KR20200009792A - Rubber composition and Tire comprising rubber composition - Google Patents

Abstract

The present invention provides a tire belt rubber composition, comprising: raw rubber selected from the group consisting of natural rubber and a blend of natural rubber and synthetic rubber derived from diene monomers; a cobalt compound; and a compound of formula (I). The tire belt rubber composition is excellent in adhesion to steel cords at a high temperature and high humidity.

Description

Tire belt rubber composition and tire comprising same

A tire belt rubber composition and a tire comprising the same.

In general, the belt of the tire functions to increase the rigidity of the tread portion by overlapping the steel cord layer. Accordingly, the belt rubber should have good adhesion with steel cords and have strong resistance to aging even in long-term driving. This requires belt rubbers that have high modulus and are advantageous for fatigue performance.

The common cobalt salt of the steel cord coated rubber mixture promotes the crosslinking reaction of sulfur contained in this rubber mixture in large quantities. This increase in crosslinking density increases the pulling force between the rubber and the steel cord.

More importantly, the cobalt salt forms cobalt (Co) ions from the brass surface during the crosslinking reaction, which helps to form copper sulfide (CuS).

The difference in efficiency between cobalt adhesion promoters lies in how quickly cobalt ions are formed. For example, zinc (Zn) or brass (Brass) is easier to work with Coalt Boron Decanoate Complexes than Cobalt Napthanate or Cobalt Stearate.

However, the adhesion between the cobalt compound and the steel cord weakens with increasing vehicle travel distance. This is an important issue as it relates to safety.

In the case of using a cobalt compound, the initial adhesive strength immediately after vulcanization is excellent, but the adhesive strength after aging due to heat and moisture is poor. Especially in hot and humid areas, the adhesion by moisture is lowered, and the steel cord is exposed to the outside, resulting in tire destruction.

One aspect is to provide a tire belt rubber composition with excellent adhesion in hot and humid areas.

Another aspect is to provide a belt comprising the tire belt rubber composition.

Another aspect is to provide a tire comprising the belt.

According to one aspect,

Raw rubbers selected from the group consisting of natural rubbers and blends of natural rubbers with synthetic rubbers derived from diene monomers;

Cobalt compounds; And

A tire belt rubber composition is provided comprising a compound of formula

<Formula 1>

According to the other side,

A belt comprising the tire belt rubber composition is provided.

According to another aspect,

A tire comprising the belt is provided.

According to one embodiment of the invention, the tire belt rubber composition comprising the raw rubber, the cobalt compound and the compound of formula 1 is excellent in adhesion to the steel cord in high temperature and high humidity region.

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

Hereinafter, an exemplary tire belt rubber composition, a belt including the same, and a tire including the belt will be described in more detail.

The inventive idea disclosed in this specification may apply various transformations and have various implementations, and specific embodiments are described in detail in the detailed description and, where necessary, specific embodiments are illustrated in the drawings. Effects and features of the inventive concept and methods of achieving them will be apparent with reference to the embodiments described below in detail with reference to the drawings. However, the inventive concept of the present specification is not limited to the embodiments disclosed below, but may be implemented in various forms.

In the following embodiments, the terms first, second, etc. are used for the purpose of distinguishing one component from other components rather than having a limiting meaning.

In the following embodiments, the singular forms “a”, “an” and “the” include plural forms unless the context clearly indicates otherwise.

In the following embodiments, the terms including or having have meant that there is a feature or component described in the specification and does not preclude the possibility of adding one or more other features or components.

If one embodiment is 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 concurrently, or may be performed in the reverse order.

DETAILED DESCRIPTION Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, and the same or corresponding components will be denoted by the same reference numerals, and redundant description thereof will be omitted. Shall be.

In the drawings, components may be exaggerated or reduced in size for convenience of description. For example, since the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of description, the inventive concept disclosed herein is not necessarily limited to the illustrated.

Tire belt rubber compositions according to one embodiment include a raw rubber selected from the group consisting of natural rubber and a blend of natural rubber and synthetic rubber derived from diene monomers; Cobalt compounds; And compounds of Formula 1

<Formula 1>

According to an embodiment of the present invention, the compound of Formula 1 may be any one of the following Formulas 1-1 to 1-3.

