KR102224750B1 - Rubber composition for tire tread and Tire comprising the rubber composition - Google Patents

Abstract

Provided are a tire tread rubber composition comprising styrene butadiene rubber (SBR) and a compound of chemical formula 1, and a tire made of the rubber composition. The tire using the tire tread rubber composition has improved abrasion performance while maintaining fuel efficiency and braking performance.

Description

Tire tread rubber composition and tire comprising the same

It relates to a tire tread rubber composition and a tire comprising the same.

Car tires support heavy loads and are objects that rotate at high speed. The tread, which has the greatest effect on the durability of the tire, is in contact with the ground, which greatly affects the driving performance of the tire.

BR rubber is blended into the tire tread compound to improve the tire's wear performance. However, by adding BR rubber to the tread, the wear performance is improved, but the wet braking performance tends to decrease.

The wet braking performance of tires is affected by the characteristics of tread compound rubber and road roughness characteristics. The wet braking performance can be improved by applying a hydrophilic reinforcing material such as silica or a grip resin that increases hysteresis properties in the blended rubber.

One aspect is to provide a tire tread rubber composition with improved wear performance while maintaining fuel economy performance and braking performance.

Another aspect is to provide a tire made of the rubber composition.

According to one aspect,

There is provided a tire tread rubber composition comprising styrene butadiene rubber (SBR) and a compound of Formula 1:

<Formula 1>

In Formula 1,

X ₁ represents CR ₁ or N, X ₂ represents CR ₂ or N, X ₃ represents CR ₃ or N, and only one of _{X 1} to X _{3 is N,}

X ₄ represents CR ₄ or N, X ₅ represents CR ₅ or N, X ₆ represents CR ₆ or N, and only one of _{X 4} to X _{6 is N,}

R ₁ to R ₆ , R ₁₁ and R ₁₂ each independently represent hydrogen, a halogen group, a C _1-10 alkyl group, or a C _6-30 aryl group,

m and n each independently represent an integer of 1 or 2.

According to the other side,

A tire made of the tire tread rubber composition is provided.

Tires using the tire tread rubber composition according to an embodiment of the present invention have improved wear performance while maintaining fuel economy performance and braking performance.

1 is a view schematically showing the structure of a tire according to an embodiment.

Hereinafter, a tire tread rubber composition and a tire will be described in more detail in an exemplary embodiment.

Since the inventive idea disclosed in the present specification can apply various transformations and have various implementations, specific implementations are described in detail in the detailed description, and when necessary, specific implementations are illustrated in the drawings. Effects and features of the creative ideas of the present specification, and a method of achieving them will be apparent with reference to implementation examples described later in detail together with the drawings. However, the creative idea of the present specification is not limited to the embodiments disclosed below, but may be implemented in various forms.

In the following embodiments, terms such as first and second are not used in a limiting meaning, but are used for the purpose of distinguishing one component from another component.

In the following embodiments, expressions in the singular include plural expressions unless the context clearly indicates otherwise.

In the following embodiments, terms such as include or have means that the features or elements described in the specification are present, and do not preclude the possibility of adding one or more other features or elements in advance.

When one embodiment can be implemented differently, a specific process order may be performed differently from the described order. For example, two processes described in succession may be performed substantially simultaneously, or may be performed in an order opposite to the described order.

Hereinafter, if necessary, embodiments of the present invention will be described in detail with reference to the accompanying drawings, and when describing with reference to the drawings, identical or corresponding components are given the same reference numerals, and redundant descriptions thereof will be omitted. To.

In the drawings, components may be exaggerated or reduced in size for convenience of description. For example, the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of description, and thus the creative ideas disclosed in the present specification are not necessarily limited to those shown.

