KR101182269B1 - Sidewall rubber composition and tire manufactured by using the same - Google Patents

Abstract

The present invention relates to a rubber composition for a tire sidewall and a tire manufactured using the same, wherein the rubber composition for a tire sidewall according to an embodiment of the present invention comprises 10 to 50 parts by weight of a polymer alloy including nitrile rubber and polyvinyl chloride. It includes 100 parts by weight of the raw material rubber, 30 to 70 parts by weight of filler, and 1 to 5 parts by weight of antioxidant. The rubber composition for a tire sidewall of the present invention can improve ozone resistance and improve low fuel efficiency while maintaining other physical properties of the rubber in an appropriate range, and also has excellent properties regarding fatigue and crack resistance, and improves ozone resistance. At the same time, the appearance of the tire can be improved by reducing whitening.

Description

Rubber composition for a tire sidewall and a tire manufactured using the same {SIDEWALL RUBBER COMPOSITION AND TIRE MANUFACTURED BY USING THE SAME}

The present invention relates to a rubber composition for a tire sidewall and a tire manufactured using the same, wherein other physical properties can be improved while maintaining ozone resistance and low fuel efficiency while maintaining within an appropriate range. In addition, the present invention relates to a rubber composition for a tire sidewall and a tire manufactured using the same, which can improve the appearance of a tire by reducing whitening while improving ozone resistance.

The sidewall of the tire is a part that is subjected to flexion or elongation while driving, and in this case, the sidewall is directly exposed to ozone in the air, and thus a strong ozone resistance is required.

Wax and amine anti-aging agents are used to prevent the aging caused by ozone in the sidewall of the tire. However, excessive use of waxes and amine antioxidants in rubber compositions results in blooming and ozone resistance. Waxes form a physical layer that protects the rubber surface from attack by ozone, and amine antioxidants. Protects the rubber surface from ozone through chemical reactions with ozone.

Blooming of wax and amine antioxidants to the surface of the tire sidewalls is influenced not only by the concentration of the wax and amine antioxidants, but also by the type and amount of rubber and various compounding agents, and also by the aging time or temperature. .

In case of excessive use of wax as an anti-aging agent, whitening occurs due to the white color of the wax itself, which damages the appearance of the tire sidewall, and in the case of using an amine antioxidant in excess, the surface of the tire sidewall Although the amount of usage is limited in appearance because it is contaminated by yellow and is contaminated with yellow, research for a method for increasing anti-aging effect without excessive use is required for proper anti-aging effect.

It is an object of the present invention to improve the ozone resistance and at the same time improve the low fuel efficiency, while maintaining other physical properties of the rubber in an appropriate range, and also excellent in fatigue characteristics and crack resistance, and improves the whitening phenomenon while improving the ozone resistance It is to provide a rubber composition for a tire sidewall that can be reduced to improve the appearance of the tire.

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

In order to achieve the above object, the rubber composition for a tire sidewall according to an embodiment of the present invention is 100 parts by weight of the raw material rubber, including 10 to 50 parts by weight of a polymer alloy including nitrile rubber and polyvinyl chloride, filler 30 to 70 Parts by weight, and 1 to 5 parts by weight of anti-aging agent.

The polymer alloy may be a polymer alloy having a weight ratio of 50:50 to 90:10 of the nitrile rubber and the polyvinyl chloride.

The antioxidant may be any one consisting of a wax, an amine antioxidant and a combination thereof.

The filler may be carbon black, the carbon black may have a nitrogen adsorption specific surface area of 30 to 300 m ² / g, and a DBP oil absorption of 60 to 210 cc / 100 g.

The raw material rubber may include 10 to 80 parts by weight of natural rubber and 10 to 70 parts by weight of butadiene rubber.

The rubber composition for the tire sidewall may further include 0 to 20 parts by weight of a softener, 1 to 8 parts by weight of vulcanizing agent, 1 to 3 parts by weight of vulcanizing agent, and 0.1 to 2 parts by weight of vulcanization accelerator, based on 100 parts by weight of the rubber material. have.

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

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

The rubber composition for a tire sidewall of the present invention includes a raw material rubber, a filler, and an anti-aging agent including a polymer alloy.