For example, the compound of Formula 1 may be Compound 1-3.

According to an embodiment of the present invention, the rubber composition may include natural rubber as a raw rubber. 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, the modified natural rubber may include epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, and the like.

Natural rubbers include various forms thereof, such as pale crepes and smoked sheets, and balata and gutta percha. The rubber may be only natural rubber or a blend of natural rubber and synthetic rubber. Synthetic polymers are derived from diene monomers and include polymers (monopolymers) made from a single monomer or mixtures (copolymers) of two or more copolymeric monomers in which the monomers are combined in an irregular distribution or block form. The monomers may or may not be substituted and may have monoolefins, including one or more double bonds, conjugated dienes and nonconjugated dienes, and cyclic monoolefins and acyclic monoolefins, in particular vinyl and vinylidene monomers. have. Examples of conjugated dienes include 1,3-butadiene, isoprene, chloroprene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene and piperylene. Examples of non-conjugated dienes include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, dicyclopentadiene, 1,5-cyclooctadiene and ethyldiene norbornene. Examples of acyclic monoolefins include ethylene, propylene, 1-butene, isobutylene, 1-pentene and 1-hexene. Examples of cyclic monoolefins include cyclopentene, cyclohexene, cycloheptene, cyclooctene and 4-methyl-cyclooctene. Examples of vinyl monomers include styrene, acrylonitrile, acrylic acid, ethylacrylate, vinyl chloride, butylacrylate, methyl vinyl ether, vinyl acetate, and vinyl pyridine. Examples of vinylidene monomers include alpha-methylstyrene, methacrylic acid, methyl methacrylate, itaconic acid, ethyl methacrylate, glycidyl methacrylate and vinylidene chloride. Representative examples of synthetic polymers used in the practice of the present invention are polychloroprene homopolymers of conjugated 1,3-dienes, such as isoprene and butadiene, and in particular polyisoprene and poly, in which all repeat units are essentially cis-1,4-structured. butadiene; Copolymers of conjugated 1,3-dienes such as isoprene and butadiene, such as ethylenically unsaturated monomers such as styrene or acrylonitrile, wherein at least one copolymerizable monomer is 50% by weight or less; And butyl rubber, which is a polymerization product of large amounts of monoolefins and small amounts of diolefins such as butadiene or isoprene. The rubber may be emulsion polymerized or solution polymerized. Preferred synthetic rubbers that may be used in the present invention include cis-1,4-polyisoprene; Polybutadiene; Polychloroprene and copolymers of isoprene and butadiene; Copolymers of acrylonitrile and butadiene; Copolymers of acrylonitrile and isoprene; Copolymers of styrene, butadiene and isoprene; Copolymers of styrene and butadiene and blends thereof. The compounds of the present invention preferably have natural rubber present, but may partially replace natural rubber with any synthetic rubber. Preferred rubbers that can be used in the present invention are natural rubbers; And cis-1,4-polyisoprene, polybutadiene, copolymers of isoprene and butadiene, copolymers of acrylonitrile and butadiene, copolymers of styrene and butadiene and isoprene, copolymers of styrene and butadiene, and blends thereof It may be a blend of synthetic rubbers selected from the group.

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

The silica can be used as long as it is generally known, for example, commercially available Z-175, US7000GR or 9000GR and the like can be used.

When the content of the silica is less than 1 part by weight based on 100 parts by weight of the raw material rubber, the effect of adding the silica is insignificant, and when it exceeds 20 parts by weight, there may be a problem in terms of processability.

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

The 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.

If the carbon adsorption specific surface area of the carbon black exceeds 300m ² / g may be detrimental processability of the rubber composition for tires, if 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 of the carbon black is less than 60cc / 100g, the reinforcing performance by the carbon black as a filler may be detrimental.

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 carbon black may be included in an amount of 30 to 80 parts by weight based on 100 parts by weight of the raw material rubber, preferably 45 to 65 parts by weight, and more preferably 53 to 57 parts by weight. When the content of the carbon black is less than 30 parts by weight, the reinforcing performance by the carbon black as a filler may be reduced, and when the content is more than 80 parts by weight, the processability of the rubber composition may be deteriorated.

