KR101140204B1 - Rubber composition for snow tire tread and snow tire manufactured by using the same - Google Patents

Abstract

The present invention relates to a rubber composition for snow tire tread and a snow tire manufactured using the same, comprising 100 parts by weight of raw material rubber, 1 to 8 parts by weight of blowing agent, and 5 to 20 parts by weight of vegetable powder filler having a particle diameter of 10 μm or less. It provides a rubber composition for snow tire tread.

The rubber composition for snow tire treads can improve the hardness of the rubber composition while simultaneously improving wet traction and ice traction so as to be suitable for a snowy snow surface, so that the rubber composition for snow tire treads has excellent braking performance on the snowy snow surface and also has excellent adjustment stability. To provide.

Snow tire, tread, rice bran, vegetable filler, plant ingredient filler, rice bran, foaming agent, foam rubber

Description

RUBBER COMPOSITION FOR SNOW TIRE TREAD AND SNOW TIRE MANUFACTURED BY USING THE SAME}

The present invention relates to a rubber composition for a snow tire tread and a snow tire manufactured using the same, and to a rubber composition for a snow tire having excellent hardness while simultaneously improving ice traction and wet traction and a snow tire manufactured using the same.

When the tire travels on a snowy road surface, the surface of the snow melts due to heat generation of the tire itself to form a thin water film, and this water film tends to reduce the anti-slip function of the tire.

The conventional snow tire has a spike pin on the surface of the tire tread to increase the driving force and the braking force of the tire, and to increase the friction between the tire and the snow surface. Such spike tires are mainly used only in extreme regions, and there are problems such as spike damage on the road surface and noise in general roads, not on ice roads. In addition, due to the problem of generating dust by road damage, its use has recently been regulated.

Conventional studless tires are mainly limited to the use of carbon black and silica as fillers, and especially when water-repellent fillers are blended, the traction performance tends to be lowered, and hydrophilic inorganic fillers are blended. In this case, since the wear resistance tends to be lowered, there is a limit in maximizing driving and braking performance on the winter snow surface.

In place of this, as a technique for improving braking performance on an ice road surface of a snow tire, a method of injecting glass fibers into a tread rubber composition, a method of injecting porous pumice, etc. has been applied. However, such glass fibers, porous pumice, and the like may be dispersed in rubber unevenly, and there is a problem in that the hardness of the entire rubber and the tire wear performance may be reduced. In addition, there is a limit to providing a rubber composition for tire treads which is excellent in both hardness and ice ice traction and wet traction simultaneously.

An object of the present invention is to provide a rubber composition for a snow tire tread and a snow tire manufactured by using the same, while applying the vegetable powder filler and the blowing agent to the raw material rubber, while also improving ice traction and wet traction.

In order to achieve the above object, the rubber composition for snow tire tread according to an embodiment of the present invention is 100 parts by weight of the raw material rubber, 1 to 8 parts by weight of the blowing agent, and 5 to 20 parts by weight of the vegetable powder filler having a particle diameter of 10㎛ or less Include.

The vegetable powder filler may be rice bran.

The blowing agent is sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, N, N'-dinitrosopentamethylenetetramine, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, azo Dicarbonamide, azobisisobutyronitrile, azobiscyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate, benzenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide ), Toluenesulfonylhydrazide, diphenylsulfon-3,3'-disulfonylhydrazide, calcium azide, 4,4'-diphenyldisulfonyl azide, p-toluenesulfonylazide and their It may be any one selected from the group consisting of a combination.

Snow tire according to another embodiment of the present invention is a snow tire comprising a rubber manufactured using a rubber composition for snow tire tread.

The rubber may be foamed by the foaming agent to have a diameter of the independent bubble of 20 to 140㎛, including 30 to 120 independent bubbles per unit area 1mm ² .

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

The rubber composition for snow tire tread includes 100 parts by weight of raw material rubber, 1 to 8 parts by weight of blowing agent, and 5 to 20 parts by weight of rice bran powder.

