KR101114858B1 - Rubber composition for tire innerliner and tire manufactured by using the same - Google Patents

Abstract

The present invention relates to a rubber composition for a tire inner liner and a tire manufactured using the same, comprising 100 parts by weight of raw rubber including 30 to 100 parts by weight of halobutyl rubber and 0 to 70 parts by weight of natural rubber, and an alkyl-phenolic resin. It provides a rubber composition for a tire inner liner comprising 2 to 20 parts by weight of a mixed homogenizer including a mixture of a coumarone-indene resin and an olefin resin.

The rubber inner liner rubber composition has a simple structure and a manufacturing method of the tire inner liner, and improves air permeability, fatigue resistance and heat aging resistance, and also has excellent adhesion to the carcass layer.

Tire, inner liner, rubber composition, halobutyl rubber, natural rubber, mixed homogenizer, alkylphenol resin, coumarone indene resin, olefin resin, carbon black

Description

RUBBER COMPOSITION FOR TIRE INNERLINER AND TIRE MANUFACTURED BY USING THE SAME}

The present invention relates to a rubber composition for a tire inner liner and a tire manufactured using the same. More particularly, the homogeneity between natural rubber and halobutyl rubber that is difficult to mix with a rubber composition for tire inner liner having a two-layer structure is difficult. It relates to a rubber composition for a tire innerliner and a tire produced using the same.

Looking at the internal structure of a conventional tubeless pneumatic tire from the inner side, the second inner liner that maintains the tire air pressure, the first inner liner acting as a complete layer of the second inner liner and the carcass layer, and the body of the tire It consists of a carcass layer.

The compounding rubber used in the carcass layer is composed of a natural rubber-based rubber composition having a ratio of 60:40 to 90:10 of normal natural rubber and styrene-butadiene rubber in order to maintain textile and adhesion. The second inner liner uses butyl rubber in an amount of 60 to 100 parts by weight in order to maintain the air pressure of the tire, and in particular, in recent years, 100 parts by weight of butyl rubber is used to further improve air permeability.

The tubeless inner liner is a portion that contacts air injected into the tire from inside the edge of the tire, and requires physical properties such as low air permeability, high carcass adhesion, excellent fatigue resistance, and heat aging stability.

In particular, low air permeability is one of the most important physical properties of the inner liner because it not only improves the driving stability by keeping the tire air pressure constant, but also reduces the rolling resistance of the tire and reduces fuel economy due to the thickness reduction of the inner liner. .

On the other hand, the prior art for reducing the air permeability has been disclosed a number of techniques relating to the rubber composition to improve the air permeability by increasing the content of halobutyl rubber.

Japanese Yokohama Rubber has disclosed a number of techniques for low permeability thermoplastic elastomer compositions in Japan, the United States, and the Republic of Korea. In particular, Korean Laid-Open Patent Publication No. 1999-36051 discloses a low-permeability thermoplastic elastomer composition comprising a barrier resin composition in a thermoplastic elastomer having a thermoplastic resin composition as a continuous phase and a rubber composition as a dispersed phase.

The thermoplastic elastomer composition has a phase structure in which the barrier resin composition is flatly dispersed in the thermoplastic elastomer, and is rich in flexibility, excellent in gas permeability, and also enables lightweight tires.

However, the technique has a problem of inserting one more layer in the tire manufacturing process, and when replacing the first and the second inner liner with the thermoplastic elastomer composition, problems such as fatigue resistance and heat aging resistance occur. .

An object of the present invention is to improve the mixing homogeneity of halobutyl rubber and natural rubber, to improve the air permeability, fatigue resistance and heat aging resistance while simplifying the composition and manufacturing method of the tire inner liner, adhesion to the carcass layer It is to provide a rubber composition for a tire inner liner having excellent performance.

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

In order to achieve the above object, the rubber composition for a tire inner liner according to an embodiment of the present invention 100 parts by weight of raw rubber, including 30 to 100 parts by weight of halobutyl rubber and 0 to 70 parts by weight of natural rubber, and alkyl-phenol 2 to 20 parts by weight of a mixed homogenizer including a mixture of a resin, a coumarone-indene resin, and an olefin resin.

The mixed homogenizer may include 1 to 50 parts by weight of the alkyl-phenolic resin, 1 to 50 parts by weight of the coumarone-indene-based resin, and 1 to 50 parts by weight of the olefinic resin.

The alkyl-phenol-based resin has a weight average molecular weight of 500 to 1500, a softening point of 85 to 105 ℃, the coumarone-indene-based resin has a weight average molecular weight of 1500 to 2500, a softening point of 90 to 150 ℃, The olefin resin may have a weight average molecular weight of 1500 to 2000, and a softening point of 85 to 110 ° C.

