KR101165295B1 - Rubber composition for tire and method of manufacturing the same - Google Patents

Abstract

The present invention comprises 100 parts by weight of raw material rubber, 30 to 90 parts by weight of filler, 0.5 to 4 parts by weight of vulcanizing agent, and 4 to 10 parts by weight of antioxidant, wherein the residual ratio of the antioxidant after vulcanization is 90% or more by weight. Provided is a rubber composition for a tire. The tire rubber composition may improve the heat aging resistance of the rubber for tires and increase the crack resistance to extend the life of the rubber, and may also reduce the blooming phenomenon by the anti-aging agent.

In addition, the present invention is a first step of kneading the first group composition comprising the raw material rubber, filler and other additives, and a second step of kneading the second group composition comprising a vulcanizing agent and an anti-aging agent with the first group composition It provides a method for producing a rubber composition for a tire comprising a. By using the rubber produced by the method of manufacturing the rubber composition for a tire, it is possible to improve the heat aging resistance of the rubber for tires and to increase the crack resistance to extend the life of the rubber, and to reduce the blooming phenomenon by the anti-aging agent.

Crack resistant, anti aging, heat aging resistant, kneading, order of loading, tire, blooming

Description

RUBBER COMPOSITION FOR TIRE AND METHOD OF MANUFACTURING THE SAME

The present invention relates to a rubber composition for a tire and a method for manufacturing the same, wherein the rubber composition for a tire can improve the heat aging resistance and increase the crack resistance to extend the life of the rubber, and also reduce the blooming phenomenon by the anti-aging agent, and It relates to a manufacturing method thereof.

In general, the aging of the rubber is caused by the attack of the double bond portion present in the polymer chain of the rubber by oxygen, ozone, heat, etc., there is a disadvantage that the durability of the rubber product due to the aging phenomenon of the rubber. And in order to improve such a fall of durability, rubber compounding is used including the anti-aging agent.

The mechanism of anti-aging that the anti-oxidant does in rubber is to prevent the anti-aging agent present in the rubber composition from moving to the rubber surface and to form a protective film on the rubber surface. It is known to be done.

The rubber used for each part of the tire such as the tread part of the tire also needs an anti-aging effect, but in particular, the bead or sidewall part of the pneumatic tire needs a characteristic of less heat aging or cracking. In order to obtain a proper anti-aging effect, various attempts have been made to use anti-aging agents in rubber compositions of different kinds, to adjust the amount used or to mix them in a specific ratio, but they do not obtain sufficient anti-aging effects or bloom. There is a disadvantage that the quality is disadvantageous, such as a phenomenon occurs.

An object of the present invention comprises 100 parts by weight of the raw material rubber, 30 to 90 parts by weight of filler, 0.5 to 4 parts by weight of vulcanizing agent, and 4 to 10 parts by weight of anti-aging agent, the residual ratio of the antioxidant after vulcanization is 90 It is to provide a rubber composition for a tire that is more than%.

Another object of the present invention is a first step of kneading a first group composition comprising raw rubber, filler and other additives, and a second step of kneading a second group composition comprising a vulcanizing agent and an anti-aging agent with the first group composition. It is to provide a method for producing a rubber composition for a tire comprising the step.

In order to achieve the above object, the rubber composition for a tire according to an embodiment of the present invention is 100 parts by weight of raw material rubber, 30 to 90 parts by weight of filler, 0.5 to 4 parts by weight of vulcanizing agent, and 4 to 10 parts by weight of anti-aging agent It includes, and the residual ratio of the anti-aging agent after vulcanization is 90% (weight / weight) or more.

The raw material rubber may be 30 to 70 parts by weight of natural rubber and 30 to 70 parts by weight of synthetic rubber.

The anti-aging agent may be N- (1,3-dimethylbutyl) -N-phenyl-p-phenylenediamine (N- (1,3-Dimethybutyl) -N-phenyl-p-phenylenediamine), poly (2,2, 4-trimethyl-1,2-dihydroquinoline (Poly (2,2,4-trimethyl-1,2-dihydroquinoline)), wax and a combination thereof may be any one selected from the group consisting of.