The raw material rubber is not particularly limited in the present invention, it 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. Therefore, the natural rubber includes natural rubber containing cis-1,4-polyisoprene as a main agent, and trans-1,4-isoprene as a main agent, for example, 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, the modified natural rubber may include epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, and the like.

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, carboxyl Acid Nitrile Butadiene High Radish, brominated polyisobutyl isoprene-co-paramethyl styrene (brominated polyisobutyl isoprene-co-paramethyl styrene, BIMS) and combinations thereof may be any one selected from the group.

The raw material rubber may be any one selected from the group consisting of styrene butadiene rubber (SBR), butadiene rubber (BR) and combinations thereof, and the styrene butadiene rubber may be an emulsion-polymerized styrene-butadiene rubber (Emulsion-polymerized Styrene Butadiene). Rubber, hereinafter referred to as "E-SBR"), solution-polymerized styrene-butadiene rubber (hereinafter referred to as "S-SBR"), and combinations thereof. However, the present invention is not limited thereto.

In particular, the raw material rubber may be selected from any one consisting of natural rubber (hereinafter referred to as "NR"), butadiene rubber (butadiene rubber, "BR") and a combination thereof. The natural rubber may be replaced by a part or all of synthetic isoprene rubber (hereinafter referred to as "IR").

The raw material rubber may be preferably used to include 50 to 90 parts by weight of NR, 10 to 50 parts by weight of BR, and more preferably 60 to 75 parts by weight of NR, 25 to 40 parts by weight of BR. Can be used.

When the NR is used in less than 50 parts by weight, the braking performance is detrimental, and when it is used in excess of 90 parts by weight, the glass transition temperature is increased, which is detrimental in terms of braking performance on the ice snow road surface.

When the butadiene rubber is used in excess of 50 parts by weight, the ratio of butadiene rubber, which is relatively weak in hardness, may be increased, so that cutting resistance and chipping resistance may be deteriorated, and when used in less than 10 parts by weight, braking performance and It may be disadvantageous in terms of wear resistance.

The foaming agent may be used as long as it is usually included in the rubber composition for snow tire treads to improve the braking performance on the ice snow surface, specifically, inorganic foaming agent, nitroso-based foaming agent, azo foaming agent, sulfonyl hydrazide-based It may be any one selected from the group consisting of a blowing agent, an azide-based blowing agent and combinations thereof.

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 blowing agent is any selected from the group consisting of azodicarbonamide (ADCA), azobisisobutyronitrile (AIBN), azobiscyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate and combinations thereof It can be one.

The sulfonylhydrazide-based blowing agent is benzenesulfonylhydrazide (BSH), p, p'-oxybisbenzenesulfonylhydrazide (0BSH), toluenesulfonylhydrazide (TSH), diphenylsulfon- It may be any one selected from the group consisting of 3,3'- disulfonyl hydrazide 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.

As the blowing agent, a sulfonyl hydrazide blowing agent and an azo blowing agent may be preferably used. More preferably, p, p'-oxybisbenzenesulfonyl hydrazide (0BSH) can be used.

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. If the content of the blowing agent is less than 1 part by weight with respect to 100 parts by weight of the raw material rubber, the foaming is too small to remove the water film due to foaming, and when used in excess of 8 parts by weight, the production of foaming holes is too large, resulting in wear resistance The physical properties of the rubber can be sharply lowered.

A foaming aid may be used 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.

These foaming aids may be used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the raw material rubber.

The vegetable powder filler may be used as a raw material including not only rice bran (rice bran), but also hulls, bran, buckwheat husk, bark from cereals such as barley, soybean hulls and the like.

The vegetable powder filler may be used by degreasing raw materials such as rice bran, or may be used without degreasing. The vegetable powder filler may be carbonized or non-carbonized.

In the case where the vegetable powder filler is a carbonized powder filler in which carbonaceous materials such as rice bran are carbonized, a sintering process is performed by impregnating raw materials such as rice bran having a particle size adjusted with a thermosetting resin and an additive, and then gradually raising the temperature in an atmosphere. Carbonized through and may be prepared through a cooling process. The thermosetting resin may preferably be a phenol resin, the final firing temperature in the firing process may be preferably 500 to 1000 ℃. The carbonized powder filler formed through the process forms a porous carbon-inorganic composite material.