The tire belt rubber composition may optionally further include various additives such as additional vulcanizing agents, vulcanization accelerators, vulcanization accelerators, anti-aging agents, antioxidants, or softeners. The various additives may 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 belt rubber composition.

As said vulcanizing agent, a sulfur type vulcanizing agent can be used preferably. 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 for producing elemental sulfur or sulfur, for example, amine disulfide, polymer sulfur, and the like can be used.

The vulcanizing agent is preferably included in an amount of 0.5 to 10.0 parts by weight based on 100 parts by weight of the raw material rubber, in that the raw material rubber is less sensitive to heat and chemically stable.

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

The vulcanization accelerators include 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-based 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 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.

The thiourea-based vulcanization accelerator, for example, thiacarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea, and any one selected from the group consisting of a combination 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. 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.

Examples of the aldehyde-amine-based or aldehyde-ammonia-based vulcanization accelerators include aldehyde selected from the group consisting of acetaldehyde-aniline reactants, butylaldehyde-aniline condensates, hexamethylenetetramine, acetaldehyde-ammonia reactants, and combinations thereof. -Amine based or aldehyde-ammonia based compounds can be used.

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

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

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

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. 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.

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 and 0.5 to 3 parts by weight based on 100 parts by weight of the raw material rubber, respectively, to serve as a suitable vulcanization accelerator. When the content of zinc oxide and the stearic acid is less than the above range, the vulcanization rate may be low, and productivity may be lowered. When the zinc oxide and the stearic acid are below the above range, a scorch phenomenon may occur and the physical properties may be reduced.

The softener is added to the rubber composition in order 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 refers to oils included in process oil or other rubber compositions. 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 Co., Ltd. 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, with the recent increase in environmental awareness, when the content of polycyclic aromatic hydrocarbons (hereinafter referred to as PAHs) contained in the aromatic oils is 3% by weight or more, it is known that cancer is likely to occur. Treated distillate aromatic extract (oil) 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 or more (210 ° F. SUS), an aromatic component in the softener of 15 to 25% by weight, and a naphthenic component. TDAE oils having 27 to 37% by weight and 38 to 58% by weight of the paraffinic component can be preferably used.

The TDAE oil has excellent properties in terms of environmental factors such as the low-temperature characteristics of the tire 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 0 to 10 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. Examples of the phenolic anti-aging agent include phenolic 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-isobutylidene-bis (4,6-dimethylphenol) and 2 Any one selected from the group consisting of, 6-di-t-butyl-p-cresol and combinations thereof can be used. As the quinoline-based antioxidant, 2,2,4-trimethyl-1,2-dihydroquinoline and its derivatives 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. Wax hydrocarbons may be preferably used as the wax.

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

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

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 the cross-section, and serves to protect the tire from the impact from the road surface, trauma. The surface of the tread portion may be formed with a plurality of blocks partitioned by grooves for drainage directivity of the tire.

Sidewalls 200 and the bead portion 300 are sequentially positioned on both sides of the tread portion along the width direction of the tire.

Sidewall 200 is a portion extending from both ends of the tread to form the side of the tire, withstands repeated repeated contraction and inflation while 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 side wall 200 to surround the end of the cord paper, and the bead part 300 includes a bead core 500 including a steel wire in the form of a ring.

A carcass layer 400 is positioned between the left and right pairs of bead portions 300, and is bonded to a tire rubber sheet in the tire to form a skeleton of the tire, and the carcass layer 400 is a bead core 500. ) The circumference is wound up from the inside of the tire to the outside.

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

The belt layer 600 may be positioned on the outer surface of the carcass layer 400 positioned in the tread portion 100 as a reinforcing layer to increase the elasticity of the tread and to have maneuverability and stability.

Tire belt rubber composition according to an embodiment of the present invention is included in the belt layer.

The tire belt rubber composition includes 0.5 to 5 parts by weight of the compound of Formula 1 with respect to 100 parts by weight of the raw material rubber of the compound of Formula 1 described above.

