KR20150134545A - Master batch for tire rubber, rubber composition for tire comprising the same and tire manufactured by using the same - Google Patents

Abstract

The present invention relates to a master batch for tire rubber, a tire rubber composition comprising the same, and a tire manufactured by using the same. The master batch for tire rubber provides a tire rubber composition with excellent manufacturing processability by solving degradation of scorch stability and a problem of not being unwound, while not influencing a curing system, and maximizing drug dispersibility and processability.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a master batch for a tire, a rubber composition for a tire including the master batch, and a tire produced using the master batch,

The present invention relates to a master batch for a tire rubber, a rubber composition for a tire comprising the rubber composition, and a tire produced using the master batch, and more particularly to a master batch for tire rubber having excellent processability and dispersibility, The present invention relates to a tire manufactured by the method.

Conventional vulcanizing agents and vulcanization accelerators used in rubber for tires were in powder form. When a powdery vulcanizing agent and a vulcanizing accelerator are put into a Banbury mixer or an open roll or the like, scattering of the powder of the powder causes contamination of the periphery of the equipment, an increase in the amount of scrap, and a variation in physical properties. As a result, vulcanizing agents and vulcanization accelerators used in tire rubber have been used in the form of a master batch (M / B) in order to improve pollution by dust generation and dispersibility with rubber in a mixing process. This masterbatch is added to the rubber composition in the form of plate or pellet, thereby improving the dispersibility in the mixing process by preventing the loss of chemicals, preventing environmental pollution and weakening the binding force between the mixed particles.

Open roll formulations are mainly used to mix rubber compositions based on natural rubber, and therefore, the use of a master batch based on natural rubber has been required to prevent degradation of the physical properties of the rubber composition. However, when a masterbatch is produced using a natural rubber having a high molecular weight, its manufacturing processability is very disadvantageous.

In addition, as the frequency of use of the open-roll compounding of silica compounds is increased, it is more advantageous to stabilize the manufacturing process and physical properties than to use a masterbatch based on natural rubber for a silica compound which does not use natural rubber, and is mainly used for silica compound It is necessary to prepare a master batch using a synthetic rubber as a binder.

Furthermore, the present applicant found that the fatty acid contained in the natural rubber combined with the zinc ion contained in the vulcanization accelerator not only adversely affected the scorch stability, but also resulted in the unfolding phenomenon in the production of the masterbatch.

Korean Patent Publication No. 10-2002-0089894 (published on November 30, 2002)

An object of the present invention is to provide a master batch for a tire rubber which can improve drug dispersion without affecting the vulcanization system in order to improve the rubber unfolding and the master batch accumulation.

Another object of the present invention is to provide a rubber composition for a tire including the master batch and a tire manufactured using the rubber composition for a tire.

In order to achieve the above object, a master batch for a tire tire according to an embodiment of the present invention comprises 5 to 25 parts by weight of a synthetic rubber; 70 to 90 parts by weight of a vulcanization accelerator; And 1 to 10 parts by weight of a processing aid comprising a fatty alcohol and a fatty ester having a carbon weight of at least 80%.

The synthetic rubber may be a styrene butadiene rubber having a styrene content of 20 to 25% by weight and a molecular weight of 250,000 to 350,000 g / mol.

The vulcanization accelerator may be selected from the group consisting of sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamate, aldehyde-amine, aldehyde-ammonia, imidazoline, And the like.

The fatty alcohols may be selected from the group consisting of octyl, decyl, octyldecyl, lauryl, myristyl, cetyl, stearyl, oleyl, And a mixture of two or more functional groups.

The fatty esters may be selected from the group consisting of a methyl group, an isopropyl group, a butyl group, an ethylhexyl group, a cetyl group, a glyceryl group, an isononyl group, a tridecyl group, an isotridecyl group, a decyl group, And may include any one selected functional group.

In one example, the processing aid may be a mixture of fatty alcohols and fatty esters having a melting point of from 40 to 50 DEG C and a carbon weight of at least 90%. Further, in another example, the processing aid may be a mixture of fatty alcohols and fatty esters having a melting point of 80 to 90 占 폚, a carbon weight of 80% or more, and an oxygen weight of 10% or more.