The carbonized rice bran powder is commercially available, such as RBC, I-CRB25, CRB, RBC powder, etc. of Sanwayu Co., Ltd., Japan.

The vegetable powder filler may have a particle diameter of 10 μm or less, preferably 0.01 to 10 μm or less, and more preferably 0.01 to 7 μm or less.

In the case of using the vegetable powder filler having a particle diameter exceeding 10 μm, the vegetable powder filler easily escapes from the rubber surface and has an adverse effect on the strength reduction of the entire rubber and tire wear performance.

The vegetable powder filler may include 5 to 20 parts by weight based on 100 parts by weight of the raw material rubber, preferably 7 to 13 parts by weight.

When the vegetable powder filler is used in an amount of less than 5 parts by weight based on 100 parts by weight of the raw rubber, sufficient ice traction effects cannot be expected since the surface of the tire tread cannot serve as a spike with the ice snow surface, and exceeds 20 parts by weight. In case of use, the tensile strength may be drastically reduced, and the effect of removing the water film may be insignificant.

When the foamed rubber using the foaming agent is used for the tire tread, the tire tread is worn while the vehicle is running, and the foaming holes inside are exposed to the surface of the tread, so that the irregularities are formed on the surface of the tread. Absorbs and removes the water film, and the edges of the irregularities serve to increase friction, and in particular, improve wet traction.

The foamed rubber foamed using the foaming agent preferably has an independent bubble diameter of 20 to 140 µm. If the size of the independent bubble is less than 20㎛, the size of the bubble is too small, so that the effect of removing the water film by the unevenness and the effect of the edge is insufficient, so that the effect of improving the wet traction is insignificant. Wear performance may be degraded.

The foamed rubber preferably contains 30 to 120 independent bubbles per unit area of 1 mm ² . If the number of closed cells per unit area 1mm ² per foam rubber 30 is less than, and the effect of insufficient effects of friction increase due to due to uneven water film removal, and the edge (edge) mothayeoseo improve wet traction insignificant, the 120 If exceeded, wear resistance may be degraded.

However, in the case of a tire using such foam rubber, the ratio of foaming holes must be increased in order to increase friction, and the increase of the foaming rate can soften the rubber composition for the tread, thereby reducing wear resistance on a non-ice snow surface. There is this.

However, the present invention uses a rubber composition for snow tires further comprising a vegetable powder filler in the foamed rubber to increase ice traction as well as wet traction. In addition, it is possible to solve the problem of lowering the hardness, which is a problem in the rubber composition for snow tire tread.

The tire tread rubber composition may optionally further include various additives such as additional vulcanizing agents, vulcanization accelerators, vulcanization accelerators, fillers, coupling agents, anti-aging agents, softeners and the like. 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) 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 3.5 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.

Examples of the vulcanization accelerator include sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamic acid, aldehyde-amine, aldehyde-ammonia, imidazoline, xanthate and teeoff. Deamide type | system | group etc. 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 one 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 dibutyldithiocarbamate, zinc diamyldithiocarbamate, zinc dipropyldithiocarbamate, zinc salt of pentamethylenedithiocarbamate and piperidine, hexadecylisopropyldithiocarbamate zinc, octadecyl Isopropyldithiocarbamate zinc dibenzyldithiocarbamate zinc, sodium diethyldithiocarbamate, pentamethylenedithicarbamate 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.

As the thioptalamide system, for example, N-cyclohexyl thiophthalimide (PVI) can be used.

The vulcanization accelerator may be included in an amount of 0.3 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. .

The inorganic vulcanization accelerator may be any one selected from the group consisting of zinc oxide (ZnO), zinc carbonate, magnesium oxide (MgO), lead oxide, potassium hydroxide, and combinations thereof. Can be. 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 for the role as a suitable vulcanization accelerator.

