KR102283602B1 - Rubber composition for tire carcass and tire manufactured by using the same - Google Patents

Abstract

The present invention relates to a rubber composition for a tire carcass and a tire manufactured by using the same. More particularly, the present invention relate to a rubber composition for a tire carcass and a tire manufactured by using the same, wherein the rubber composition contains raw rubber, a reinforcing filler, a vulcanizing agent, a vulcanization accelerator, and a softener, wherein the reinforcing filler includes graphene, wherein the content of graphene is 10 to 20 parts by weight based on 100 parts by weight of the raw rubber.

Description

A rubber composition for a tire carcass and a tire manufactured using the same

The present invention relates to a rubber composition for a tire carcass and a tire manufactured using the same, and more particularly, to a tire car with improved tensile properties and improved electrical conductivity so that static electricity generated from automobiles and tires can be transferred to the ground. It relates to a rubber composition for a car and a tire manufactured using the same.

The carcass of a tire is the most important part (skeletal part) that becomes the skeleton of a tire, and refers to the entire layer of fabric made of tire cord paper. The carcass serves to withstand the pressure, load, and impact of the tire inside. In a tubular tire, a tube containing high pressure air is protected and the load is supported, while a thick rubber layer is attached to the part in contact with the road surface to cope with trauma or wear.

Recently, the tire industry is continuously developing technologies to reduce tire rolling resistance and minimize the braking distance on wet roads by using silica as a reinforcing filler instead of carbon black in response to the demand for eco-friendly tires and low fuel consumption.

When silica is used excessively instead of carbon black, which has been widely used as a filler for tire tread rubber, electrical conductivity is reduced and static electricity generated from the vehicle cannot be transferred to the ground, causing inconvenience to the driver and risk of fire and explosion. also exist

In order to solve the problem of static electricity in tires containing silica, many technologies have been developed in terms of tire design. In order to facilitate this technology, it is necessary to introduce a technology for improving the electrical conductivity of the rubber composition for a tire carcass. As a result, the tire industry has generally used a method of manufacturing by increasing the content of carbon black.

However, such an increase in the carbon black content increases the heat generation of the tire, thereby reducing LRR (Low Rolling Resistance) performance. Therefore, it is necessary to introduce a technology that improves the electrical conductivity while maintaining the LRR performance by minimizing the heat of the tire.

Accordingly, it is an object of the present invention to provide a rubber composition for a tire carcass with improved electrical conductivity so that static electricity generated from automobiles and tires can be transferred to the ground by adding graphene to the rubber composition for a tire carcass.

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

A rubber composition for a tire carcass according to an aspect of the present invention for solving the above problems includes a raw material rubber, a reinforcing filler, a vulcanizing agent, a vulcanization accelerator and a softener, and the reinforcing filler includes graphene, , The content of the graphene is characterized in that 10 to 20 parts by weight based on 100 parts by weight of the raw rubber.

At this time, the rubber composition for carcass is extruded under a water content of less than 2 wt% after mixing the raw rubber, the reinforcing filler, the vulcanizing agent, the vulcanization accelerator and the softening agent under water-containing conditions. It may be a master batch (Wet master batch, WMB).

In addition, the raw rubber is polyisoprene rubber, polybutadiene rubber, conjugated diene rubber, vinyl aromatic copolymer rubber, nitrile copolymer rubber, hydrogenated nitrile rubber (NBR), olefin rubber, ethylene modified with maleic acid- It may be at least one selected from the group consisting of propylene rubber, butyl rubber, a copolymer of isobutylene and a vinyl aromatic monomer, a copolymer of isobutylene and a diene monomer, an acrylic rubber, a halogenated rubber, and a chloroprene rubber.

In addition, the reinforcing filler may include any one selected from the group consisting of silica, carbon black, and mixtures thereof.

Meanwhile, a tire according to another aspect of the present invention is characterized in that it is manufactured using the above-described rubber composition for a tire carcass according to the present invention.

According to the present invention, graphene is added to the rubber composition for a tire carcass to improve electrical conductivity so that static electricity generated from automobiles and tires can be transferred to the ground.

And, instead of adding carbon black or silica, by adding graphene with high electrical conductivity and high aspect ratio, the dispersibility of the reinforcing filler in the rubber composition for carcass is improved, and not only the electrical conductivity of the rubber composition for carcass, but also , and the tensile properties are also improved.