The rubber composition for the tire inner liner may further include 20 to 70 parts by weight of carbon black having a DBP oil absorption of 50 to 100 ml / 100 g, a tint value of 30 to 80, and an iodine adsorption amount of 20 to 80 mg / g. have.

A tire according to another embodiment of the present invention is manufactured by using the tire innerliner rubber composition.

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

The rubber composition for the tire inner liner is 100 parts by weight of raw rubber including 30 to 100 parts by weight of halobutyl rubber and 0 to 70 parts by weight of natural rubber, and an alkyl-phenol-based resin, a coumarone-indene-based resin and an olefin-based resin. 2 to 20 parts by weight of the mixed homogenizer including the mixture.

As the raw material rubber, halobutyl rubber can be preferably used.

The halobutyl rubber is a type of isobutylene-isoprene rubber (IIR) in which isobutylene and a small amount of isoprene are ion-polymerized in a liquid state at a low temperature to halogenate the butyl rubber. The halobutyl rubber includes bromo butyl rubber (BIIR) and chloro butyl rubber (CIIR), which can be prepared by reacting a bromine atom or a chlorine atom in a state where butyl rubber is dissolved in a light aliphatic hydrocarbon such as hexane. Commercially used halobutyl rubber usually contains 1.9 to 2.1 wt% bromine or 1.1 to 1.3 wt% chlorine.

The halobutyl rubber may have a Mooney viscosity of 35 to 40, and may be included in 30 to 100 parts by weight based on 100 parts by weight of the raw rubber. The halobutyl rubber having a Mooney viscosity may be included in an amount of 30 parts by weight or more based on 100 parts by weight of the raw material rubber, thereby improving air permeability of the tire inner liner.

The halobutyl rubber may be used as long as it has a Mooney viscosity in the above range, but is not particularly limited in the present invention. In particular, the tire inner liner rubber composition may improve the fatigue resistance and air permeability as it contains a mixed homogeneous agent can lower the content of halobutyl rubber compared to the rubber composition for the tire inner liner. Therefore, the halobutyl rubber may be included in 50 to 80 parts by weight based on 100 parts by weight of the raw rubber.

The raw rubber except for the halobutyl rubber is preferably a natural rubber, the content of the natural rubber may be 0 to 70 parts by weight based on 100 parts by weight of the raw rubber except for the content of the halobutyl rubber, preferably 20 to It may be 50 parts by weight.

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

The general natural rubber may be used as long as it is known as natural rubber, and the origin and the like are not limited. 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. Therefore, the natural rubber includes, in addition to the natural rubber containing cis-1,4-polyisoprene as a main agent, for example, a natural containing trans-1,4-isoprene as a main agent such as a balata, which is a kind of rubber of South American sapotagua. Rubber may also be included.

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

The mixed homogenizer is added to improve the air permeability and fatigue resistance of the tire inner liner, and to adjust the content of halobutyl rubber to improve adhesive performance.

The mixed homogeneous agent includes a mixture of an alkyl-phenolic resin, a coumarone-indene-based resin, and an olefinic resin, and is included in an amount of 2 to 20 parts by weight based on 100 parts by weight of the raw material rubber. When the content of the mixed homogeneous agent is less than 2 parts by weight based on 100 parts by weight of the raw material rubber, the air permeability or fatigue resistance of the desired rubber inner liner rubber composition may not be achieved, and when the content exceeds 20 parts by weight The processability of the may be lowered, fatigue resistance, rotational resistance performance and elongation of the tire inner liner may be lowered.

The alkyl-phenol-based resin has a weight average molecular weight of 500 to 1500, a softening point of 85 to 105 ℃, the coumarone-indene-based resin has a weight average molecular weight of 1500 to 2500, a softening point of 90 to 150 ℃, It is preferable to use an olefin resin having a weight average molecular weight of 1500 to 2000 and a softening point of 85 to 110 ° C, because the pressure-sensitive adhesive is mixed well at a temperature below the rubber compounding temperature.

The mixed homogeneous agent may include 10 to 30 parts by weight of the alkyl-phenol-based resin, 1 to 15 parts by weight of the coumarone-indene-based resin, and 10 to 50 parts by weight of the olefin resin. When the mixed homogeneous agent includes the alkyl-phenolic resin, the coumarone-indene-based resin and the olefin-based resin in the content range, the air permeability of the tire inner liner is improved by improving the mixed homogeneity of halobutyl rubber and natural rubber. In addition, the fatigue resistance and heat aging resistance may be improved, and the adhesion to the carcass layer may also be improved.

