CN108794817B - Tire comprising a rubber composition for protecting sidewalls from ozone damage - Google Patents

Abstract

The present invention relates to a rubber composition capable of protecting tire sidewalls from ozone damage and tires manufactured using the composition. Specifically, it relates to a tire that includes an anti-aging rubber sheet between the sidewall and the carcass, and the anti-aging rubber sheet comprises 100 parts by weight of raw rubber, 20-60 parts by weight of carbon black, amine A rubber composition containing 2 to 5 parts by weight of an anti-aging agent is produced. The tire produced by using the rubber composition of the present invention can significantly improve the ozone resistance without changing the blackness of its appearance.

Description

Tire comprising a rubber composition for protecting sidewalls from ozone damage

technical field

The present invention relates to a rubber composition capable of protecting tire sidewalls from ozone damage and tires manufactured using the composition. Specifically, it relates to a rubber composition that has excellent ozone resistance to aging phenomena caused by ozone or ultraviolet rays by disposing a rubber composition in the form of a sheet between a tire sidewall and a carcass, thereby being able to remove ozone from ozone. A rubber composition for protecting a sidewall and a tire manufactured using the same.

Background technique

A variety of information related to the tire is recorded on the sidewall of the tire. Unlike the tread that is in contact with the ground, the sidewall must have the characteristics of resistance to external environmental factors such as sunlight, temperature, ozone, oxygen, and weather.

The sidewall of the tire is irradiated by the light from the sun, and it performs frequent flexion and extension movements. It is necessary to release the heat generated by the tire to the outside. Therefore, it is required to have weather resistance, aging resistance, bending resistance, heat resistance, heat resistance and ozone resistance. sex. In order to obtain the desired properties of the sidewall, various additives are used. As a commonly used material, a rubber composition in which a large amount of an amine-based anti-aging agent or a wax is formulated into a diene-based rubber component is widely used.

However, this amine anti-aging agent will precipitate onto the rubber surface over time, thereby discoloring the rubber. In order to prevent such appearance discoloration, only a very small amount of anti-aging agent is added to the rubber component or no anti-aging agent is added at all, and a method of formulating a large amount of wax is used to replace the anti-aging agent.

As described above, in the case of the rubber composition using a large amount of wax, the ozone resistance in static state can be maintained, and the deterioration of the appearance caused by the amine-based antiaging agent can be prevented to a certain extent.

However, the other physical properties required for the sidewall rubber, ie, heat resistance, ozone resistance under dynamic conditions, and weather resistance, cannot be solved.

In order to fundamentally solve this problem, although amine anti-aging agents or waxes should not be used, if amine anti-aging agents or waxes are not added, the main physical properties required for sidewall rubber are weather resistance, ozone resistance, and resistance. The heat will be greatly reduced.

Therefore, it is necessary to make efforts in the following aspects: to seek the optimal mixture of amine-based antiaging agents that can minimize the discoloration of tire appearance and maximize the weather resistance, ozone resistance, and heat resistance of tire sidewalls ratio, or develop new age inhibitors that can minimize discoloration, or change the structure of the tire sidewall.

prior art literature

Patent Literature

(Patent Document 1) Korean Patent Publication No. 1995-0003044 (1995.03.30.)

SUMMARY OF THE INVENTION

technical problem to be solved

An object of the present invention is to provide a tire in which a sheet containing a rubber composition for protecting a tire sidewall portion from ozone is located between the sidewall portion and the carcass.

Solutions to technical problems

According to a preferred embodiment of the present invention, a tire can be provided, comprising an anti-aging rubber sheet between the sidewall and the carcass. 60 parts by weight and 2-5 parts by weight of amine anti-aging agent are produced from the rubber composition.

The amine anti-aging agent can be selected from 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 Any selected from the group consisting of base-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-octyl-p-phenylenediamine and combinations thereof A sort of.

The sidewall may contain 100 parts by weight of raw rubber and 0 parts by weight or more and less than 2 parts by weight of an amine-based antiaging agent.

The rubber composition may further comprise 1-3 parts by weight of any anti-aging agent selected from the group consisting of phenols, quinolines, imidazoles, metal carbamates, waxes and combinations thereof.

The rubber composition may further comprise 1-3 parts by weight of 2,2,4-trimethyl-1,2-dihydroquinoline.

