KR101594825B1 - Method for preparing purified carbon black, rubber composition for tire including the purified carbon black and tire manufactured by using the same - Google Patents

Abstract

The process for preparing purified carbon black according to an embodiment of the present invention includes irradiating microwave to a mixed solution containing an acidic or basic aqueous solution and crude carbon black.
The process for producing the purified carbon black efficiently provides high purity purified carbon black for a short period of time. Further, the purified carbon black tends to be dispersed in rubber or the like. Accordingly, it is possible to provide a rubber composition for a tire which can realize weight reduction of a tire having an improved dispersion degree by using the carbon black.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a process for producing purified carbon black, a rubber composition for a tire including the purified carbon black, and a tire produced using the same. BACKGROUND ART [0002] }

The present invention relates to a process for producing purified carbon black, a rubber composition for a tire containing purified carbon black, and a tire produced using the same, and more particularly, to a process for producing purified carbon black which can produce highly purified high purity carbon black A rubber composition for a tire capable of realizing reduction in weight of a tire by using purified carbon black, and a tire manufactured using the rubber composition.

Carbon black is used for rubber additives such as rubber reinforcing materials; Resin colorants, printing inks, paints and the like; And applications for imparting conductivity to resins and the like.

The production method of carbon black includes the following: 1) a furnace method in which a raw material is incompletely burnt, 2) a contact which is burned with a burner chip to convert to a flame, the flame is brought into contact with a channel steel, And 3) a thermal method for pyrolyzing natural gas.

Among them, the plain method is most commonly used. In the furnace method, creosote oil or petroleum-based heavy oil is mainly used as a raw material, and these are incompletely buried in the reaction furnace together with an amount of air less than the theoretical amount for complete combustion to be incompletely burnt, Finally, it is captured with water and obtained as an aqueous dispersion.

These raw materials for carbon black include metal components such as iron, nickel, and vanadium. These metal components are concentrated in the production process of carbon black, and there is also the incorporation of metal components from cooling water and production facilities, so that the crude carbon black contains various metal components. Therefore, it is required to remove their metal components as much as possible to make them high in purity.

As a method for reducing the amount of metal in the crude carbon black, a method in which an aqueous dispersion of carbon black is contacted with various water-soluble chelating agents to elute the metal components contained in the carbon black and is captured by the chelating agent and transferred to a liquid phase (Patent Document 1), a method of separating the aqueous dispersion of carbon black by stirring after strong stirring, and the like (Patent Document 2).

Japanese Patent Application Laid-Open No. 2005-113091 (published on April 28, 2005) Japanese Unexamined Patent Publication No. 2005-220320 (Publication Date: Aug. 18, 2005)

It is an object of the present invention to provide a method for producing purified carbon black capable of producing carbon black of high purity with high efficiency.

It is another object of the present invention to provide a rubber composition for a tire which can realize reduction in weight and the like of a tire.

It is still another object of the present invention to provide a tire produced using the rubber composition for a tire.

In order to accomplish the above object, a method of producing purified carbon black according to an embodiment of the present invention includes irradiating microwave to a mixed solution containing an acidic aqueous solution or basic aqueous solution and crude carbon black.

The mixed solution may further include a surface treating agent.

The step of irradiating the mixed solution with microwaves may include irradiating the mixed solution with a microwave having a frequency of 915 MHz to 2450 MHz.

The step of irradiating microwave to the mixed solution may include irradiating the mixed solution with microwave of 60 to 1200 watts.

The step of irradiating the mixed solution with microwaves may further include stirring the mixed solution. The method may further include the step of stirring the mixed solution after the step of irradiating the mixed solution with microwaves. The method may further include a step of circulating the mixed solution after the step of stirring the mixed solution.

A rubber composition for a tire according to another embodiment of the present invention comprises a raw rubber and carbon black prepared by the above method.

The carbon black may be included in an amount of 5 to 60 parts by weight based on 100 parts by weight of the raw rubber.

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

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

The method for preparing purified carbon black according to an embodiment of the present invention includes irradiating microwave to a mixed solution containing crude carbon black.

The crude carbon black may include a reaction product containing carbon black after the carbon black is produced but not purified. Therefore, the crude carbon black may contain impurities such as metal components in addition to carbon black.