Specifically, the alkyl-phenol resin may be a styrene resin, and the coumarone-indene-based resin may include one containing 5 to 15 parts by weight of coumarone and 20 to 50 parts by weight of indene. The resin may be prepared by reacting isobutylene and maleic anhydride, but the present invention is not limited thereto.

The tire inner liner rubber composition may further include carbon black as a reinforcing filler.

The carbon black may have a DBP oil absorption of 50 to 100 ml / 100 g, a tint value of 30 to 80, and an iodine adsorption amount of 20 to 80 mg / g, but the present invention is not limited thereto. When using carbon black having a DBP oil absorption of 50 to 100ml / 100g, a tint of 30 to 80, and an iodine adsorption amount of 20 to 80mg / g, the dispersion degree of carbon black as a rubber composition for tire innerliner Can be effectively improved.

The carbon black may be a general GPF (General Purpose Furnace) grade carbon black, for example, can be used N660 grade.

The carbon black may be included in an amount of 20 to 70 parts by weight based on 100 parts by weight of the raw material rubber. When the content of the carbon black is less than 20 parts by weight, the reinforcing performance by the carbon black as a filler may be reduced, and when the content of the carbon black exceeds 70 parts by weight, the processability of the rubber composition may be deteriorated.

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

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

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

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

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

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

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

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

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

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

Examples of the dithiocarbamic acid-based vulcanization accelerators include ethylphenyldithiocarbamate zinc, butylphenyldithiocarbamate zinc, sodium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate Zinc dibutyl dithiocarbamate, zinc diamyldithiocarbamate, zinc dipropyldithiocarbamate, zinc complex of pentamethylenedithiocarbamate and piperidine, zinc hexadecylisopropyldithiocarbamate, octa Decylisopropyldithiocarbamate zinc dibenzyldithiocarbamate zinc, sodium diethyldithiocarbamate, pentamethylenedithiocarbamate piperidine, dimethyldithiocarbamate selenium, diethyldithiocarbamate tellurium, Any one dithiocarbamic acid compound selected from the group consisting of diamyl dithiocarbamate cadmium and combinations thereof can be used.

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

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

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

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

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

In particular, the zinc oxide and the stearic acid may be used together as the vulcanization accelerator, in which case the zinc oxide is dissolved in the stearic acid to form an effective complex with the vulcanization accelerator, thereby releasing advantageous sulfur during the vulcanization reaction. It facilitates the crosslinking reaction of the rubber.

When using the zinc oxide and the stearic acid together may be used in 1 to 5 parts by weight and 0.5 to 3 parts by weight with respect to 100 parts by weight of the raw material rubber, respectively, to serve as a suitable vulcanization accelerator.

The tire inner liner rubber composition may further include a filler in addition to the carbon black. The filler may be any one selected from the group consisting of silica, calcium carbonate, clay (aluminum hydride silicate), aluminum hydroxide, lignin, silicate, talc and combinations thereof.

The silica has a nitrogen adsorption specific surface area (N ₂ SA) of 100 to 180 m ₂ / g, CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area may be 110 to 170 m 2 / g, but the present invention This is not limited to this.

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

The silica can be used both wet or dry method, and commercially available products such as ultra-sil VN2 (manufactured by Degussa Ag), ultra-sil VN3 (manufactured by Degussa Ag), Z1165MP (manufactured by Rhodia) or Z165GR (manufactured by Rhodia) Can be.

The silica may be included in an amount of 20 to 90 parts by weight based on 100 parts by weight of the raw material rubber, preferably 30 to 70 parts by weight, and more preferably 40 to 60 parts by weight. When the content of the silica is less than 20 parts by weight, the strength improvement of the rubber may be insufficient and the braking performance of the tire may be reduced, and when the content of the silica exceeds 90 parts by weight, wear performance may be reduced.

When the rubber composition for tire innerliner includes silica, a coupling agent may be further included to improve dispersibility of the silica.

Examples of the coupling agent include a sulfide silane compound, a mercapto silane compound, a vinyl silane compound, an amino silane compound, a glycidoxy silane compound, a nitro silane compound, a chloro silane compound, a methacryl silane compound, and a combination thereof. It can be used any one selected from the group consisting of, sulfide-based silane compound can be preferably used.

The sulfide-based silane compound may be 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-trimethoxy Sisylethyl) disulfide, bis (4-trimethoxysilylbutyl) disulfide, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethyl Thiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide and combinations thereof It may be any one selected from the group consisting of.