The rubber composition for a tire according to another embodiment of the present invention includes 100 parts by weight of a raw rubber and 0.5 to 5 parts by weight of a master batch for the tire rubber.

The raw material rubber may include any one selected from the group consisting of butadiene rubber, styrene butadiene rubber, and mixtures thereof.

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 masterbatch for a tire tire according to one embodiment of the present invention comprises 5 to 25 parts by weight of a synthetic rubber; 70 to 90 parts by weight of a vulcanization accelerator; And 1 to 10 parts by weight of a processing aid comprising a fatty alcohol and a fatty ester having a carbon weight of at least 80%. The masterbatch improved the workability by adding a large amount of a vulcanization accelerator and a small amount of processing aid using synthetic rubber as a binder.

The use of synthetic rubber as a binder in the masterbatch solves the problem that the fatty acid contained in the natural rubber is bonded or reacted with the zinc ion contained in the vulcanization accelerator to thereby disadvantageously scorch stability, .

Examples of the synthetic rubber that may be employed as the binder include styrene butadiene rubber (SBR), modified styrene butadiene rubber, butadiene rubber (BR), modified butadiene rubber, chlorosulfonated polyethylene rubber, epichlorohydrin 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 Butadiene rubber, maleic acid styrene-butadiene rubber, carboxylic acid styrene-butadiene rubber, epoxy isoprene rubber, ethylene-maleic anhydride copolymer, styrene-butadiene rubber, styrene-butadiene rubber, Propylene rubber, carboxyl (Meth) acrylonitrile-butadiene rubber, brominated polyisobutyl isoprene-co-paramethyl styrene (BIMS), and combinations thereof.

In one example, in order to uniformly blend a large amount of vulcanization accelerator into rubber for tire and to further improve the workability of the rubber for tire, the synthetic rubber has heat resistance and a styrene content of 20 to 25% by weight , And styrene-butadiene rubber having a molecular weight of 250,000 to 350,000 g / mol.

In order to improve the scorch stability and minimize the unevenness of the rubber, and to improve the dispersibility of the master batch and to improve the dispersibility of the chemical without affecting the vulcanization system, May be used in an amount of 5 to 25 parts by weight relative to the parts.

The vulcanization accelerator refers to an accelerator that accelerates the vulcanization rate of the rubber composition for a tire or accelerates the retarding action in the initial vulcanization step. As the vulcanization accelerator, those used in the rubber composition for a tire may be used without limitation.

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 vulcanization accelerators selected from the group consisting of N, N-diphenylguanidine, diorthotolylguanidine, triphenylguanidine, orthotolylbiguanide, diphenylguanidine phthalate, Based compound can be used.

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 have an oil content of 1 to 2% by weight in the total content of the vulcanization accelerator.

The vulcanization accelerator may be used in an amount of 70 to 90 parts by weight based on 100 parts by weight of the master batch for the entire tire rubber so as to improve rubber unfolding and aggregation of the master batch and to exhibit an appropriate vulcanization promoting effect in a state of no problem in workability .

The processing aid is added in order to provide a master batch for tire tread having good dispersibility, which improves rubber unfolding and aggregation of masterbatches and has no problem in workability.

The processing aid may comprise a mixture of fatty alcohols and fatty esters having a carbon weight of at least 80%.

The fatty alcohols having a carbon weight of 80% or more in the above are preferably selected from octyl, decyl, octyldecyl, lauryl, myristyl, cetyl, stearyl, oleyl, A benzyl group, and a mixture thereof.

In the above, the fatty ester is preferably selected from the group consisting of methyl group, isopropyl group, butyl group, ethylhexyl group, cetyl group, glyceryl group, isononyl group, tridecyl group, isotridecyl group, decyl group, isodecyl group, And the like.