Invention effect

For the tire manufactured using the rubber composition for protecting the tire sidewall from the ozone environment according to the present invention, the blackness of the appearance is not changed, and the ozone resistance can be remarkably improved.

Description of drawings

1 is a cross-sectional view of a tire sidewall portion according to an embodiment of the present invention.

FIG. 2 is an enlarged schematic view of a cross-section of a sidewall portion of a tire according to an embodiment of the present invention.

3 is a schematic view of a tire cross-sectional layer with a rubber composition for protecting a tire sidewall from ozone damage according to one embodiment of the present invention located between the sidewall and the carcass.

Description of reference numerals

1: Sidewall

2: Carcass

3: Anti-aging rubber sheet

Detailed ways

Hereinafter, the embodiments of the present invention will be described in detail to ensure that those skilled in the art can easily implement them. However, the present invention can be realized in many different forms, and is not limited to the embodiments listed here.

The terms used in the description of the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. An expression of the singular includes the meaning of the plural, as long as it is not explicitly defined differently from the literary and political terms. Terms such as "comprising" or "having" described in the description of the present invention should be understood as follows, that is, it refers to the existence of the features, numbers, steps, actions, constituent elements, parts or combinations thereof described in the description, and cannot be excluded in advance. The presence or additional possibility of one or more other features or numbers, steps, acts, constituent elements, components, or combinations thereof.

1 is a schematic structural diagram of a cross-section of a tire sidewall portion, FIG. 2 is a schematic view of an enlarged sidewall portion, and FIG. 3 is a schematic view of a sheet located between the sidewall portion and the carcass. A rubber composition according to an embodiment of the present invention is included.

According to an embodiment of the present invention, there is provided a tire including an anti-aging rubber sheet between a sidewall portion and a carcass, and the anti-aging rubber sheet may contain a rubber composition to which an amine anti-aging agent is added.

In the rubber sheet for anti-aging, the amine anti-aging agent is transferred to the sidewall portion with the passage of time, so that the weather resistance, ozone resistance and heat resistance of the sidewall portion can be improved. At the same time, the amount of the amine-based anti-aging agent in the sidewall portion is minimized, thereby preventing discoloration of the initial sidewall portion.

The schematic structure of the sidewall portion of the tire is shown in the above-mentioned FIGS. 1 and 2. It is composed of the outermost layer, namely, the sidewall rubber 1 and the carcass 2 that supports the tire structure. An anti-aging rubber sheet 3 for protecting a tire sidewall from ozone damage according to an embodiment.

The anti-aging rubber sheet 3 according to an embodiment of the present invention may be composed of a rubber composition comprising 100 parts by weight of raw rubber, 20-60 parts by weight of carbon black and 2-5 parts by weight of amine anti-aging agent.

The anti-aging rubber sheet 3 may be located between the sidewall rubber 1 and the carcass 2 .

In the anti-aging rubber sheet 3 of the present invention, any one or more kinds of rubber selected from the group consisting of natural rubber, modified natural rubber, and synthetic rubber can be used as the raw rubber.

Although the natural rubber contains cis-1,4-polyisoprene as a main component, it may also contain trans-1,4-polyisoprene depending on the required properties. Therefore, in addition to the natural rubber containing cis-1,4-polyisoprene as the main component, the natural rubber may also contain, for example, balata, a type of sapodaceae rubber produced in South America. Such as natural rubber containing trans-1,4-isoprene as the main component.

The modified natural rubber refers to the modification or purification of the ordinary natural rubber. For example, the modified natural rubber includes epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber and the like.

The synthetic rubber includes, but is not limited to, from styrene-butadiene rubber (SBR), modified styrene-butadiene rubber, butadiene rubber (BR), modified butadiene rubber, isoprene rubber, neoprene rubber, chlorosulfone Polyethylene Rubber, Chlorinated Ethylene 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, EPDM rubber, Hypalon rubber, neoprene, ethylene vinyl acetate rubber, acrylic rubber, hydrin rubber, Vinyl benzyl chloride-styrene butadiene rubber, bromomethylbutyl styrene rubber, maleic acid-styrene butadiene rubber, carboxylated styrene-butadiene rubber, epoxy isoprene rubber, maleic acid Ethylene propylene rubber, carboxynitrile butadiene rubber, BIMS (brominated polyisobutyl isoprene-co-paramethyl styrene; brominated polyisobutyl isoprene-co-paramethyl styrene) selected from the group consisting of and mixtures thereof any kind.

