Patent Publication Number: US-2002010283-A1

Title: Rubber composition

Description:
BACKGROUND OF THE INVENTION  
       [0001] 1. Field of the Invention  
       [0002] The present invention relates to a rubber composition, and more particularly, to a rubber composition used for tire treads and the like having high breakage resistance after heat aging.  
       [0003] 2. Description of the Related Art  
       [0004] In a rubber composition composed of natural rubber and/or diene-based synthetic rubber, the lowering of breakage resistance during heat aging due to oxygen in the air is a problem which cannot be avoided to a certain extent, and various antioxidants have been developed for solving this problem. Among such antioxidants, a 2-mercapto-benzothiazole compound which has been conventionally used as a vulcanization accelerator is known to have an effect as an antioxidant.  
       [0005] Recently, with the increasing engine power of automobiles, the construction of highway networks and the development of low profile tires, the temperature of a tire while driving has increased, and the physical properties of the tire are showing greater charges than ever during heat aging. Generally, the problem is solved by increasing the amount of antioxidant. However, it is difficult to increase the amount of antioxidant more than currently used since bloom then occurs.  
       [0006] In addition, when the amount of a 2-mercaptobenzothiazole compound, such as 2-mercaptobenzothiazolyl disulfide, is increased, because this compound is a vulcanization accelerator, the modulus increases and sufficient breakage resistance properties cannot be obtained, and in particular, elongation at break is markedly decreased.  
       [0007] Further, as disclosed in Japanese Patent Application Laid-Open (JP-A) No. 56-139542 and Japanese Patent Application Publication (JP-B) No. 3-2183, 4-methyl-2-mercaptobenzothiazole, 4-methyl-2-mercaptobenzothiazolyl disulfide, 4-ethyl-2-mercaptobenzothiazole and 4-ethyl-2-mercaptobenzothiazolyl disulfide are effective at suppressing increasing modulus of a tire after driving or after heat aging and are therefore expected to improve elongation at break after heat aging. In fact, these 2-mercaptobenzothiazole compounds can improve elongation at break after heat aging as expected when used in a composition mainly composed of SBR. However, in a composition containing not less than 50 parts by weight of natural rubber or polyisoprene rubber based on 100 parts by weight of rubber components, because these 2-mercaptobenzothiazole compounds cause a marked lowering of breaking strength after heat aging, the desired object cannot be completely achieved. Moreover, these 4-alkyl-2-mercaptobenzothiazole compounds, when used in a composition mainly composed of SBR, suppress increasing modulus after heat aging and are not able to improve breaking strength although elongation at break improves.  
       SUMMARY OF THE INVENTION  
       [0008] The present invention has been made in view of the above-described fact, and the object thereof is to provide a rubber composition having higher breakage resistance after heat aging as compared with the conventional technique.  
       [0009] The mercaptobenzothiazole compound used as a vulcanization accelerator as described above is conventionally known to have a role as an antioxidant. The present inventors have noticed the effect of this compound as an antioxidant, and have investigated to obtain a higher antioxidant effect in consideration of the mechanism suggested by G. Scott et al. and, as a result, have found that the object can be accomplished by the following means, completing the present invention.  
       [0010] Namely, the rubber composition of the present invention comprising 0.2 to 10 parts by weight of at least one compound selected from the group consisting of 2-mercaptobenzothiazole compound containing an alkoxy groups represented by the following general formulae (I), (II) and (III) based on 100 parts by weight of at least one rubber raw material selected from the group consisting of natural rubber and diene-based synthetic rubbers:  
                 
 
                 
 
                 
 
       [0011] wherein R 1  represents an alkyl group, alkenyl group or cycloalkyl group having 1 to 8 carbon atoms; R 2  represents a hydrogen atom or an amino group represented by —N(R 3 )R 4 ; R 3  and R 4 each independently represent a hydrogen atom or an alkyl group or cyclohexyl group having 2 to 4 carbon atoms (wherein, R 3  and R 4  do not simultaneously represent a hydrogen atom); R 5  and R 6  each independently represent an alkyl group, alkenyl group or cycloalkyl group having 1 to 8 carbon atoms; X represents a Zn atom, Cu atom or an amino group represented by &gt;N—R 9 ; R 9  represents an alkyl group or cyclohexyl group having 2 to 4 carbon atoms; and R 7  and R 8  have the same meaning as R 5 .  
       DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS  
       [0012] The rubber raw material used in the present invention is at least one material selected from the group consisting of natural rubber and diene-based synthetic rubbers. Namely, natural rubber (NR) and many diene-based synthetic rubbers may be used alone or as a blend of two or more of them. Examples of diene-based synthetic rubbers include polyisoprene rubber (IR), polybutadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber (IIR), chlorobutyl rubber, bromobutyl rubber, acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR) and the like.  
       [0013] In the present invention, among these rubber raw materials, for example, NR alone, SBR alone, an NR/SBR blend, an NR/SBR/BR blend and the like are ideal to use. When a blend of two or more rubbers is used as the rubber raw material, it is preferable that not less than 50 parts by weight of NR and/or IR is contained based on 100 parts by weight of the rubber raw material.  
       [0014] The 2-mercaptobenzothiazole compound containing an alkoxy group which is used as a vulcanization accelerator in the present invention is represented by the above-described general formula (I), (II) or (III), and is used alone or in combination of two or more.  
       [0015] In the formulae, R 1  represents an alkyl group, alkenyl group or cycloalkyl group having 1 to 8 carbon atoms, R 2  represents a hydrogen atom or an amino group represented by —N (R 3 ) R 4 . R 3  and R 4  each independently represent a hydrogen atom or an alkyl group or cyclohexyl group having 2 to 4 carbon atoms (however, R 3  and R 4  cannot simultaneously represent hydrogen atoms). R 5  and R 6  each independently represent an alkyl group, alkenyl group or cycloalkyl group having 1 to 8 carbon atoms. X represents a Zn atom, Cu atom or an amino group represented by &gt;N—R 9 , and R 9  represents an alkyl group or cyclohexyl group having 2 to 4 carbon atoms. R 7  and R 8  have the same meaning as R 5 .  
       [0016] In these formulae, it is preferable from the point of view of the effects of the invention that alkoxy groups —OR 1 , —OR 5 , —OR 6 , —OR 7  and —OR 8  each independently represent a methoxy group, ethoxy group or butoxy group, and an ethoxy group is more preferable.  
       [0017] Examples of the alkoxy group-containing 2-mercaptobenzothiazole compound represented by the general formula (I) include 4-methoxy-2-mercaptobenzothiazole, 5-methoxy-2-mercaptobenzothiazole, 6-methoxy-2-mercaptobenzothiazole, 7-methoxy-2-mercaptobenzothiazole, 4-ethoxy-2-mercaptobenzothiazole, 5-ethoxy-2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 7-ethoxy-2-mercaptobenzothiazole, 4-butoxy-2-mercaptobenzothiazole, 5-butoxy-2-mercaptobenzothiazole, 6-butoxy-2-mercaptobenzothiazole, 7-butoxy-2-mercaptobenzothiazole, N-tert-butyl-4-methoxy-2-benzothiazolylsulfenamide, N-tert-butyl-5-methoxy-2-benzothiazolylsulfenamide, N-tert-butyl-6-methoxy-2-benzothiazolylsulfenamide, N-tert-butyl-7-methoxy-2-benzothiazolylsulfenamide, N-tert-butyl-4-ethoxy-2-benzothiazolylsulfenamide, N-tert-butyl-5-ethoxy-2-benzothiazolylsulfenamide, N-tert-butyl-6-ethoxy-2-benzothiazolylsulfenamide, N-tert-butyl-7-ethoxy-2-benzothiazolylsulfenamide, N-tert-butyl-4-butoxy-2-benzothiazolylsulfenamide, N-tert