The carbon black that can be applied to the method for producing the purified carbon black is not particularly limited. Therefore, a carbon black in an untreated state suitable for the purpose of use of the carbon black can be used. In one example, when preparing purified carbon black for application to tires, the nitrogen surface area per gram (N ₂ SA) is 20 to 170 m ² / g and the DBP (n-dibutyl phthalate) oil absorption Carbon black containing 70 to 140 cc / 100 g of carbon black may be used. When a carbon black having the above range is used, it is possible to provide a tire excellent in workability and reinforcement performance.

The mixed solution may include an acidic aqueous solution or a basic aqueous solution.

As the acidic aqueous solution, for example, an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, an aqueous nitric acid solution or a mixture thereof can be used. In one example, the acidic aqueous solution may be a mixture of a 37% aqueous hydrochloric acid solution and a 40% aqueous sulfuric acid solution in a weight ratio of 1:10 to 10: 1, a 37% aqueous hydrochloric acid solution and a 40% nitric acid aqueous solution at a ratio of 1:10 to 10: 1 Or a mixture of 40% sulfuric acid aqueous solution and 40% nitric acid aqueous solution at a weight ratio of 1:10 to 10: 1 may be used. When such a mixture is used, purified carbon black can be produced with high efficiency in a short time. As a result of several experiments, it was possible to purify carbon black with the highest efficiency when the above-mentioned acid aqueous solutions were mixed at a weight ratio of 1: 1 to 5: 1.

As the basic aqueous solution, for example, an aqueous solution of hydrogen peroxide, an aqueous solution of ammonium hydroxide or a mixture thereof can be used. In one example, a basic aqueous solution may be a mixture of 30% aqueous hydrogen peroxide solution and 30% aqueous ammonium hydroxide solution at a weight ratio of 1:10 to 10: 1. When such a mixture is used, purified carbon black can be produced with high efficiency in a short time. As a result of several experiments, when the basic aqueous solutions were used in a weight ratio of 1: 1, the purification efficiency of carbon black was the most excellent.

The crude carbon black may be contained in the mixed solution in an amount of 0.1 to 30 parts by weight or 0.5 to 10 parts by weight based on 100 parts by weight of the acidic or basic aqueous solution to produce purified carbon black with high efficiency. If the content of the crude carbon black is less than the above range, the purification rate and the purification efficiency are lowered. If the content of the crude carbon black is more than the above range, the process for producing purified carbon black by the increase in viscosity due to carbon black is continued It can be difficult.

The mixed solution may further include a surface treating agent. When the surface treatment agent is added to the mixed solution, the surface of the carbon black can be modified during production of the purified carbon black to obtain purified and surface-treated carbon black.

As the surface treatment agent, an appropriate one may be selected depending on the use of the carbon black. In one example, in the case of producing carbon black to be applied to a tire, as the surface treatment agent, a compound having a carboxyl group such as a quinone compound, a quinone imine compound, a quinone diimine compound and a mixture thereof and an amino benzoic acid may be used .

The surface treating agent may be included in the mixed solution in an amount of 5 to 10 parts by weight based on 100 parts by weight of the crude carbon black to improve the dispersibility of the carbon black.

In addition to the above-mentioned components, the mixed solution may further include known additives used in the art to prepare purified carbon black.

The time point at which the mixed solution is produced can be appropriately controlled according to the structure of the production apparatus and components contained in the mixed solution, for example, crude carbon black, and / or an acidic or basic aqueous solution. The mixed solution may be prepared before the step of irradiating the microwave, or may be produced under irradiation of microwave. In addition, the mixing solution may be prepared before the step of irradiating the microwave, and the mixed solution may be further injected by injecting components of the mixed solution in the step of irradiating the microwave.

In one example, the mixed solution may be prepared prior to the step of irradiating the microwave. The prepared mixed solution can be moved to a step of continuously irradiating the microwave through a pump, for example.

The step of irradiating the microwave may be performed by irradiating microwave to the mixed solution contained in the reactor. As the microwave, a kind of electromagnetic wave located between the infrared ray and the air wave region in the electromagnetic spectrum can be used.

In one example, the step of irradiating the microwave may be performed by irradiating a microwave having a frequency of 915 MHz to 2450 MHz to the mixed solution. At this time, it is possible to irradiate the microwave having one frequency or the microwave having a plurality of frequencies simultaneously or sequentially. In the case of simultaneously irradiating microwave having various frequencies in the above range, uniform heating is possible in a large apparatus, and it is advantageous in that purified carbon can be produced by a large-scale continuous process.