The polymer alloy included in the raw material rubber includes nitrile rubber and polyvinyl chloride. The polymer alloy refers to a multicomponent polymer including two or more polymers. Specifically, the polymer alloy refers to a case in which a non-chemical bond and a chemical bond with complementary forces act between the polymers. It is distinguished from a blend.

The polymer alloys include nitrile rubber (NBR) and polyvinyl chloride (PVC). The nitrile rubber (acrylonitrile butadiene rubber) means a synthetic rubber obtained by hybridizing butadiene and acrylonitrile. The polymer alloy may include a nitrile rubber and a polymer of polyvinyl chloride, and may have excellent oil resistance and excellent weather resistance.

When the polymer alloy is used in place of a part of the raw rubber, aging resistance and ozone resistance of the rubber may be improved, and reinforcement may be improved.

The polymer alloy may be a weight ratio of 50:50 to 90:10 of the nitrile rubber and the polyvinyl chloride, preferably a weight ratio of 50:50 to 80:20, and more preferably 50:50 to 70:30. When the weight ratio of the nitrile rubber and the polyvinyl chloride is in the above range, the properties of using the polymer alloy can be properly expressed, and the properties of the rubber required for the rubber for tires can also be appropriately shown.

100 parts by weight of the raw material rubber may include 10 to 50 parts by weight of the polymer alloy, preferably 10 to 40 parts by weight, and more preferably 15 to 35 parts by weight.

When 100 parts by weight of the raw material rubber comprises 10 parts by weight to 50 parts by weight of the polymer alloy, the amount of the anti-aging agent that causes the appearance contamination of the sidewall may be reduced to maintain or improve ozone resistance while reducing the contamination of the appearance. It can also improve fuel efficiency.

In addition to the polymer alloy, the raw material rubber may further include any one selected from the group consisting of natural rubber, diene-based synthetic rubber, and combinations thereof.

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

The general natural rubber may be used as long as it is known as a natural rubber, and is not limited to the country of origin or grade. The natural rubber contains cis-1,4-polyisoprene as a main agent, but may also include trans-1,4-polyisoprene depending on the required properties. Accordingly, the natural rubber includes, in addition to natural rubber containing cis-1,4-polyisoprene as a main agent, for example, natural containing trans-1,4-isoprene as a main agent such as balata, which is a kind of rubber of South American sapotaceae. Rubber may also be included.

The modified natural rubber means a modified or refined general natural rubber. For example, the modified natural rubber may include epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, and the like.

The synthetic rubber is styrene butadiene rubber (SBR), modified styrene butadiene rubber, butadiene rubber (BR), modified butadiene rubber, nitrile butadiene rubber (NBR), modified nitrile butadiene rubber, ethylene propylene diene (EPDM) rubber, vinyl benzyl chloride styrene Butadiene rubber, maleic acid styrene butadiene rubber, carboxylic acid styrene butadiene rubber, epoxy isoprene rubber, carboxylic acid nitrile butadiene rubber, and combinations thereof. The styrene butadiene rubber may be any one selected from the group consisting of emulsion-polymerized styrene-butadiene rubber, solution-polymerized styrene-butadiene rubber, and combinations thereof.

The raw rubber may preferably include any one selected from the group consisting of natural rubber, butadiene rubber and combinations thereof.

100 parts by weight of the raw rubber may include 10 to 80 parts by weight, preferably 30 to 80 parts by weight, and more preferably 30 to 75 parts by weight of the natural rubber. When 100 parts by weight of the raw material rubber includes 10 parts by weight to 80 parts by weight of the natural rubber, overall mechanical properties may be improved and fatigue properties may be improved.

100 parts by weight of the raw rubber may include 10 to 70 parts by weight of the butadiene rubber, preferably 10 to 50 parts by weight. 100 parts by weight of the raw rubber may improve resilience when the butadiene rubber is included in 10 parts by weight to 70 parts by weight, and may improve low temperature characteristics.

The butadiene rubber may have a glass transition temperature (Tg) of -86 to -126 ° C, preferably -99 to -112 ° C, and more preferably -104 to -108 ° C. When the butadiene rubber of the glass transition temperature is used, there is an effect that the low temperature characteristics and the rebound elasticity may be particularly advantageous.

