight of shell mill.
The rubber composition for the tire tread is reduced in the strength of the entire rubber that can be generated by using the foaming agent to weaken the force to resist deformation, the wear performance of the tire is reduced, or the adjustment stability to the rapid deformation of the rubber in accordance with the steering of the vehicle This sudden drop does not occur, it is environmentally friendly, provides excellent tire strength, and greatly improves the ice coefficient of friction of the tire.

Description

Rubber composition for tire tread, a manufacturing method thereof and a tire manufactured by the manufacturing method TECHNICAL FIELD

The present invention relates to a rubber composition for a tire tread, a manufacturing method thereof, and a tire manufactured by the manufacturing method. More particularly, it is environmentally friendly, provides excellent tire strength, and can greatly improve the ice friction coefficient of a tire. It relates to a rubber composition for tire tread, a manufacturing method thereof, and a tire manufactured using the manufacturing method.

As a conventional method for improving the ice sheet braking performance of a tire, a method of attaching a spike to the surface of the tread has been used, but as the interest on the environment increases due to the problem that the spike damages the road surface and generates dust. Its use is regulated.

In order to replace this, techniques for improving braking performance on the ice road surface of winter tires have been developed by making foamed pores in the tread rubber or by injecting a material such as glass fiber. Techniques for adding porous pumice, layered silica and the like are also disclosed.

In addition, in order to improve the performance of the foamed rubber, a technique of simultaneously using glass fiber, silica, etc. together with foaming has been disclosed, and a method of using waste tire powder with foaming as pulverized powder has been proposed.

However, in the case where pores are formed in the rubber by foaming by adding a foaming agent in this way, the strength of the entire rubber is lowered, the force to resist deformation is weakened, and the wear performance of the tire is easily reduced, and the tread according to the steering of the vehicle. There is a problem that the adjustment stability is sharply lowered due to the rapid deformation of the rubber.

An object of the present invention is to reduce the wear resistance of the tire while reducing the strength of the entire rubber due to the use of a foaming agent to weaken the deformation resistance, or the rapid adjustment stability of the rubber due to the rapid deformation of the rubber in accordance with the steering of the vehicle It is to provide a rubber composition for a tire tread that does not cause a problem of deterioration, which is environmentally friendly, provides excellent tire strength, and which can greatly improve the ice coefficient of friction of tires.

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

Still another object of the present invention is to provide a tire manufactured by the method for producing a 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 100 parts by weight of raw rubber, 10 to 100 parts by weight of reinforcing filler, 1 to 8 parts by weight of foaming agent, and 5 to coconut shell mill 40 parts by weight.

The coconut shell mill may have an average particle diameter of 0.50 mm or less.

The blowing agent may be any one selected from the group consisting of inorganic blowing agents, nitroso blowing agents, azo blowing agents, sulfonyl hydrazide blowing agents, azide blowing agents, and combinations thereof.

The raw material rubber may include 40 to 90 parts by weight of natural rubber and 10 to 60 parts by weight of butadiene rubber.

Rubber composition for tire treads according to another embodiment of the present invention is a coconut shell processing step of producing a coconut shell in the form of pellets, a crushing step of grinding the coconut shell of the pellet form, and the coconut shell crushed and raw rubber, Formulating a reinforcing filler, blowing agent and other additives to produce a rubber composition for a tire tread.

A tire according to another embodiment of the present invention is manufactured using the method for preparing the tire tread rubber composition.

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

The tread rubber composition includes raw rubber, reinforcing filler, foaming agent, and 5 to 40 parts by weight of coconut shell ground based on 100 parts by weight of the raw rubber.

That is, the rubber composition for tire treads includes coconut shell pulverized powder in order to improve braking performance on winter snow or ice road without reducing the strength of the rubber. In addition, the coconut shell pulverized powder may be exposed to the surface of the tire tread to serve as a spike to improve the ice sheet braking performance, and when present in the rubber to improve the strength of the rubber.

