KR101314554B1 - Rubber composition for tire cord topping and tire manufactured by using the same - Google Patents

Abstract

The present invention relates to a rubber composition for tire cord topping and a tire manufactured using the same, including 100 parts by weight of raw material rubber and 3 to 10 parts by weight of calcium oxide surface-treated with paraffin oil.
The rubber composition for topping the tire cord may improve adhesion and aging resistance between the tire cord and the rubber composition for topping by removing moisture or air present at the adhesive interface between the tire cord and the topping rubber composition.

Description

RUBBER COMPOSITION FOR TIRE CORD TOPPING AND TIRE MANUFACTURED BY USING THE SAME}

The present invention relates to a rubber composition for tire cord topping and a tire manufactured using the same, and more particularly, to remove water or air present at an adhesive interface between the tire cord and the rubber composition for topping, thereby removing the tire cord and the rubber for topping. The present invention relates to a rubber composition for tire cord topping that can improve adhesion between the compositions and aging resistance, and a tire manufactured using the same.

Tires use steel or nylon cords. The steel cord is adhered to a tread portion (belt or body fly) or carcass to enhance durability, and the nylon cord is used for ride comfort on the sidewall portion.

The carcass and the belt are the most important parts that become skeletons in the tire, and thus play a role of withstanding the air pressure, load, and impact inside the tire, and thus may be said to be the most important part in tire durability. In addition, since the durability of the tire is the performance most closely associated with life, steady research and development has been continued to increase its durability.

The durability of the tire is greatly influenced by the cord and topping rubber composition, and the adhesion performance at the cord and rubber interface is a major determinant of durability. Therefore, many studies have been conducted to improve the composition of the adhesive system, the improvement of the adhesion assistant, the performance improvement, and other adhesive strengths to improve the durability of the tire.

On the other hand, the adhesion performance at the steel cord and rubber interface shows a property that is vulnerable to heat and moisture. In particular, the presence of moisture or oxygen oxidizes the metal material present at the interface, and when the amount of the oxide is increased, the adhesive interface is destroyed. Therefore, it is important to control the moisture or oxygen on the adhesive interface.

An object of the present invention is to remove the moisture or air present in the adhesive interface between the tire cord and the topping rubber composition to improve the adhesive strength and aging resistance between the tire cord and the rubber composition for topping to improve the rubber composition for the tire cord topping To provide.

Another object of the present invention is to provide a tire manufactured using the rubber composition for topping the tire cord.

In order to achieve the above object, the rubber composition for topping the tire cord according to an embodiment of the present invention comprises 100 parts by weight of raw rubber, and 3 to 10 parts by weight of calcium oxide surface-treated with paraffin oil.

The calcium oxide surface-treated with the paraffin oil may have a weight ratio of calcium oxide and paraffin oil of 70:30 to 95: 5.

The rubber composition for topping the tire cord may include 20 to 90 parts by weight of carbon black, 0.5 to 2.5 parts by weight of cobalt salt, and 2 to 4 parts by weight of resorcinol resin based on 100 parts by weight of the raw material rubber.

Tire according to another embodiment of the present invention is manufactured using the rubber composition for the tire cord topping.

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

The rubber composition for topping the tire cord includes 100 parts by weight of raw rubber, and 3 to 10 parts by weight of calcium oxide surface-treated with paraffin oil.

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

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

The above-mentioned general natural rubber may be used as long as it is known as natural rubber, and the country of origin and the like are not limited. The natural rubber includes cis-1,4-polyisoprene as a main component, but may also include trans-1,4-polyisoprene depending on required characteristics. Therefore, in addition to natural rubber containing cis-1,4-polyisoprene as a main component, natural rubber including trans-1,4-isoprene as a main component, such as balata, Rubber may also be included.

The modified natural rubber means that the general natural rubber is modified or purified. For example, examples of the modified natural rubber include epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber.