In one example, the processing aid may be a mixture of fatty alcohols and fatty esters having a melting point of from 40 to 50 DEG C and a carbon weight of at least 90%. The processing aid can improve the dispersibility of the filler as well as the chemical agent and can act as a plasticizer of a green compound to improve flow and provide a masterbatch of a smooth surface. As such a processing aid, DF-908F available from Dongbu Chemical Co., Ltd. may be used.

In another example, the processing aid may be a mixture of fatty alcohols and fatty esters having a melting point of 80 to 90 占 폚, a carbon weight of 80% or more, and an oxygen weight of 10% or more. The processing aid can serve to improve the dispersion of the filler and the flowability of the compound, and it is possible to improve the dispersibility of the drug without affecting the curing system of the rubber composition for a tire. As such a processing aid, commercially available WB222 from Strucktol can be used. Use of the processing aid deviating from the above-mentioned melting point may be detrimental to the chemical dispersion during the compounding for preparing the master batch.

The processing aid is added in an amount of 1 to 10 parts by weight per 100 parts by weight of the master batch for the entire tire rubber so as to improve the rubber unfolding and aggregation of the master batch and maximize the flowability and the chemical dispersibility without affecting the vulcanization system Can be used.

The rubber masterbatch for a tire may further include components commonly employed in the art in addition to the above-mentioned components. Further, the master batch can be produced by a conventional method employed in the art.

The rubber composition for a tire according to another embodiment of the present invention includes the master batch for the tire rubber.

The rubber composition for a tire includes 100 parts by weight of a raw rubber and 0.5 to 5 parts by weight of a master batch for the tire rubber.

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.

Among these raw materials, any one selected from the group consisting of butadiene rubber, styrene butadiene rubber, and mixtures thereof may be employed. Since the master batch for the tire rubber has high workability especially for butadiene rubber and styrene butadiene rubber, it is possible to provide a rubber composition for a tire having excellent manufacturing processability when a butadiene rubber and / or a styrene butadiene rubber is used as raw material rubber.

Specifically, when the solution-polymerized styrene-butadiene rubber is employed as the styrene-butadiene rubber and the nickel butadiene rubber is used as the butadiene rubber, the miscibility with the master batch for tire tread described above can be further improved.

The rubber composition for a tire may further include various additives such as an additional vulcanizing agent, a vulcanization accelerator, a vulcanization accelerator, a filler, a coupling agent, an anti-aging agent or a softening agent. 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.

As the vulcanization accelerator, the above-described master batch for tire tread can be used. However, the present invention is not limited to this, and other vulcanization accelerators may be added in addition to the master batch for tire rubber.

Other vulcanization accelerators that can be used in addition to the masterbatch for tire rubber include all vulcanization accelerators of the same or different kinds as the vulcanization accelerator added in the production of the master batch. Examples of the vulcanization accelerator include the vulcanization accelerator described above.

If the vulcanization accelerator is a master batch for a tire rubber, 0.5 to 5 parts by weight of a master batch may be used based on 100 parts by weight of the raw rubber. When a vulcanization accelerator other than the masterbatch is further added, 0.5 to 4 parts by weight of another vulcanization accelerator may be used based on 100 parts by weight of the raw rubber. In this range, it is possible to maximize the productivity improvement and the rubber property improvement by accelerating the vulcanization rate.

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.

The rubber composition for a tire may further comprise a filler. The filler may be any one selected from the group consisting of carbon black, silica, calcium carbonate, clay (hydrated aluminum silicate), aluminum hydroxide, lignin, silicate, talc, and combinations thereof.

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 90 parts by weight, and further preferably 40 to 90 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.

When silica is used as the filler, a coupling agent may be further added to improve the dispersibility of silica.

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 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 master batch for a tire tire according to the present invention can improve the scraper stability of the master batch and the unfolding phenomenon of the master batch while maximizing the chemical dispersibility and processability without affecting the vulcanization system, Composition can be provided.