When the content of the compound of Formula 1 is less than 0.5 parts by weight based on 100 parts by weight of the raw material rubber, the effect of adding the compound of Formula 1 is insignificant, and when it exceeds 5 parts by weight, there may be a problem in that the adhesive strength decreases. The content of the compound of Formula 1 may be preferably 1.0 to 4.0 parts by weight based on 100 parts by weight of the raw rubber.

The tire belt rubber composition further includes a cobalt compound in addition to the compound of Formula 1 described above.

As the cobalt compound, cobalt salt, cobalt-boron ester, organic acid cobalt salt, inorganic acid cobalt salt, bicobalt salt, and the like are used, and as an adhesive system, in addition to cobalt salt alone, cobalt-RH, cobalt-HRH, Methylene acceptor: phenolic, resorcinol, cresol, etc. or donor: hexamethylenetetraamine (HMT), hexamethoxymethylmelamine (HMMA), pentamethoxymethylmelamine (PMMA); have.

 In general, to improve adhesion, the adhesion system of the adhesive compound rubber is improved (cobalt-RH, cobalt-HRH, modified system thereof), the resin and the performance of the resin used as an adhesion aid, the cobalt salt used as an adhesion aid, the adhesion Improvement of the vulcanization system of rubber and the use of new formulations (adjuvant, carbon black, silica, polymers, chemicals).

The content of the cobalt compound may include 0.1 to 3 parts by weight based on 100 parts by weight of the raw rubber, but is not limited thereto.

When the content of the cobalt compound is less than 0.1 part by weight based on 100 parts by weight of the raw material rubber, the effect of adding the cobalt is insignificant, and when the content of the cobalt is more than 3 parts by weight, there may be a problem that the adhesive strength is reduced. The content of the cobalt compound may be preferably 0.5 to 0.7 parts by weight based on 100 parts by weight of the raw rubber.

The tire belt rubber composition may be prepared through a conventional two-step continuous manufacturing process. That is, during the first step of thermomechanical treatment or kneading at a maximum temperature ranging from 110 to 190 ° C., preferably from 130 to 180 ° C. and the finishing step in which the crosslinking system is mixed, typically less than 110 ° C., for example It can be prepared in a suitable mixer using a second step of mechanical treatment at a low temperature of 40 to 100 ℃, but is not limited thereto.

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

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

The tire belt rubber composition according to another embodiment of the present invention may be used in a steel belt to form a belt for a tire.

Tire according to another embodiment of the present invention includes the step of using the belt when forming a green tire. The method for manufacturing a tire belt using the tire belt rubber composition and the method for molding a green tire using the belt may be applied to any method used in the manufacture of a tire in the related art. Is omitted.

The present invention is described in more detail through the following examples and comparative examples. However, the examples are provided to illustrate the present invention, and the scope of the present invention is not limited only to these examples.

Example  1 to 3 and Comparative example  1 to 5

The composition shown in Table 1 below was added to the half-barrier mixer to mix the rubber compositions of Examples and Comparative Examples.

Material (phr) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Example 1 Example 2 Example 3 Natural rubber 100 100 100 100 100 100 100 100 Carbon black ^{1 )} 60 60 60 60 60 60 60 60 Cobalt ^{2 )} One One One One 3.5 One One One Formaldehyde resin One One One One One One One One Benzoic acid POB ^{3 )} - - - 7 One 0.5 One 5 A ⁴⁾ - One - - - - - - B ⁵⁾ - - One - - - - - sulfur 7.5 7.5 7, .5 7.5 7.5 7.5 7.5 7.5 Accelerator ^{6 )} 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

1) Carbon Black: N326 (OCI)

2) Cobalt: C-22.5 (Taekwang Fine Chemical)

3) POB: para-hydroxyl benzoic acid

4) A:

5) B:

6) Accelerator: DCBS (SHANDONG SUNSHINE)

The prepared rubber sheet was vulcanized at 160 ° C. for 10 minutes to prepare specimens for measurement of tear properties and fatigue properties. In addition, the steel sheet (3 * 0.30 HT) in the rubber sheet prepared above and vulcanized at 160 ℃ for 16 minutes in a vulcanizer to prepare a specimen for measuring the adhesive force.

