KR101165294B1 - Rubber composition for tire tread, method for manufacturing tire and tire manufactured by the method - Google Patents

Abstract

The present invention relates to a rubber composition for a tire tread, a method for manufacturing a tire, and a tire manufactured using the same, comprising 100 parts by weight of raw material rubber, 10 to 100 parts by weight of reinforcing filler, 1 to 8 parts by weight of foaming agent, and a coupling agent. It provides a rubber composition for a tire tread comprising 10 to 60 parts by weight of the coupled eggshell ground.

The rubber composition for the tire tread is reduced in the strength of the entire rubber that can be generated by using the foaming agent to weaken the force to resist deformation, the wear performance of the tire is reduced, or the adjustment stability to the rapid deformation of the rubber in accordance with the steering of the vehicle This sudden drop does not occur, it is environmentally friendly, provides excellent tire strength, and greatly improves the ice coefficient of friction of the tire.

Tires, treads, raw rubber, carbon black, silica, foaming agents, foam rubber, eggshells, ground products, coupling agents

Description

RUBBER COMPOSITION FOR TIRE TREAD, METHOD FOR MANUFACTURING TIRE AND TIRE MANUFACTURED BY THE METHOD}

The present invention relates to a rubber composition for tire tread, a method for manufacturing a tire, and a tire manufactured using the same, which is environmentally friendly, provides excellent tire strength, and has a rubber composition for tire tread that can greatly improve the ice coefficient of ice friction of a tire. It relates to a tire manufacturing method and a tire produced using the same.

As a conventional method for improving the ice sheet braking performance of a tire, a method of attaching a spike to the surface of the tread has been used, but as the interest on the environment increases due to the problem that the spike damages the road surface and generates dust. Its use is regulated.

To replace this, techniques for improving the braking performance on the ice road surface of winter tires have been developed by making foam-type pores in tread rubber or injecting a material such as glass fiber, and recently replacing glass fiber. Techniques for adding porous pumice, layered silica and the like are also disclosed.

In addition, in order to improve the performance of the foamed rubber, a technique of simultaneously using a glass fiber, silica and the like with foaming has been disclosed, and a method of using waste tire powder with foaming as pulverized powder has been proposed.

However, in the case where pores are formed in the rubber by foaming by adding a foaming agent in this way, the strength of the entire rubber is lowered, the force to resist deformation is weakened, and the wear performance of the tire is easily reduced, and the tread according to the steering of the vehicle. There is a problem that the adjustment stability is sharply lowered due to the rapid deformation of the rubber.

An object of the present invention is to reduce the wear resistance of the tire while reducing the strength of the entire rubber due to the use of a foaming agent to weaken the deformation resistance, or the rapid adjustment stability of the rubber due to the rapid deformation of the rubber in accordance with the steering of the vehicle It is to provide a rubber composition for a tire tread that does not cause a problem of deterioration, which is environmentally friendly, provides excellent tire strength, and which can greatly improve the ice coefficient of friction of tires.

Another object of the present invention is to provide a method for producing a tire using the eggshell ground powder coupled with a coupling agent.

Still another object of the present invention is to provide a tire manufactured by the tire manufacturing method.

In order to achieve the above object, the rubber composition for a tire tread according to an embodiment of the present invention is coupled to 100 parts by weight of raw rubber, 10 to 100 parts by weight of reinforcing filler, 1 to 8 parts by weight of foaming agent, and a coupling agent. 10 to 60 parts by weight of eggshell grounds.

The eggshell ground powder coupled with the coupling agent is immersed in a basic aqueous solution of eggshell ground for 24 to 96 hours and dried, and then mixed with a coupling agent and a solvent to give an ultrasonic vibration of 10 to 100 KHz at 10 to 50 ℃. It can be prepared by adding for 10 to 60 minutes and drying.

The coupling agent may be included in an amount of 5 to 20 parts by weight based on 100 parts by weight of the eggshell ground product.

The eggshell ground powder coupled with the coupling agent may have an average particle diameter of 0.50 mm or less.

Tire manufacturing method according to another embodiment of the present invention is a grinding step of grinding the egg shell, sifting to prepare an egg shell grinding, immersion step of immersing the egg shell grinding in a basic aqueous solution for 24 to 96 hours After the addition of the egg shell mill and the coupling agent to the solvent, the coupling step of applying an ultrasonic vibration of 10 to 100 KHz for 10 to 60 minutes while mixing at 10 to 50 ℃, the coupled egg shell mill Drying to dry, and blending the dried coupled eggshell mill with raw rubber, reinforcing filler, foaming agent and other additives to produce a tire.

