KR102205463B1 - Rubber composition for tire belt and Tire comprising same - Google Patents

Abstract

Tire belt rubber composition containing a compound containing a thiocarbamoyldithio group and a bis-citraconimide compound, a tire belt containing the rubber composition, and the belt Tires are provided.

Description

Tire belt rubber composition and tire comprising the same TECHNICAL FIELD

It relates to 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 by overlapping the steel cord layer. Therefore, the belt rubber must have good adhesion to the steel cord and have strong resistance to aging even during long-term running. For this, a belt rubber that has a high modulus and is advantageous for fatigue performance is required.

The common cobalt salt of the steel cord coated rubber mixture accelerates the crosslinking reaction of the sulfur contained in the rubber mixture. 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 they form cobalt ions. For example, zinc (Zn) or brass (Brass) works more easily with Coalt Boron Decanoate Complexes than Cobalt Napthanate or Cobalt Stearate.

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

There may be several causes of such weakening of adhesion, but one of the reasons is that the physical properties of the belt rubber itself are weakened due to the breakage of crosslinking between the rubber molecular chains due to continuous bending and fatigue caused by driving. Since the vehicle is driven at high speed, the internal temperature of the tire reaches about 120°C. At such a high temperature, it causes friction with the ground, and by the continuous rotational motion, fatigue begins to accumulate due to bending, and weak areas between the rubber molecular chains begin to break. The three-dimensional network is destroyed, resulting in a decrease in elasticity, and the cracks generated may progress over time, leading to a large-scale accident where the belt layer of the tire speararion.

Therefore, along with the adhesive strength of the tire belt rubber, the physical properties of the tire belt rubber itself are also very important, and there is a continuous demand for this.

One aspect is to provide a tire belt rubber composition comprising a compound comprising a thiocarbamoyldithio group and a bis-citraconimide-based compound as a tire belt rubber composition.

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

Another aspect is to provide a tire with the tire belt.

According to one aspect,

There is provided a tire belt rubber composition comprising a compound containing a thiocarbamoyldithio group and a bis-citraconimide-based compound.

According to the other side,

There is provided a tire belt comprising the tire belt rubber composition.

According to another aspect,

A tire provided with the tire belt is provided.

According to one aspect, a tire belt rubber composition containing a compound containing a thiocarbamoyldithio group and a bis-citraconimide-based compound is a high-temperature, harsh rubber molecular chain crosslinked. Even after disconnection in the environment, carbon-carbon bonds are generated and connected, thereby maintaining the physical properties of the belt rubber, which can greatly contribute to tire safety.

1 is an exemplary diagram showing a state in which rubber molecular chains crosslinked in a harsh environment of high temperature are broken (left) and reconnected (right).
2 is an enlarged view of the left circle of FIG. 1.
3 is an enlarged view of the right ellipse of FIG. 1.
4 is a diagram schematically showing the structure of a tire according to an embodiment.

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

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 implementation examples 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, a singular expression includes a plural expression 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 belt rubber composition according to an embodiment includes a compound containing a thiocarbamoyldithio group and a bis-citraconimide-based compound.

The thiocarbamoyl disthio group is a substituent having a chemical structure of -SS-(C=S)-NH ₂ , and according to an embodiment of the present invention, the compound containing the thiocarbamoyl disthio group is 1 ,6-bis(N,N-dibenzylthiocarbamoyldithio)-hexane[1,6-bis(N,N-dibenzylthiocarbamoyldithio)-hexane].

1,6-bis(N,N-dibenzylthiocarbamoyldisio)-hexane[DBTH] has the following structure.

Sulfur connecting the rubber molecular chain and usually form a three dimensional network by binding to the radical is generated by cleavage at 160 ℃ as the structure of the S _8, double bond next to the seat (allylic position) of the generated radicals are predominantly rubber molecular chain, That is, it is crosslinked to exhibit elasticity.

On the other hand, when curing at high temperature at 180°C, reversal may occur, and DBTH has been used to prevent this. DBTH is decomposed in the vulcanization process and plays a role in reducing the sulfur rank between rubber molecular chains to prevent reversal, but has a disadvantage in that tear and fatigue properties become weak.

In particular, in the case of a belt rubber that causes friction with the ground at a high temperature of 120°C and accumulates fatigue due to continuous rotational motion of the tire, strong resistance to fatigue properties is required.

The tire belt rubber composition according to an embodiment of the present invention solves this problem by including a bis-citraconimide-based compound.

According to an embodiment of the present invention, the bis-citraconimide-based compound is 1,1'-[1,3-phenylenebis(methylene)]bis(3-methyl-1H-pyrrole- 2,5-dione)[1,1'-[1,3-Phenylenebis(methylene)]bis(3-methyl-1H-pyrrole-2,5-dione)].