The coconut shell mill is also referred to as coco-peat, co-pit, coir or coirdust. The coconut shell mill is a by-product of the coconut industry, and is generally made from a fiber layer (Husk) that extracts palm fibers used as garden baskets, bed mattresses, car seat fillers, ropes, roof buffers, and the like.

The coconut shell mill is dark brown, excellent in moisture and dehumidification ability and low in salt content, constituents of cellulose and lignin account for 90% by weight or more, and the particles have a porous network structure, which is advantageous for securing breathability. Do.

The coconut shell mill is a chemically inert material containing a large amount of lignin components and is relatively stable to decomposition, and various physical properties appear depending on the production method and processing technology in the processing process.

The coconut shell pulverized in recent years can be preferably used to crush the coco peat produced by compression in the shape of a brick for convenience of transportation. That is, the coco shell may be pulverized with an ultra centrifugal mill to produce a coconut shell pulverized product.

The coconut shell pulverized product may have an average particle diameter of 0.50 mm or less, and preferably 0.01 to 0.50 mm. If the average particle diameter of the coconut shell pulverization exceeds 0.50 mm, there is a possibility that the wear performance of the tire is sharply lowered due to a sharp decrease in tensile strength or the like.

The coconut shell mill may be included in 5 to 40 parts by weight of 100 parts by weight of the raw material rubber. When the content of the coconut shell crushed product is less than 5 parts by weight based on 100 parts by weight of the raw material rubber, there is almost no effect of improving the ice coefficient of friction. You can't.

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. For example, examples of the modified natural rubber include epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber.

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 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.

In particular, when the rubber composition for the tire tread is for the tire tread in winter, the raw material rubber may be made of natural rubber and butadiene rubber. In this case, the content of the natural rubber is 40 to 90 parts by weight, the content of the butadiene rubber may be 10 to 60 parts by weight. If the content of the butadiene rubber is less than 10 parts by weight may have a problem that the wear performance is lowered, if it exceeds 60 parts by weight may have a problem that the workability is lowered.

The rubber composition for tire treads includes reinforcing fillers to reinforce strength. The reinforcing filler may be any one selected from the group consisting of carbon black, silica, and combinations thereof.

The reinforcing filler may be included in 10 to 100 parts by weight based on 100 parts by weight of the raw material rubber, preferably 40 to 80 parts by weight. If the content of the reinforcing filler is out of the above range, the wear performance of the tire may be drastically reduced, and the braking performance may be reduced on the wet road surface. Specifically, when the content of the reinforcing filler is less than 10 parts by weight, the reinforcing performance by the reinforcing filler may decrease, and when the content of the reinforcing filler exceeds 100 parts by weight, the processability of the rubber composition may be deteriorated.

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 silica has a nitrogen adsorption specific surface area (N ₂ SA) of 100 to 180 m ₂ / g, and a CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area It may be 110 to 170 m 2 / g, but the present invention is not limited thereto.

When the nitrogen adsorption specific surface area of the silica is less than 100 m 2 / g, reinforcing performance by the filler silica may be detrimental, and when it exceeds 180 m 2 / g, the workability of the rubber composition may be deteriorated. Further, when the CTAB adsorption specific surface area of the silica is less than 110 m 2 / g, reinforcing performance by silica may be disadvantageous, and when it exceeds 170 m 2 / g, the workability of the rubber composition may be disadvantageous.

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 blowing agent is included in the rubber tread rubber composition to improve the braking performance on the ice-snow road surface, specifically, inorganic foaming agent, nitroso foaming agent, azo foaming agent, sulfonyl hydrazide foaming agent, azide foaming agent and these It may be any one selected from the group consisting of, but the present invention is not limited thereto.

The inorganic blowing agent may be any one selected from the group consisting of sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, and combinations thereof.

The nitroso blowing agent may be any one selected from the group consisting of N, N'-dinitrosopentamethylenetetramine (DPT), N, N'-dimethyl-N, N'-dinitrosoterephthalamide and combinations thereof. Can be.

The azo foaming agent is any one selected from the group consisting of azodicarbonamide (ADCA), azobisisobutyronitrile (AIBN), azobiscyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate and combinations thereof Can be.