A tire according to another embodiment of the present invention is manufactured using the tire manufacturing method.

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

The tread rubber composition includes raw material rubber, reinforcing filler, foaming agent, and eggshell ground powder coupled with 10 to 60 parts by weight of a coupling agent based on 100 parts by weight of the raw material rubber.

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 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.

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, bromo methyl 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 High It may be a p-methyl styrene (brominated polyisobutyl isoprene-co-paramethyl styrene, BIMS), and one selected from the group consisting of -, bromo mineyi suited polyisobutyl isoprene-co.

In particular, when the rubber composition for the tire tread is for the tire tread in winter, the raw material rubber may be made of natural rubber and butadiene rubber. In this case, the content of the natural rubber is 40 to 90 parts by weight, the content of the butadiene rubber may be 10 to 60 parts by weight. If the content of the butadiene rubber is less than 10 parts by weight may have a problem that the wear performance is lowered, if it exceeds 60 parts by weight may have a problem that the workability is lowered.

The rubber composition for tire treads includes reinforcing fillers to reinforce strength. The reinforcing filler may be any one selected from the group consisting of carbon black, silica, and combinations thereof.

The reinforcing filler may be included in 10 to 100 parts by weight based on 100 parts by weight of the raw material rubber, preferably 40 to 80 parts by weight. If the content of the reinforcing filler is out of the above range, the wear performance of the tire may be drastically reduced, and the braking performance may be reduced on the wet road surface. Specifically, when the content of the reinforcing filler is less than 10 parts by weight, the reinforcing performance by the reinforcing filler may decrease, and when the content of the reinforcing filler exceeds 100 parts by weight, the processability of the rubber composition may be deteriorated.

The carbon black may have a nitrogen adsorption specific surface area (N ₂ SA) of 30 to 300 m ² / g and a DBP (n-dibutyl phthalate) oil absorption of 60 to 180 cc / 100 g, but the present invention This is not limited to this.

When the nitrogen adsorption specific surface area of the carbon black exceeds 300m ² / g may be disadvantageous in workability of the rubber composition for tires, less than 30m ² / g may be disadvantageous reinforcement performance by the carbon black filler. In addition, when the DBP oil absorption of the carbon black exceeds 180cc / 100g, the workability of the rubber composition may be lowered. If the DBP oil absorption amount of the carbon black is less than 60cc / 100g, the reinforcing performance by the carbon black as a filler may be disadvantageous.

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

The silica has a 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.

When the nitrogen adsorption specific surface area of the silica is less than 100 m 2 / g, reinforcing performance by the filler silica may be detrimental, and when it exceeds 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, the reinforcing performance by silica may be disadvantageous, and when it exceeds 170 m 2 / g, the processability of the rubber composition may be disadvantageous.

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 blowing agent is included in the rubber tread rubber composition to improve the braking performance on the ice snow road surface, any one can be used as long as it is commonly used. Specifically, the blowing agent may be any one selected from the group consisting of an inorganic blowing agent, a nitroso blowing agent, an azo blowing agent, a sulfonyl hydrazide blowing agent, an azide blowing agent, and a combination thereof, but the present invention is limited thereto. It is not.

The inorganic blowing agent may be any one selected from the group consisting of sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, and combinations thereof.

The nitroso blowing agent may be any one selected from the group consisting of N, N'-dinitrosopentamethylenetetramine (DPT), N, N'-dimethyl-N, N'-dinitrosoterephthalamide and combinations thereof. Can be.

The azo foaming agent is any one selected from the group consisting of azodicarbonamide (ADCA), azobisisobutyronitrile (AIBN), azobiscyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate and combinations thereof Can be.

The sulfonyl hydrazide blowing agent is benzenesulfonyl hydrazide (BSH), p, p'- oxybis (benzenesulfonyl hydrazide) (0BSH), toluenesulfonyl hydrazide (TSH), di Phenylsulfon-3,3'-disulfonylhydrazide and combinations thereof.

The azide blowing agent may be any one selected from the group consisting of calcium azide, 4,4'-diphenyldisulfonyl azide, p-toluenesulfonyl azide and combinations thereof.

The blowing agent may be used in an amount of 1 to 8 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the raw material rubber. When the content of the blowing agent is less than 1 part by weight based on 100 parts by weight of the raw material rubber, the foaming is too small, so that the effect of removing the water film due to foaming is insignificant. The physical properties of rubbers such as these can be drastically lowered.

It is also possible to optionally use a foaming aid together with the blowing agent. When the foaming aid is used together with the foaming agent, there is an advantageous effect in terms of lowering the decomposition temperature of the foaming agent, promoting decomposition, homogenizing the bubbles.