The microwave can be irradiated with an appropriate output to the crude carbon black. In one example, the microwave can be irradiated to the mixed solution at an output of 60 to 1200 watts. In the case of irradiating a microwave having an output in the above range, the production time can be shortened, and a suitable production temperature can be maintained, thereby improving purification efficiency and purification speed.

In the step of irradiating the microwave, the temperature of the reactor can be appropriately controlled in consideration of the production time and the production efficiency. In one example, the temperature of the reactor can be adjusted to 60 to 200 占 폚. If the temperature of the reactor is lower than the above range, the purification efficiency or the purification rate may be lowered. If the temperature is higher than the above range, the stability of the process may be exceeded and the energy is excessively used.

The temperature of the reactor can be controlled by several factors. The temperature of the reactor can be suitably controlled by, for example, the frequency, output or irradiation time of the microwave.

In the step of irradiating the microwave, the pressure of the reactor can be appropriately controlled in consideration of the manufacturing time and the manufacturing efficiency. In one example, the pressure of the reactor can be adjusted to 14 to 200 PSI per square inch or 120 to 150 PSI. If the pressure of the reactor is less than the above range, the reaction rate may become slow and the refining time may become longer. If the pressure of the reactor exceeds the above range, a commonly used Teflon reactor may cause a risk of explosion Which may adversely affect the stability and economics of the equipment.

The pressure of the reactor can be controlled, for example, by a pressure regulator which is arranged separately from the reactor. In one example, the pressure regulator may include a pressure sensing part for sensing the pressure of the reactor, and a gas injection part and a valve regulating part operated by the pressure sensing part. Therefore, when the pressure of the reactor is lower than the above range, the gas is injected through the gas injection unit. When the pressure of the reactor is higher than the above range, It can be discharged. However, the method of controlling the pressure of the reactor is not limited to the above-mentioned contents, and the method used in the art can be used without limitation.

The reactor may be at least partially permeable to microwaves. In one example, at least a portion of the reactor may be formed of Teflon or quartz that is permeable to microwaves. The reactor may be constituted by a material which can transmit microwaves as a whole, or a material which can partially transmit microwaves. When a part of the reactor is made of a material capable of transmitting microwaves, the other part may be made of a known material capable of withstanding high pressure and high temperature during the reaction. For example, the area of the reactor where microwaves are not transmitted may be made of stainless steel or Hastelloy C material.

The mixed solution exposed to the microwaves can be stirred. Stirring of the mixed solution exposed to the microwaves may be performed in the step of irradiating the microwaves or may be performed after the step of irradiating the microwaves.

In the above, the former means that the step of irradiating the microwave further includes stirring the mixed solution. In this case, the mixed solution can be stirred under irradiation of microwave. When such a method is used, a reactor equipped with a stirrer may be used as the reactor.

The latter means performing the step of stirring the mixed solution after the step of irradiating the microwave.

In one example, the step of irradiating the microwave and the step of stirring the mixed solution can be carried out in one reactor. That is, in this case, the apparatus can be constituted by a method (former method) of producing purified carbon black so as to include a step of irradiating microwaves including the stirring. Here, the step of irradiating the microwave and the step of stirring the mixed solution may be performed one time in sequence, and may be repeated two or more times.

In another example, the step of irradiating the microwave and the step of stirring the mixed solution may be carried out in two reactors. That is, after the step of irradiating the microwave in one of the two reactors (hereinafter referred to as the first reactor), the mixed solution exposed to the microwave is moved to another reactor (hereinafter referred to as the second reactor) Followed by stirring. When two reactors are used, the above-described pressure regulator can be installed in the second reactor. The step of irradiating the microwave and the step of stirring the mixed solution may be performed one time in sequence, and may be repeated two or more times. When the above steps are repeated two or more times, the manufacturing method may further include circulating the mixed solution. That is, the mixed solution of the second reactor may be transferred to the first reactor using a pressure regulator provided in the second reactor. For example, if the first reactor is connected to the second reactor and the pressure of the second reactor is controlled to be greater than about 150 PSI to 200 PSI, the mixed solution can be transferred to the first reactor through the pipe connected to the second reactor .

The irradiation of the microwave and the stirring of the mixed solution can be carried out for a suitable time in consideration of the purity of the desired carbon black, the content of the crude carbon black to be purified, the content of the impurities of the crude carbon black, and the output of microwave. In one example, irradiation of microwave and agitation of the mixed solution can be controlled to 20 minutes to 4 hours. Carbon black purified at high efficiency with respect to the same energy can be produced within the above time range.

