KR101594910B1 - Rubber composition for tire bead filler and tire manufactured by using the same - Google Patents

Abstract

The present invention relates to a rubber composition for a tire bead filler and a tire produced using the tire bead filler, wherein the rubber composition for a tire bead filler comprises 1 to 50 parts by weight of a hard clay surface-coated with an alkylphenol- 50 to 100 parts by weight of carbon black and 0.2 to 10 parts by weight of a curing agent, thereby exhibiting improved hardness characteristics, reinforcing performance and rolling resistance characteristics.

Description

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

The present invention relates to a rubber composition for a tire bead filler excellent in rolling resistance performance and hardness characteristics, and a tire produced using the rubber composition.

The tire bead filler rubber is required to have higher rigidity and hardness than other rubber compound parts in order to support the load of the vehicle transmitted to the rim when the rim is mounted on the tire, High rubber rigidity is required.

In order to improve the rigidity of the tire bead filler rubber, a method of increasing the hardness and rigidity of the rubber by increasing the content of an inorganic material such as clay is used. However, when the content of the clay is high, the rubber hardness is increased but the heat generation between the clay and the rubber is increased, so that the rolling resistance performance is lowered, the rubber compounding property is deteriorated, and the tensile strength is lowered. In addition, conventionally used clay has a low oil adsorption amount and thus has a low reinforcing effect on the rubber composition.

Another method for improving the rigidity of the tire bead filler rubber is to increase the hardness and rigidity of the rubber by increasing the content of the reinforcing resin such as resorcinol formaldehyde resin. However, when the content of the reinforcing resin is high, the rubber hardness at room temperature is high. However, at the high temperature, which is a driving condition after the tire is mounted, the rigidity of the resin is lowered and the rigidity of the rubber is also lowered.

As another method, a method of improving rubber hardness by using a reinforcing resin together with a general clay was used. However, when such a general clay is added, there is a problem that viscoelasticity is lowered because of difficulty in dispersing. In order to solve such a problem, the compounding temperature must be increased and dispersed. In addition, the reinforcement effect of rubber is low due to the low development level of clay.

Korean Patent Registration No. 0913594 (Registered on August 17, 2009) Korean Patent Publication No. 2002-0047892 (published on June 22, 2002)

An object of the present invention is to provide a rubber composition for a tire bead filler excellent in rolling resistance performance and hardness characteristics.

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

In order to achieve the above object, the rubber composition for a tire bead filler according to an embodiment of the present invention comprises 1 to 50 parts by weight of a hard clay surface-coated with an alkylphenolic resin, 50 to 50 parts by weight of carbon black, 100 parts by weight, and 0.2 to 10 parts by weight of a curing agent.

In the hard clay coated with the alkyl phenolic resin, the hard clay may have a specific surface area of 10 to 100 m ² / g and an oil adsorption amount of 10 to 60 g / 100 g.

In addition, the alkylphenol-based resin forms a crosslinking with the curing agent.

The alkylphenol-based resin may be contained in an amount of 30 to 50 parts by weight based on 100 parts by weight of the hard clay.

The alkylphenol-based resin may be a parabutylphenol-formaldehyde resin, a para-tert-butylphenol-formaldehyde resin, a para-octylphenol-formaldehyde resin, (Paraoctylphenol-Formaldehyde Resin), Octyl-butylphenol-Formaldehyde Resin, and mixtures thereof.

In the rubber composition for a tire bead filler, the carbon black may have a particle size distribution (D50 / M) of 0.7 or less.

The curing agent may be hexamethylene methyltetramine.

The rubber composition for a tire bead filler is characterized by comprising 1.5 to 2 parts by weight of a vulcanization accelerator, 3 to 7 parts by weight of a vulcanizing agent, 1 to 2 parts by weight of stearic acid, 1 to 5 parts by weight of zinc oxide, And 1 to 5 parts by weight of an inhibitor.