1,1'-[1,3-phenylenebis(methylene)]bis(3-methyl-1H-pyrrole-2,5-dione) has the following structure.

It will be described using the drawings as follows.

Referring to FIG. 1, the crosslinked rubber molecular chains are disconnected in a harsh environment at high temperature (left of FIG. 1), and the tire belt rubber composition according to an embodiment of the present invention has a carbon-carbon bond formed again. The 3D network is restored (right side of Fig. 1). Fig. 2 is an enlarged view of the left circular part of Fig. 1, and Fig. 2 shows that a part including two double bonds exists in the rubber molecular chain.

Two double bond moieties present in the rubber molecular chain as shown in Fig. 2 and 1,1'-[1,3-phenylenebis(methylene)]bis(3-methyl-1H-pyrrole-2,5-dione) When this Diels-Alder bond is performed, the broken rubber molecular chains are reconnected as shown on the right side of FIG. 1. The oval part on the right side of FIG. 1 is enlarged and shown in FIG. 3, and FIG. 3 shows 1,1'-[1,3-phenylenebis(methylene)]bis(3-methyl-1H-pyrrole-2,5- It is shown schematically that the imide moiety of dione) is bonded with two double bond moieties present in the rubber molecular chain to form a CC bond.

Therefore, the tire belt rubber composition according to an embodiment of the present invention has excellent tear properties, fatigue properties, and the like, since the broken rubber molecular chains can be recombined under severe conditions.

According to an embodiment of the present invention, the rubber composition is 1,6-bis(N,N-dibenzylthiocarbamoyldithio)-hexane[1,6-bis(N ,N-dibenzylthiocarbamoyldithio)-hexane] may be included in an amount of 0.1 to 1.0 parts by weight.

When the content of the 1,6-bis(N,N-dibenzylthiocarbamoyldithio)-hexane is less than 0.1 parts by weight based on 100 parts by weight of the raw rubber, the 1,6-bis(N,N- The effect of adding dibenzylthiocarbamoyl disio)-hexane is insignificant, and when it exceeds 1.0 part by weight, there may be a problem of deteriorating physical properties.

According to one embodiment of the present invention, the rubber composition may include 1.0 to 2.0 parts by weight of a bis-citraconimide compound based on 100 parts by weight of the raw rubber.

When the content of the biscitraconimide group is less than 1.0 parts by weight based on 100 parts by weight of the raw rubber, there may be no effect of adding the biscitraconimide group, and when it exceeds 2.0 parts by weight, the physical properties There may be a deteriorating problem.

According to one embodiment of the present invention, the rubber composition may include natural rubber as a raw material 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 also contain trans-1,4-polyisoprene depending on the 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.

Natural rubbers include their various forms, for example pale crepes and smoked sheets, and balata and gutta percha. The rubber may be just natural rubber or may be a blend of natural and synthetic rubber. The synthetic polymer is derived from a diene monomer, and includes a polymer (homopolymer) prepared from a single monomer or a mixture (copolymer) of two or more types of copolymeric monomers in which the monomers are bonded in an irregular distribution or block form. The monomer may be substituted or unsubstituted, and may have one or more double bonds, a conjugated diene and a non-conjugated diene, and a monoolefin including a cyclic monoolefin and a non-cyclic mono olefin, and in particular, vinyl and vinylidene monomers. have. Examples of the conjugated diene 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, ethyl acrylate, vinyl chloride, butyl acrylate, 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-diene such as isoprene and butadiene, and in particular polyisoprene and polypolyisoprene in which all repeat units are essentially linked in a cis-1,4- structure. butadiene; Copolymers of conjugated 1,3-diene such as isoprene and butadiene, in which at least one copolymerizable monomer is 50% by weight or less (eg, ethylenically unsaturated monomers such as styrene or acrylonitrile); And butyl rubber, which is a polymerization product of a large amount of monoolefin and a small amount of diolefin (eg butadiene or isoprene). The rubber may be emulsion polymerized or solution polymerized.

Preferred synthetic rubbers that can also be used in the present invention include cis-1,4-polyisoprene; Polybutadiene; Polychloroprene and copolymers of isoprene and butadiene; A copolymer of acrylonitrile and butadiene; A copolymer of acrylonitrile and isoprene; Styrene, a copolymer of butadiene and isoprene; Copolymers of styrene and butadiene and blends thereof. Since the compound of the present invention is used as a wire coating composition, it is preferred that natural rubber is present, but it is also possible to partially replace the 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, a copolymer of isoprene and butadiene, a copolymer of acrylonitrile and butadiene, a copolymer of styrene and butadiene and isoprene, a copolymer 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 present invention, the rubber composition may include a filler, for example, may include silica 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.