Synthetic rubber is styrene butadiene rubber (SBR), modified styrene butadiene rubber, butadiene rubber (BR), modified butadiene rubber, chloro sulfonated polyethylene rubber, epichlorohydrin rubber, fluorine rubber, silicone rubber, nitrile rubber, hydrogenated Nitrile Rubber, Nitrile Butadiene Rubber (NBR), Modified Nitrile Butadiene Rubber, Chlorinated Polyethylene Rubber, Styrene Ethylene Butylene Styrene (SEBS) Rubber, Ethylene Propylene Rubber, Ethylene Propylene Diene (EPDM) Rubber, Hypalon Rubber, Chloroprene Rubber, Ethylene vinyl acetate rubber, acrylic rubber, hydrin rubber, vinyl benzyl chloride styrene butadiene rubber, bromo methyl styrene butyl rubber, maleic acid styrene butadiene rubber, carboxylic acid styrene butadiene rubber, epoxy isoprene rubber, maleic acid ethylene propylene rubber, carboxylic acid Nitrile Butadiene High It may be a p-methyl styrene (brominated polyisobutyl isoprene-co-paramethyl styrene, BIMS), and one selected from the group consisting of -, bromo mineyi suited polyisobutyl isoprene-co.

The calcium oxide surface-treated with the paraffin oil reacts with moisture or air present at the adhesive interface between the tire cord and the topping rubber composition to convert into calcium hydroxide to remove moisture and air, thereby improving adhesion and aging resistance. Can be improved.

The calcium oxide surface-treated with the paraffin oil may have a weight ratio of calcium oxide and paraffin oil of 70:30 to 95: 5, and 80:20 to 90:10. When the weight ratio of calcium oxide and paraffin oil is within the above range, the reaction between water or oxygen in the air and calcium oxide can be most effectively suppressed, so that the storage efficiency is excellent, so that the reaction efficiency in the compounded rubber is more preferable. Do.

In addition, when the weight ratio of the paraffin oil of the calcium oxide surface-treated with the paraffin oil is less than 5, the calcium oxide may be deteriorated during storage or rubber compounding, and when it exceeds 30, the reaction of the calcium oxide by the excessive paraffin oil may be caused. To reduce its efficiency.

The calcium oxide surface-treated with the paraffin oil may be included in an amount of 3 to 10 parts by weight based on 100 parts by weight of the raw material rubber. If the content of the calcium oxide surface-treated with the paraffin oil is less than 3 parts by weight, the addition effect may be insignificant, and if it exceeds 10 parts by weight, the mechanical properties of the compounded rubber may be reduced.

The rubber composition for a tire further includes a cobalt salt, thereby further improving adhesion. Cobalt salts include cobalt naphthenate, cobalt neodecanoate, cobalt aceto acetylate, cobalt boron neodecanoate, and combinations thereof. Any one selected from the group consisting of can be used.

The cobalt salt may be included in an amount of 0.5 to 2.5 parts by weight based on 100 parts by weight of the raw material rubber. If the content of the cobalt salt is less than 0.5 parts by weight may not be sufficient to form an adhesive interface, when the content of more than 2.5 parts by weight may help to improve the adhesion, there is a fear that the heavy metal content increases.

The rubber composition for topping the tire cord may further include a scorch retardant. The retardant may be any one selected from the group consisting of phthalic anhydride, salicylic acid, sodium acetate, N-cyclohexyl thioptalimide, and combinations thereof. The retardant may be 0.1 to 0.5 parts by weight based on 100 parts by weight of the raw material rubber.

The rubber composition for topping the tire cord may optionally further include various additives such as additional vulcanizing agents, vulcanization accelerators, vulcanization accelerators, fillers, coupling agents, anti-aging agents, softeners or pressure-sensitive adhesives. The various additives can be used as long as it is commonly used in the field of the present invention, the content thereof is not particularly limited, depending on the compounding ratio used in the conventional rubber cord topping rubber composition.

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

The sulfur-based vulcanizing agent may be inorganic vulcanizing agents such as powdered sulfur (S), insoluble sulfur (S), precipitated sulfur (S), colloidal sulfur (colloid sulfur). Specifically, as the sulfur vulcanizing agent, a vulcanizing agent which produces elemental sulfur or sulfur, for example, amine disulfide, polymer sulfur, or the like can be used.

The vulcanizing agent is preferably included in an amount of 0.5 to 4.0 parts by weight based on 100 parts by weight of the raw material rubber, in that the raw material rubber is less sensitive to heat and chemically stable.

The vulcanization accelerator refers to an accelerator that promotes the rate of vulcanization or promotes delay in the initial vulcanization stage.