The sulfonylhydrazide-based blowing agent is benzenesulfonylhydrazide (BSH), p, p'-oxybis (benzenesulfonylhydrazide) (0BSH), toluenesulfonylhydrazide (TSH), diphenyl It may be any one selected from the group consisting of sulfone-3,3'-disulfonylhydrazide and combinations thereof.

The azide blowing agent may be any one selected from the group consisting of calcium azide, 4,4'-diphenyldisulfonyl azide, p-toluenesulfonyl azide and combinations thereof.

The blowing agent may be used in an amount of 1 to 8 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the raw material rubber. When the content of the blowing agent is less than 1 part by weight based on 100 parts by weight of the raw material rubber, the foaming is too small, so that the effect of removing the water film due to foaming is insignificant. The physical properties of rubbers such as these can be drastically lowered.

In addition, a foaming auxiliary may be optionally used together with the foaming agent. When the foaming auxiliary is used together with the foaming agent, there is an advantageous effect in terms of lowering the decomposition temperature of the foaming agent, accelerating the decomposition, and uniformizing the bubbles.

The organic acid may be any one selected from the group consisting of salicylic acid, phthalic acid, stearic acid, oxalic acid, and combinations thereof. The organic acid may be selected from the group consisting of organic acids, urea, urea derivatives and combinations thereof. have.

The foaming aid may be included in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the raw material rubber.

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, a softening agent or a pressure- 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 said vulcanizing agent, a sulfur type vulcanizing agent can be used preferably. 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 vulcanizing agent is preferably included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the raw material rubber, which is preferable in that the raw material 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 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 0.1 to 10 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 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 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 10 parts by weight based on 100 parts by weight of the raw material rubber, respectively, in order to serve as a proper vulcanization accelerating auxiliary.

Although the kind of the coupling agent is not particularly limited in the present invention, 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, Any one selected from the group consisting of methacrylic silane compounds and combinations thereof can 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 added in an amount of 20 parts by weight or less based on 100 parts by weight of rubber, and preferably 5 to 20 parts by weight. When the coupling agent is added in excess of 20 parts by weight based on 100 parts by weight of the rubber, the coupling agent remains in the rubber composition after the coupling, thereby lowering the physical properties of the tire tread.

The softener is added to the rubber composition to impart plasticity to the rubber to facilitate processing or to lower the hardness of the vulcanized rubber, and refers to oils and other materials used in rubber compounding or rubber production. The softener may be any one selected from the group consisting of petroleum oil, vegetable oil and combinations thereof, but the present invention is not limited thereto.

The petroleum oil may be any one 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, recently, when the content of the polycyclic aromatic hydrocarbons (hereinafter referred to as PAHs) contained in the aromatic oil is higher than 3 wt% together with the increase of the environmental consciousness, treated distillate aromatic extract oil, mild extraction solvate (MES) oil, residual aromatic extract (RAE) oil or heavy naphthenic oil.

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.

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.

It is preferable that the softening agent is used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the raw material rubber in order to improve the workability of the raw material rubber.

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 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.

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

The pressure-sensitive adhesive further improves the tack performance between the rubber and the rubber and improves the physical properties of the rubber by improving the mixing properties, dispersibility and processability of other additives such as fillers.

As the pressure-sensitive adhesive, a natural resin-based pressure-sensitive adhesive such as a rosin-based resin or a terpene-based resin and a synthetic resin-based pressure-sensitive adhesive such as a petroleum resin, a coal tar, or an alkylphenolic resin can be used.

The rosin-based resin may be any one selected from the group consisting of rosin resins, rosin ester resins, hydrogenated rosin ester resins, derivatives thereof, and combinations thereof. The terpene resin may be any one selected from the group consisting of terpene resin, terpene phenol resin, and combinations thereof.

Wherein the petroleum resin is selected from the group consisting of an aliphatic resin, an acid-modified aliphatic resin, an alicyclic resin, a hydrogenated alicyclic resin, an aromatic (C9) resin, a hydrogenated aromatic resin, a C5-C9 copolymer resin, a styrene resin, And a combination thereof.