The foaming aid may be any one selected from the group consisting of organic acids, urea, urea derivatives, and combinations thereof, and the organic acids may be any one selected from the group consisting of salicylic acid, phthalic acid, stearic acid, oxalic acid, and combinations thereof. have.

The foaming aid may be included in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the raw material rubber.

The rubber composition for tire treads includes eggshell ground powder coupled with a coupling agent to improve ice braking performance without reducing the strength of the rubber. The tire tread rubber composition further includes an egg shell pulverized product which is coupled with a coupling agent while improving braking performance on snow or ice road in winter as the foamed rubber foamed using the foaming agent.

Since the eggshell ground powder coupled with the coupling agent forms a bond with the raw rubber, the tire tread is worn and the eggshell ground powder coupled with the coupling agent does not easily fall off even when exposed to the surface. Therefore, the eggshell ground powder coupled with the coupling agent exposed on the surface serves as a spike to improve the ice sheet braking performance. In addition, the eggshell ground powder coupled with the coupling agent present in the rubber serves as a filler to improve the strength of the rubber.

The eggshell ground powder coupled with the coupling agent is not particularly limited in particle size or type, but may have an average particle diameter of 0.50 mm or less, and preferably 0.01 to 0.50 mm. When the average particle diameter of the eggshell ground powder coupled with the coupling agent exceeds 0.50 mm, there is a possibility that the wear performance of the tire may be sharply lowered due to a sudden decrease in tensile strength.

Eggshell ground powder coupled to the coupling agent may be 10 to 60 parts by weight, preferably 15 to 50 parts by weight based on 100 parts by weight of the raw material rubber. If the eggshell ground powder coupled with the coupling agent is less than 10 parts by weight based on 100 parts by weight of the raw material rubber, the role of the spike of the eggshell ground powder coupled with the coupling agent cannot be sufficiently expected on the worn surface of the tire tread. If it exceeds 60 parts by weight, the tensile strength of the rubber may drop sharply.

The eggshell ground powder coupled with the coupling agent is immersed in a basic aqueous solution of eggshell ground for 24 to 96 hours and dried, and then mixed with a coupling agent and a solvent to give an ultrasonic vibration of 10 to 100 KHz at 10 to 50 ℃. It may be prepared by adding for 10 to 60 minutes and drying.

Although the kind of the coupling agent is not particularly limited in the present invention, 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, Any one selected from the group consisting of methacrylic silane compounds and combinations thereof 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-trimeth 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 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 dimethyl methoxysilane, and combinations thereof Can be.

The coupling agent may be added in an amount of 20 parts by weight or less based on 100 parts by weight of the eggshell ground product, preferably 5 to 20 parts by weight. When the coupling agent is added in excess of 20 parts by weight based on 100 parts by weight of the eggshell ground powder, the coupling agent remains in the rubber composition after coupling, thereby lowering the physical properties of the tire tread.

The tire tread rubber composition may optionally further include various additives such as additional vulcanizing agents, vulcanization accelerators, vulcanization accelerators, 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 conventional tire tread rubber composition.

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), tetra Organic vulcanizing agents, such as ethylethyluram disulfide (TEET) 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 0.1 to 10 parts by weight based on 100 parts by weight of the raw material rubber, which is preferable 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 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 0.1 to 10 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 the zinc oxide and the stearic acid are used together, it may be used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the raw material rubber, respectively, to serve as an appropriate vulcanization accelerator.

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. , TDAE (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 low temperature characteristics of the tire tread including the TDAE oil, fuel efficiency, and the likelihood of causing cancer of PAHs.

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

The softener is preferably used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the raw material rubber, in terms of improving 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.

In addition to the anti-aging action, the anti-aging agent should have a high solubility in rubber, low volatility, inert to rubber, and should 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.

The pressure-sensitive adhesive may be included in 0.5 to 10 parts by weight based on 100 parts by weight of the raw material rubber. If the content of the pressure-sensitive adhesive is less than 0.5 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 exceeds 10 parts by weight, rubber properties may be reduced.

A tire manufacturing method according to another embodiment of the present invention includes a grinding step, dipping step, coupling step, drying step, and manufacturing a tire.

First, the egg shells are ground and sieved to prepare an egg shell mill. The eggshell pulverized product is not particularly limited in particle size or type, the average particle diameter may be 0.50mm or less, preferably 0.01 to 0.50mm. When the average particle diameter of the eggshell pulverized product exceeds 0.50mm, there is a possibility that the wear performance of the tire is sharply lowered due to a sharp decrease in tensile strength.