The rubber composition for a tire may be prepared by kneading the first group composition including the raw material rubber and the filler, and then kneading the second group composition including a vulcanizing agent and an anti-aging agent with the first group composition.

Still another object of the present invention is a first step of kneading a first group composition comprising raw rubber, fillers and other additives, and a second group composition comprising a vulcanizing agent and an anti-aging agent and a first group composition. It is to provide a method for producing a rubber composition for a tire comprising two steps.

The first step is made for 1 to 2 minutes at a temperature of 160 to 190 ℃, the second step may be made for 1 to 4 minutes at a temperature of 110 to 150 ℃.

The first group composition comprises the raw material rubber 30 to 70 parts by weight of natural rubber and 30 to 70 parts by weight of synthetic rubber, the filler comprises 30 to 90 parts by weight based on 100 parts by weight of the raw material rubber, the second The group composition may include 0.5 to 4 parts by weight of the vulcanizing agent based on 100 parts by weight of the raw material rubber, and may include 4 to 10 parts by weight of the anti-aging agent based on 100 parts by weight of the raw material rubber.

The anti-aging agent may be N- (1,3-dimethylbutyl) -N-phenyl-p-phenylenediamine (N- (1,3-Dimethybutyl) -N-phenyl-p-phenylenediamine), poly (2,2, 4-trimethyl-1,2-dihydroquinoline (Poly (2,2,4-trimethyl-1,2-dihydroquinoline)), wax and a combination thereof may be any one selected from the group consisting of.

Still another object of the present invention is to provide a tire manufactured using the method for producing a rubber composition for a tire.

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

(Rubber composition for tires)

The rubber composition for a tire according to an embodiment of the present invention includes a raw material rubber, a filler, a vulcanizing agent, and an anti-aging agent, and the residual ratio of the anti-aging agent after vulcanization is 90% (weight / weight) or more.

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 modified natural rubber.

The general natural rubber may be used as long as it is known as a natural rubber, the country of 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. Accordingly, the natural rubber includes, in addition to natural rubber containing cis-1,4-polyisoprene as a main agent, for example, natural containing trans-1,4-isoprene as a main agent such as balata, which is a kind of rubber of South American sapotaceae. Rubber may also be included.

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

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

The synthetic rubber may preferably be butadiene rubber. When the butadiene rubber is used as the synthetic rubber, there is an advantageous effect in terms of improving resilience and wear resistance.

The raw material rubber may preferably include 30 to 70 parts by weight of the natural rubber and 30 to 70 parts by weight of the synthetic rubber, more preferably 40 to 60 parts by weight of the natural rubber and 40 to 60 parts by weight of the synthetic rubber. can do.

When the raw material rubber contains less than 30 parts by weight of the natural rubber, the durability of the tire may be lowered, and when it contains more than 70 parts by weight, fatigue resistance may be disadvantageous. When the raw material rubber contains less than 30 parts by weight of the synthetic rubber, fatigue resistance may be detrimental, and when it contains more than 70 parts by weight, aging performance may be reduced.

In particular, when using the rubber composition for tire beads, the raw material rubber may include 30 to 50 parts by weight of the natural rubber and 50 to 70 parts by weight of the synthetic rubber. When the raw material rubber includes the natural rubber and the synthetic rubber in the content range, there is an advantageous effect in that fatigue resistance, crack resistance, and resilience can be increased.

In addition, when the rubber composition is used for the tire sidewall, the raw material rubber may include 50 to 70 parts by weight of the natural rubber and 30 to 50 parts by weight of the synthetic rubber. When the raw material rubber includes the natural rubber and the synthetic rubber in the content range, there is an advantageous effect in that aging resistance and durability can be increased.

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

The carbon black may have a DBP (n-dibutyl phthalate) oil absorption of 60 to 180cc / 100g, a Tint value of 50 to 120%, and an I ₂ adsorption amount of 30 to 100 mg / g, preferably The carbon black may have a DBP (n-dibutyl phthalate) oil absorption of 80 to 100cc / 100g, a Tint value of 50 to 100%, and an I ₂ adsorption amount of 30 to 50 mg / g. When the carbon black having the above-mentioned DBP (n-dibutyl phthalate) oil absorption, tint (Tint) value and I ₂ adsorption amount is in the above range, rubber having appropriate hardness, modulus and durability can be manufactured.