The method for producing the purified carbon black may further include, for example, a step of irradiating microwaves or a step of filtering the mixed solution after the step of stirring the mixed solution. Accordingly, the mixed solution that has been subjected to the irradiation of the microwave and / or the stirring of the mixed solution is filtered, and if necessary, the filtered material is vacuum dried to obtain purified carbon black. The carbon black produced by the above method may have a higher purity than the conventional carbon black. For example, the purity of the carbon black may be 95 to 99.9%.

A rubber composition for a tire according to another embodiment of the present invention comprises a raw rubber and the purified carbon black.

The carbon black may be one produced by the above-described method for producing purified carbon black. Therefore, the carbon black may have the above-described nitrogen adsorption specific surface area and / or DBP oil absorption. In addition, the carbon black may be surface-treated for affinity with rubber as described above.

The carbon black can be produced with high purity by the production method. As a result, the carbon black can exhibit the same or superior physical properties as the existing carbon black even when using a smaller amount than the conventional carbon black. In one example, the rubber composition for a tire may contain carbon black in an amount of 5 to 60 parts by weight or 5 to 55 parts by weight based on 100 parts by weight of the raw rubber. By controlling the content of carbon black as described above, the content of carbon black in the rubber composition for a conventional tire can be reduced by about 20%, and a light tire compared with the conventional tire can be provided.

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 rubber composition for a tire 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. Any of the various additives may 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 is dependent on the blending ratio used in a conventional rubber composition for a tire.

As the vulcanizing agent, a sulfur vulcanizing agent can be preferably 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.

It is preferable that the vulcanizing agent is contained in an amount of 0.5 to 4.0 parts by weight based on 100 parts by weight of the raw material rubber in view of providing a vulcanization effect that 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 10 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 addition to the carbon black, the filler may further include any one selected from the group consisting of silica, calcium carbonate, clay (hydrated aluminum silicate), aluminum hydroxide, lignin, silicate, talc, and combinations thereof.

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. If the content of the silica is less than 20 parts by weight, the strength of the rubber may not be improved and the braking performance of the tire may be deteriorated. If the content of the silica exceeds 90 parts by weight, the wear performance may be deteriorated.

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 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, 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 has favorable characteristics for environmental factors such as low temperature property and fuel efficiency of tire including TDAE oil and possibility of cancer induction of PAHs.

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.

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 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 or resorcinol formaldehyde resin, and the p-tert-alkylphenol formaldehyde resin may be a p-tert-butyl-phenol formaldehyde resin, - octyl-phenol formaldehyde, and combinations thereof.

The pressure-sensitive adhesive may be included in an amount of 2 to 4 parts by weight based on 100 parts by weight of the raw rubber. If the amount of the pressure-sensitive adhesive is less than 2 parts by weight based on 100 parts by weight of the raw material rubber, the adhesion performance may be deteriorated. If the amount is more than 4 parts by weight, rubber properties may be deteriorated.

The rubber composition for a tire can be produced through a conventional two-step continuous production process. That is, during the finishing step in which the first stage of thermomechanical treatment or kneading and the crosslinking system are mixed at a maximum temperature of 110 to 190 占 폚, preferably at a high temperature of 130 to 180 占 폚, typically less than 110 占 폚, And a second step of mechanical treatment at a low temperature of 40 to 100 DEG C in a suitable mixer, but the present invention is not limited thereto.

The rubber composition for a tire 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.

A tire according to another embodiment of the present invention is manufactured using the rubber composition for a tire. The method of manufacturing a tire using the rubber composition for a tire 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 process for producing purified carbon black of the present invention provides highly purified carbon black efficiently in a short period of time. Further, the purified carbon black tends to be dispersed in rubber or the like. Accordingly, it is possible to provide a rubber composition for a tire which can realize weight reduction of a tire having an improved dispersion degree by using the carbon black.

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 purified carbon black and rubber composition for tire]

Manufacturing example  1. Preparation of purified carbon black (A)

37% hydrochloric acid aqueous solution and 40% nitric acid aqueous solution at a weight ratio of 3: 1. 100 parts by weight of the mixture was mixed with 5 parts by weight of crude carbon black having a nitrogen adsorption specific surface area of 140 m ² / g and a DBP oil absorption amount of 130 cc / 100 g to prepare a mixed solution.