The tire tread rubber composition according to an embodiment may include a styrene butadiene rubber (SBR) and a compound of Formula 1 below:

<Formula 1>

In Formula 1,

X ₁ may _{represent CR 1} or N, X ₂ may _{represent CR 2} or N, X ₃ may _{represent CR 3} or N, and _{only one of X 1} to X ₃ may be N,

X ₄ may _{represent CR 4} or N, X ₅ may _{represent CR 5} or N, X ₆ may _{represent CR 6} or N, and _{only one of X 4} to X ₆ may be N,

R ₁ to R ₆ , R ₁₁ and R ₁₂ may each independently represent hydrogen, a halogen group, a C _1-10 alkyl group, or a C _6-30 aryl group,

m and n may each independently represent an integer of 1 or 2.

For example, the R ₁ to R ₆ , R ₁₁ and R ₁₂ are independently of each other hydrogen, F, Cl, Br, I, methyl group, ethyl group, n -propyl group, isopropyl group, n -butyl group, sec- Butyl group, isobutyl group, tert -butyl group, n -pentyl group, tert -pentyl group, neopentyl group, isopentyl group, sec -pentyl group, 3-pentyl group, sec -isopentyl group, n -hexyl group , Isohexyl group, sec -hexyl group, tert -hexyl group, n -heptyl group, isoheptyl group, sec -heptyl group, tert -heptyl group, n -octyl group, isooctyl group, sec -octyl group, tert -oxy Tyl group, n -nonyl group, isononyl group, sec -nonyl group, tert -nonyl group, n -decyl group, isodecyl group, sec -decyl group, tert -decyl group, phenyl group, pentalenyl group, naphthyl group, a Julenyl group, indacenyl group, acenaphthyl group, phenalenyl group, phenanthrenyl group, anthracenyl group, fluoranthenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, perylenyl group, pentaphenyl group, It may be a heptalenyl group, a naphthacenyl group, a picenyl group, a hexaenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group, an ovalenyl group, and the like.

When BR is added to improve wear performance, there is a performance trade off problem that degrades wet braking performance.

The tread rubber composition according to an embodiment of the present invention can improve abrasion performance without such Trade Off. By adding the compound of Formula 1 to the rubber compound, it is possible to improve the wear performance without reducing wet braking and fuel economy performance.

In addition, it is possible to improve wet braking while maintaining abrasion performance when the compound of Formula 1 is incorporated while replacing BR which was added for conventional wear improvement with SBR.

According to an embodiment of the present invention, the compound of Formula 1 may be added in a non-productive step. What is added in the non-productive step than in the productive step shows better results in the physical properties of the final vulcanized rubber.

According to an embodiment of the present invention, in Formula 1, X ₁ may represent N, X ₂ may _{represent CR 2} , X ₃ may _{represent CR 3} , and X ₄ may represent N. And X ₅ may _{represent CR 5} , X ₆ may _{represent CR 6} , and R ₂ , R ₃ , R ₅ , R ₆ , R ₁₁ and R ₁₂ may independently represent hydrogen or a halogen group. .

According to an embodiment of the present invention, in Formula 1, X ₂ may represent N, X ₁ may _{represent CR 1} , X ₃ may _{represent CR 3} , and X ₅ may represent N. And, X ₄ may _{represent CR 4} , X ₆ may represent _{CR 6,}

R ₁ , R ₃ , R ₄ , R ₆ , R ₁₁ and R ₁₂ may each independently represent hydrogen or a halogen group.

According to an embodiment of the present invention, in Formula 1, X ₃ may represent N, X ₁ may _{represent CR 1} , X ₂ may _{represent CR 2} , and X ₆ may represent N. And X ₄ may _{represent CR 4} , X ₅ may represent _{CR 5,}

R ₁ , R ₂ , R ₄ , R ₅ , R ₁₁ and R ₁₂ may each independently represent hydrogen or a halogen group.

For example, the halogen group may be I.

According to one embodiment of the present invention, the rubber composition may contain 1.0 to 2.0 parts by weight of the compound of Formula 1 based on 100 parts by weight of the raw rubber.

According to one embodiment of the present invention, the rubber composition may further include butadiene rubber (BR).

According to an embodiment of the present invention, the rubber composition further comprises butadiene rubber (BR), and the compound of Formula 1 is 1.0 based on 100 parts by weight of butadiene rubber (BR) and styrene butadiene rubber (SBR) as raw rubbers. It may contain to 2.0 parts by weight.