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

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

The present invention relates to a rubber composition for a tire bead filler, which comprises a hard clay surface-treated with an alkylphenol-based resin to improve hardness and strength characteristics, The alkylphenol-based resin reacts with the curing agent to form crosslinking, thereby improving the reinforcing property of the rubber composition. Moreover, by using the carbon black having a uniform particle size, the rubber reinforcing effect is increased, The use of black is reduced, and the heat resistance between the carbon black and the rubber is lowered to improve the rolling resistance performance.

That is, the rubber composition for a tire bead filler according to an embodiment of the present invention comprises 1 to 50 parts by weight of a hard clay surface-coated with an alkylphenolic resin, 50 to 100 parts by weight of carbon black, And 0.2 to 10 parts by weight of a curing agent.

In the rubber composition, the raw material rubber may be any one selected from the group consisting of natural rubber, synthetic rubber, and mixtures thereof, and natural rubber may be preferable.

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.

In the rubber composition, the hard clay surface-coated with the alkylphenol-based resin is the surface of the hard-clay surface coated with the alkylphenol-based resin by a mixing process at a temperature of 100 ° C or higher between the alkylphenol-based resin and the hard clay. Since the alkylphenol-based resin is coated on the hard clay in this manner, there is no fear of lowering the hard clay dispersibility and lowering the viscoelasticity when the alkylphenol-based resin and the hard clay are added to the rubber composition, respectively .

The hard clay surface-coated with the alkylphenol-based resin has an effect of improving hardness and strength properties of the rubber composition by the hard clay itself, and the alkylphenol-based resin present on the hard clay surface is then used as an additive By forming a crosslinking reaction with the curing agent, the reinforcing performance of the rubber composition can be improved.

The hard clay contains not less than 80% of particles having a particle diameter of 0.4 탆 or less. In the present invention, since hard clay having a specific surface area of about 10 to 100 m ² / g and an oil adsorption amount of about 10 to 60 g / 100 g is used, the amount of oil adsorption is larger than that of a general clay, It is remarkable. When the specific surface area is less than 10 m ² / g, dispersion in the rubber is difficult, and when it exceeds 100 m ² / g, there is a fear that the rubber physical properties are lowered. On the other hand, when the oil adsorption amount is less than 10 g / 100 g, it is difficult to impregnate the alkylphenol resin. More preferably, the hard clay may have a specific surface area of about 30 to 80 m ² / g and an oil adsorption amount of 20 to 60 g / 100 g.

In addition, the alkylphenol-based resin specifically includes parabutylphenol-formaldehyde resin, para-tert-butylphenol-formaldehyde resin, para-octylphenol-formaldehyde resin, Formaldehyde resin or octyl-butylphenol-formaldehyde resin, etc., may be used.

The alkyl phenolic resin may be included in an amount of 30 to 50 parts by weight based on 100 parts by weight of the hard clay. If the content of the alkylphenol-based resin is less than 30 parts by weight, the amount of the alkylphenol-based resin coated on the hard clay surface is low, so that the hard clay dispersibility and the rubber composition reinforcing performance are not improved by the use of the alkylphenol- On the other hand, if the amount exceeds 50 parts by weight, the improvement effect is lower than the usage amount.

The hard clay coated with the alkylphenol-based resin may be included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the raw rubber. When the content of the surface hard clay is less than 1 part by weight, the hardness and the reinforcement performance of the rubber composition are not greatly improved by the use of the hard clay coated with the surface, and when the hard clay content exceeds 50 parts by weight, The performance such as elongation and tensile strength may be lowered. Considering the remarkable effect of improving the hardness, tensile strength and elongation ratio of the hard clay coated with the alkylphenol-based resin, the surface-coated hard clay is used in an amount of 5 to 50 parts by weight, Or 10 to 15 parts by weight.

In addition, in the above rubber composition, the carbon black improves the rolling resistance performance as well as the reinforcing performance of the rubber composition.