However, the egg shell may be optionally washed with neutral water prior to crushing the egg shell, and then dried in a vacuum oven at 50 to 70 ° C. for 2 to 4 hours.

Next, the eggshell ground is immersed in a basic aqueous solution for 24 to 96 hours. The reason why the eggshell crushed product is immersed in a basic aqueous solution is to remove the white film inside the eggshell. The basic aqueous solution may use a strong base such as NaOH or KOH, and preferably 3.0% to 5.0% of NaOH.

The eggshell grounds immersed in the basic aqueous solution may optionally be dried for 2 to 4 hours in a vacuum oven at 50 to 70 ℃.

In the coupling step, the eggshell pulverized product and the coupling agent are added to the solvent, and then the eggshell pulverized coupled with the coupling agent is applied by applying ultrasonic vibration of 10 to 100 KHz for 10 to 60 minutes while mixing at 10 to 50 ° C. Prepare water.

The reason for applying the ultrasonic vibration of 10 to 100KHz for 10 to 60 minutes while mixing at 10 to 50 ℃ in the coupling step is to prevent the aggregation of eggshell particles in the mixture, if the temperature is less than 10 ℃ There may be a problem of clumping of the shell particles and the solvent may easily evaporate above 50 ° C.

If the vibration of the ultrasonic wave is less than 10KHz, eggshell particles may be agglomerated and exceed the size of the particles no longer smaller than 100KHz. In addition, if the time for applying the ultrasonic vibration is less than 10 minutes, eggshell particles can be agglomerated, the size of the particles no longer smaller than 60 minutes.

The said coupling agent and the said solvent are not specifically limited in this invention, The said coupling agent can use the said coupling agent normally used for the rubber composition for tires, The said solvent can use acetone suitably.

The coupling agent may be added in an amount of 20 parts by weight or less based on 100 parts by weight of the eggshell ground product, preferably 5 to 20 parts by weight. When the coupling agent is added in excess of 20 parts by weight based on 100 parts by weight of the eggshell ground powder, the coupling agent remains in the rubber composition after coupling, thereby lowering the physical properties of the tire tread.

The eggshell ground powder coupled with the coupling agent may be dried for 2 to 4 hours in a vacuum oven at 50 to 70 ℃.

The eggshell ground powder coupled with the dried coupling agent may be blended with raw rubber, reinforcing filler, foaming agent and other additives to produce a tire according to conventional methods. Specifically, the tire may be manufactured through a conventional two-step continuous manufacturing process. That is, during the finishing step in which the first step of thermomechanical treatment or kneading at a maximum temperature ranging from 110 to 190 ° C., preferably from 130 to 180 ° C. (called 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 tread is not limited to the tread (tread cap and tread base), and may be included in various rubber components constituting the tire. Such rubber components include sidewalls, sidewall inserts, apex, chafers, wire coats or innerliners, and the like.

A tire according to another embodiment of the present invention is manufactured according to the manufacturing method of the tire. 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.

In the rubber composition for tire tread of the present invention, the strength of the entire rubber that may be generated by using the foaming agent decreases, and the force to resist deformation decreases, and the wear performance of the tire decreases, or due to the rapid deformation of the rubber according to the steering of the vehicle. The problem that adjustment stability is not sharply degraded does not occur, it is environmentally friendly, provides excellent tire strength, and greatly improves the ice friction coefficient of the tire.

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]

Using a composition as shown in Table 1 below to prepare a rubber composition for tire treads according to the following examples and comparative examples. The rubber composition was prepared according to a conventional method for preparing a rubber composition.

(Comparative Example 1)

55 parts by weight of carbon black, 35 parts by weight of aromatic oil, and zinc oxide based on 100 parts by weight of raw material rubber, which is comprised of 65 parts by weight of natural rubber and 35 parts by weight of 1,4-cis polybutadiene rubber, which are typically used in the rubber tread composition for winter tires. 3 parts by weight, stearic acid 1 part by weight, anti-aging agent (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine) 2.5 parts by weight, vulcanization accelerator (N-tert-butyl-2-benzo 1.8 parts by weight of thiazylsulfenamide), 2 parts by weight of sulfur, and 3 parts by weight of blowing agent (p, p-oxybis benzene sulfonyl hydrazide (OBSH)) were used. The silver particle diameter was ground to 0.125 mm or less and blended in a half-barrier mixer to prepare a rubber tread rubber composition.

(Example 1)

A rubber composition for tire treads was prepared in the same manner as in Comparative Example 1 except that 20 parts by weight of the egg shell ground powder coupled with a coupling agent instead of the egg shell ground powder was prepared in Comparative Example 1.