The filler may be any one selected from the group consisting of carbon black, silica, calcium carbonate, clay (aluminum hydride silicate), aluminum hydroxide, lignin, silicate, talc and combinations thereof.

Carbon black has a nitrogen surface area per gram (N ₂ SA) value of 30 to 300 m ² / g, preferably an N ₂ SA value of 85 to 120 m ² / g, and n-dibutyl phthalate (DBP). The oil absorption may be 60 to 180 cc / 100 g.

The carbon black may include 30 to 80 parts by weight based on 100 parts by weight of the raw rubber. When the carbon black is used in an amount less than 30 parts by weight based on 100 parts by weight of the raw material rubber, the reinforcing performance of the carbon black, which is a filler, may be reduced, and when used in excess of 80 parts by weight, the processability of the tread rubber composition may be deteriorated. have.

The silica may be used to have a nitrogen adsorption amount of 100 to 180 m 2 / g, having a CTAB value of 110 to 170 m 2 / g, but the present invention is not limited thereto. 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 content of the silica may be included in 20 to 90 parts by weight based on 100 parts by weight of the raw rubber. 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.

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-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 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. The softener may be any one selected from the group consisting of process oil, vegetable oil, and combinations thereof, but the present invention is not limited thereto.

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

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

Representative examples of the paraffin-based processing oil may include P-1, P-2, P-3, P-4, P-5, P-6, etc. of Michang Oil Co., and the representative examples of the naphthenic processing oil. Michang Oil Co., Ltd. N-1, N-2, N-3, etc. are mentioned, A typical example of the said aromatic type processing oil is A-2, A-3 of Michang Oil Co., Ltd., etc. 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") contained in the aromatic process oil 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 processing oil used as the softening agent 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 an aromatic component in the softening agent, TDAE oils having a naphthenic component of 27 to 37% by weight and a paraffinic component of 38 to 58% by weight can be preferably used.

The processing 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 tread including the processing 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 5 to 150 parts by weight based on 100 parts by weight of the raw material rubber in that the workability of the raw material rubber is improved.

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, any wax can be used as long as it is used as an anti-aging agent in a rubber composition for tires, but preferably waxy hydrocarbons can be used.

The anti-aging agent may be N- (1,3-dimethylbutyl) -N-phenyl-p-phenylenediamine (N- (1,3-Dimethybutyl) -N-phenyl-p-phenylenediamine, 6PPD), N-phenyl N-phenyl-n-isopropyl-p-phenylenediamine (3PPD), poly (2,2,4-trimethyl-1,2-dihydroquinoline (Poly (2,2) , 4-trimethyl-1,2-dihydroquinoline, RD) and a combination thereof can be preferably used.

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 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.

Provided is a snow tire manufactured using the rubber composition for the snow tire tread according to another embodiment of the present invention. The method for manufacturing the snow tire using the rubber composition for the snow tire tread is applicable to any method used in the related art, and thus detailed description thereof will be omitted.

The rubber composition for snow tire tread of the present invention can improve the hardness of the rubber composition while simultaneously improving wet traction and ice traction so as to be suitable for a snowy snow surface, so that the snow tire tread has excellent braking performance on the snow surface and also has excellent adjustment stability. Provide a rubber composition.

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.

Rubber specimens were prepared using rubber compositions for snow tire treads according to Examples 1 to 3 and Comparative Examples 1 to 5 using the compositions shown in Table 1 below. Preparation of the tire tread rubber composition was in accordance with a conventional tire tread rubber production method.