The vulcanization accelerators include sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamic acid, aldehyde-amine, aldehyde-ammonia, imidazoline, xanthate and their Any one selected from the group consisting of a combination can be used.

Examples of the sulfenamide vulcanization accelerators include N-cyclohexyl-2-benzothiazylsulfenamide (CBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS), and N, N-dicyclohexyl. Any selected from the group consisting of -2-benzothiazylsulfenamide, N-oxydiethylene-2-benzothiazylsulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide and combinations thereof The sulfenamide type compound of can be used.

Examples of the thiazole vulcanization accelerators include 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), sodium salt of 2-mercaptobenzothiazole and zinc salt of 2-mercaptobenzothiazole. , Copper salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-di Any thiazole compound selected from the group consisting of ethyl 4-morpholinothio) benzothiazole and combinations thereof can be used.

Examples of the thiuram-based vulcanization accelerators include tetramethyl thiuram disulfide (TMTD), tetraethyl thiuram disulfide, tetramethyl thiuram monosulfide, dipentamethylene thiuram disulfide, dipentamethylene thiuram monosulfide and dipentamethylene. Any thiuram-based compound selected from the group consisting of thiuram tetrasulfide, dipentamethylene thiuram hexasulfide, tetrabutyl thiuram disulfide, pentamethylene thiuram tetrasulfide, and combinations thereof can be used.

As the thiourea vulcanization accelerator, for example, thiocarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea, and any combination thereof is selected from the group of thiourea Compounds can be used.

As the guanidine-based vulcanization accelerator, for example, any one guanidine-based compound selected from the group consisting of diphenylguanidine, diorthotolylguanidine, triphenylguanidine, orthotolylbiguanide, diphenylguanidine phthalate, and combinations thereof can be used. Can be.

Examples of the dithiocarbamic acid-based vulcanization accelerators include ethylphenyldithiocarbamate zinc, butylphenyldithiocarbamate zinc, sodium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, Zinc dibutyldithiocarbamate, zinc diamyldithiocarbamate, zinc dipropyldithiocarbamate, zinc salt of pentamethylenedithiocarbamate and piperidine, hexadecylisopropyldithiocarbamate zinc, octadecyl Isopropyldithiocarbamate zinc dibenzyldithiocarbamate zinc, sodium diethyldithiocarbamate, pentamethylenedithiocarbamate piperidine, dimethyldithiocarbamate selenium, diethyldithiocarbamate tellurium, dia One dithiocarbamic acid compound selected from the group consisting of cadmium didicarbamate and combinations thereof can be used.

The aldehyde-amine-based or aldehyde-ammonia based vulcanization accelerator, for example, acetaldehyde-aniline reactant, butylaldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde-ammonia reactant and combinations thereof -Amine based or aldehyde-ammonia based compounds can be used.

As said imidazoline type vulcanization accelerator, imidazoline type compounds, such as 2-mercaptoimidazoline, can be used, for example, As said xanthate type vulcanization accelerator, xanthate type, such as zinc dibutyl xanthogenate Compounds can be used.

The vulcanization accelerator may be included in an amount of 0.5 to 4.0 parts by weight based on 100 parts by weight of the raw material rubber in order to maximize productivity and rubber properties by promoting the vulcanization rate.

The vulcanization accelerator is a compounding agent used in combination with the vulcanization accelerator to complete its promoting effect. Any one selected from the group consisting of inorganic vulcanization accelerators, organic vulcanization accelerators and combinations thereof can be used. .

As the inorganic vulcanization accelerating aid, any one selected from the group consisting of zinc oxide (ZnO), zinc carbonate, magnesium oxide (MgO), lead oxide, potassium hydroxide and combinations thereof may be used have. The organic vulcanization accelerator is selected from the group consisting of stearic acid, zinc stearate, palmitic acid, linoleic acid, oleic acid, lauric acid, dibutyl ammonium oleate, derivatives thereof, and combinations thereof. You can use either one.

In particular, the zinc oxide and the stearic acid may be used together as the vulcanization accelerating assistant. In this case, the zinc oxide is dissolved in the stearic acid to form an effective complex with the vulcanization accelerator, Thereby facilitating the crosslinking reaction of the rubber.