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 : Manufacture of master batch for tire tire]

Masterbatches were prepared in the following Examples and Comparative Examples using the compositions shown in Table 1 below. Specifically, the composition as shown in Table 1 below was blended and extruded using an extruder. The extrudate was passed through a tank containing a release agent alkylsulfonic salt having a pH of 6.0 to 8.0 to prepare a pellet-shaped master batch.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Natural Rubber ⁽¹⁾ 15 Synthetic rubbers ⁽²⁾ 15 15 15 Vulcanization accelerators ⁽³⁾ 80 80 80 80 Processing aid A ⁽⁴⁾ 5 5 Processing aid B ⁽⁵⁾ 5 Processing aid C ⁽⁶⁾ 5

(Unit: parts by weight)

(1) Natural rubber: A diene-based natural rubber (trade name: SVR-3L) made of latex,

(2) Synthetic rubber: A styrene butadiene rubber having a styrene content of 20 to 25% by weight, a molecular weight of 250,000 to 350,000 g / mol and a Mooney viscosity of 47 to 57 at 100 DEG C (manufactured by LG Chem, : SEETEC SB1502)

(3) Vulcanization accelerator: A vulcanization accelerator (trade name: Puyang, trade name: ZBEC (dibenzyldithiocarbamate)) having a melting point of 179 to 190 DEG C and an oil content of 1 to 2 wt%

(4) Processing aid A: A mixture of a fatty alcohol and a fatty ester (trade name: DF-908F manufactured by Dong-Eun Chemical Co., Ltd.) having a melting point of 40 to 50 캜, a weight loss of about 1 wt%

(5) Processing aid B: A mixture of a fatty acid ester and a zinc soap having a melting point of 55 to 70 DEG C (manufactured by Rhein Chemie, Aflux42)

(6) Processing aid C: Wax mixture (Struktol, trade name: WB222) containing a fatty alcohol and a high molecular weight fatty alcohol having a melting point of 80 to 90 占 폚, a carbon content of 80% or more and an oxygen content of 10%

[ Experimental Example  1: Measurement of physical properties of prepared master batch]

The physical properties of the master batches prepared in the above Examples and Comparative Examples were measured, and the results are shown in Table 2 below.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Hardness 69 84 66 71 Appearance and manufacturing processability Very bad Bad Great Great

(1) The hardness was measured by DIN 53505.

(2) Appearance and manufacturing processability were evaluated by visually observing the produced pellets. Specifically, if the shape of the pellet is selected as shown in the following photograph 1 and the aggregation phenomenon is not observed, the result is 'excellent'. If the cutting shape is uneven, the pellet is formed as shown in photograph 3 When a long pellet is observed, it is marked as 'very bad'.

[Picture 1]

[Picture 2]

[Picture 3]

Referring to Table 2, as in Comparative Example 1, the masterbatch using the natural rubber had a poor scorch stability due to the binding of the zinc ion contained in the fatty acid and the vulcanization accelerator contained in the natural rubber, And manufacturing processability were found to be disadvantageous.

Also, as shown in Comparative Example 2, when the hardness of the masterbatch is high, the extruder rotor is disadvantageously affected by extreme shear as the shear is increased.

However, in Examples 1 and 2 using a synthetic rubber instead of natural rubber and using a mixture of fatty alcohols and fatty esters having a carbon weight of 80% or more as a processing aid, it has a low hardness and produces a master batch of excellent manufacturing processability and appearance Could.

[ Experimental Example  2: Evaluation of physical properties of a tire to which a master batch is applied]

The rubber compositions for tires were prepared by applying the master batches prepared in Comparative Examples 1 to 2 and Examples 1 and 2 to the same compound. Specifically, 96.25 phr of solution-polymerized styrene butadiene rubber (S-SBR), 20 phr of nickel butadiene rubber (Ni-BR), 80 phr of silica, 6.5 phr of coupling agent, 3 phr of softener, 3 phr of zinc oxide, 2 phr of stearic acid, 1.4 phr of the first vulcanization accelerator and 2 phr of the second vulcanization accelerator were blended to prepare a rubber composition for a tire. Herein, the rubber compositions for tires of Comparative Examples 1 to 2 and Examples 1 to 2 were prepared using the master batches of Comparative Examples 1 to 2 and Examples 1 to 2 as the second vulcanization accelerator. The production of the rubber composition was in accordance with the usual production method of the rubber composition.