The coal tar may be a coumarone-indene resin.

The alkylphenol resin may be a p-tert-alkylphenol formaldehyde resin and the p-tert-alkylphenol formaldehyde resin may be a p-tert-butyl-phenol formaldehyde resin, p-tert- And a combination thereof.

The pressure-sensitive adhesive may be included in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the raw material rubber. If the content of the pressure-sensitive adhesive is less than 0.5 parts by weight based on 100 parts by weight of the raw material rubber, the adhesive performance may be detrimental, and when the content of the pressure-sensitive adhesive exceeds 10 parts by weight, rubber properties may be reduced.

According to another aspect of the present invention, there is provided a method of preparing a rubber tread rubber composition, which includes a coconut shell processing step of preparing coconut shells in pellet form, a pulverizing step of grinding coconut shells in pellet form, and the coconut shell milled product. Blending the raw rubber, reinforcing filler, foaming agent and other additives to produce a rubber tread rubber composition.

The pellet-shaped coconut shell may be manufactured by molding the coconut shell through a mold by pressing or pushing the coconut shell with mechanical force.

Coconut shell in the pellet form may be pulverized with an ultra centrifugal mill to produce a coconut shell pulverized product. The average particle diameter of the coconut shell grind may be 0.50 mm or less, preferably 0.01 to 0.50 mm. If the average particle diameter of the coconut shell pulverization exceeds 0.50 mm, there is a possibility that the wear performance of the tire is sharply lowered due to a sharp decrease in tensile strength or the like.

The coconut shell grind may be blended with raw rubber, reinforcing fillers, foaming agents and other additives, and then made into tires according to conventional methods. Specifically, the tire may be manufactured 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 the non-production step) and the crosslinking system are mixed, typically It can be prepared in a suitable mixer using a second step (called a production step) of mechanical treatment at a low temperature of less than 110 ° C., for example 40-100 ° C., but the invention is not limited thereto.

The rubber composition for a tire tread is not limited to a tread (a tread cap and a tread base) but 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 according to the manufacturing method of the tire. 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.

In the rubber composition for tire tread of the present invention, the strength of the entire rubber that may be generated by using the foaming agent decreases, and the force to resist deformation decreases, and the wear performance of the tire decreases, or due to the rapid deformation of the rubber according to the steering of the vehicle. The problem that adjustment stability is not sharply reduced does not occur, it is environmentally friendly, provides excellent tire strength, and can greatly improve the ice sheet friction coefficient.

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.

[Production Example: Production of Rubber Composition]

Using a composition as shown in Table 1 below to prepare a rubber composition for tire treads according to the following examples and comparative examples. The rubber composition was prepared according to a conventional method for preparing a rubber composition.

(Comparative Example 1)

50 parts by weight of carbon black, 30 parts by weight of aromatic oil, 3 parts by weight of zinc oxide, 1 part by weight of stearic acid, an anti-aging agent based on 100 parts by weight of the raw material rubber consisting of 60 parts by weight of natural rubber and 40 parts by weight of 1,4-cis polybutadiene rubber (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine) 3 parts by weight, vulcanization accelerator (N-tert-butyl-2-benzothiazylsulfenamide) 2 parts by weight, sulfur 2 Parts by weight, 3 parts by weight of blowing agent (p, p-oxybis benzene sulfonyl hydrazide) were used and blended in a half-barrier mixer to prepare a rubber composition for tire tread.

(Example 1)

A rubber tread rubber composition was prepared in the same manner as in Comparative Example 1 except that 10 parts by weight of the coconut shell pulverized product having an average particle diameter of 0.125 mm was further added.

At this time, the coconut shell crushed coco-peat (coco-peat) was used to grind in an ultra centrifugal mill.

(Example 2)

A rubber tread rubber composition was prepared in the same manner as in Example 1, except that 20 parts by weight of the coconut shell crushed product was used.