Specifically, it is preferable that the carbon black has a particle size distribution (D50 / M) of 0.7 or less. The carbon black having the above characteristics is a carbon black having a small particle size distribution, that is, a constant particle size. By using such a carbon black, the rubber reinforcing effect is greatly improved to reduce the amount of the reinforcing resin used, It is possible to improve the rolling resistance performance by reducing the heat generated between the black rubber and the rubber. The above D50 / M value △ D ₅₀ is the width of the particle size distribution curve of the carbon black in one-half of the height of the highest peak in the particle size distribution curve of the carbon black, the primary particle size is M (M, Mean of the carbon black Diameter of Primary Particle. If the particle size distribution (D50 / M) of the carbon black exceeds 0.7, the particle size distribution is large and the hardness of the rubber composition may be lowered.

The carbon black may have a BET specific surface area of 100 to 400 m < 2 > / g and a hydrogen ion index of 4 to 12 while satisfying the above-described particle size distribution condition. By simultaneously satisfying the above-described particle size distribution condition and the specific surface area and the hydrogen ion index, it is possible to exhibit an increased reinforcing performance and an improved rolling resistance effect.

The carbon black may be contained in an amount of 50 to 100 parts by weight based on 100 parts by weight of the raw rubber. When the content of the carbon black is less than 50 parts by weight, the effect of improving the reinforcing performance by the use of the carbon black is insignificant. If the content of the carbon black exceeds 100 parts by weight, the homogeneity of the rubber composition due to the use of the excess carbon black is deteriorated, May be deteriorated. Considering the remarkable effect of improving the reinforcing performance and the rolling resistance performance by using the carbon black, it is more preferable that the carbon black is included in an amount of 70 to 85 parts by weight based on 100 parts by weight of the raw rubber.

Further, in the rubber composition, the curing agent forms a crosslinking bond with the alkylphenol-based resin described above to improve the reinforcing performance of the rubber composition.

When the hardener is used in the production process of the hard clay coated with the alkylphenolic resin, hardening occurs in the surface coating of the hard clay, and the dispersibility in the rubber is remarkably lowered. Also, The hardening effect may be markedly reduced if the hardening agent is coated by lowering the reaction temperature to 90 DEG C or lower than 80 DEG C after coating the surface of the hard clay of the alkylphenol-based resin. Accordingly, the effect of using the curing agent can be remarkably improved when the curing agent is included in the rubber composition for a tire bead filler.

The curing agent can be used without any particular limitation as long as it can form a crosslinking with the alkylphenolic resin. Specifically, the curing agent is selected from the group consisting of trimethylamine, N-methyl aziridine, dimethylethylamine (DMEA), N-methylazetidine, N-ethyl aziridine, diethylmethylamine (DEMA), dimethylisopropylamine Dimethyl-n-propylamine (DMPA), N-propyl aziridine, N-isopropyl aziridine, N-ethyl azetidine, N-methyl pyrrolidine, N, N, N ' Aminomethane, triethylamine (TEA), methylethyl-n-propylamine, methylethyl-isopropylamine, dimethyl-n-butylamine, dimethyl- sec- butylamine, dimethyl- N, N, N ', N'-tetramethyldiaminoethane, dimethylpentylamine, methylethylbutylamine, N-methylpyrrolidine, N-methylpyrrolidine, N-methylpiperidine, hexamethylenetetramine, dimethylpiperazine, Amine, diethylpropylamine, dipropylmethylamine, N-propylpyrrolidine, N-ethylpiperidine, dimethylhexylamine, methylethylpentylamine, diethylbutylamine, dipropylethylamine , N-butylpyrrolidine, N-propylpiperidine, diethylpiperazine, dimethylheptylamine, methylethylhexylamine, diethylpentylamine, tripropylamine, N-pentylpyrrolidine, N- Amine compounds such as benzylamine, diethylamine, diethylamine, diethylamine, diethylamine, diethylamine, diethylamine, diethylamine, diethylamine, diethylamine, The above mixture may be used.