In particular, as the synthetic rubber, butadiene rubber is preferably used, and high-cis butadiene rubber is more preferably used. The high cis-butadiene rubber can use a product with a cis-1,4 content of 96% by weight or more and a glass transition temperature (Tg) of -104 to -107°C. The high-cis-butadiene rubber has more excellent low-temperature properties and restitution elasticity within the range of the cis-1,4 content and the glass transition temperature.

In order to improve the appearance, prevent tearing and maintain fatigue resistance, the raw rubber can also use natural rubber or a mixed rubber composed of modified natural rubber and synthetic rubber. In this case, natural rubber or modified natural rubber and synthetic rubber may be mixed in a weight ratio of 1:9 to 9:1. If the natural rubber or modified natural rubber is contained in a weight ratio of less than 1, fatigue resistance may be lowered, resulting in poor appearance. If the synthetic rubber is contained in a weight ratio of less than 1, tear resistance and rupture resistance are lowered.

In the anti-aging rubber sheet 3 of the present invention, the amine anti-aging agent can be used in a proportion of 2 to 5 parts by weight per 100 parts by weight of the raw rubber, and the amine anti-aging agent is composed of N-phenylene -N'-(1,3-Dimethyl)-p-phenylenediamine (6PPD), N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N -Phenyl-N'-isopropyl-p-phenylenediamine (IPPD), N,N'-diphenyl-p-phenylenediamine, N,N'-diaryl-p-phenylenediamine, Any one selected from the group consisting of N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-octyl-p-phenylenediamine, and combinations thereof. More preferably, as the amine anti-aging agent, 6PPD or IPPD having excellent heat aging resistance and ozone resistance can be used. If the amount of the amine-based antiaging agent used is less than 2 parts by weight, the antiaging effect will be insufficient. If it exceeds 5 parts by weight, its migration to the sidewall portion increases, resulting in discoloration.

The type of carbon black contained in the anti-aging rubber sheet ³ of the present invention is not particularly limited. Acid dibutyl ester) adsorption value is 100-110g/100g, and iodine adsorption value is in the range of 90-120mg/g. When the nitrogen adsorption specific surface area, DBP oil absorption, and iodine adsorption value of the carbon black are within the above-mentioned ranges, a rubber composition for tires having both suitable reinforcing properties and suitable processability can be produced.

Representative examples of the carbon black include, but are not limited to, 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 etc.

The carbon black may be used in an amount of 20 to 60 parts by weight per 100 parts by weight of the raw rubber. If the amount of the carbon black used is less than 20 parts by weight, the reinforcing properties of the rubber sheet may be insufficient, thereby reducing tire durability. If the carbon black is used in excess of 60 parts by weight, the hysteresis of the rubber sheet is increased, thereby reducing the low fuel consumption performance of the tire.

In addition, the rubber sheet 3 for anti-aging of the present invention may further contain an additional anti-aging agent in addition to the amine-based anti-aging agent. The anti-aging agent is an additive used to stop the chain reaction of automatic oxidation of tires under the action of oxygen. The anti-aging agent can be appropriately selected from the group consisting of phenols, quinolines, imidazoles, metal carbamates, waxes, and combinations thereof and used.

The phenolic antiaging agent can be composed of phenolic 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-isobutylene-bis( 4,6-xylenol), 2,6-di-tert-butyl-p-cresol, and combinations thereof, select any one of them for use.

The quinoline anti-aging agent can use 2,2,4-trimethyl-1,2-dihydroquinoline and its derivatives, specifically, can be made from 6-ethoxy-2,2,4 -Trimethyl-1,2-dihydroquinoline, 6-anilino-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4 -Any one selected from the group consisting of trimethyl-1,2-dihydroquinoline and combinations thereof is used.

The wax is preferably a wax-containing hydrocarbon.

The anti-aging agent other than amines needs to have the effect of preventing aging, and must also meet the following conditions: high solubility to rubber; low volatility, must be inert to rubber; can not hinder vulcanization and the like. Considering the above conditions, the content of the anti-aging agent is 1 to 3 parts by weight relative to 100 parts by weight of the raw rubber.