(Example 3)

Except for using the coconut shell pulverized in 30 parts by weight in Example 1 was carried out in the same manner as in Example 1 to prepare a rubber tread rubber composition.

(Comparative Example 2)

Except for using the coconut shell pulverized in 2 parts by weight in Example 1 was carried out in the same manner as in Example 1 to prepare a rubber tread rubber composition.

(Comparative Example 3)

Except for using the coconut shell pulverized in 50 parts by weight in Example 1 was carried out in the same manner as in Example 1 to prepare a rubber tread rubber composition.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Natural rubber 60 60 60 60 60 60 Butadiene rubber 40 40 40 40 40 40 Carbon black 50 50 50 50 50 50 Aromatic oils 30 30 30 30 30 30 Zinc oxide 3 3 3 3 3 3 Stearic acid One One One One One One Antioxidant 3 3 3 3 3 3 Vulcanization accelerator 2 2 2 2 2 2 brimstone 2 2 2 2 2 2 blowing agent 3 3 3 3 3 3 Coconut Husk Grind - 2 50 10 20 30

(Unit: parts by weight)

Experimental Example: Measurement of Physical Properties of 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. The physical property was measured according to the following method.

Hardness was measured using a Shore A durometer.

The 300% modulus is the tensile strength at 300% elongation measured according to the ISO 37 standard, and the higher the value, the better the strength.

Elongation (%) and tensile strength (kgf / cm ² ) were measured using an Instron tester according to ASTM D412 test method.

The coefficient of friction is the result of measuring the ice friction coefficient after abrasion at 0 ° C. using a dynamic friction tester. Ice friction performance is the higher the value, the better the performance.

Properties Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Seal
Properties Hardness (Shore A) 55 54 65 55 56 60 300% modulus (kgf / cm ² ) 66 66 85 68 72 77 Elongation (%) 405 405 351 394 383 371 Tensile strength (kgf / cm ² ) 151 151 192 153 167 178 Coefficient of friction 100 100 96 104 109 103

Referring to Table 2, Examples 1 to 3 and Comparative Examples 2 to 3 are used coconut shell milled in the foam rubber. That is, Comparative Example 2 is less than 5 parts by weight based on 100 parts by weight of the raw material of the coconut shell, compared with Comparative Example 1 has little effect of improving the coefficient of ice friction, modulus and tensile strength was similar, Comparative Example 3 shows that the coconut shell pulverized product is used in excess of 40 parts by weight with respect to 100 parts by weight of the raw material rubber, and the elongation rate is drastically reduced and the hardness is greatly increased to improve the ice sheet friction coefficient.

On the other hand, in Examples 1 to 3, the coefficient of ice friction was improved compared to Comparative Example 1. In particular, in Example 2, where the coconut shell crushed product was used at 20 parts by weight based on 100 parts by weight of the raw material rubber, the ice coefficient of friction was large. It can be seen that the improvement.

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 right.

Claims (6)

100 parts by weight of raw rubber, including 40 to 90 parts by weight of natural rubber and 10 to 60 parts by weight of butadiene rubber,
10 to 100 parts by weight of reinforcing fillers,
1 to 8 parts by weight of a sulfonylhydrazide blowing agent, and
10 to 30 parts by weight of coconut shell ground
And a rubber composition for a tire tread. The method of claim 1,
The coconut shell pulverized product is a rubber composition for tire tread having an average particle diameter of 0.50mm or less. delete delete Coconut shell processing step of making coconut shell into pellets,
A grinding step of pulverizing the coconut shell of the pellet form, and
100 parts by weight of the raw material rubber, including 10 to 30 parts by weight of the coconut shell pulverized product, 40 to 90 parts by weight of natural rubber, and 10 to 60 parts by weight of butadiene rubber, 10 to 100 parts by weight of reinforcing filler, and sulfonyl hydrazide-based foaming agent. 1 to 8 parts by weight and other additives to prepare a rubber tread rubber composition
≪ / RTI > A tire manufactured by the method for producing a rubber composition for tire tread according to claim 5.