The filler may be any one selected from the group consisting of carbon black, silica and combinations thereof.

The carbon black may be used without limitation as long as the carbon black can be used in the rubber composition for tires, and specifically, carbon black having the following characteristics may be used.

The carbon black may have a nitrogen adsorption specific surface area (N ₂ SA) of 30 to 300 m ² / g, preferably 50 to 90 m ² / g. The carbon black may have 60-210 cc / 100 g of n-dibutyl phthalate (DBP) oil absorption, and preferably 80-125 cc / 100 g of DBP oil absorption.

When the carbon black having the value of the nitrogen adsorption specific surface area and the DBP oil absorption value is used as the filler as the carbon black, rubber for tires having appropriate reinforcement and appropriate processability can be produced.

Representative examples of the carbon black are N110, N121, N134, N220, N231, N234, N242, N293, N299, S315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582 , N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 or N991.

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

The silica can be used both wet or dry method, and commercially available ultra-sil 7000 (manufactured by Evonik Degussa), Ultra-sil VN2 (manufactured by Evonik Degussa), Ultra-sil VN3 (manufactured by Evonik Degussa), Zeosil 1165MP (Rhodia) etc. can be used

The filler may be included in 30 to 70 parts by weight, 35 to 50 parts by weight, and 39 to 49 parts by weight based on 100 parts by weight of the raw material rubber. If the content of the filler is less than 30 parts by weight, the reinforcing performance by the filler may be lowered. If the content of the filler exceeds 70 parts by weight, the processability of the rubber composition may be deteriorated.

The tire sidewall rubber composition may further include other fillers in addition to the filler. The other filler may be any one selected from the group consisting of calcium carbonate, clay (aluminum hydrated silica), aluminum hydroxide, lignin, silicate, talc and combinations thereof.

The tire sidewall rubber composition further includes an anti-aging agent.

The anti-aging agent is an additive used to stop the chain reaction in which the tire is automatically oxidized by oxygen.

The anti-aging agent is included in 1 to 5 parts by weight based on 100 parts by weight of the raw material rubber. When the antioxidant is included in less than 1 part by weight, ozone resistance may drop, and when used in excess of 5 parts by weight, bleaching may occur to deteriorate the appearance of the tire.

As the anti-aging agent, any one selected from the group consisting of amine-based, phenol-based, quinoline-based, imidazole-based, carbamic acid metal salts, waxes, and combinations thereof may be appropriately selected.

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

The amine-based antioxidants are preferably N- (1,3-dimethylbutyl) -N-phenyl-p-phenylenediamine (N- (1,3-Dimethybutyl) -N-phenyl-p-phenylenediamine, 6PPD, 6C), N-phenyl-n-isopropyl-p-phenylenediamine (N-phenyl-n-isopropyl-p-phenylenediamine, 3PPD) and combinations thereof may be used.

The phenolic anti-aging agent is phenolic 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-isobutylidene-bis (4,6-dimethylphenol), 2 Any one selected from the group consisting of, 6-di-t-butyl-p-cresol and combinations thereof can be used.

As the quinoline anti-aging agent, 2,2,4-trimethyl-1,2-dihydroquinoline and derivatives thereof may be used, and specifically 6-ethoxy-2,2,4-trimethyl-1,2-di Hydroquinoline, 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, paraffin wax, waxy hydrocarbon, microcrystalline wax may be used.

The anti-aging agent may preferably be any one composed of a wax, an amine-based anti-aging agent and a combination thereof. In the case of using any one composed of a wax, an amine-based antioxidant and a combination thereof as the anti-aging agent can be improved at the same time ozone resistance and oxidation resistance.

The tire sidewall rubber composition may optionally further include various additives such as additional vulcanizing agents, vulcanization accelerators, vulcanizing agents, coupling 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 depends on the compounding ratio used in the conventional rubber sidewall rubber composition, the amount used according to the formulation of the other rubber composition This can be adjusted.

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

The sulfur-based vulcanizing agents include inorganic vulcanizing agents such as powdered sulfur (S), insoluble sulfur (S), precipitated sulfur (S) and colloidal sulfur, tetramethylthiuram disulfide (TMTD) and tetraethyl. Organic vulcanizing agents such as tetraethyltriuram disulfide (TETD) and dithiodimorpholine can be used. Specifically, as the sulfur vulcanizing agent, a vulcanizing agent which produces elemental sulfur or sulfur, for example, amine disulfide, polymer sulfur, or the like can be used.