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 of 110 to 170 m 2 / g used It can be used, but the present invention is not limited thereto. When using the silica in the nitrogen adsorption specific surface area and CTAB adsorption specific surface area in the above range it can be produced a rubber having an excellent durability with an appropriate reinforcing effect.

The filler may be included in 30 to 90 parts by weight, preferably 40 to 75 parts by weight based on 100 parts by weight of the raw material rubber. When the rubber composition for the tire contains less than 30 parts by weight of the filler, the reinforcing effect by the filler may be insignificant, and when the filler contains more than 90 parts by weight, the exothermic performance and crack resistance may be reduced. have.

In particular, when the rubber composition is for beads, the filler may include 70 to 75 parts by weight of the carbon black with respect to 100 parts by weight of the raw material rubber. When the content of the filler is in the above range, the hardness and modulus of the rubber may be improved, so that the strain may be less and the durability may be improved.

In addition, when the rubber composition is for side walls, the filler may include 40 to 50 parts by weight of the carbon black with respect to 100 parts by weight of the raw material rubber. When the content of the filler is in the above range, the reinforcing effect of the rubber may be reduced, but may be favorable to heat generation and excellent crack resistance.

The rubber composition may further include other fillers selected from the group consisting of calcium carbonate, clay (aluminum hydrated silica), aluminum hydroxide, lignin, silicate, talc, and combinations thereof.

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.

Sulfur may be preferably used as the vulcanizing agent, and the vulcanizing agent may be included in an amount of 0.5 to 4 parts by weight, and preferably 3 to 4 parts by weight, based on 100 parts by weight of the raw material rubber. When the vulcanizing agent is included in an amount of 0.5 to 4 parts by weight based on 100 parts by weight of the raw material rubber, it is preferable in that the raw rubber is less sensitive to heat and chemically stable as an appropriate vulcanizing effect.

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.

As the wax, waxy hydrocarbon or the like may be preferably used.

As the anti-aging agent, N- (1,3-dimethylbutyl) -N-phenyl-p-phenylenediamine (N- (1,3-Dimethybutyl) -N-phenyl-p-phenylenediamine, 6PPD), poly (2 , 2,4-trimethyl-1,2-dihydroquinoline (Poly (2,2,4-trimethyl-1,2-dihydroquinoline), RD), waxes and combinations thereof may be used. In the case of using the anti-aging agent, ozone resistance and oxidation resistance may be improved.

The 6PPD may have a melting point (M.P.) of 41 to 51 ° C, the RD may have a M.P. of 80 to 100 ° C, and the wax may have a M.P. of 65 to 70 ° C. In the case of using the anti-aging agent in the M.P. range, the anti-aging agent is adequately liquefied at the time of incorporation of rubber, which has an advantageous effect in dispersion.

When the anti-aging agent is used in combination of 6PPD, RD and wax, the 6PPD, RD and wax may be used in a weight ratio of 1.5: 0.5: 1.5 to 4.0: 4.0: 2.0. When the anti-aging agent is composed of the combination of 6PPD, RD, and wax in the weight ratio, there is an excellent effect in heat aging resistance.

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

The anti-aging agent may have a residual ratio of the anti-aging agent after vulcanization is 90% (weight / weight) or more, preferably 90 to 95% (weight / weight). The residual ratio of the antioxidant is a ratio of the weight of the antioxidant contained in the rubber composition for the tire after vulcanization per 100 parts by weight of the raw material rubber to the weight of the anti-aging agent contained in the rubber composition for the tire before vulcanization per 100 parts by weight of the raw material rubber. It is expressed as a percentage (%).

In general, the anti-aging agent is destroyed in the manufacturing process of the tire from kneading to vulcanization, and the anti-aging agent after vulcanization remains at a low rate. / Weight) to improve the heat aging resistance, high crack resistance and can provide a rubber composition that extends the life of the rubber, it is possible to reduce the blooming phenomenon by the antioxidant.

The tire rubber composition may optionally further include various additives such as additional vulcanization accelerators, vulcanization accelerators, coupling agents, softeners or pressure-sensitive adhesives. The various additives can be used as long as it is commonly used in the field to which the present invention belongs, and their content is not particularly limited, depending on the compounding ratio used in a conventional rubber composition for tires.