-butyl-5-butoxy-2-benzothiazolylsulfenamide, N-tert-butyl-6-butoxy-2-benzothiazolylsulfenamide, N-tert-butyl-7-butoxy-2-benzothiazolylsulfenamide, N-ethyl-4-methoxy-2-benzothiazolylsulfenamide, N-ethyl-5-methoxy-2-benzothiazolylsulfenamide, N-ethyl-6-methoxy-2-benzothiazolylsulfenamide, N-ethyl-7-methoxy-2-benzothiazolylsulfenamide, N-ethyl-4-ethoxy-2-benzothiazolylsulfenamide, N-ethyl-5-ethoxy-2-benzothiazolylsulfenamide, N-ethyl-6-ethoxy-2-benzothiazolylsulfenamide, N-ethyl-7-ethoxy-2-benzothiazolylsulfenamide, N-ethyl-4-butoxy-2-benzothiazolylsulfenamide, N-ethyl-5-butoxy-2-benzothiazolylsulfenamide, N-ethyl-6-butoxy-2-benzothiazolylsulfenamide, N-ethyl-7-butoxy-2-benzothiazolylsulfenamide, N-cyclohexyl-4-methoxy-2-benzothiazolylsulfenamide, N-cyclohexyl-5-methoxy-2-benzothiazolylsulfenamide, N-cyclohexyl-6-methoxy-2-benzothiazolylsulfenamide, N-cyclohexyl-7-methoxy-2-benzothiazolylsulfenamide, N-cyclohexyl-4-ethoxy-2-benzothiazolylsulfenamide, N-cyclohexyl-5-ethoxy-2-benzothiazolylsulfenamide, N-cyclohexyl-6-ethoxy-2-benzothiazolylsulfenamide, N-cyclohexyl-7-ethoxy-2-benzothiazolylsulfenamide, N-cyclohexyl-4-butoxy-2-benzothiazolylsulfenamide, N-cyclohexyl-5-butoxy-2-benzothiazolylsulfenamide, N-cyclohexyl-6-butoxy-2-benzothiazolylsulfenamide, N-cyclohexyl-7-butoxy-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-4-methoxy-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-5-methoxy-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-6-methoxy-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-7-methoxy-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-4-ethoxy-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-5-ethoxy-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-6-ethoxy-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-7-ethoxy-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-4-butoxy-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-5-butoxy-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-6-butoxy-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-7-butoxy-2-benzothiazolylsulfenamide, and the like.  
       [0018] Examples of 2-mercaptobenzothiazole compound containing an alkoxy group represented by the general formula (II) include di-4-methoxy-2-benzothiazolyl disulfide, di-5-methoxy-2-benzothiazolyl disulfide, di-6-methoxy-2-benzothiazolyl disulfide, di-7-methoxy-2-benzothiazolyl disulfide, di-4-ethoxy-2-benzothiazolyl disulfide, di-5-ethoxy-2-benzothiazolyl disulfide, di-6-ethoxy-2-benzothiazolyl disulfide, di-7-ethoxy-2-benzothiazolyl disulfide, di-4-butoxy-2-benzothiazolyl disulfide, di-5-butoxy-2-benzothiazolyl disulfide, di-6-butoxy-2-benzothiazolyl disulfide, di-7-butoxy-2-benzothiazolyl disulfide, and the like.  
       [0019] Examples of the 2-mercaptobenzothiazole compound containing an alkoxyl group represented by the general formula (III) include zinc salt of 4-methoxy-2-mercaptobenzothiazole, zinc salt of 5-methoxy-2-mercaptobenzothiazole, zinc salt of 6-methoxy-2-mercaptobenzothiazole, zinc salt of 7-methoxy-2-mercaptobenzothiazole, zinc salt of 4-ethoxy-2-mercaptobenzothiazole, zinc salt of 5-ethoxy-2-mercaptobenzothiazole, zinc salt of 6-ethoxy-2-mercaptobenzothiazole, zinc salt of 7-ethoxy-2-mercaptobenzothiazole, zinc salt of 4-butoxy-2-mercaptobenzothiazole, zinc salt of 