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

The rubber composition for a tire carcass according to an aspect of the present invention includes a raw material rubber, a reinforcing filler, a vulcanizing agent, a vulcanization accelerator and a softener, the reinforcing filler includes graphene, and the content of the graphene is , characterized in that 10 to 20 parts by weight based on 100 parts by weight of the raw rubber.

The graphene used in the present invention has high mechanical strength, excellent electrical conductivity similar to copper, and has a high charge mobility that is about 100 times that of silica. Therefore, even when a relatively small amount is used, the physical properties and electrical conductivity of the rubber composition can be improved.

According to the present invention, by including 10 to 20 parts by weight of graphene based on 100 parts by weight of the raw rubber, the electrical conductivity is improved so that static electricity generated from automobiles and tires can be transferred to the ground, and reinforcement in the rubber composition for carcass It also improves the dispersibility and tensile properties of the sex filler.

When the content of the graphene is less than 10 parts by weight, the effect of increasing the static electricity transfer ability does not occur, and when it exceeds 20 parts by weight, the overall performance of the tire decreases (lap time by 2 seconds / 40km mileage) due to the overall increase in modulus can occur

The raw 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.

As the general natural rubber, any known natural rubber may be used, and the country of origin is not limited. The natural rubber mainly includes cis-1,4-polyisoprene, but may also include trans-1,4-polyisoprene according to required properties. Accordingly, in the natural rubber, in addition to natural rubber containing cis-1,4-polyisoprene as a main component, natural rubber containing trans-1,4-isoprene as a main component, such as Valata, which is a type of rubber of the Sapotaceae family from South America, as a main component It may also include rubber.

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

In addition, the synthetic rubber is styrene butadiene rubber (SBR), modified styrene butadiene rubber, butadiene rubber (BR), polybutadiene rubber such as modified butadiene rubber, polyisoprene rubber, butyl rubber (BR), chlorosulfonated polyethylene rubber, epi Chlorohydrin rubber, fluororubber, silicone rubber, nitrile rubber, hydrogenated nitrile butadiene rubber (hydrogenated NBR), chlorinated polyethylene rubber, styrene ethylene butylene styrene (SEBS) rubber, olefin rubber, ethylene propylene rubber, ethylene propylenediene (EPDM) rubber, ethylene propylene maleate rubber, hypalon rubber, acrylic rubber, halogenated rubber, chloroprene rubber, ethylene vinyl acetate rubber, hydrin rubber, vinyl benzyl chloride styrene butadiene rubber, bromomethyl styrene butyl rubber, styrene butadiene maleate rubber , carboxylic acid styrene butadiene rubber, epoxy isoprene rubber, carboxylic acid nitrile butadiene rubber, brominated polyisobutyl isoprene-co-paramethyl styrene (BIMS), and combinations thereof. It may be selected from the group, and more preferably, the raw material rubber is styrene-butadiene rubber, polybutadiene rubber, polyisoprene rubber, butyl rubber, hydrogenated nitrile butadiene rubber (hydrogenated NBR), olefin rubber, maleic acid ethylene propylene rubber, acrylic It may be any one selected from the group consisting of rubber, halogenated rubber, chloroprene rubber, and mixtures thereof.

And, the reinforcing filler may further include any one selected from the group consisting of silica, carbon black, and mixtures thereof. The content is preferably included in an amount of 10 to 100 parts by weight based on 100 parts by weight of the raw rubber.

The silica may have a nitrogen surface area per gram (N2SA) 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 the present invention provides this It is not limited.

If the nitrogen adsorption specific surface area of the silica is less than 100 m 2 /g, the reinforcing performance by the silica filler may be disadvantageous, and if it exceeds 180 m 2 /g, the processability of the rubber composition may be disadvantageous. In addition, if the CTAB adsorption specific surface area of the silica is less than 110 m 2 /g, the reinforcing performance by the silica filler may be disadvantageous, and if it exceeds 170 m 2 /g, the processability of the rubber composition may be disadvantageous.

As the silica, both those manufactured by a wet method or a dry method may be used, and commercially available products include Ultrasil VN2 (manufactured by Degussa Ag), Ultrasil VN3 (manufactured by Degussa Ag), Z1165MP (manufactured by Rhodia) or Z165GR (manufactured by Rhodia). can

In addition, the carbon black may have a nitrogen surface area per gram (N2SA) of 30 to 300 m ² /g, and an n-dibutyl phthalate (DBP) oil absorption of 60 to 180 cc/100 g, but this The invention is not limited thereto.