When the content of the silica is less than 1 part by weight based on 100 parts by weight of the raw 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 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, 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, 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.

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 reinforcement performance by carbon black as a filler may be disadvantageous. In addition, if the DBP oil absorption amount of the carbon black exceeds 180cc/100g, the processability of the rubber composition may be deteriorated, and if 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 30 to 80 parts by weight, preferably 45 to 65 parts by weight, and more preferably 53 to 57 parts by weight based on 100 parts by weight of the raw rubber. If 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 deteriorated, and if it exceeds 80 parts by weight, the processability of the rubber composition may be disadvantageous.

The tire belt 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. The various additives may be used as long as they are commonly used in the field to which the present invention pertains, and their content is not particularly limited as a bar depending on the blending ratio used in a typical tire belt rubber composition.

As the curing agent, a sulfur-based curing agent may 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 it is preferable that the raw rubber is less sensitive to heat and 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 can 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, zinc salt of 2-mercaptobenzothiazole , Copper salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-di Ethyl 4-morpholinothio) benzothiazole and any one thiazole-based compound selected from the group consisting of combinations thereof may be used.

Examples of the thiuram-based vulcanization accelerator include tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram disulfide, dipentamethylenethiurammonosulfide, 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.

The aldehyde-amine-based or aldehyde-ammonia-based vulcanization accelerator is, 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. As the xanthate-based vulcanization accelerator, for example, xanthate-based zinc dibutyl xanthogenate Compounds can be used.

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

The vulcanization accelerator aid is a blending agent used in combination with the vulcanization accelerator to complete its 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 either.

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 crosslinking reaction of 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 productivity may be lowered. 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 decrease.

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 paraffinic 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 representative examples of the naphthenic oil are 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, MES (mild extraction solvate) oil, RAE (residual aromatic extract) oil, or heavy naphthenic oil may be preferably used.

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

The TDAE oil is advantageous in terms of environmental factors such as 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 softener 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 antiaging 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 action, 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, for example, in 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. 4, 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.

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

The sidewall 200 is a part that extends from both ends of the tread to form the side 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 rolling 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 may be positioned on the outer surface of the carcass layer 400 positioned on the tread portion 100 as a reinforcing layer that increases the elasticity of the tread and has maneuverability and stability.

The rubber composition according to an embodiment of the present invention is included in the belt layer. When the steel belt compound is vulcanized, it proceeds at a high temperature (180℃) to improve productivity. In this case, the steel belt compound with a high ratio of natural rubber destroys the crosslinked structure of the rubber due to the reversal phenomenon. Deterioration occurs. Therefore, preventing the aging of the physical properties of the compound composition in such high-temperature vulcanization can ensure productivity and belt stability at the same time. In particular, the steel belt has a large role of physically supporting and protecting the tire against the load of the vehicle. Therefore, the tear properties and fatigue properties of the steel cord rubber are important.

The tire belt rubber composition according to an embodiment of the present invention has excellent tear properties and fatigue properties since the broken rubber molecular chains can be recombined under severe conditions.

The tire belt rubber composition may include a cobalt compound.

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, and the like, and as an adhesion system, a cobalt salt alone, cobalt-RH, cobalt-HRH, in addition to resins [for example, Methylene acceptor: phenolic, resorcinol, cresol, etc., or donor: hexamethylenetetraamine (HMT), hexamethoxymethylmelamine (HMMA), pentamethoxymethylmelamine (PMMA)] have.

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 Improvements in 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 0.1 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 parts by weight based on 100 parts by weight of the raw rubber, the effect of adding the cobalt is insignificant, and when it exceeds 3 parts by weight, there may be a problem that the adhesive strength decreases. 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 manufactured 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 at a high temperature of 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 the 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 portion 100. The cap ply 800 may suppress the flow of the belt layer 600 while driving to maintain the performance of the tire.

4 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, etc. have. Further, the tire may be a radial tire or a bias tire, preferably a radial tire.

A tire belt according to another embodiment of the present invention includes the tire belt rubber composition.

The tire according to another embodiment of the present invention includes the step of using the belt when forming a green tire. The method of manufacturing a tire belt using the tire belt rubber composition and the method of forming a green tire using a regular belt can be applied to any method as long as it is a method conventionally used for manufacturing a tire, and detailed in the present specification Description is omitted.

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 to 3 and Comparative example 1 to 3

The compositions shown in Table 1 were added to the Banbari mixer to mix the rubber compositions of Examples and Comparative Examples.