The mercapto silane compound includes 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl triethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and combinations thereof. It may be any one selected from the group consisting of. The vinyl silane compound may be any one selected from the group consisting of ethoxysilane, vinyltrimethoxysilane, and combinations thereof. The amino 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 compounds include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane And combinations thereof may be any one selected from the group consisting of. The nitro 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. It can be any one.

The methacrylic silane compound is any one selected from the group consisting of γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl methyldimethoxysilane, γ-methacryloxypropyl dimethyl methoxysilane, and combinations thereof Can be.

The coupling agent may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the raw material rubber to improve dispersibility of the silica. When the content of the coupling agent is less than 1 part by weight, the improvement of dispersibility of silica may be insufficient, resulting in deterioration of workability of rubber or low fuel consumption performance, and in the case of more than 20 parts by weight, the interaction between silica and rubber is too strong, resulting in low fuel efficiency. May be good but the braking performance may be very poor.

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

However, it is known that cancer is more likely to occur when the content of polycyclic aromatic hydrocarbons (hereinafter referred to as "PAHs") included in the aromatic oils is 3% by weight or more with the recent increase of environmental awareness. For example, treated distillate aromatic extract (TDAE) oil, mild extraction solvate (MES) oil, residual aromatic extract (RAE) oil or heavy naphthenic oil may 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 the possibility of causing cancer of PAHs while improving the low-temperature characteristics and fuel efficiency of the tire inner liner including the TDAE oil.

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

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

The anti-aging agent is an additive used to stop the chain reaction in which the tire is automatically oxidized by oxygen. As the anti-aging agent, any one selected from the group consisting of 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 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.

Wax hydrocarbon may be preferably used as the wax.

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

The pressure-sensitive adhesive further improves the tack performance between the rubber and the rubber, and 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.

Specifically, the pressure-sensitive adhesive may be preferably a C5-based resin or a C9-based resin, and commercially, Exxon's Escorez 1100, Kolon Emulsion Coumarone Indene Resin, and the like may be used.

The pressure-sensitive adhesive may be included in 2 to 4 parts by weight based on 100 parts by weight of the raw material rubber. When the content of the pressure-sensitive adhesive is less than 2 parts by weight based on 100 parts by weight of the raw material rubber, the adhesive performance may be detrimental, and when the content of the pressure-sensitive adhesive is more than 4 parts by weight, rubber properties may be reduced.

The rubber inner liner rubber composition may be prepared through a conventional two-step continuous manufacturing process. That is, during the finishing step in which the first step of thermomechanical treatment or kneading at a maximum temperature ranging from 110 to 190 ° C., preferably from 130 to 180 ° C. (called the “production” step), and the crosslinking system are mixed, But may be prepared in a suitable mixer using a second step (called "non-production" step) of mechanical treatment at a low temperature of less than 110 ℃, for example 40 to 100 ℃, but the present invention is not limited thereto. .

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

Tire according to another embodiment of the present invention is manufactured using the rubber composition for the tire inner liner. The method for manufacturing a tire using the rubber composition for tire innerliner can 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 tire inner liner of the present invention improves the mixing homogeneity of halobutyl rubber and natural rubber, improves air permeability, fatigue resistance and heat aging resistance while simplifying the construction and manufacturing method of tire inner liner. The adhesiveness to the casing layer is also excellent.

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.

[Production Example: Production of Rubber Composition]

After mixing in a Banbury mixer at the mixing ratio shown in Table 1 and then released at a constant temperature to prepare a rubber composition for a tire innerliner according to the following examples and comparative examples.

Specifically, the raw material rubber, two-thirds of carbon black, mixed homogenizer, pressure-sensitive adhesive, zinc oxide, stearic acid and softener were mixed in a Banbury mixer and then discharged at 160 ° C. 1/3 of the carbon black and softener were added to the blended rubber, mixed in a Banbury mixer, and discharged at 160 ° C. A vulcanizing agent and a vulcanization accelerator were added to the blended rubber, mixed in a Banbury mixer, and released after 1 minute and 30 seconds.