Table 1

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 NR ⁽¹⁾ 70 70 70 70 70 70 70 70 BR ⁽²⁾ 30 30 30 30 30 30 30 30 Foaming Agents ⁽³⁾ 4 4 4 - 4 4 4 4 Vegetable Powder Fillers1 ⁽⁴⁾ 5 10 20 10 - - 3 25 Vegetable Powder Filler2 ⁽⁵⁾ - - - - - 10 - - Carbon Black ⁽⁶⁾ 70 70 70 70 70 70 70 70 Process Oils ⁽⁷⁾ 12 12 12 12 12 12 12 12 Stearic acid 2 2 2 2 2 2 2 2 Zinc oxide 4 4 4 4 4 4 4 4 Antioxidant ⁽⁸⁾ 2 2 2 2 2 2 2 2 Vulcanizer ⁽⁹⁾ 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Accelerators ⁽¹⁰⁾ One One One One One One One One

(Unit: parts by weight)

Corporation

(1) STR-20 to NR

(2) BR low cis butadiene rubber (high-cis BR) (Kumho Petrochemical)

(3) P, P-oxybis benzene sulfonyl hydrazide (OBSH) as blowing agent

(4) Vegetable powder filler, carbonized rice bran powder filler with particle diameter less than 10㎛

(5) Carbohydrate powder filler, carbonized rice bran powder filler with particle diameter more than 10㎛

(6) Carbon black, carbon black with N ₂ SA value of 96 m 2 / g

(7) Aromatic oil as process oil

(8) N- (1,3-dimethylbutyl) -N-phenyl-p-phenylenediamine as an anti-aging agent (N- (1,3-Dimethybutyl) -N-phenyl-p-phenylenediamine, 6PPD)

 (9) Oil treated sulfur

(10) N-cyclohexyl thiophthalimide (PVI) as a vulcanization accelerator

The physical properties of the rubber composition for snow tire treads of Examples 1 to 3 and Comparative Examples 1 to 5 having the composition of Table 1 were measured and the results are shown in Table 2 below.

The following hardness is the value measured with the Shore A type hardness tester.

The following tensile properties (300% modulus and tensile strength) were measured according to ASTM D412 test method using an Instron tester.

The following ice traction and wet traction were measured using an Abrasion and skid tester, and Comparative Example 1 was expressed as 100 based on this. The larger the value of ice traction and wet traction, the better the braking performance.

[Table 2]

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Hardness 59 62 60 57 55 54 56 58 300% modulus
(kgf / cm ² ) 123 126 115 117 97 95 105 100 The tensile strength
(kgf / cm ² ) 196 212 204 190 150 143 176 151 Wear resistance 106 110 104 102 93 91 97 93 Ice traction 125 134 128 100 90 97 98 95 Wet traction 111 116 107 100 105 102 101 93

Referring to Table 2, it can be seen that in Examples 1 to 3, not only the values of ice traction and wet traction, but also hardness, 300% modulus, and tensile strength were superior to Comparative Examples 1 to 5.

In particular, it can be seen that 300% modulus and tensile strength of the Comparative Example 3 using the vegetable powder filler having a particle diameter of more than 10 μm is greatly decreased. In addition, in the case of Comparative Example 5 using a vegetable powder filler in excess of 20 parts by weight per 100 parts by weight of the raw material rubber, it can be seen that the ice traction and wet traction index as well as 300% modulus and tensile strength, which are tensile properties, are greatly decreased.

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, 1 to 8 parts by weight of blowing agent, and 5 to 20 parts by weight of a vegetable powder filler having a particle diameter of 10 μm or less, Wherein the vegetable powder filler is carbonized rice bran powder rubber composition for snow tire tread. delete The method of claim 1, The blowing agent is sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, N, N'-dinitrosopentamethylenetetramine, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, azo Dicarbonamide, azobisisobutyronitrile, azobiscyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate, benzenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide ), Toluenesulfonylhydrazide, diphenylsulfon-3,3'-disulfonylhydrazide, calcium azide, 4,4'-diphenyldisulfonyl azide, p-toluenesulfonylazide and their Rubber composition for a snow tire tread which is any one selected from the group consisting of a combination. A snow tire comprising a rubber prepared using the rubber composition for snow tire tread according to claim 1. 5. The method of claim 4, The rubber is a snow tire is foamed by the foaming agent having a diameter of 20 to 140㎛ of the independent bubble, including 30 to 120 independent bubbles per unit area 1mm ² .