Evaluation example

The physical properties of the specimens prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were evaluated as follows, and the results are shown in Table 2 below.

HD (hardness)

More than 6mm thick, 10mm diameter according to ASTM D2240-97 using Shore A hardness tester

In the above smooth aspect, one specimen was measured a total of five times and was determined as the average value.

Tensile Properties

Tensile strength measurement of the crosslinked specimen was carried out in accordance with ASTM D412 using a tensile tester (INSTRON). The test specimen was manufactured in the form of a sheet using a hydraulic press and a dumbbell type using a specimen cutter. Test conditions were measured at 500 mm / min tensile rate at room temperature

M-300 represents the stress value at 300% elongation of the tensile tester and measured the force per unit area.

Tensile strength (T / S) is a value representing the stress value until the test piece is broken in the tensile tester was measured the force received per unit area.

E / B is the elongation at break of the specimen in the tensile tester.

Adhesion

The initial adhesive force of the comparative example 1 was set to 100, and the initial adhesive force, the heat resistant adhesive force, and the wet heat adhesive force of the other comparative example and the Example were measured and compared.

The heat-resistant adhesive strength represents the adhesive strength between the steel cord and the vulcanized rubber after aging at 100 ° C. for 12 days, and the higher the value, the higher the tire safety.

The wet heat adhesive strength is the value of the adhesive strength between the steel cord and the vulcanized rubber after aging at 85 ° C. 95% humidity for 12 days. The higher the value, the higher the tire safety.

Tire durability (hr)

Tire endurance was aged 35 days at 60 ℃, 95% humidity after injecting air of 80% oxygen / 20% nitrogen at 350kpa internal pressure. After that, the tire breaking time was measured while driving 60 km / h at 200% load. The higher the time, the more stable the tire.

Evaluation item Comparative example Example One 2 3 4 5 One 2 3 HD [hardness] 76 75 75 75 76 75 75 76 M-300 (kgf / cm ² ) 155 150 152 154 160 158 155 155 T / S (kgf / cm ² ) 230 232 240 246 240 240 250 243 E / B (%) 440 440 430 420 410 470 460 470 Initial adhesion 100 100 98 102 115 98 100 102 Heat resistance index 40 55 60 45 25 60 70 65 Wet heat adhesiveness (index) 55 50 45 50 25 70 80 75 Tire durability (hr) 35 36 20 27 17 200 245 220

From the results of Table 2, the vulcanized rubber of the compositions of Examples 1 to 3 of the present invention, HD, M-300, T / S, initial, etc. showed similar levels as those of Comparative Examples 1 to 5, E / B, It can be seen that the heat-resistant adhesive strength, wet heat adhesive strength, tire durability, and the like are much better than those of the comparative example. In addition, it can be seen that the embodiment of the present invention shows better physical properties than Comparative Examples 2 and 3 using benzoic acid derivatives A or B.

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

Claims (7)

Raw rubbers selected from the group consisting of natural rubbers and blends of natural rubbers with synthetic rubbers derived from diene monomers;
Cobalt compounds; And
A tire belt rubber composition comprising a compound of formula
<Formula 1>

. The method of claim 1, wherein the rubber is natural rubber; And cis-1,4-polyisoprene, polybutadiene, copolymers of isoprene and butadiene, copolymers of acrylonitrile and butadiene, copolymers of styrene and butadiene and isoprene, copolymers of styrene and butadiene, and blends thereof A tire belt rubber composition, which is a blend of synthetic rubbers selected from the group. The tire belt rubber composition of claim 1, wherein the compound of Formula 1 is any one of Formulas 1-1 to 1-3:

. The tire belt rubber composition according to claim 1, wherein the rubber composition comprises 0.5 to 5 parts by weight of the compound of Formula 1 based on 100 parts by weight of the raw rubber. The tire belt rubber composition according to claim 1, wherein the rubber composition comprises 0.1 to 3 parts by weight of the cobalt compound with respect to 100 parts by weight of the raw rubber. A belt comprising the tire belt rubber composition of any one of claims 1 to 5. A tire comprising the belt of claim 6.

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