[Table 1] (Unit: parts by weight)

Comparative example Example Natural rubber 20 20 Halobutyl rubber ¹⁾ 80 80 Carbon black ²⁾ 55 55 Mixed homogenizer ³⁾ - 10 Adhesive 1 ⁴⁾ 3.0 3.0 Adhesive 2 ⁵⁾ 3.0 3.0 Softener ⁶⁾ 6.0 6.0 Zinc oxide 4.0 4.0 Stearic acid 1.0 1.0 Vulcanization accelerator 1 ⁷⁾ 1.5 1.5 Vulcanization accelerator 2 ⁸⁾ 1.0 1.0 Vulcanizing agent ⁹⁾ 1.0 1.0

1) Halobutyl Rubber: CB1240 ^？ (manufactured by Lanxess)

2) Carbon black: GPF grade carbon black with DBP oil absorption of 50-100ml / 100g, tint value of 30-80, iodine adsorption amount of 20-80mg / g

3) Mixed Homogenizer: HMA-201 (Yujin emulsified product, Coumarone- with 33 weight parts of alkyl-phenolic resin having a weight average molecular weight of 1000 and a softening point of 95 ° C., 2000 and a weight average molecular weight of 2000 ° C. 33 parts by weight of indene resin and a weight average molecular weight of 1700, mixed with 34 parts by weight of olefin resin having a softening point of 100 ° C.)

4) Adhesive 1: C-5 resin

5) Adhesive 2: C-9 resin

6) Softener: N-2 Oil (Unchanged Oil)

Vulcanization Accelerator 1: Dibenzothiazyl disulfide (MBTS)

Vulcanization accelerator 2: N-tert-butyl-2-benzothiazylsulfenamide (TBBS)

9) Vulcanizer: Sulfur

Experimental Example: Measurement of Physical Properties of Prepared Rubber Composition

The rubber compositions prepared in Examples and Comparative Examples were vulcanized at 160 ° C. for 20 minutes, and tensile properties, Tanδ fatigue resistance, crack resistance, and heat resistance were measured according to ASTM regulations for the vulcanized sheet. It summarized in Table 2.

TABLE 2

Comparative example Example Tensile Properties Hardness 52 51 100% modulus 13 12 Elongation rate 756 791 The tensile strength 80 82 Fatigue resistance K cycle 10.0 11.0 Crack resistance mm / 8 million cyc 3.7 2.9 tanδ ＠ 60 ℃ 0.247 0.245 Air permeability cc? cm / m ² ? hr? atm
6.9E + 12 6.0E + 12

Hardness was measured after 1 hour in the combustion chamber by ASTM shore-A method.

100% modulus (kgf / cm ² ) was measured by a tensile tester (Instron Co., Ltd.) by cutting the specimen into dumbbell-shaped, 100% modulus refers to the stress acting on the specimen when the specimen is stretched 100%.

Elongation (%) was measured by the method of expressing the strain value in% until a test piece was cut in the tensile tester (made by Instron).

Tensile strength (kgf / cm ² ) was measured by the method of ASTM D 790.

Fatigue resistance was measured by ASTM method and measured under 120% extension.

Crack resistance was measured using a Demmattia tester according to ASTM regulations.

tan delta (Tan Delta) was evaluated using a Dynamic Mechenical Thermal Spectrometer (DMTS) and temperature sweep was performed. Test conditions were performed under tension and torque type under 0.5% strain and 10Hz.

Air permeability is a value measured based on ASTM test conditions at a measurement temperature of 30 ° C. using a specimen having a diameter of 50 mm and a thickness of 250 μm. The unit is cc? Cm / m ² ? Hr? Atm.

Referring to Table 2, it can be seen that the rubber composition of the embodiment has excellent tensile resistance and crack resistance, and excellent air permeability and fatigue resistance compared to the rubber composition of the comparative example.

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 (5)

100 parts by weight of raw rubber, including 30 to 100 parts by weight of halobutyl rubber and 0 to 70 parts by weight of natural rubber, and Mixed homogenizer including styrene resin, coumarone-indene resin containing coumarone and indene in a weight ratio of 5:20 to 15:50, and a mixture of olefin resins prepared by reacting isobutylene and maleic anhydride. 2 to 20 parts by weight, 20 to 70 parts by weight of carbon black having a DBP oil absorption of 50 to 100 ml / 100 g, a tint value of 30 to 80, and an iodine adsorption amount of 20 to 80 mg / g A rubber composition for a tire innerliner comprising a. The method of claim 1, The mixed homogenizer 1 to 50 parts by weight of the styrene resin, 1 to 50 parts by weight of the coumarone-indene-based resin and 1 to 50 parts by weight of the olefin resin A rubber composition for a tire innerliner comprising a. The method of claim 1, The styrene resin has a weight average molecular weight of 500 to 1500, a softening point of 85 to 105 ℃, The kumaron-indene-based resin has a weight average molecular weight of 1500 to 2500, a softening point of 90 to 150 ℃, The olefin resin has a weight average molecular weight of 1500 to 2000, a softening point of 85 to 110 ℃ rubber composition for inner liner. delete A tire manufactured using the rubber composition for tire innerliner according to any one of claims 1 to 3.