When the zinc oxide and the stearic acid are used together, they may be used in an amount of 1 to 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 topping the tire cord may further include 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 it is less than 60 cc / 100 g, the reinforcing performance by carbon black as a filler may be deteriorated.

Examples of the carbon black include N110, N121, N134, N220, N231, N234, N242, N293, N299, S315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 or N991.

The carbon black may be included in an amount of 20 to 90 parts by weight based on 100 parts by weight of the raw material rubber, preferably 45 to 65 parts by weight, and more preferably 53 to 57 parts by weight. When the content of the carbon black is less than 20 parts by weight, the reinforcing performance by the carbon black as a filler may be reduced, and when the content of the carbon black exceeds 90 parts by weight, the processability of the rubber composition may be deteriorated.

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

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

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

The silica may be contained in an amount of 20 to 90 parts by weight based on 100 parts by weight of the raw rubber, more preferably 30 to 70 parts by weight, and further preferably 40 to 60 parts by weight. 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 is any one selected from the group consisting of γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl methyldimethoxysilane, γ-methacryloxypropyl dimethyl methoxysilane, and combinations thereof Can be.

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

The petroleum oil may be any one selected from the group consisting of paraffinic oil, naphthenic oil, aromatic oil, and combinations thereof.

Examples of the paraffin oil include P-1, P-2, P-3, P-4, P-5 and P-6 of Mychang Oil Co., N-1, N-2 and N-3 of Kokai Co., Ltd., and representative examples of the aromatic oils include A-2 and A-3 of Mingchang Oil Co.,

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

Particularly, the oil used as the softening agent preferably has a total content of PAHs components of not more than 3 wt%, a kinematic viscosity of not less than 95 (210 S SUS), an aromatic component of 15 to 25 wt%, a naphthene component Of 27 to 37% by weight and a paraffinic component of 38 to 58% by weight can be preferably used.

The TDAE oil is advantageous in terms of environmental factors such as the low-temperature characteristics of the tire cord topping including the TDAE oil, fuel efficiency, and the likelihood of causing cancer of PAHs.

The plant oils include castor oil, cottonseed oil, linseed oil, canola oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, pine tar, tall oil, corn oil, rice bran oil, safflower oil, sesame oil, olive oil, sunflower oil, palm kernel oil, camellia oil It may be used any one selected from the group consisting of jojoba oil, macadamia nut oil, saflower flower oil, tung oil and combinations thereof.

The softening agent is preferably used in an amount of 0 to 150 parts by weight based on 100 parts by weight of the raw material rubber, in terms of improving the processability of the raw material rubber.

The anti-aging agent is an additive used to stop the chain reaction in which the tire is automatically oxidized by oxygen. As the anti-aging agent, any one selected from the group consisting of an amine type, a phenol type, a quinoline type, an imidazole type, a carbamic acid metal salt, a wax and a combination thereof can be appropriately selected and used.

As the amine antioxidant, N-phenyl-N '-(1,3-dimethyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine ( 6PPD), N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-diaryl-p-phenylenediamine, N-phenyl Any one selected from the group consisting of -N'-cyclohexyl p-phenylenediamine, N-phenyl-N'-octyl-p-phenylenediamine, and combinations thereof can be used. 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.

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

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

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

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

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

The coal tar may be a coumarone-indene resin.

The alkylphenol resin may be a p-tert-alkylphenol formaldehyde resin 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 topping the tire cord may be manufactured through a conventional two-step continuous manufacturing process. That is, during the finishing step in which the first step of thermomechanical treatment or kneading at a maximum temperature ranging from 110 to 190 ° C., preferably from 130 to 180 ° C. (called the non-production step) and the crosslinking system are mixed, typically It can be prepared in a suitable mixer using a second step (called a production step) of mechanical treatment at a low temperature of less than 110 ° C., for example 40-100 ° C., but the invention is not limited thereto.

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

A tire according to another embodiment of the present invention is manufactured using the rubber composition for topping the tire cord. The method of manufacturing a tire using the tire cord topping rubber composition may be applied to any method used in the manufacture of a tire in the related art, and thus detailed description thereof will be omitted.

The tire may be a passenger car tire, a racing tire, an airplane tire, a farm tire, an off-the-road tire, a truck tire or a bus tire. In addition, the tire may be a radial tire or a bias tire, and is preferably a radial tire.