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 sulfenamides, thiazoles, thiurams, thioureas, guanidines, dithiocarbamic acids, aldehydes-amines, aldehydes-ammonias, imidazolines, xanthates and the like. 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.

Examples of the thiourea vulcanization accelerators include thiourea selected from the group consisting of thiacarbamide, diethylthioiso, dibutylthiourea, trimethylthiourea, diorthotolylthiourea, and combinations thereof. System compounds can be used.

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

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

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

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

The vulcanization accelerator may be included in an amount of 0.5 to 4.0 parts by weight based on 100 parts by weight of the raw 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 rubber, respectively, to serve as a suitable vulcanization accelerator.

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. Any one selected from the group consisting of can be 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-based 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 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 dimethylmethoxysilane, and combinations thereof Can be.

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, when the content of polycyclic aromatic hydrocarbons (PAHs) contained in the aromatic oils is more than 3% by weight with the recent increase of environmental awareness, it is known that cancer is likely to occur, and treated distillate aromatic extract oil, mild extraction solvate (MES) oil, residual aromatic extract (RAE) oil or heavy naphthenic oil can be preferably used.

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

The TDAE oil is advantageous 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 rubber for tires 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 softener 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 that the processability of the rubber composition is improved.

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

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

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

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

The coal tar may be a coumarone-indene resin.

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

The pressure-sensitive adhesive may be 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 composition for a tire may be prepared by kneading the first group composition including the raw material rubber and the filler, and then kneading the second group composition including a vulcanizing agent and an anti-aging agent with the first group composition. However, any one consisting of a vulcanization accelerator, a vulcanization accelerator and a combination thereof among the other additives may be included as the first group composition or may be included as the second group composition.

The rubber composition for a tire may be included in various rubber components constituting the tire. Components of the tire include treads (tread caps and tread bases), sidewalls, sidewall inserts, apex, chafers, wire coats or innerliners, and the like. It can be preferably used as rubber for tire beads or sidewalls.

(Manufacturing method of rubber composition for tire)

Method for producing a rubber composition according to another embodiment of the present invention comprises the first step of kneading the first group composition comprising the raw rubber, filler and other additives, and the second group composition comprising a vulcanizing agent and an anti-aging agent And a second step of kneading with the first group composition.

The first step is a step of kneading the first group composition is made for 1 to 2 minutes at a temperature of 160 to 190 ℃, preferably for 1 to 2 minutes at a temperature of 180 to 190 ℃.

The first group composition includes raw rubber, fillers and other additives. Specific configurations and contents of the raw material rubber and the filler are as mentioned in the rubber composition for tires. However, any one consisting of a vulcanization accelerator, a vulcanization accelerator and a combination thereof among the other additives may be included as the first group composition or may be included as the second group composition.

The second step is a step of kneading the second group composition with the first group composition may be made for 1 to 4 minutes at a temperature of 110 to 150 ℃, may be made for 1 to 2 minutes at a temperature of 120 to 140 ℃. .

The second group composition includes a vulcanizing agent and an anti-aging agent. Specific configurations and contents of the vulcanizing agent and the anti-aging agent are the same as those mentioned in the description of the rubber composition for a tire.

An additional kneading process may be further included between the first step and the second step. Specifically, the method for preparing a rubber composition for a tire is to add a first group composition comprising a raw material rubber, a filler and other additives so as to sufficiently disperse the components of the rubber composition kneaded in the first step and the first step In order to further knead the rubber composition in order to, and may comprise a second step of kneading the rubber composition and the second group composition kneaded in the third step. In addition, the manufacturing method of the rubber composition for the tire may further add a fourth step kneading process between the third step and the second step for sufficient dispersion.

When the kneading process is all three steps in the manufacturing method of the rubber composition for the tire, the third step may be performed for 1 to 2 minutes at a temperature of 170 to 190 ℃. In addition, when the kneading process is all four steps in the manufacturing method of the rubber composition for the tire, the third step may be performed for 1 to 2 minutes at a temperature of 170 to 190 ℃, the fourth step is 160 to 180 ℃ At a temperature of 1 to 2 minutes.