More preferably, the anti-aging rubber sheet 3 of the present invention further contains 1 to 3 parts by weight of 2,2,4-trimethyl-1,2-dihydroquinoline (RD) per 100 parts by weight of the raw rubber. . Compared with 6PPD or IPPD, although RD has poor ozone resistance, it is inexpensive and has advantages in physical properties such as heat aging resistance and fatigue resistance. The higher the content of RD, the more the migration of the amine-based antiaging agent to the sidewall rubber is increased, whereby the ozone resistance can be improved.

If the RD is contained in an amount of less than 1 part by weight, the movement of the amine-based anti-aging agent in the anti-aging rubber sheet is restricted, and the anti-aging effect on the sidewall portion cannot be achieved. If it exceeds 5 parts by weight, the movement of the amine-based anti-aging agent is excessively accelerated, thereby causing discoloration of the sidewall portion caused by the amine-based anti-aging agent. In addition, excessive use of RD reduces the adhesion between the anti-aging rubber sheet and the sidewall rubber or carcass rubber, resulting in a decrease in tire durability performance.

The anti-aging rubber sheet 3 containing the amine anti-aging agent can be selected from the reinforcing agent, active agent, processing oil, vulcanizing agent and vulcanization accelerator commonly used in rubber compositions for tires as required. The technical field of the present invention Various commonly used additives are used in the specified content according to the ratio used in the ordinary tire rubber composition.

As the vulcanizing agent, a sulfur-based vulcanizing agent is preferably used. The sulfur-based vulcanizing agent can use inorganic vulcanizing agents such as powder sulfur (S), insoluble sulfur, precipitated sulfur, colloid sulfur, elemental sulfur, polymer sulfur, etc. and sulfur-producing vulcanizing agents, such as: amine disulfide amine disulfide, tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), dithiodimorpholine and other organic vulcanizing agents .

If the content of the vulcanizing agent is 1.5-2.5 parts by weight relative to 100 parts by weight of the raw rubber, a more suitable vulcanization effect can be obtained, so that the raw rubber will not be too sensitive to heat and can maintain good chemical stability sex.

The vulcanization accelerator refers to an accelerator for accelerating the vulcanization rate or accelerating the retarding action in the initial vulcanization stage.

The vulcanization accelerator can be selected from sulfenamides, thiazoles, thiurams, thioureas, guanidines, dithiocarbamic acids, aldehyde amines, aldehyde ammonia, imidazolines, xanthates. Use any one of the classes and their combinations.

The sulfenamide vulcanization accelerator can be selected from, for example, N-cyclohexyl-2-benzenesulfinamide (CBS), N-tert-butyl-2-benzenesulfinamide (TBBS), N,N - Bicyclohexyl-2-benzenesulfinamide, N-oxydiethyl-2-benzenesulfinamide, N,N-diisopropyl-2-benzothiazolesulfinamide and combinations thereof Select any one of the sulfenamide compounds from the group to use.

The thiazole type vulcanization accelerator can be selected from 2-mercaptobenzothiazole (MBT), dibenzothiazole disulfide (MBTS), 2-mercaptobenzothiazole sodium salt, 2-mercaptobenzothiazole zinc salt, 2-mercaptobenzothiazole -Mercaptobenzothiazole copper salt, 2-mercaptobenzothiazole cyclohexylamine salt, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl 4-mo Any thiazole compound is selected and used from the group consisting of thio) benzothiazole and its combination.

The thiuram-based vulcanization accelerator can be selected from, for example, tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide, bis(II) disulfide. pentylthiuram, bispentylthiuram monosulfide, bispentylidehiuram tetrasulfide, bispentylthiuram hexasulfide, tetrabutylthiuram disulfide, cyclopentanethiuram Any one thiuram compound is selected and used from the group consisting of Lamb tetrasulfide and its combination.

The thiourea vulcanization accelerator can be selected from the group consisting of thiourea, diethylthiourea, dibutylthiourea, trimethylthiourea, di-o-tolylthiourea and combinations thereof. Urea compounds are used.