For example, the rubber composition may include 1.0 to 1.5 parts by weight of the compound of Formula 1 based on 100 parts by weight of butadiene rubber (BR) and styrene butadiene rubber (SBR) as raw rubbers.

When the compound of Formula 1 is less than 1.0 part by weight, there is no significant change in fuel efficiency and braking performance, but wear performance is not good, and when it exceeds 1.5 parts by weight, fuel efficiency and braking performance are maintained, but wear performance is not good.

According to an embodiment of the present invention, the compound of Formula 1 may be any one of the following compounds:

One

2

3

4

According to one embodiment of the present invention, the tire tread composition may further include synthetic rubber other than styrene butadiene rubber (SBR) as a raw material rubber.

The synthetic rubber may include at least one selected from butadiene rubber (BR), isoprene-containing styrene butadiene rubber, nitrile-containing styrene butadiene rubber, neoprene rubber, chlorobutyl rubber, and bromobutyl rubber. The content of the synthetic rubber may be, for example, 10 to 30 parts by weight based on 100 parts by weight of the raw rubber.

According to an embodiment of the present invention, the rubber composition may include 10 to 25 parts by weight of butadiene rubber (BR) and 60 to 90 parts by weight of styrene butadiene rubber (SBR) based on 100 parts by weight of raw rubber. .

The rubber composition may further include natural rubber in addition to synthetic rubber as raw rubber. The natural rubber may be a general natural rubber or a modified natural rubber.

The general natural rubber may be used as long as it is known as natural rubber, and the country of origin is not limited. The natural rubber mainly contains cis-1,4-polyisoprene, but may contain trans-1,4-polyisoprene depending on required properties. Therefore, in addition to natural rubber containing cis-1,4-polyisoprene as a main body, the natural rubber includes trans-1,4-isoprene as a main body, such as Valata, a kind of rubber of the Sapota family from South America. It may also contain rubber.

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

According to one embodiment of the present invention, the rubber composition may include a filler, for example, may include silica and/or carbon black.

Any of the silicas generally known may be used, and for example, commercially available Z-175, US7000GR, or 9000GR may be used.

According to an embodiment of the present invention, the content of silica may be 80 to 120 parts by weight based on 100 parts by weight of the raw rubber. When the silica content is in the constant range, the physical properties of the tread rubber are optimal.

The silica may have a nitrogen surface area per gram (N ₂ SA) of 100 to 180 m ² /g, and a specific surface area of CTAB (cetyl trimethyl ammonium bromide) adsorption of 110 to 170 m ² /g, The present invention is not limited thereto.

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

According to an embodiment of the present invention, the rubber composition may include a silane coupling agent to improve dispersion of silica. Any silane coupling agent may be used as long as it is conventionally used in the field to which the present invention belongs, and the content thereof is not particularly limited as it depends on the blending ratio used in the conventional tire tread rubber composition.

The carbon black may have a nitrogen adsorption specific surface area (nitrogen surface area per gram, N ₂ SA) of 30 to 300 m ² /g, and an oil absorption of DBP (n-dibutyl phthalate) 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 300 m 2} /g, the processability of the rubber composition for tires may be disadvantageous, and ^{when it is less than 30 m 2} /g, the reinforcing performance by carbon black as a filler may be disadvantageous. In addition, when the DBP oil absorption of the carbon black exceeds 180cc/100g, the processability of the rubber composition may be deteriorated, and when it is less than 60cc/100g, the reinforcing performance by carbon black as a filler may be disadvantageous.

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

The carbon black may be included in an amount of, for example, 3 to 10 parts by weight, and is preferably included in an amount of 4 to 7 parts by weight, based on 100 parts by weight of the raw rubber.

The tire tread rubber composition may optionally further include various additives such as an additional vulcanization agent, a vulcanization accelerator, a vulcanization accelerator, an anti-aging agent, an antioxidant, or a softener. Any of the various additives may be used as long as they are commonly used in the field to which the present invention belongs, and their content is not particularly limited, as it depends on the blending ratio used in a typical tire tread rubber composition.