In the manufacturing method of the rubber composition, unlike the usual case in which the anti-aging agent is added in the first step, the anti-aging agent is added together with the vulcanizing agent in the second step of the kneading process to improve the heat aging resistance of the rubber and crack resistance. It can improve the durability and extend the life of rubber.

That is, in general, since the process of kneading the raw material rubber and the filler in the first step is performed at a relatively high temperature, when the anti-aging agent is kneaded in the first step, destruction of the antioxidant may occur due to a chemical reaction at a high temperature. And, due to this, the heat aging performance may be significantly reduced.

However, when the anti-aging agent is introduced in the second step of delaying the addition of the anti-aging agent as much as possible, the destruction of the anti-aging agent can be prevented, thereby improving heat aging resistance and cracking resistance. It can extend the life. In addition, it is possible to reduce the blooming phenomenon caused by the movement of the antioxidant to the rubber surface by using an excessive amount of the antioxidant.

A tire according to another embodiment of the present invention is manufactured by the method for producing a rubber composition for the tire. Except as specifically mentioned in the present invention, the tire manufacturing method may be applied to any method that is conventionally used for the production of tires, and thus, detailed description thereof will be omitted.

The rubber composition for a tire of the present invention and a method for manufacturing the same may improve heat aging resistance and crack resistance to extend the life of the rubber, and may also reduce blooming phenomenon caused by using an excessive amount of an anti-aging agent.

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

[ Manufacturing example : Preparation of Rubber Composition]

To prepare a rubber composition for the tire according to the following Examples and Comparative Examples using the composition shown in Table 1. In the preparation of the rubber composition for tires, the rubber composition having the composition shown in Table 1 was added to and mixed with the Bunbari mixer in the order shown in the table. The kneaded rubber was vulcanized at 150 ° C. for 30 minutes, and tensile properties, Tanδ, deformation resistance, and crack resistance were measured for the vulcanized sheet in accordance with the relevant regulations of ASTM. The test results are shown in Table 2 below.

Table 1

Item Comparative Example 1 Example 1 Comparative Example 2 Example 2 Kneading
Step name One 3 2 One 3 2 One 3 4 2 One 3 4 2 Kneading temperature
(℃) 190 183 135 190 183 135 185 185 170 130 185 185 170 130 Kneading time
(min) 1.8 One 2 1.8 One 2 1.5 2 One 1.5 1.5 2 One 1.5 Natural rubber 60 - - 60 - - 40 - - - 40 - - - Synthetic rubber ^{1 )} 40 - - 40 - - 60 - - - 60 - - - Carbon Black ^{2 )} 40 - - 40 - - 75 - - - 75 - - - Zinc oxide 5 - - 5 - - 5 - - - 5 - - - Stearic acid 1.5 - - 1.5 - - 1.5 - - - 1.5 - - - Antioxidant ^{3 )} 10 - - - - 10 4 - - - - - - 4 Vulcanizing agent ^{4 )} - - 3 - - 3 - - - 4 - - - 4

(Unit: parts by weight)

Corporation

1) RM-BR with synthetic rubber (FP, High cis, product made by LG Chem)

2) Carbon black carbon black with DBP (n-dibutyl phthalate) oil absorption 80 to 100cc / 100g, Tint value 50 to 100%, I ₂ adsorption amount 30 to 50mg / g

3) Mixing 6PPD, RD, Wax in the weight ratio of 1.5 to 4: 0.5 to 4: 1.5 to 2 as an anti-aging agent

4) Sulfur as a vulcanizing agent

In Table 2, the residual amount of the antioxidant is represented by converting the amount of the antioxidant remaining in the rubber composition after vulcanization in terms of the weight of the antioxidant per 100 parts by weight of the raw material rubber, and the residual ratio of the antioxidant is added to 100 parts by weight of the raw material rubber. The weight of the inhibitor and the weight of the antioxidant remaining in the rubber composition after vulcanization are expressed as a percentage.

In Table 2, the tensile properties were measured by using an instron after cutting the prepared rubber specimen into a dumbbell. Crack resistance was measured by the method according to the relevant regulations of ASTM, and measured after deformation at 100 ° C. × 24 hours. Tan δ was evaluated using DMTS and temperature sweep was performed. Test conditions were tested in tension and torque type under 0.5% strain, 10 Hz.