If the nitrogen adsorption specific surface area of the carbon black ^{exceeds 300 m 2} /g, the processability of the rubber composition for carcass may be disadvantageous, and ^{if it is less than 30 m 2} /g, the reinforcing performance by carbon black as a filler may be disadvantageous. . In addition, if the DBP oil absorption amount of the carbon black exceeds 180cc/100g, the processability of the rubber composition may be reduced, and if it is less than 60cc/100g, the reinforcing performance by the carbon black as a filler may be disadvantageous.

Representative 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, N550, N582 , N630, N642, N650, N660, N683, N754, N762, N765, N774, N787, N907, N908, N990 or N991.

As the vulcanizing agent, a sulfur-based vulcanizing agent, an organic peroxide, a resin vulcanizing agent, and a metal oxide such as magnesium oxide may be used.

The sulfur-based vulcanizing agent is an inorganic vulcanizing agent such as powdered sulfur (S), insoluble sulfur (S), precipitated sulfur (S), colloidal sulfur, and tetramethylthiuram disulfide (TMTD), tetraethyl An organic curing agent such as tetraethyltriuram disulfide (TETD) or dithiodimorpholine may be used. As the sulfur vulcanizing agent, specifically elemental sulfur or a vulcanizing agent for generating sulfur, for example, amine disulfide, polymeric sulfur, and the like may be used.

The organic peroxide is benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl 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 may be used.

It is preferable that the vulcanizing agent be included in an amount of 0.5 to 5.0 parts by weight based on 100 parts by weight of the raw rubber in terms of making the raw rubber less sensitive to heat and chemically stable as an appropriate vulcanizing effect.

The vulcanization accelerator refers to an accelerator that promotes a vulcanization rate or a delayed action in the initial vulcanization stage.

Examples of the vulcanization accelerator include sulfenamide-based, thiazole-based, thiuram-based, thiourea-based, guanidine-based, dithiocarbamic acid-based, aldehyde-amine-based, aldehyde-ammonia-based, imidazoline-based, xanthate-based and their Any one selected from the group consisting of combinations may be used.

Examples of the sulfenamide-based vulcanization accelerator include N-cyclohexyl-2-benzothiazylsulfenamide (CBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS), N,N-dicyclohexyl Any one selected from the group consisting of -2-benzothiazylsulfenamide, N-oxydiethylene-2-benzothiazylsulfenamide, N,N-diisopropyl-2-benzothiazolesulfenamide, and combinations thereof of sulfenamide compounds may be used.

Examples of the thiazole-based vulcanization accelerator include 2-mercaptobenzothiazole (MBT), dibenzothiazyldisulfide (MBTS), sodium salt of 2-mercaptobenzothiazole, 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 one thiazole-based compound selected from the group consisting of ethyl4-morpholinothio)benzothiazole and combinations thereof may be used.

Examples of the thiuram-based vulcanization accelerator include tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram disulfide, dipentamethylenethiuram monosulfide, and dipentamethylene. Any one thiuram-based compound selected from the group consisting of thiuram tetrasulfide, dipentamethylene thiuram hexasulfide, tetrabutyl thiuram disulfide, pentamethylene thiuram tetrasulfide, and combinations thereof may be used.

The thiourea-based vulcanization accelerator is, for example, any one selected from the group consisting of thiacarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea, and combinations thereof. compounds may 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, diphenylguanidinephthalate, and combinations thereof may be used. can

Examples of the dithiocarbamic acid-based vulcanization accelerator include zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, Zinc dibutyldithiocarbamate, zinc diamyldithiocarbamate, zinc dipropyldithiocarbamate, complex salt of zinc pentamethylenedithiocarbamate and piperidine, hexadecylisopropyldithiocarbamate zinc, octadecyl Zinc isopropyldithiocarbamate, zinc dibenzyldithiocarbamate, sodium diethyldithiocarbamate, piperidine pentamethylenedithiocarbamate, selenium dimethyldithiocarbamate, tellunium diethyldithiocarbamate, dia Any one dithiocarbamic acid-based compound selected from the group consisting of cadmium mildithiocarbamate and combinations thereof may be used.

The aldehyde-amine-based or aldehyde-ammonia-based vulcanization accelerator is, for example, an aldehyde selected from the group consisting of acetaldehyde-aniline reactants, butylaldehyde-aniline condensates, hexamethylenetetramine, acetaldehyde-ammonia reactants, and combinations thereof. -Amine-based or aldehyde-ammonia-based compounds may be used.