As the vulcanizing agent, a sulfur-based vulcanizing agent can be preferably used. The sulfur-based vulcanizing agents include inorganic vulcanizing agents such as powdered sulfur (S), insoluble sulfur (S), precipitated sulfur (S), and colloidal sulfur, and tetramethylthiuram disulfide (TMTD), tetraethyl Organic vulcanizing agents such as tetraethyltriuram disulfide (TETD) and dithiodimorpholine may be used. As the sulfur vulcanizing agent, specifically elemental sulfur or a vulcanizing agent that produces sulfur, for example, amine disulfide, polymer sulfur, or the like may be used.

It is preferable that the vulcanizing agent be included in an amount of 0.5 to 10.0 parts by weight based on 100 parts by weight of the raw rubber, as an appropriate vulcanizing effect, and that the raw rubber is less sensitive to heat and is chemically stable.

The vulcanization accelerator refers to an accelerator that accelerates the vulcanization rate or accelerates the delaying action in the initial vulcanization step.

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

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

Examples of the thiazole-based vulcanization accelerator 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-based compound selected from the group consisting of ethyl 4-morpholinothio)benzothiazole and combinations thereof may be used.

Examples of the thiuram-based vulcanization accelerator include tetramethyl thiuram disulfide (TMTD), tetraethyl thiuram disulfide, tetramethyl thiuram monosulfide, dipentamethylene thiuram disulfide, dipentamethylene thiuram monosulfide, dipentamethylene Thiuram tetrasulfide, dipentamethylene thiuram hexasulfide, tetrabutyl thiuram disulfide, pentamethylene thiuram tetrasulfide, and any one thiuram-based compound selected from the group consisting of a combination thereof may be used.

As the thiourea-based curing accelerator, for example, any one thiourea-based selected from the group consisting of thiacarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea, and combinations thereof 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. I can.

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

Examples of the aldehyde-amine-based or aldehyde-ammonia-based vulcanization accelerator include, for example, an aldehyde selected from the group consisting of acetaldehyde-aniline reactant, butylaldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde-ammonia reactant, and combinations thereof. -Amine-based or aldehyde-ammonia-based compounds can be used.

As the imidazoline-based vulcanization accelerator, an imidazoline-based compound such as 2-mercaptoimidazoline may be used, and as the xanthate-based vulcanization accelerator, for example, a xanthate-based zinc dibutylxanthogenate or the like can be used. 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 through acceleration of the vulcanization speed.

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

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

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

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 and 0.5 to 3 parts by weight based on 100 parts by weight of the raw rubber, respectively, to serve as an appropriate vulcanization accelerator. When the content of the zinc oxide and the stearic acid is less than the above range, the vulcanization rate may be slow and thus productivity may decrease, and when the content of the zinc oxide and the stearic acid is less than the above range, a scorch phenomenon may occur and physical properties may be deteriorated.

The softening agent is added to the rubber composition to facilitate processing by imparting plasticity to the rubber or to reduce the hardness of the vulcanized rubber, and refers to oils and other materials used during rubber compounding or rubber production. The softener means process oil or oils included in other rubber compositions. As the softener, any one selected from the group consisting of petroleum oils, vegetable oils, and combinations thereof may be used, but the present invention is not limited thereto.

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

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

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

In particular, the oil used as the emollient has a total content of PAHs of 3% by weight or less with respect to the entire oil, and a kinematic viscosity of 95 or more (15 to 25% by weight of the aromatic component in the 210 μ softener, and 27 to 37 of the naphthenic component. TDAE oil having 38 to 58% by weight and paraffinic component may be preferably used.

The TDAE oil is advantageous in terms of environmental factors such as cancer-causing potential of PAHs while improving low-temperature characteristics and fuel economy performance of 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 , Jojoba oil, macadamia nut oil, saflower oil, tung oil, and any one selected from the group consisting of a combination thereof may be used.