The organic peroxide may be benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di ( t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3- Bis (t-butylperoxypropyl) benzene, di-t-butylperoxy-diisopropylbenzene, t-butylperoxybenzene, 2,4-dichlorobenzoyl peroxide, 1,1-dibutylperoxy-3 Any one selected from the group consisting of, 3,5-trimethylsiloxane, n-butyl-4,4-di-t-butylperoxyvalerate and combinations thereof can be used.

The vulcanizing agent may be included in an amount of 1 to 3 parts by weight, and preferably 1.5 to 2.0 parts by weight, based on 100 parts by weight of the raw rubber. When the vulcanizing agent is used in the above range of content, it is preferable in that the raw rubber is less sensitive to heat and chemically stable with an appropriate vulcanizing effect.

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.

As the vulcanization accelerator, sulfenamide-based may be preferably used. Specifically, N-tert-butyl-2-benzothiazylsulfenamide (TBBS) may be used.

The vulcanization accelerator may be included in an amount of 0.1 to 2 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the raw rubber in order to maximize productivity and rubber properties by promoting the vulcanization rate.

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

The inorganic vulcanizing active agent may be any one selected from the group consisting of zinc oxide (ZnO), zinc carbonate, magnesium oxide (MgO), lead oxide, potassium hydroxide, and combinations thereof. . The organic vulcanizing agent 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. Either one can be used.

In particular, the zinc oxide and the stearic acid may be used together as the vulcanizing agent, in which case the zinc oxide is dissolved in the stearic acid to form an effective complex with the vulcanization accelerator, thereby making favorable sulfur during the vulcanization reaction. To facilitate the crosslinking reaction of the rubber.

The vulcanizing agent may be included in an amount of 1 to 8 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the raw material rubber.

In the case where the zinc oxide and the stearic acid are used together as the vulcanizing activator, in order to serve as a suitable vulcanizing activator, 1 to 5 parts by weight and 0.5 to 3 parts by weight, preferably 1 to 4 parts by weight, respectively, based on 100 parts by weight of the raw rubber Parts and 0.5 to 2 parts by weight.

The softener is added to the rubber composition to impart plasticity to the rubber to facilitate processing or to lower the hardness of the vulcanized rubber, and refers to oils and other materials used in rubber compounding or rubber production.

The softener may be any one selected from the group consisting of petroleum oil, vegetable oil and combinations thereof, but the present invention is not limited thereto.

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

Representative examples of the paraffinic oil include P-1, P-2, P-3, P-4, P-5, and P-6 of Michang Oil, Inc. A representative example of the naphthenic oil is Michang oil. N-1, N-2, N-3, etc. of the corporation | Co., Ltd. are mentioned, As a representative example of the said aromatic oil, A-2, A-3, etc. of Michang Oil Corporation are mentioned.

Recently, as the environmental awareness increases, the content of polycyclic aromatic hydrocarbons (hereinafter referred to as 'PAHs') contained in the aromatic oil is more than 3% by weight, which is known to cause cancer. (treated distillate aromatic extract) oil, mild extraction solvate (MES) oil, residual aromatic extract (RAE) oil or heavy naphthenic oil can be preferably used.

In particular, the oil used as the softener has a total content of PAHs component of 3% by weight or less, a kinematic viscosity of 95 ° C or more (210 ° F SUS), an aromatic component in the softener of 15 to 25% by weight, naphthenic TDAE oils with 27 to 37% by weight and 38 to 58% by weight of paraffinic components can be preferably used.

The TDAE oil has excellent properties in terms of environmental factors such as low-temperature characteristics of the tire sidewall 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 softener may be used in an amount of 0 to 100 parts by weight, and preferably 0 to 20 parts by weight, based on 100 parts by weight of the raw rubber. When using the softener in the range of the content can be excellent in the processability of the raw rubber.

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

As the pressure-sensitive adhesive, natural resin-based pressure-sensitive adhesives such as rosin-based resins or terpene-based resins, and synthetic resin-based pressure-sensitive adhesives such as petroleum resins, coal tar, or alkyl phenol-based resins may be used.