The physical properties of the rubber specimens obtained from the rubber compositions for tires of Comparative Examples 1 to 2 and Examples 1 and 2 were measured, and the results are shown in Table 3 below.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Mooney viscosity 90 82 81 80 Hardness (Shore A) 73 71 71 72 300% Modulus (MPa) 130 139 143 136 0 deg. 0.276 0.284 0.290 0.282 60 deg. 0.134 0.134 0.131 0.133 Q Chemical Dispersion (CV) 4.13 3.83 1.50 2.21

(1) Mooney viscosity (ML1 + 4 (100 占 폚)) was measured according to ASTM standard D1646. The Mooney viscosity is a value indicating the viscosity of the unvulcanized rubber. The lower the numerical value, the better the flowability and the better the extrusion processability.

(2) The hardness was measured by DIN 53505. The hardness indicates the adjustment stability, and the higher the value, the better the adjustment stability performance.

(3) The 300% modulus was measured according to the ISO 37 standard.

(4) Viscoelasticity was evaluated by measuring G ', G "and tan δ from -60 ° C to 70 ° C under 0.5% strain and 10Hz frequency using an RDS measuring instrument. The 0 ° C tan δ indicates the braking performance. The higher the value, the better the braking performance. The 60 ° tan δ indicates the rotational resistance characteristic, and the lower the value, the better the performance.

(5) Q The drug dispersibility was determined by taking ten test specimens randomly from the mixed rubber, obtaining the maximum torque point using MDR (Alpha Tech), and calculating the coefficient of variation from each standard deviation and average value. Q The drug dispersion shows that the lower the coefficient of variation (CV), the better the dispersibility.

Referring to Table 3, when a master batch of a vulcanization accelerator using a mixture of a synthetic rubber and a fatty alcohol and a fatty ester having a carbon weight of 80% or more is used, it has no effect on the existing properties and can be mixed in a Banbury mixer or an open roll And that the Q coefficient of chemical dispersion coefficient was low.

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)

5 to 25 parts by weight of a synthetic rubber;
70 to 90 parts by weight of a vulcanization accelerator; And
1 to 10 parts by weight of a processing aid comprising a fatty alcohol and a fatty ester having a carbon weight of at least 80%.
The method according to claim 1,
Wherein the synthetic rubber is a styrene butadiene rubber having a styrene content of 20 to 25% by weight and a molecular weight of 250,000 to 350,000 g / mol.
The method according to claim 1,
The vulcanization accelerator may be selected from the group consisting of sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamate, aldehyde-amine, aldehyde-ammonia, imidazoline, A master batch for a tire rubber.
The method according to claim 1,
The fatty alcohols may be selected from the group consisting of octyl, decyl, octyldecyl, lauryl, myristyl, cetyl, stearyl, oleyl, And a mixture of two or more functional groups selected from the group consisting of:
The method according to claim 1,
The fatty esters may be selected from the group consisting of a methyl group, an isopropyl group, a butyl group, an ethylhexyl group, a cetyl group, a glyceryl group, an isononyl group, a tridecyl group, an isotridecyl group, a decyl group, Wherein the master batch comprises one selected functional group.
The method according to claim 1,
Wherein the processing aid is a mixture of fatty alcohols and fatty esters having a melting point of from 40 to 50 DEG C and a carbon weight of at least 90%.
The method according to claim 1,
Wherein the processing aid is a mixture of fatty alcohols and fatty esters having a melting point of from 80 to 90 DEG C and a carbon weight of at least 80% and an oxygen weight of at least 10%.
100 parts by weight of raw rubber, and
A rubber composition for a tire comprising 0.5 to 5 parts by weight of a masterbatch for tire tread according to claim 1.
9. The method of claim 8,
Wherein the raw material rubber comprises any one selected from the group consisting of butadiene rubber, styrene butadiene rubber, and mixtures thereof.
A tire produced from the rubber composition for a tire according to claim 8.