The softening agent is preferably used in an amount of 0 to 10 parts by weight based on 100 parts by weight of the raw rubber in that it improves the processability of the raw rubber.

The anti-aging agent is an additive used to stop a 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 and used.

Examples of the amine-based anti-aging agent 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 may be used. The phenolic antioxidants include phenolic 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), 2 ,6-di-t-butyl-p-cresol, and any one selected from the group consisting of combinations thereof may be used. As the quinoline-based antioxidant, 2,2,4-trimethyl-1,2-dihydroquinoline and derivatives thereof may be used, and specifically, 6-ethoxy-2,2,4-trimethyl-1,2-di Consisting of hydroquinoline, 6-anilino-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline and combinations thereof Any one selected from the group can be used. As the wax, waxy hydrocarbon may be preferably used.

In addition to the anti-aging effect, the anti-aging agent must have a high solubility in rubber, low volatility, and inert to rubber, and not inhibit vulcanization, etc., 1 to 10 parts by weight of the raw rubber. It may be included in parts by weight.

A typical amount of the antioxidant may be included in, for example, about 1 to about 5 parts by weight. Representative antioxidants are, for example, diphenyl-p-phenylenediamine and others, but are not limited thereto.

Referring to FIG. 1, the tire 10 includes a tread part 100, a sidewall part 200, and a bead part 300.

The tread portion 100 is a portion in contact with the ground in cross section, and serves to protect the tire from impact and trauma from the road surface. A plurality of blocks partitioned by grooves may be formed on the surface of the tread portion as described above to improve the drainage characteristics of the tire.

A rubber composition according to an embodiment of the present invention is included in the tread.

The sidewall 200 and the bead 300 are sequentially positioned on both sides along the width direction of the tire with the tread portion as the center.

The sidewall 200 is a part that extends from both ends of the tread to form the side surfaces of the tire, withstands continuously repeated contraction and expansion during driving, and protects the carcass layer 400 located on the inner surface. Do it.

The bead part 300 is provided at both ends of the sidewall 200 to surround the end of the cord paper, and the bead part 300 includes a bead core 500 including a ring-shaped steel wire.

A carcass layer 400 is positioned between the pair of left and right bead portions 300, and is bonded to the tire rubber sheet inside the tire to form the skeleton of the tire, and the carcass layer 400 is the bead core 500 ) It is winding up from the inside of the tire to the outside.

An inner liner 700 is located on one side of the inner side of the carcass layer 400 and serves to prevent air inside the tire from escaping to the outside.

The belt layer 600 is positioned on the outer surface of the carcass layer 400 located on the tread portion 100 as a reinforcing layer that increases the elasticity of the tread and has maneuverability and stability.

The belt layer rubber may include a cobalt compound, and the cobalt compound is a cobalt salt, a cobalt-boron ester, an organic acid cobalt salt, an inorganic acid cobalt salt, a non-cobalt salt, etc., and as an adhesion system, cobalt salt alone, cobalt- In addition to RH and cobalt-HRH, resins (e.g., methylene acceptor: phenolic, resorcinol, cresol, etc., or donor: hexamethylenetetraamine (HMT), hexamethoxymethylmelamine (HMMA), pentamethoxymethyl) Melamine (PMMA)] modified adhesive system.

In general, to improve adhesion, improve the adhesion system of adhesive compounded rubber (cobalt-RH, cobalt-HRH, their modification system), improve resins used as adhesion aids and improve performance, improve cobalt salts used as adhesion aids, adhesion Improvement of the vulcanization system of rubber and the use of new compounding compositions (reinforcing agents, carbon black, silica, polymers, chemicals) are being used.

The content of the cobalt compound may include 0.2 to 5.0 parts by weight based on 100 parts by weight of the raw rubber, but is not limited thereto.

A cap ply 800 including a hybrid cord may be disposed between the belt layer 600 and the tread portion 100. The cap ply 800 may suppress the flow of the belt layer 600 during driving to maintain the performance of the tire.