Material (phr) Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Natural rubber 100 100 100 100 100 100 Carbon black ¹⁾ 60 60 60 60 60 60 Stearic acid One One One One One One Active ZnO 10.0 10.0 10.0 10.0 10.0 10.0 Amine-based anti-aging agent ²⁾ 2.5 2.5 2.5 2.5 2.5 2.5 Quinoline anti-aging agent ³⁾ 0.5 0.5 0.5 0.5 0.5 0.5 sulfur 7.5 7.5 7.5 7.5 7.5 7.5 Accelerator ⁴⁾ 0.5 0.5 0.5 0.5 0.5 0.5 Cobalt ⁵⁾ 0.5 0.5 0.5 0.5 0.5 0.5 DBTH - 0.5 1.5 0.1 0.5 1.0 Biscitraconimide ⁶⁾ - 2.5 2.0 1.0 1.5 2.0

1) Carbon Black: N326 (OCI)

2) Amine-based anti-aging agent: 6PPD (DUSLO)

3) Quinoline-based anti-aging agent: TMQ (Songwon Industries)

4) Accelerator: DCBS (SHANDONG SUNSHINE)

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

6) Biscitraconimide: 1,1'-[1,3-phenylenebis(methylene)]bis(3-methyl-1H-pyrrole-2,5-dione)

The prepared rubber sheet was vulcanized at 180° C. for 12 minutes to prepare a specimen for measuring tear properties and fatigue properties. In addition, a steel cord (2+2*0.35HT) was put in the rubber sheet prepared above, and a specimen was prepared for measuring adhesion at 180° C. for 12 minutes in a curing machine.

Evaluation example

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

T/S (tensile strength)

Tensile strength was a value representing the stress value until the test piece was broken in a tensile testing machine, and the force received per unit area was measured.

Tan δ @ 60℃

The viscoelasticity was measured by using a Gabo viscometer measuring instrument and measuring the Tan δ value from -60°C to 80°C under 10Hz frequency at 0.2% strain. At this time, the temperature having the highest Tan δ value is defined as the glass transition temperature, and the smaller the Tan δ value at 60°C, the less heat generated during driving, indicating excellent rotational resistance.

Tear Tear

It was measured according to ASTM standard D624. Tear property is a numerical expression of the resistance to cracking of the crosslinked rubber, and the higher the value, the better.

Fatigue properties (measure crack growth)

It was measured according to ASTM standard D813. Crack Grawth is a comparative measure of the degree of crack growth over time due to repetitive motion.

Heat-resistant adhesion measurement

It was measured according to ASTM standard D-2229. Heat-resistant adhesion is the value of adhesion between the steel cord and the vulcanized rubber at high temperatures, and the higher the value, the higher the safety of the tire.

Evaluation item Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Remark T/S(tensile strength) (kgf/cm ² ) 172 187 165 197 196 195 The higher the better Tan δ @ 60℃ 0.157 0.149 0.160 0.132 0.136 0.133 The lower the better Tear (kgf/cm) 53 53 53 56 53 42 The higher the better Crack Growth(mm) 16.6 16.23 17.2 16.03 15.46 17.5 The lower the better Heat-resistant adhesion (kgf) 56.2 53.8 52 62.4 58.1 54 The higher the better

From the results of Table 2, the tensile strength of the vulcanized rubber of the compositions of Examples 1 to 3 of the present invention, Tan δ @ 60°C, Tear, fatigue properties (Crack Growth), and the adhesion of the steel belt, etc. of Comparative Examples 1 to 3 It can be seen that it is superior to the case.

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 (8)

Raw rubber made of natural rubber, filler made of carbon black; Vulcanization accelerating aid; Amine-based anti-aging agents; Quinoline-based antioxidants; Sulfur-based curing agents; Sulfenamide vulcanization accelerators; Cobalt compounds; 1,6-bis(N,N-dibenzylthiocarbamoyldisio)-hexane; And 1,1'-[1,3-phenylenebis(methylene)]bis(3-methyl-1H-pyrrole-2,5-dione); and a tire belt rubber composition consisting of
A tire belt comprising a steel cord,
Including 0.1 to 3.0 parts by weight of the cobalt compound based on 100 parts by weight of the raw rubber,
Tire belt comprising more than 7 to 10 parts by weight of the sulfur-based curing agent based on 100 parts by weight of raw rubber. delete delete The method of claim 1, wherein the rubber composition is 1,6-bis(N,N-dibenzylthiocarbamoyldisio)-hexane[1,6-bis(N,N-) based on 100 parts by weight of the raw rubber. Dibenzylthiocarbamoyldithio)-hexane] containing 0.1 to 1.0 parts by weight of a tire belt. The method of claim 1, wherein the rubber composition is 1,1'-[1,3-phenylenebis(methylene)]bis(3-methyl-1H-pyrrole-2,5-dione) based on 100 parts by weight of the raw rubber. Tire belt containing 1.0 to 2.0 parts by weight. delete delete A tire provided with the tire belt of claim 1.

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