As the imidazoline-based vulcanization accelerator, for example, an imidazoline-based compound such as 2-mercaptoimidazoline may be used. compounds may be used.

The vulcanization accelerator may be included in an amount of 0.1 to 1.5 parts by weight based on 100 parts by weight of the raw rubber in order to maximize productivity and rubber properties through acceleration of the vulcanization rate.

The softening agent is added to the rubber composition in order to provide plasticity to the rubber to facilitate processing or to reduce the hardness of the vulcanized rubber. do. As the softening agent, any one selected from the group consisting of petroleum oils, vegetable oils and combinations thereof may be used, but the present invention is not limited thereto.

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

Representative examples of the paraffinic oil include P-1, P-2, P-3, P-4, P-5, and P-6 of Michang Oil Co., Ltd., and a representative example of the naphthenic oil is Michang oil. and N-1, N-2, and N-3 of Co., Ltd., and representative examples of the aromatic oil include A-2 and A-3 of Michang Oil Co., Ltd.

However, when the content of polycyclic aromatic hydrocarbons (hereinafter referred to as "PAHs") contained in the aromatic oil is 3% by weight or more, with the recent increase in environmental awareness, it is known that there is a high possibility of causing cancer. TDAE (treated distillate aromatic extract) oil, MES (mild extraction solvate) oil, RAE (residual aromatic extract) oil, or heavy naphthenic oil can be preferably used.

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

The TDAE oil has advantageous properties with respect to environmental factors such as cancer-causing potential of PAHs while excellent low-temperature characteristics and fuel efficiency of a tire including the TDAE oil.

The vegetable 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 , jojoba oil, macadamia nut oil, safflower oil, tung oil, and any one selected from the group consisting of combinations thereof may be used.

The softening agent is preferably used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the raw rubber in terms of improving the processability of the raw rubber.

On the other hand, the rubber composition for carcass, the raw rubber, the reinforcing filler, the vulcanizing agent, the vulcanization accelerator and the softening agent are mixed under water-containing conditions, and then extruded with a water content of less than 2% by weight to be wet It may be a master batch (Wet master batch, WMB).

When the wet master batch is formed in this way, dispersibility can be further improved, and electrical conductivity can be further improved.

The content of silica and/or carbon black included in the wet master batch may be 10 to 40 parts by weight based on 100 parts by weight of the raw rubber, and additionally required silica and/or carbon black is further mixed separately from the wet master batch. and may constitute a rubber composition for carcass.

In addition, the rubber composition for a tire carcass of the present invention may optionally further include various additives such as an additional coupling agent, a vulcanization accelerator, an anti-aging agent, or a processing aid. Any of the above various additives may be used as long as they are commonly used in the field to which the present invention pertains, and their content is not particularly limited as it depends on a compounding ratio used in a typical tire carcass rubber composition.

The coupling agent may be additionally included to improve dispersibility of the reinforcing filler.

As the coupling agent, a sulfide-based silane compound, a mercapto-based silane compound, a vinyl-based silane compound, an amino-based silane compound, a glycidoxy-based silane compound, a nitro-based silane compound, a chloro-based silane compound, a methacrylic silane compound, and combinations thereof Any one selected from the group consisting of may be used, and a sulfide-based silane compound may be preferably used.

The sulfide-based silane compound is bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(4-triethoxysilylbutyl)tetrasulfide, bis(3-tri Methoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(4-trimethoxysilylbutyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(2 -triethoxysilylethyl)trisulfide, bis(4-triethoxysilylbutyl)trisulfide, bis(3-trimethoxysilylpropyl)trisulfide, bis(2-trimethoxysilylethyl)trisulfide, bis (4-trimethoxysilylbutyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)disulfide, bis(4-triethoxysilylbutyl)disulfide, bis( 3-trimethoxysilylpropyl)disulfide, bis(2-trimethoxysilylethyl)disulfide, bis(4-trimethoxysilylbutyl)disulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl Tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-trimethoxysilylethyl-N ,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzothiazoletetrasulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, 3 - It may be any one selected from the group consisting of trimethoxysilylpropyl methacrylate monosulfide and combinations thereof.

The mercapto silane compound is 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and combinations thereof. It 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 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltri It may be any one selected from the group consisting of methoxysilane and combinations thereof.