에 이르는 최대 온도, 바람직하게는 135 내지 160

의 온도에서 열기계적 처리 또는 혼련시키는 제1 단계(non-productive step)및 가교결합 시스템이 혼합되는 피니싱 단계 동안, 전형적으로 110

미만, 예를 들면 40 내지 100

의 저온에서 기계적 처리하는 제2 단계(productive step)를 사용하여 적당한 혼합기 속에서 제조할 수 있으나, 이에 한정되는 것은 아니다.The tire tread rubber composition may be prepared through a conventional two-step continuous manufacturing process. I.e. 110 to 190

Maximum temperature up to, preferably from 135 to 160

During the first step of thermomechanical treatment or kneading at a temperature of (non-productive step) and the finishing step in which the crosslinking system is mixed, typically 110

Less than, for example 40 to 100

It can be prepared in a suitable mixer using a second step (productive step) of mechanical treatment at a low temperature, but is not limited thereto.

The tire according to another embodiment of the present invention includes the step of using the tire tread rubber composition when forming a green tire. The method of shaping a green tire using the tire tread rubber composition may be applied to any method used in conventional tire manufacturing, and detailed descriptions thereof will be omitted herein.

1 illustrates a tire for a passenger car, but is not limited thereto, and may be a tire for a passenger car, a tire for racing, an airplane tire, a tire for agricultural machinery, an off-the-road tire, a truck tire, a bus tire, and the like. have. In addition, the tire may be a radial tire or a bias tire, preferably a radial tire.

The present invention will be described in more detail through the following examples and comparative examples. However, the examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Example 1, 2 and Comparative example 1, 2

Each of the components in Table 1 below was added to a Banbury mixer in the ratio (unit: parts by weight) and mixed. After all the ingredients were added to the Tangential type Banbury mixer, the ratio of each ingredient was adjusted so that the fill factor of 1.65L capacity was 0.65 to 0.70.

division Comparative example One Comparative example 2 Example One Example 2 BR 15 15 15 - SBR 85 85 85 100 Silica ^{1 )} 100 100 100 100 Silane coupling agent ^{2 )} 8.0 8.0 8.0 8.0 Oil ^{3 )} 35.6 35.6 35.6 35.6 Compound 1 ⁴⁾ - - 1.24 1.24 Compound 100 ⁵⁾ - 1.24 - - Active ZnO 2.0 2.0 2.0 2.0 Accelerator ⁶⁾ 1.5 1.5 1.5 1.5 sulfur 1.1 0.88 0.88 0.88

1) EVONIK, HD-165GR

2) Si-69

3) RAE

4)

One

5)

100

6) Accelerator: N,N-Dicyclohexyl-2-benzothiazolesulfenamide

When mixing the rubber composition, compound 1 and compound 100 were added in the first step.

Evaluation example

Evaluation of vulcanized rubber properties

The rubber sheets prepared from the rubber compositions of Comparative Examples 1 and 2 and Examples 1 and 2 were vulcanized in a curing machine at 165° C. for 10 minutes to prepare a specimen. For each specimen, physical properties such as hardness and tensile strength were evaluated. The results are shown in Table 4 below.

HD(hardness)

According to ASTM D2240-97, a single specimen was measured five times on a smooth surface with a thickness of 6 mm or more and a diameter of 10 mm or more using a Shore A type hardness tester, and the average value was determined.

Tensile properties

The measurement of the tensile strength of the crosslinked specimen was performed according to ASTM D412 using a tensile tester (INSTRON). The measurement specimen was manufactured in a sheet form using a hydraulic press and a dumbbell type using a specimen cutter. As for the test conditions, the tensile speed was measured at 500 mm/min at room temperature. Tensile strength (T/S) is a value representing the stress value until the test piece is broken in a tensile tester, and the force received per unit area was measured.

Elongation

The elongation was measured by a method in which the strain value until the test piece was broken in a tensile tester was expressed in %.

Dynamic characteristics

As a dynamic characteristic, viscoelasticity was measured using a Gabo viscometer measuring device to measure Tanδ values from -80°C to 70°C under 10Hz frequency at 0.2% strain. At this time, the temperature having the highest Tanδ value is defined as the glass transition temperature, and the smaller the Tanδ value at 60°C, the less heat generated during driving and the better the rolling resistance (RR).