In the following Table 2, the tensile aging item shows the tensile characteristics of the rubber aged for the indicated time at the indicated temperature. Tensile aging below indicates that the smaller the value, the less aging occurs.

[Table 2]

Item Comparative Example 1 Example 1 Comparative Example 2 Example 2 Residual amount of antioxidant (phr) 5 9.5 1.68 3.6 Residual Ratio of Anti-aging Agent (%) 50 95 42 90 Tensile Properties Hardness 52 52 74 73 Modulus 15 15 52 52 Tensile aging
100 ℃ x24h Hardness 55 53 77 76 Modulus 26 22 65 63 Tensile aging
100 ℃ x48h Hardness 58 55 79 77 Modulus 31 28 72 68 Tan δ @ 60 ℃ 0.116 0.115 0.176 0.170 Crack resistance - usually Great usually Great

In Table 2, phr means parts per hundred rubber, that is, parts by weight per 100 parts by weight of raw rubber.

Referring to Table 2, in the case of Example 1 and Example 2 in which the time of adding the anti-aging agent is changed compared to Comparative Example 1 and Comparative Example 2 having the same composition of the rubber composition while maintaining the tensile characteristics and tensile aging characteristics and It was found that the crack resistance was excellent.

In addition, photographs evaluating the crack resistance of the rubber specimens prepared in Examples 1 and 2 and Comparative Examples 1 and 2 are shown in FIGS. 1 to 4. 1 is a photograph evaluating the crack resistance of the rubber specimen prepared in Comparative Example 1, Figure 2 is a photograph evaluating the crack resistance of the rubber specimen prepared in Example 1, Figure 3 is prepared in Comparative Example 2 Fig. 4 is a photograph evaluating the crack resistance of one rubber specimen, and Fig. 4 is a photograph evaluating the crack resistance of the rubber specimen prepared in Example 2;

1 to 4, compare FIGS. 1 and 3 showing crack resistance of Comparative Examples 1 and 2 with FIGS. 2 and 4 showing crack resistance of Examples 1 and 2. When the rubber composition of the same composition ratio was used, it was found that the cracks of FIGS. 2 and 4 showing Examples 1 and 2 were significantly less than those of FIGS. 1 and 3.

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.

1 is a photograph evaluating the crack resistance of a rubber specimen according to Comparative Example 1.

Figure 2 is a photograph evaluating the crack resistance of the rubber specimen according to Example 1.

Figure 3 is a photograph evaluating the crack resistance of the rubber specimens according to Comparative Example 2.

Figure 4 is a photograph evaluating the crack resistance of the rubber specimen according to Example 2.

Claims (9)

delete delete delete delete A first step of kneading the first group composition including the raw material rubber and the filler for 1 to 2 minutes at a temperature of 160 to 190 ° C, and A second step of kneading the second group composition comprising a vulcanizing agent and an anti-aging agent with the first group composition at a temperature of 110 to 150 ° C. for 1 to 4 minutes Method for producing a rubber composition for a tire comprising a. delete The method of claim 5, The first group composition comprises the raw material rubber 30 to 70 parts by weight of natural rubber and 30 to 70 parts by weight of synthetic rubber, the filler comprises 30 to 90 parts by weight based on 100 parts by weight of the raw material rubber, The second group composition may include 0.5 to 4 parts by weight of the vulcanizing agent based on 100 parts by weight of the raw material rubber, and 4 to 10 parts by weight of the anti-aging agent based on 100 parts by weight of the raw material rubber. Manufacturing method. The method of claim 5, The anti-aging agent may be N- (1,3-dimethylbutyl) -N-phenyl-p-phenylenediamine (N- (1,3-Dimethybutyl) -N-phenyl-p-phenylenediamine), poly (2,2, Of the rubber composition for tires, which is any one selected from the group consisting of 4-trimethyl-1,2-dihydroquinoline (Poly (2,2,4-trimethyl-1,2-dihydroquinoline)), waxes and combinations thereof. Manufacturing method. A tire manufactured using the method for producing a rubber composition for a tire according to any one of claims 5, 7 and 8.

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