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

The petroleum resin is aliphatic resin, acid modified aliphatic resin, alicyclic resin, hydrogenated alicyclic resin, aromatic (C9) resin, hydrogenated aromatic resin, C5-C9 copolymer resin, styrene resin, styrene copolymer resin and It may be any one selected from the group consisting of a combination thereof.

The coal tar may be a coumarone-indene resin.

The alkyl phenol resin may be p-tert-alkyl phenol formaldehyde resin, the p-tert-alkyl phenol formaldehyde resin may be p-tert-butyl-phenol formaldehyde resin, p-tert-octyl-phenol formaldehyde and It may be any one selected from the group consisting of a combination thereof.

The pressure-sensitive adhesive may be contained in an amount of 0 to 4 parts by weight based on 100 parts by weight of the raw material rubber in that the rubber property can be prevented from being lowered while maintaining the proper adhesiveness.

The rubber composition for the tire sidewall 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 'non-production' step) and the crosslinking system are mixed, Typically produced in a suitable mixer using a second step (called '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 sidewall is not limited to the sidewall (sidewall cap and sidewall base), and may be included in various rubber components constituting the tire. Such rubber components include treads, tread inserts, apex, chafers, wire coats or innerliners, and the like.

A tire according to another embodiment of the present invention is manufactured using the rubber composition for the tire sidewall. The method for manufacturing a tire using the rubber sidewall rubber composition may be applied to any method that is conventionally used for the production of tires, 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 the tire sidewall of the present invention and the tire manufactured by using the same may improve ozone resistance and at the same time improve low fuel efficiency while maintaining other physical properties within an appropriate range, and also improve properties regarding fatigue characteristics and crack resistance. Can be. In addition, it is possible to improve the appearance of the tire by reducing the whitening phenomenon while improving the ozone resistance.

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

[ Manufacturing example : Preparation of Rubber Composition]

Next, using the composition shown in Table 1, the rubber compositions according to the following examples and comparative examples were blended into a half-barrier mixer to prepare rubber specimens, and the unvulcanized physical properties of the rubber specimens and the properties vulcanized at 160 ° C. were measured.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Natural rubber 50 50 50 50 50 50 50 50 Butadiene rubber 50 30 40 30 20 10 30 30 Polymer Alloy1 ㅡ ㅡ 10 20 30 40 ㅡ ㅡ Polymer Alloy 2 ㅡ ㅡ ㅡ ㅡ ㅡ ㅡ 20 ㅡ Polymer Alloy 3 ㅡ ㅡ ㅡ ㅡ ㅡ ㅡ ㅡ 20 Polymer Alloy 4 ㅡ 20 ㅡ ㅡ ㅡ ㅡ ㅡ ㅡ Carbon black 50 44 47 44 40 40 40 40 Amine
Anti-aging 3 1.5 2 1.5 1.5 1.5 1.5 1.5 Wax 3 2 2 2 1.5 1.5 1.5 1.5 Process oil 5 5 5 5 5 5 5 5 Zinc oxide 3 3 3 3 3 3 3 3 Stearic acid One One One One One One One One brimstone 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Vulcanization accelerator 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 week)
Natural Rubber: TSR20 Grade
Butadiene rubber (BR): Butadiene rubber with Tg (glass transition temperature) of -106 ℃
Polymer alloy 1: It contains polyvinyl chloride and nitrile rubber and the composition ratio of NBR and PVC (polyvinyl chloride) is 70:30.
Polymer alloy 2: It contains polyvinyl chloride and nitrile rubber and the composition ratio of NBR and PVC (polyvinyl chloride) is 50:50.
Polymer alloy 3: It contains polyvinyl chloride and nitrile rubber and the composition ratio of NBR and PVC (polyvinyl chloride) is 90:10.
Polymer alloy 4: Contains nitrile rubber and does not contain PVC (polyvinyl chloride), so the composition ratio of NBR and PVC (polyvinyl chloride) is 100: 0.
Carbon Black: N330
Amine antioxidant (6C): N-1,3-dimethylbutyl-N-phenyl-p-phenylenediamine
Wax: Paraffin Wax
Process oil: TDAE (Treated Distillate Aromatic Extract) Oil
Vulcanization accelerator: TBBS (N-isobutyl-2-benzothiazyl sulfenamide)
* Antioxidants include amine antioxidants and waxes.
(Unit: parts by weight)

Table 2 shows the results of measuring physical properties of the comparative examples and examples.