0℃ tanδ indicates wet performance, and it can be said that the higher the value, the better.

Wear

William Abrasion

Lambourn Abrasion

-. Abrasion test: Contact between tread rubber and wheel (abrasive) among vulcanized rubber

Set the pressure (load) and measure the amount of wear caused by rotating friction.

-. Wear rate (%): In the weight of the initial specimen, the percentage of the amount worn away by friction

-. William: The specimen is fixed, the grinding stone rotates, and the measurement method with high severity

-. Lambourn: By rotating the axis of the specimen and the grinding stone at the same time, the difference in rotation speed between the two axes is reduced.

A device that causes abrasion by slipping

-. For both William and Lambourn, lower values are better (meaning less wear)

The evaluation results are shown in Table 2 below.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Hardness 73 74 74 74 300% modulus (kg/cm2) 104 105 115 122 Tensile strength (kg/cm2) 225 227 231 230 0℃ E'' 40 38 39 58 60℃ tanδ 0.150 0.151 0.147 0.148 William Abrasion (wt.loss %) 0.646 0.602 0.287 0.679 Lambourn Abrasion (wt.loss %) 0.160 0.154 0.143 0.118

From the results of Table 2, it can be seen that physical properties such as hardness, modulus, and tensile strength were similar in Examples 1 and 2 and Comparative Examples 1 and 2.

0°C E'' corresponding to wet braking performance is equivalent to Comparative Examples 1 and 2 in Example 1, and it can be seen that Example 2 is superior to Comparative Examples 1 and 2, and 60°C tanδ corresponding to fuel economy performance It can be seen that Examples 1 and 2 are superior to Comparative Examples 1 and 2.

In the case of abrasion, it can be seen that Example 2 in William Abrasion is equivalent to Comparative Examples 1 and 2, and Example 1 is superior to Comparative Examples 1 and 2, and in Lambourn Abrasion, Examples 1 and 2 are Comparative Examples 1 and 2 It can be seen that it is better than 2.

As described above, although it has been described with reference to preferred embodiments of the present invention, those skilled in the art will variously modify the present invention within the scope not departing from the spirit and scope of the present invention described in the following claims. Or it can be implemented by modification.

10: tire
100: tread
200: side wall part
300: bead part
400: carcass layer
500: bead core
600: belt layer
700: inner liner
800: cap fly

Claims (10)

Raw rubber consisting of styrene butadiene rubber (SBR) and butadiene rubber (BR); And a tire tread rubber composition comprising a compound of the following formula (1):
<Formula 1>

In Formula 1,
X ₂ represents N, X ₁ represents CR ₁ , X ₃ represents CR ₃ , X ₅ represents N, X ₄ represents CR ₄ , X ₆ represents CR ₆ , R ₁ , R ₃ , R ₄ , R ₆ , R ₁₁ and R ₁₂ each independently represent hydrogen or a halogen group; or
X ₃ represents N, X ₁ represents CR ₁ , X ₂ represents CR ₂ , X ₆ represents N, X ₄ represents CR ₄ , X ₅ represents CR ₅ , R ₁ , R ₂ , R ₄ , R ₅ , R ₁₁ and R ₁₂ each independently represent hydrogen or a halogen group,
m and n each independently represent an integer of 1 or 2. delete delete delete delete The method of claim 1,
Tire tread rubber composition wherein the rubber composition comprises 1.0 to 2.0 parts by weight of the compound of Formula 1 based on 100 parts by weight of raw rubber. The method of claim 1,
Tire tread rubber composition wherein the compound of Formula 1 is any one of the following compounds:

3

4 The method of claim 1,
Tire tread rubber composition wherein the rubber composition contains silica as a filler. The method of claim 8,
The silica is a tire tread rubber composition comprising 80 to 120 parts by weight based on 100 parts by weight of raw rubber. A tire made of the tire tread rubber composition of claim 1.

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