The glycidoxy silane compound is γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane And it may be any one selected from the group consisting of combinations 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. may be any one of

The methacrylic silane compound is any one selected from the group consisting of γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl methyldimethoxysilane, γ-methacryloxypropyl dimethylmethoxysilane, 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. When the content of the coupling agent is less than 1 part by weight, the dispersibility improvement of the reinforcing filler is insufficient, so that the processability of the rubber or low fuel consumption performance may be reduced. If it exceeds 20 parts by weight, the interaction between the reinforcing filler and the rubber may Because it is too strong, it may have excellent fuel economy performance, but may adversely affect braking performance.

The vulcanization accelerator is a compounding agent used in combination with the vulcanization accelerator to complete the accelerating effect, and any one selected from the group consisting of an inorganic vulcanization accelerator, an organic vulcanization accelerator, and combinations thereof may be used. .

As the inorganic vulcanization accelerator, any one selected from the group consisting of zinc oxide (ZnO), zinc carbonate, magnesium oxide (MgO), lead oxide, potassium hydroxide, and combinations thereof can be used. there is. The organic-based 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 any one of them.

In particular, the zinc oxide and the stearic acid can be used together as the vulcanization accelerator. In this case, the zinc oxide is dissolved in the stearic acid to form an effective complex with the vulcanization accelerator to release advantageous sulfur during the vulcanization reaction. It facilitates the crosslinking reaction of rubber by making it.

When the zinc oxide and the stearic acid are used together, 0.5 to 5 parts by weight and 0.5 to 2.5 parts by weight based on 100 parts by weight of the raw rubber, respectively, to serve as an appropriate vulcanization accelerator. When the content of the zinc oxide and the stearic acid is less than the above range, the vulcanization rate is slow and productivity may be reduced.

The antioxidant is an additive used to stop the chain reaction in which the tire is automatically oxidized by oxygen. As the antioxidant, 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 and used.

The amine-based antioxidants include 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 may be used.

The phenolic antioxidants include 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 may be used.

As the quinoline-based antioxidant, 2,2,4-trimethyl-1,2-dihydroquinoline and its derivatives may be used, and specifically, 6-ethoxy-2,2,4-trimethyl-1,2-di consisting of 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 may be used.

Preferably, waxy hydrocarbon may be used as the wax.

In addition to the anti-aging action, the anti-aging agent should have high solubility in rubber, low volatility and inert rubber, and should not inhibit vulcanization. It may be included in parts by weight.

Meanwhile, a tire according to another aspect of the present invention is manufactured using the above-described rubber composition for a tire carcass of the present invention.

The tire may be a tire for a passenger car, a tire for racing, an airplane tire, a tire for an agricultural machine, 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, preferably a radial tire.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

[Production Example: Preparation of rubber composition for tire carcass]

Rubber compositions for tire carcass according to the following Comparative Examples and Examples were prepared using the compositions shown in Table 1 below. The rubber composition was prepared according to a conventional method for preparing a rubber composition.

For reference, in the comparative example, graphene was not added, in Examples 1 and 2, graphene was added, in Example 1, 10 parts by weight of graphene was added, and in Example 2, 20 parts by weight of graphene was added. It is prepared by adding a wet master batch.

comparative example Example 1 Example 2 Raw rubber ¹⁾ 100 100 - Wet Masterbatch ²⁾ - - 169 graphene ³⁾ - 10 - carbon black ⁴⁾ 50 50 20.59 process oil ⁵⁾ 9 9 - ZnO/stearic acid 3/1.5 3/1.5 - Anti-aging agent ⁶⁾ 0.75 0.75 - wax ⁷⁾ 1.5 1.5 - Vulcanizing agent (sulfur) 3.44 3.44 - vulcanization accelerator ⁸⁾ 0.4 0.4 -

(Unit: parts by weight) 1) Raw rubber: STR20 (Teck Bee Hang Co.)

2) Wet master batch (WMB): 100 parts by weight of raw rubber, 20 parts by weight of graphene, 9 parts by weight of process oil, 3 parts by weight of zinc oxide, 1.5 parts by weight of stearic acid, 0.75 parts by weight of antioxidant, 1.5 parts by weight of wax, 3.44 parts by weight of a vulcanizing agent (sulfur), 0.4 parts by weight of a vulcanization accelerator, and 29.41 parts by weight of carbon black are mixed under water-containing conditions, and then extruded with a water content of less than 2% by weight

3) Graphene: product of Hanwha Chemical

4) Carbon black: HAF N330/GPF N660 (Korea Carbon Co.)