At this time, the egg shell ground powder coupled with the coupling agent was washed with neutral water, dried in a vacuum oven at 60 ° C. for 3 hours, and then pulverized, sieved, and soaked in a 4.0% NaOH aqueous solution for 72 hours. . Then, after drying for 3 hours at 60 ℃ vacuum oven, 47KHz ultrasonic vibration was applied for 30 minutes while mixing with acetone and coupling agent (3-aminopropyltriethoxysilane) at room temperature and after 30 minutes reaction at 100 ℃ Again dried for 3 hours at 60 ℃ vacuum oven was used.

(Example 2)

A rubber tread rubber composition was prepared in the same manner as in Example 1 except that the eggshell ground powder coupled to the coupling agent in Example 1 was used in an amount of 35 parts by weight.

(Example 3)

A rubber composition for tire treads was prepared in the same manner as in Example 1 except for using 50 parts by weight of the eggshell ground powder coupled to the coupling agent.

(Comparative Example 2)

A rubber composition for tire treads was prepared in the same manner as in Example 1 except for using 5 parts by weight of the eggshell ground powder coupled to the coupling agent.

(Comparative Example 3)

A rubber composition for tire treads was prepared in the same manner as in Example 1 except for using 65 parts by weight of the eggshell ground powder coupled to the coupling agent.

[Table 1] (Unit: parts by weight)

Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Natural rubber 65 65 65 65 65 65 Butadiene rubber 35 35 35 35 35 35 Carbon black 55 55 55 55 55 55 Aromatic oils 35 35 35 35 35 35 Zinc oxide 3 3 3 3 3 3 Stearic acid One One One One One One Antioxidant 2.5 2.5 2.5 2.5 2.5 2.5 Vulcanization accelerator 1.8 1.8 1.8 1.8 1.8 1.8 brimstone 2 2 2 2 2 2 blowing agent 3 3 3 3 3 3 Eggshell Grind 35 - - - - - Eggshell grounds coupled with a coupling agent - 5 65 20 35 50

Experimental Example: Measurement of Physical Properties of Prepared Rubber Composition

The measurement results of various physical properties of the rubber compositions prepared in Examples and Comparative Examples are shown in Table 2 below.

Hardness was measured using a Shore A durometer.

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

Elongation and tensile strength were measured using an Instron tester according to ASTM D412 test method.

The coefficient of friction is the result of measuring the ice friction coefficient after abrasion at 0 ° using a dynamic friction tester, and was expressed by indexing Comparative Example 1 as 100. Ice friction performance is the higher the value, the better the performance.

[Table 2]

Properties Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Seal
Properties Shore A 55 47 64 52 59 62 300% modulus (kgf / cm ² ) 66 57 76 60 69 71 Elongation (%) 400 482 309 455 427 364 Tensile strength (kgf / cm ² ) 145 123 116 141 156 142 Coefficient of friction 100 101 98 110 121 112

Referring to Table 2, Examples 1 to 3 and Comparative Examples 2 to 3 are used in the egg shell ground powder coupled to the foam rubber as a coupling agent, Comparative Example 2 is egg shell ground powder coupled to the coupling agent Was used less than 10 parts by weight based on 100 parts by weight of the raw material rubber, there is little effect of improving the ice friction coefficient compared to Comparative Example 1, the modulus and tensile strength was reduced, Comparative Example 3 crushed eggshell coupled with a coupling agent Water was used in excess of 60 parts by weight based on 100 parts by weight of the raw material rubber, the elongation rate is sharply lowered and the hardness is greatly increased to improve the ice friction coefficient.

On the other hand, in Examples 1 to 3, the coefficient of ice friction was improved compared to Comparative Example 1, in particular, in the case of Example 2 using the eggshell ground powder coupled with the coupling agent at 35 parts by weight based on 100 parts by weight of the raw material rubber It can be seen that the ice friction coefficient is greatly improved.

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 (6)

delete delete delete delete A pulverizing step of crushing the egg shells and sieving to prepare an egg shell crushed product, Immersion step of immersing the eggshell grounds in a basic aqueous solution for 24 to 96 hours, A coupling step of adding the eggshell pulverized product and the coupling agent to a solvent and applying ultrasonic vibration of 10 to 100 KHz for 10 to 60 minutes while mixing at 10 to 50 ° C., A drying step of drying the coupled eggshell ground product, and Preparing a tire by combining the dried eggshell ground powder with the raw rubber, reinforcing filler, foaming agent and other additives. Manufacturing method of a tire comprising a. A tire manufactured using the method for manufacturing a tire according to claim 5.