The rubber composition for a tire cord topping of the present invention can improve the adhesion and aging resistance between the tire cord and the topping rubber composition by removing water or air present at the adhesive interface between the tire cord and the topping rubber composition.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[Production Example: Production of Rubber Composition]

To prepare a rubber composition for topping the tire cord according to the following examples and comparative examples using the composition shown in Table 1. The rubber composition was vulcanized at 160 ° C. in a rubber specimen obtained by blending in a half-barrier mixer.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Natural rubber ¹⁾ 100 100 100 100 100 Carbon black ²⁾ 60 60 60 60 60 Calcium oxide - 3 - - - Calcium oxide, surface-treated with paraffin oil ³⁾ - - 3 5 10 Process oil ⁴⁾ 3 3 3 3 3 Cobalt adhesive ⁵⁾ One One One One One Resorcinol Resin ⁶⁾ 2 2 2 2 2 Zinc oxide 10 10 10 10 10 Stearic acid One One One One One Antioxidant ⁷⁾ One One One One One Antioxidant ⁸⁾ One One One One One Vulcanizing agent ⁹⁾ 8 8 8 8 8 Retardant ¹⁰⁾ 0.3 0.3 0.5 0.5 0.5 Vulcanization accelerator ¹¹⁾ 0.6 0.6 0.5 0.5 0.5

(Unit: parts by weight)

1) Natural rubber: STR 20

2) Carbon Black: HAF / LS N326

3) Calcium oxide surface-treated with paraffin oil: weight ratio of calcium oxide and paraffin oil is 85:15

4) process oil: N-2 oil

5) Cobalt Adhesive: Cobalt Boron Neodecanoate

6) Resorcinol Resin: Resocinol-Formaldehyde Resin

7) Antioxidants: N-phenyl-N '-(1,3-dimethyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (6PPD)

8) Antioxidant: 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ)

9) Vulcanizer: Insoluble Sulfur

10) Retardant: N-cyclohexyl thiophthalimide (PVI)

11) Vulcanization accelerator: N, N-dicyclohexyl-2-benzothiazylsulfenamide

Experimental Example: Measurement of Physical Properties of Prepared Rubber Composition

The physical properties of the rubber specimens prepared in Examples and Comparative Examples were measured, and the results are shown in Table 2 below. 2 + 2 (0.25) HT was used as the steel cord for the adhesion test.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 The tensile strength Hardness (Shore A) 74 74 74 75 75 300% modulus
(kg / cm2) 165 164 162 164 161 Cutting strength (kg / ㎠) 220 219 216 221 219 Adhesion
(kgf / in) Early 65 65 68 72 73 Heat aging 45 48 51 55 56 Hydrothermal aging 52 55 57 61 63 Moisture aging 49 51 55 59 60 Brine aging 46 47 49 51 51

Tensile Test Conditions: Measured using an Instron tester (crosshead speed: 500 mm / min).

-Adhesive force measuring condition

Thermal Aging: 100 ° C x 1 Week (In Air)

Hydrothermal aging: 70 ° C x 1 week (water)

Moisture aging: 70 ° C x 1 week (relative humidity 96)

Chlorine Aging: Room temperature X1 (20% NaCl solution)

Referring to Table 2, the rubber specimens prepared in Examples 1 to 3 are superior to Comparative Example 1 while maintaining the tensile strength, such as 300% modulus and cutting strength, compared to the rubber specimens prepared in Comparative Example 1 It can be seen.

This is believed to be the result of improved adhesion performance and aging resistance at the cord and rubber interface by using calcium oxide surface-treated with paraffin oil in the rubber composition for tire cord topping.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of right.

Claims (4)

100 parts by weight of raw rubber,
3 to 10 parts by weight of calcium oxide surface-treated with paraffin oil
20 to 90 parts by weight of carbon black,
0.5 to 2.5 parts by weight of cobalt salt, and
2 to 4 parts by weight of resorcinol resin,
The calcium oxide surface-treated with paraffin oil is a rubber composition for topping the tire cord is a weight ratio of calcium oxide and paraffin oil 70:30 to 95: 5. delete delete A tire manufactured using the rubber composition for tire cord topping according to claim 1.