The guanidine vulcanization accelerator can be used by selecting any guanidine compound from the group consisting of diphenylguanidine, di-o-tolylguanidine, triphenylguanidine, o-tolyl biguanide, diphenylguanidine phthalate and combinations thereof. .

The dithiocarbamate vulcanization accelerator can be made from zinc ethylphenyl dithiocarbamate, zinc butylphenyl dithiocarbamate, sodium dimethyl dithiocarbamate, dimethyl dithiocarbamate. Zinc Dicarbamate, Zinc Diethyldithiocarbamate, Zinc Dibutyl Dithiocarbamate, Zinc Diamyl Dithiocarbamate, Zinc Dipropyl Dithiocarbamate, Pentamethylene Dithiocarbamate Zinc thiocarbamate and piperidine complex salt, zinc hexadecyl isopropyl dithiocarbamate, zinc octadecyl isopropyl dithiocarbamate, zinc bibenzyl dithiocarbamate, Sodium ethyl dithiocarbamate, piperidine pentamethylene dithiocarbamate, selenium dimethyl dithiocarbamate, tellurium diethyl dithiocarbamate, cadmium diamyl dithiocarbamate and Any one of the dithiocarbamate compounds is selected and used from the combination composition group.

The aldehyde-amine or aldehyde-ammonia vulcanization accelerator can be selected from the group consisting of acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde-ammonia reactant and combinations thereof Any aldehyde amine or aldehyde amine compound is used.

The imidazoline-based vulcanization accelerator may use imidazoline-based compounds such as 2-mercaptoimidazoline, and the xanthate-based vulcanization accelerator may use xanthate-based compounds such as zinc dibutylxanthate.

In order to maximize the production efficiency by accelerating the vulcanization rate and enhance the physical properties of the rubber, the vulcanization accelerator is contained in an amount of 0.6 to 1.2 parts by weight relative to 100 parts by weight of the raw rubber.

The vulcanization accelerator, as a compounding agent used in combination with the vulcanization accelerator to give full play to its accelerating effect, can be composed of inorganic vulcanization accelerators, organic vulcanization accelerators, and combinations thereof. Choose any one of the groups to use.

The inorganic vulcanization accelerator can be selected from the group consisting of zinc oxide (ZnO), zinc carbonate (Zinc Carbonate), magnesium oxide (MgO), lead oxide (Lead Oxide), potassium hydroxide and combinations thereof. kind of use. The organic vulcanization accelerator can be selected from stearic acid, zinc stearate, palmitic acid, linoleic acid, oleic acid, lauric acid, dibutyl ammonium oleate, and their derivatives. Select any one of the group consisting of and its combination to use.

In particular, the vulcanization accelerator may use the zinc oxide together with the stearic acid. In this case, the zinc oxide will dissolve in the stearic acid and form an effective complex with the vulcanization accelerator, so that free sulfur can be generated in the vulcanization reaction, so that the The crosslinking reaction of the rubber becomes easier.

When the zinc oxide and the stearic acid are used together, 2.0 to 4.0 parts by weight can be used with respect to 100 parts by weight of the raw rubber in order to function as a suitable vulcanization accelerator. If the content of the zinc oxide and the stearic acid is less than the above range, the vulcanization rate will be slowed down, resulting in a decrease in production efficiency. If each exceeds the above-mentioned range, a scorching phenomenon will occur, resulting in a decrease in physical properties.

A softener is a substance added to a rubber composition in order to impart plasticity to rubber to make processing easier or to reduce the hardness of vulcanized rubber. It refers to oils used in rubber compounding or rubber manufacturing and other Material. The softeners refer to process oils or oils contained in other rubber compositions. The softener can be used by selecting any one from the group consisting of petroleum-based oils, vegetable oils and fats, and combinations thereof, but the present invention is not limited thereto.

The petroleum-based oil may be used in any one selected from the group consisting of paraffin-based oil, naphthenic-based oil, aromatic-based oil, and combinations thereof.

Representative examples of the paraffinic oils include P-1, P-2, P-3, P-4, P-5, P-6, etc. produced by Meichang Oil Co., Ltd. The naphthenic oils Representative examples include N-1, N-2, N-3, etc. produced by Meichang Oil Co., Ltd., and representative examples of the aromatic oils include A-2 produced by Meichang Oil Co., Ltd. , A-3, etc.