300% modulus (Modulus, unit kgf / ㎠) is the tensile strength at 300% elongation, measured according to the ISO 37 standard, the higher the value shows excellent strength.

Elongation was measured according to the ISO 37 standard, and the elongation at break is shown.

60 ° C Tan δ is a measure of rotational resistance at 60 ° C, and the lower the value, the better the low fuel consumption characteristics.

In the static ozone test, 20% of the specimen was elongated and ozonated at 50pphm and 40 ℃ for ozone aging. The ozone aging degree of the specimen was measured by

The degree of ozone aging is expressed by the following numerical value by observing the degree of ozone cracks generated during the bending fatigue movement.

    * Number of cracks: A <B <C, crack size: 1 <2 <3 <4 <5

Fatigue characteristics indicate fatigue resistance. Six samples were measured in a fatigue tester at 118% strain and 50% residual ratio was obtained for six samples.

Crack growth is an evaluation of the crack resistance. The crack growth is measured by giving a crack at an initial stage, and then measuring how much the crack is growing during the bending fatigue movement.

Appearance evaluated the change in the blackness of the compound rubber, and the grade 1 shows little change in blackness, the grade 2 shows a slight drop in blackness, and the grade 3 shows a marked change in blackness. It is shown.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 300% modulus (kgf / ㎠) 60 61 61 56 55 59 52 60 Elongation (%) 651 665 660 642 665 560 570 650 60 ℃ Tan δ 0.126 0.122 0.118 0.115 0.110 0.112 0.118 0.124 Static ozone resistance B3 B3 A3 A2 A2 A2 A2 B2 Dynamic ozone resistance C4 C4 B3 B2 A3 A4 B4 C3 Fatigue characteristics (k cycle) 104 100 101 106 99 86 75 102 Crack growth (mm) 45 42 38 35 32 40 45 43 Exterior Grade 3 Grade 2 Grade 2 Grade 1 Grade 1 Grade 1 Grade 1 Grade 2

Referring to Table 2, Examples 1 to 6 showed excellent results in terms of both dynamic ozone characteristics and static ozone characteristics compared to Comparative Examples 1 and 2, and showed an excellent effect in the evaluation of appearance. In the case of Examples 1 to 5, the 300% modulus and elongation showing mechanical properties are at an appropriate level, and the crack growth rate is also at an appropriate level or shows excellent results, while the 60 ° C tan delta value is better than that of Comparative Examples 1 and 2, resulting in low fuel efficiency. Also showed excellent results. In particular, Examples 1 to 3 also showed excellent results compared to Comparative Examples 1 and 2 in terms of crack growth rate.

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 rights.

Claims (7)

100 parts by weight of raw rubber containing 10 to 50 parts by weight of a polymer alloy containing nitrile rubber and polyvinyl chloride,
30 to 70 parts by weight of the filler, and
Antioxidant 1 to 5 parts by weight
Including,
The polymer alloy is a weight ratio of the nitrile rubber and the polyvinyl chloride of 50:50 to 70:30,
The filler is carbon black having a nitrogen adsorption specific surface area of 30 to 300m ² / g, DBP oil absorption of 60 to 210cc / 100g,
The antioxidant is any one consisting of a wax, an amine antioxidant and combinations thereof
Rubber composition for tire sidewalls. delete delete delete The method of claim 1,
The raw material rubber is a rubber composition for a tire sidewall comprising 10 to 80 parts by weight of natural rubber and 10 to 70 parts by weight of butadiene rubber. The method of claim 1,
The rubber composition for the tire sidewalls is based on 100 parts by weight of the raw material rubber
0 to 20 parts by weight of softener,
1 to 8 parts by weight of vulcanizing agent,
1-3 parts by weight of vulcanizing agent, and
0.1-2 parts by weight of vulcanization accelerator
The rubber composition for a tire sidewall that further comprises. The tire manufactured using the rubber composition for tire sidewalls of any one of Claims 1, 5, and 6.