Among the above-mentioned curing agents, hexamethylenemethyltetramine may be more preferable considering the remarkable improvement effect.

The curing agent may be included in an amount of 0.2 to 10 parts by weight based on 100 parts by weight of the raw rubber. If the content of the curing agent is less than 0.2 parts by weight, the crosslinking reaction between the curing agent and the alkylphenol-based resin is low and the effect of improving the reinforcing performance of the rubber composition is insignificant. When the content of the curing agent is more than 10 parts by weight, The physical properties of the rubber composition can be lowered. Considering the remarkable improvement effect of the use of the curing agent, it is more preferable that the curing agent is included in an amount of 2 to 4 parts by weight based on 100 parts by weight of the raw rubber.

In addition to the above-mentioned components, the rubber composition according to the present invention may further include an additive used in a rubber composition for a bead filler such as a vulcanizing agent, a vulcanization accelerator, a vulcanization accelerator, an anti-aging agent, a softening agent or a pressure- 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 depends on the compounding ratio used in a rubber composition for a tire bead filler.

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 included in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the raw material rubber, from the viewpoint that the raw rubber is less sensitive to heat and chemically stable, more preferably 3 to 7 weight ≪ / RTI >

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.

Of these, N, N-dimethylcyclohexylammonium dibutyldithiocarbamate, N-tert-butyl-2-benzothiazylsulfenamide, N-cyclohexyl-2-benzothiazylsulfenamide and mixtures thereof It is preferable to use a vulcanization accelerator selected from the viewpoint that the crosslinking reaction rate can be controlled stably.

The vulcanization accelerator may be included in an amount of 0.5 to 4 parts by weight based on 100 parts by weight of the raw rubber in order to maximize the productivity and the rubber properties by promoting the vulcanization speed. Considering the remarkable improvement effect of the vulcanization accelerator More preferably 1.5 to 2 parts by weight.

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. More preferably 1 to 2 parts by weight of stearic acid and 1 to 5 parts by weight of zinc oxide.

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 softener preferably has a total content of PAHs components of not more than 3 wt%, a kinematic viscosity of not less than 95 (210 F SUS), an aromatic component of 15 to 25 wt% in a softener, A TDAE oil having 27 to 37% by weight of a component and 38 to 58% by weight of a paraffin component can be preferably used.

The TDAE oil has favorable properties for environmental factors such as low temperature property and fuel consumption performance of tire bead filler 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 mixtures thereof Any one selected from the group can be used. Among them, 1,2-dihydroquinoline may be more preferable.

As the wax, waxy hydrocarbons and the like can be 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, And may be included in an amount of 1 to 7 parts by weight considering the remarkable improvement effect.

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.

Specifically, the rubber composition for a tire bead filler is a combination of other additives optimally suited for the purpose of the present invention, which comprises 3 to 7 parts by weight of sulfur as a vulcanizing agent, N-cyclohexyl-2-benzothiazyl sulfenamide 1.5 To 2 parts by weight of stearic acid, 1 to 2 parts by weight of stearic acid, 1 to 5 parts by weight of zinc oxide, and 1 to 5 parts by weight of 1,2-dihydroquinoline or waxy hydrocarbons as an antioxidant.

As described above, the rubber composition for a tire bead filler according to the present invention comprises a hard clay surface-coated with an alkylphenol-based resin, a curing agent capable of forming a crosslinking reaction with the alkylphenol-based resin, and a carbon black having a narrow particle distribution It is possible to improve the hardness characteristics, the reinforcing performance and the rolling resistance performance of the rubber composition and improve the performance of the tire bead contacting the rim when mounted on the tire rim.