However, with the continuous strengthening of people's awareness of environmental protection, people have realized that when the content of polycyclic aromatic hydrocarbons (Polycyclic Aromatic Hydrocarbons, hereinafter referred to as "PAHs") contained in the aromatic oil exceeds 3% by weight, cancer is induced possibility is high. Therefore, TDAE (treated distillate aromatic extract) oil, MES (mild extraction solvate) oil, RAE (residual aromatic extract) oil or heavy naphthene can be preferably used base oil.

In particular, the oil used as the softener is preferably used with a total content of PAHs of 3% by weight or less with respect to the entire oil, a kinematic viscosity of 95 or more (210°F SUS), and an aromatic component of 15 to 15°F in the softener. 25% by weight, 27-37% by weight of naphthenic components, and 38-58% by weight of paraffin components.

The TDAE oil can not only make the tire sidewalls containing the TDAE oil have good low temperature characteristics and fuel consumption performance, but also be beneficial to environmental protection and reduce the risk of PAHs carcinogenicity.

The vegetable oil can be made from castor oil, cottonseed oil, linseed oil, canola oil, soybean oil, palm oil, coconut oil, peanut oil, pine oil, pine tar, tall oil, corn oil, rice bran oil, red Any one selected from the group consisting of flower oil, sesame oil, olive oil, sunflower oil, palm kernel oil, camellia oil, jojoba oil, macadamia oil, safflower oil, tung oil, and combinations thereof is used.

The content of the softener relative to 100 parts by weight of the raw rubber is 2.0 to 6.0 parts by weight, which is beneficial to improve the processability of the raw rubber.

Since the sidewall rubber composition 1 of the present invention does not use an amine-based antiaging agent or the content thereof is less than 1 part by weight, discoloration of the sidewall portion can be prevented. At the same time, the use of the anti-aging rubber sheet 3 containing 2 to 5 parts by weight of amine anti-aging agent can prevent ozone cracking and cracking caused by aging that may occur during use.

The anti-aging rubber sheet 3 and the sidewall rubber composition 1 can be produced by a conventional two-step continuous manufacturing process. That is, it can be produced in a suitable mixer by the following two steps: that is, at a maximum temperature of 110 to 190 ° C, preferably, at a high temperature of 130 to 180 ° C, thermomechanical treatment or mixing is carried out. 1 step (referred to as the "non-production step"); during the finishing step of mixing the cross-linking binding system, the first step of mechanical treatment is typically below 110°C, for example, at a low temperature of 40-100°C. 2 steps (referred to as "production steps"), but the present invention is not limited to this.

The anti-aging rubber sheet and the sidewall rubber composition are not limited to the sidewall portion, and may be included in various rubber constituents constituting the tire. The rubber constituents include tread, apex, chafer, wire coat, or inner liner, and the like.

In the tire according to another embodiment of the present invention, the anti-aging rubber sheet 3 is placed between the sidewall 1 and the carcass 2 in the form of a sheet. The method for producing the tire containing the anti-aging rubber sheet can be any method for producing a tire according to the prior art, and detailed descriptions thereof will be omitted in this specification.

Tires according to another embodiment of the present invention include tires for passenger cars, tires for racing, tires for aircraft, tires for agricultural machinery, tires for off-the-road, tires for trucks, tires for buses, and the like. In addition, the tire may be a radial tire or a bias tire, preferably a radial tire.

Hereinafter, preferred embodiments are listed in order to facilitate the understanding of the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

[Production example: Production of rubber composition]

Using the compositions shown in the following Table 1, the rubber compositions of Production Examples 1 to 3 were produced. The rubber composition of Production Example 1 is a rubber composition for a sidewall, and the rubber compositions of Production Examples 2 and 3 are rubber compositions for protecting the sidewall from ozone. The production of the rubber composition can be carried out by a common production method of the rubber composition, which is not particularly limited.