The mixed solution was irradiated with a microwave having an output of 600 W, and the carbon black was purified at 175 캜 for 30 minutes. The purity of the purified carbon black (A) was 99.5%.

Manufacturing example  2. Preparation of carbon black (B)

The crude carbon black (B) used in Production Example 1 was prepared. The purity of the crude carbon black (B) was 95%.

Example  1 to 3 and Comparative Example

Rubber compositions for tires 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 Example 1 Example 2 Example 3 Rubber raw material ⁽¹⁾ 100 100 100 100 Carbon black (A) 50 45 40 Carbon black (B) 50 Zinc oxide 5 5 5 5 Stearic acid 2 2 2 2 Antioxidant 2 2 2 2 brimstone 2 2 2 2 Vulcanization accelerator 1.5 1.5 1.5 1.5

(Unit: parts by weight)

(1) Raw material rubber: NR (STR-20)

[ 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.

Comparative Example Example 1 Example 2 Example 3 Fairness 100 ℃ Viscosity 66 69 66 63 Scotch time (t5) 23.2 21.8 23.6 23.8 Tensile properties
Hardness 66 68 67 65 300% modulus 170 178 172 169 The tensile strength 280 292 287 283 Elongation 440 424 436 449 LB wear Wear (Index) 100 109 105 102 My Cut Chipping Castle Wear (Index) 100 97 98 101 Hysteresis 60 占 폚 tan? (Index) 100 99 103 107

(1) Mooney Viscosity (ML1 + 4, 100 ° C): Measured using a Mooney MV2000 (Alpha Technology) instrument with a large rotor, preheating for 1 minute, rotor operating time of 4 minutes, Respectively. The Mooney viscosity means that the higher the value, the greater the viscosity of the rubber, indicating that the workability is disadvantageous.

(2) Scorch time was measured with a Muni viscometer. The scorch time is a measure of the time it takes to rise five points from the Mooney minimum, indicating that the longer the scorch stability is, the better.

(3) The hardness is a value measured with a Shore A type hardness meter. The hardness indicates the steering stability. The higher the value, the better the steering stability.

(4) 300% Modulus (kgf / cm 2) is the tensile strength at 300% elongation measured according to ISO 37 standard, and the higher the value, the better the strength.

(5) Tensile strength (Kgf / cm ² ) was measured by the method of ASTM D 790, and the higher the value, the better the strength.

(6) The elongation at break (%) was measured by a method in which the strain value until the test piece was broken in a tensile tester in%.

(7) The index of abrasion is the index of the loss of rubber worn by rotating at 25% slip ratio and 1.5 kg load at room temperature as a ratio of Lambourn abrasion tester to 100 as a comparative example. The higher the wear rate, the better the wear performance.

(8) The chit chipping property was evaluated using an indoor durability tester. The measurement result is shown by an index with the comparative example being 100. The larger the value, the better the performance.

(9) 60 占 폚 tan? Is used as a substitute resin for the low fuel consumption performance of the tire, and Comparative Example 1 is set to 100, and indexed based on this value. The higher the index, the better the performance.

As shown in Table 2, the carbon black prepared using microwave showed the same basic properties as those of the conventional carbon black even when a small amount of carbon black was used. Particularly, in the hysteresis and wear test, it was confirmed that the example using the carbon black manufactured using the microwave showed superior performance to the comparative example using the conventional carbon black.

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 (10)

Irradiating microwave to a mixed solution containing an acidic aqueous solution or basic aqueous solution and crude carbon black and a surface treatment agent.
delete The method according to claim 1,
Wherein the step of irradiating microwave to the mixed solution comprises irradiating microwave having a frequency of 915 MHz to 2450 MHz to the mixed solution.
The method according to claim 1,
Wherein the step of irradiating microwave to the mixed solution comprises irradiating the mixed solution with microwave of 60 to 1200 watts.
The method according to claim 1,
Wherein the step of irradiating microwave to the mixed solution further comprises stirring the mixed solution.
The method according to claim 1,
Further comprising the step of stirring the mixed solution after irradiating microwave to the mixed solution.
The method according to claim 6,
And circulating the mixed solution after the step of stirring the mixed solution.
A rubber composition for a tire comprising a raw rubber and carbon black produced by the process according to claim 1.
9. The method of claim 8,
Wherein the carbon black is contained in an amount of 5 to 60 parts by weight based on 100 parts by weight of the raw rubber.
A tire produced by using the rubber composition for a tire according to claim 8.