The rubber composition for a tire bead filler can be produced through a conventional two-step continuous manufacturing process. That is, during the finishing step in which 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 bead filler is not limited to a bead filler and may be included in various rubber components constituting the tire. Examples of the rubber component include treads (cap tread and base tread), sidewalls, sidewall inserts, apex, chafer, wire coat or inner liner.

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

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

The rubber composition for a tire bead filler of the present invention is excellent in hardness characteristics, reinforcing performance and rolling resistance performance.

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.

[Preparation Example: Preparation of surface-coated clay]

The alkyl phenol-based resin were mixed in a 25 ℃ by introducing 50 parts by weight - Hard clay (HG-90 ^®, Kalmin Co., Ltd.) 100 parts by weight of the alkyl phenol-based resins (formaldehyde resin (Paraoctylphenol-Formaldehyde Resin) p-octylphenol) with respect to the A surface coated hard clay was prepared. At this time, the specific surface area of the hard clay used in the production of the surface coated hard clay is 30 to 80 m ² / g, and the oil adsorption amount is 10 to 60 g / 100 g.

[Examples and Comparative Examples: Production of rubber composition for tire bead filler]

Rubber compositions for tire bead fillers according to the following Examples and Comparative Examples were prepared using the compositions shown in Table 1 below. The production of the rubber composition was in accordance with the usual production method of the rubber composition.

Example Comparative Example One 2 3 4 5 6 One 2 3 Natural Rubber ⁽¹⁾ 100 100 100 100 100 100 100 100 100 Carbon black ⁽²⁾ 85 85 85 85 85 85 85 85 85 Hard clay ⁽³⁾ surface-coated with an alkyl phenolic resin, 1.0 5.0 10.0 15.0 20.0 25.0 - - - Hard clay ⁽⁴⁾ - - - - - - 15 - - The alkylphenol-based resin ⁽⁵⁾ - - - - - - - - 7.5 Zinc oxide 5 5 5 5 5 5 5 5 5 Stearic acid 2 2 2 2 2 2 2 2 2 Antioxidants ⁽⁶⁾ One One One One One One One One One Hardening agents ⁽⁷⁾ 0.4 1.0 2.2 3.3 4.4 5.5 3.3 3.3 3.3 Vulcanization accelerators ⁽⁸⁾ 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Sulfur ⁽⁹⁾ 7 7 7 7 7 7 7 7 7

(Unit: parts by weight)

(1) Natural rubber: SMR CV60 ^® (Standard Malaysian Rubber)

(2) carbon black having a BET of 100 m ² / g, a hydrogen ion index of 7 to 11, and a particle size distribution (D50 / M) of 0.7

(3) Hard clay coated with an alkylphenol resin prepared in the above production example

(4) Hard clay (HG-90 ^®, Kalmin Co., Ltd.) (specific surface area: 30 to 80m ² / g, oil adsorption amount: 10 to 60g / 100g)

(5) Paraoctylphenol-formaldehyde resin

(6) Anti-aging agent: 1,2-dihydroquinoline

(7) Hardener: hexamethylene methyl tetramine

(8) Vulcanization accelerator: N, N-dimethylcyclohexylammonium dibutyldithiocarbamate

(9) Sulfur: Insoluble sulfur.

[Experimental Example: Measurement of Physical Properties of the 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.

Specifically, the pattern viscosity (M.V, 125 ° C) and scorch stability (min) of the rubber specimens were measured at MV2000.

The hardness of the rubber specimens was measured by the ASTM shore-A hardness method after the rubber specimens were allowed to stand for 1 hour in a temperature-controllable combustion chamber.

The 100% modulus was measured from a curve of strain-stress when a test piece was stretched with a specimen having a length of 20 mm and a width of 5 mm using a dumbbell having a length of 100 mm, an outer width of 25 mm and an inner width of 5 mm, % Stress on the elongation was measured.

The elongation at break was expressed as a percentage of the stress (strain) until the test piece was broken in the tensile tester.