【Table 1】

Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Natural Rubber¹⁾ 50 50 50 Butadiene rubber²⁾ 50 50 50 Carbon Black³⁾ 50 50 50 6PPD⁴⁾ - 3 3 RD⁵⁾ 1 1 2 WAX⁶⁾ 1 1 1 Processing oil⁷⁾ 5 5 5 Zinc oxide 3 3 3 Stearic acid 1 1 1 sulfur 1.8 1.8 1.8 Vulcanization accelerator⁸⁾ 0.7 0.7 0.7

(unit: parts by weight)

1) Natural rubber: TSR20 grade

2) Butadiene rubber (BR): Butadiene rubber with Tg (glass transition temperature) of -106°C (BR1208 manufactured by LG Chemical)

3) Carbon black: N330

4) 6PPD: N-phenyl-N'-(1,3-dimethyl)-p-phenylenediamine (Kumanox-13 manufactured by Kumho Petrochemical)

5) RD: 2,2,4-trimethyl-1,2-dihydroquinoline (Vulkanox HS/LG from LANXESS)

6) WAX: Paraffin wax

7) Processed oils: softeners for TDAE (treated distilled aromatic extract) oils

8) Vulcanization accelerator: TBBS (N-tert-butyl-2-benzenesulfinamide)

[Comparative example]

In terms of tire production, the sidewall portion was produced using the rubber composition produced in Production Example 1, and the carcass portion was produced using a generally used rubber composition for a carcass.

[Example 1]

The rubber composition for protecting tire sidewalls from ozone destruction produced in Production Example 2 was added in the form of flakes between the sidewall portion and the carcass portion containing the rubber composition produced in Production Example 1, thereby Manufactured tires.

[Example 2]

The rubber composition for protecting tire sidewalls from ozone destruction produced in Production Example 3 was added in the form of flakes between the sidewall portion and the carcass portion containing the rubber composition produced in Production Example 1, thereby Manufactured tires.

[Experimental example: Evaluation of ozone resistance of tire sidewalls]

Only the sidewalls of the tires of the comparative examples and the examples were cut, and aged in an environment with an ozone concentration of 50 pphm and a temperature of 40° C., and the degree of ozone burst generation was observed. The results are shown in Table 2. processed and compared.

【Table 2】

Comparative example Example 1 Example 2 Static ozone resistance C4 B1 A1 Exterior Level 1 Level 1 Level 1

Number of cracks: A<B<C

Crack size: 1<2<3<4<5

Blackness Evaluation: Level 1 - Little change in blackness.

Level 2 - Blackness is slightly reduced.

Level 3 - Significant change in blackness.

As shown in the results in Table 2, Examples 1 and 2 in which the anti-aging rubber sheet containing an amine-based anti-aging agent was used, compared with the comparative example in which the sheet was not used and only the side rubber composition was used. Ozone resistance is significantly improved. The degree of discoloration caused by the amine anti-aging agent maintained a similar standard to the comparative example without the amine anti-aging agent.

In addition, as can be seen from Example 2, if the content of RD in the anti-aging rubber sheet is increased, the migration of the amine anti-aging agent to the sidewall rubber is increased, and the static ozone resistance can be improved.

Based on the above results, the content of the amine-based antiaging agent that causes discoloration in the sidewall rubber composition can be reduced to less than 2 wt. parts, more preferably, to less than 1 part by weight.

In the foregoing description, preferred embodiments of the present invention have been described in detail. However, the scope of the right of the present invention is not limited to this, and various modifications and improvements implemented by those skilled in the art using the basic concept of the present invention defined in the claims also belong to the scope of the right of the present invention.

Claims (4)

1. A tire, characterized in that: Including the anti-aging rubber sheet arranged between the sidewall and the carcass, The anti-aging rubber sheet comprises a rubber composition comprising: 100 parts by weight of raw rubber, 20-60 parts by weight of carbon black, and 2-5 parts by weight of an amine anti-aging agent, The sidewall includes: 100 parts by weight of raw rubber and 0 parts by weight or more and less than 2 parts by weight of an amine-based antiaging agent. 2. The tire according to claim 1, wherein: The amine anti-aging agent is composed of 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'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-octyl-p-phenylenediamine, and any combination thereof selected from the group consisting of kind. 3. The tire according to claim 1, wherein: The rubber composition further comprises 1-3 parts by weight of any anti-aging agent selected from the group consisting of phenols, quinolines, imidazoles, metal carbamates, waxes and combinations thereof. 4. The tire according to claim 1, wherein: The rubber composition further comprises 1-3 parts by weight of 2,2,4-trimethyl-1,2-dihydroquinoline.

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