5) Process oil: The total content of PAHs (PolyCyclic Aromatic Hydocarbons) component is 3% by weight or less, the kinematic viscosity is 95 (210°F SUS), the aromatic component in the softener is 10% by weight, the naphthenic component is 40% by weight, and the paraffinic component is TDAE oil containing 40% by weight

6) Anti-aging agent: 6PPD

7) Wax: waxy hydrocarbon

8) Vulcanization accelerator: N-cyclohexyl-2-benzothiazylsulfenamide (CBS)

[Experimental Example: Measurement of physical properties of rubber composition of Preparation Example]

Mooney viscosity, hardness, modulus, etc. were measured for the rubber specimens prepared in Comparative Examples and Examples, and the results are shown in Table 2.

division comparative example Example 1 Example 2 Raw material properties Mooney Viscosity (ML1+4 (100 ℃)) 53 53 53 tensile properties Hardness 64 63 64 100% modulus kgf/cm ² 26.0 26.7 26.8 300% modulus 130 130 132 The tensile strength 212 218 249 elongation % 442 445 493 viscoelastic properties 60℃ tanδ Index 100 99 101 electrical conductivity resistance Ω 2.73E+07 1.73E+07 1.43E+06

1) Mooney viscosity (ML1+4 (100 ℃)) was obtained using a Mooney MV2000 (Alpha Technology) instrument at a large rotor, preheating for 1 minute, rotor operation time for 4 minutes, and a temperature of 100 ℃.

2) Hardness was measured according to DIN 53505.

3) Tensile properties were measured using an Instron tester according to the ASTM D412 test method.

4) Viscoelastic properties were measured using a DMTS tester while performing strain sweeps up to 0.5 to 10% of dynamic strain under the conditions of 10 Hz and 60 ℃. At this time, the lower the 60 ℃ tanδ value, the lower the rotational resistance performance. The comparative example was expressed by indexing it as a reference (100), and the larger the indexing value, the higher the rolling resistance performance.

5) Electrical conductivity was measured at room temperature using a STA (Semiconductor Test Analyzer) tester with a 4-Point-Probe tip.

As shown in Table 2, as a result of the electrical conductivity measurement, the case of Examples 1 and 2 showed a lower resistance value than that of the Comparative Example, and as a result of the addition of graphene, the electrical conductivity tends to be improved. In the case of Example 2, the resistance value is very low compared to that of Example 1 and Comparative Example, which indicates that the dispersibility of the rubber composition is further improved by wet master batching, and the electrical conductivity properties are also greatly increased.

Considering the above results comprehensively, only a small amount of graphene added (Example 1) shows a result of improving electrical conductivity and other physical properties compared to the comparative example, and when dispersing by wet masterbatch (Example 2) ), it was confirmed that more improved electrical conductivity properties were exhibited.

Although the preferred embodiment of the present invention has been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also provided. is within the scope of the

Claims (5)

Including raw material rubber, reinforcing filler, vulcanizing agent, vulcanization accelerator and softening agent,
The reinforcing filler comprises graphene,
The content of the graphene is 10 to 20 parts by weight based on 100 parts by weight of the raw rubber,
The rubber composition for tire carcass, characterized in that the raw rubber, the graphene, the vulcanizing agent, the vulcanization accelerator and the softening agent are mixed under water-containing conditions and then subjected to a wet master batch (WMB). According to claim 1,
The wet master batch is a rubber composition for a tire carcass, characterized in that it is extruded with a moisture content of less than 2% by weight. According to claim 1,
The raw rubber is polyisoprene rubber, polybutadiene rubber, conjugated diene rubber, vinyl aromatic copolymer rubber, nitrile copolymer rubber, hydrogenated nitrile rubber (NBR), olefin rubber, ethylene-propylene rubber modified with maleic acid. , butyl rubber, copolymer of isobutylene and vinyl aromatic monomer, copolymer of isobutylene and diene monomer, acrylic rubber, halogenated rubber and chloroprene rubber, characterized in that at least one selected from the group consisting of tire carcass rubber composition. According to claim 1,
The reinforcing filler is a rubber composition for a tire carcass, characterized in that it comprises any one selected from the group consisting of silica, carbon black, and mixtures thereof. A tire manufactured using the rubber composition for a tire carcass according to any one of claims 1 to 4.