Tan? Was measured according to the following formula using RDS (Rheo Dynamic Spectroscopy).

[Equation 1]

tan? = (G "/ G ')

(Where G 'is the viscous modulus and G' is the elastic modulus)

In this case, the lower the tan δ value of 60 ° C, the better the LRR performance.

Example Comparative Example One 2 3 4 5 6 One 2 3 Micheal   Pattern viscosity (125 ° C) 70 73 74 80 80 86 60 69 80 Scorch stability (min) 12.7 12.0 12.0 11.6 11.0 10.6 13.0 11.2 10.2 Seal
Properties Hardness 76 80 83 85 88 90 77 71 77 100% modulus (kgf / cm2) 73 79 80 84 87 92 74 67 79 Elongation at break (%) 177 185 190 195 186 175 192 187 180 Tensile strength (kgf / cm2) 185 197 201 210 203 196 201 187 187 Tanδ (60 DEG C) 0.17 0.19 0.20 0.21 0.28 0.31 0.25 0.21 0.25

From the results shown in the above Table 2, the rubber compositions of Examples 1 to 6, in which hard clay was coated with the alkylphenol-based resin, exhibited higher rubber viscosity and shorter scorch stability than Comparative Example 1. In addition, the hardness and 100% modulus were higher than those of Comparative Example 1. These results show that the rubber compositions of Examples 1 to 6 were hard-clay coated with an alkylphenol-based resin, whereby the alkylphenol-based resin was crosslinked with the curing agent in the rubber composition to improve the reinforcing property. In terms of tensile strength and elongation, the rubber compositions of Examples 3 and 4 including the hard clay surface-coated with the alkylphenol-based resin were higher than those of Comparative Example 1. In particular, the hard clay coated with the alkylphenol- Was 15 parts by weight, the rubber composition of Example 4 exhibited the highest tensile strength and elongation. However, as the content of the hard clay surface-coated with the alkylphenol-based resin in the rubber composition was increased, the hardness was high but the elongation and tensile strength were lowered.

As a result of the evaluation of the viscoelasticity, the rubber compositions of Examples 1 to 4 showed lower results in comparison with Comparative Examples 1 and 2 in the case of tan? (60 占 폚), so that when hard clay surface-coated with alkylphenol- It can be seen that the low rotational resistance (LRR) performance is increased.

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 (9)

With respect to 100 parts by weight of the raw rubber,
1 to 50 parts by weight of a hard clay surface-coated with an alkylphenol-based resin having a specific surface area of 10 to 100 m ² / g and an oil adsorption amount of 10 to 60 g / 100 g,
50 to 100 parts by weight of carbon black having a particle size distribution (D50 / M) of 0.7 or less, and
0.2 to 10 parts by weight of hexamethylenemethyltetramine
And a rubber composition for a tire bead filler. delete The method according to claim 1,
Wherein the alkylphenol-based resin forms crosslinking with the hexamethylenemethyltetramine. The method according to claim 1,
Wherein the alkylphenol-based resin is contained in an amount of 30 to 50 parts by weight based on 100 parts by weight of the hard clay. The method according to claim 1,
Wherein said alkylphenol-based resin is selected from the group consisting of parabutylphenol-formaldehyde resin, para-tert-butylphenol-formaldehyde resin, paraoctylphenol resin, -Formaldehyde Resin, Octyl-butylphenol-Formaldehyde Resin, and mixtures thereof. The rubber composition for a tire bead filler according to claim 1, delete delete The method according to claim 1,
A tire further comprising 1.5 to 2 parts by weight of a vulcanization accelerator, 3 to 7 parts by weight of a vulcanizing agent, 1 to 2 parts by weight of stearic acid, 1 to 5 parts by weight of zinc oxide, and 1 to 5 parts by weight of an anti- Rubber composition for bead filler. A tire produced by using the rubber composition for a tire bead filler according to claim 1.