5-butoxy-2-mercaptobenzothiazole, zinc salt of 6-butoxy-2-mercaptobenzothiazole, zinc salt of 7-butoxy-2-mercaptobenzothiazole, copper salt of 4-methoxy-2-mercaptobenzothiazole, copper salt of 5-methoxy-2-mercaptobenzothiazole, copper salt of 6-methoxy-2-mercaptobenzothiazole, copper salt of 7-methoxy-2-mercaptobenzothiazole, copper salt of 4-ethoxy-2-mercaptobenzothiazole, copper salt of 5-ethoxy2-mercaptobenzothiazole, copper salt of 6-ethoxy-2-mercaptobenzothiazole, copper salt of 7-ethoxy-2-mercaptobenzothiazole, copper salt of 4-butoxy-2-mercaptobenzothiazole, copper salt of 5-butoxy-2-mercaptobenzothiazole, copper salt of 6-butoxy-2-mercaptobenzothiazole, copper salt of 7-butoxy-2-mercaptobenzothiazole, N-ethyl-(4-methoxy-2-benzothiazolyl)sulfenimide, N-ethyl-(5-methoxy-2-benzothiazolyl) sulfenimide, N-ethyl-(6-methoxy-2-benzothiazolyl) sulfenimide, N-ethyl-(7-methoxy-2-benzothiazolyl)sulfenimide, N-t-butyl(4-methoxy-2-benzothiazolyl) sulfenimide, N-t-butyl(5-methoxy-2-benzothiazolyl)sulfenimide, N-t-butyl(6-methoxy-2-benzothiazolyl)sulfenimide, N-t-butyl(7-methoxy-2-benzothiazolyl)sulfenimide, N-cyclohexyl(4-methoxy-2-benzothiazolyl)sulfenimide, N-cyclohexyl(5-methoxy-2-benzothiazolyl)sulfenimide, N-cyclohexyl(6-methoxy-2-benzothiazolyl)sulfenimide, N-cyclohexyl(7-methoxy-2-benzothiazolyl)sulfenimide, N-ethyl(4-ethoxy-2-benzothiazolyl)sulfenimide, N-ethyl(5-ethoxy-2-benzothiazolyl)sulfenimide, N-ethyl(6-ethoxy-2-benzothiazolyl)sulfenimide, N-ethyl(7-ethoxy-2-benzothiazolyl)sulfenimide, N-t-butyl(4-ethoxy-2-benzothiazolyl)sulfenimide, N-t-butyl(5-ethoxy-2-benzothiazolyl)sulfenimide, N-t-butyl(6-ethoxy-2-benzothiazolyl)sulfenimide. N-t-butyl(7-ethoxy-2-benzothiazolyl)sulfenimide, N-cyclohexyl(4-ethoxy-2-benzothiazolyl)sulfenimide, N-cyclohexyl(5-ethoxy-2-benzothiazolyl)sulfenimide, N-cyclohexyl(6-ethoxy-2-benzothiazolyl)sulfenimide, N-cyclohexyl(7-ethoxy-2-benzothiazolyl)sulfenimide, N-ethyl-(4-butoxy-2-benzothiazolyl)sulfenimide, N-ethyl-(5-butoxy-2-benzothiazolyl)sulfenimide, N-ethyl-(6-butoxy-2-benzothiazolyl)sulfenimide, N-ethyl-(7-butoxy-2-benzothiazolyl)sulfenimide, N-t-butyl(4-butoxy-2-benzothiazolyl)sulfenimide, N-t-butyl(5-butoxy-2-benzothiazolyl)sulfenimide, N-t-butyl(6-butoxy-2-benzothiazolyl)sulfenimide, N-t-butyl(7-butoxy-2-benzothiazolyl)sulfenimide, N-cyclohexyl(4-butoxy-2-benzothiazolyl)sulfenimide, N-cyclohexyl(5-butoxy-2-benzothiazolyl)sulfenimide, N-cyclohexyl(6-butoxy-2-benzothiazolyl)sulfenimide, N-cyclohexyl(7-butoxy-2-benzothiazolyl)sulfenimide, and the like.  
       [0020] In these 2-mercaptobenzothiazole compounds containing an alkoxy group which are vulcanization accelerators, it is preferable that the position of the alkoxy group in the aromatic monocyclic ring in the general formulae (I), (II) and (III) is 4 or 6, and more preferably, the position is 4. Further, a benzothiazole compound having an alkoxy group at 4 or 6 position in an aromatic monocyclic ring is preferred in view of the easy availability of the material and the ease of synthesis. Moreover, benzothiazolylsulfenamide, benzothiazolyl disulfide and benzothiazolylsulfenimide having an alkoxy group at 4 or 6 position in an aromatic monocyclic ring are also preferred in view of their scorch properties. Further, a compound having an alkoxy group at 4 position in an aromatic monocyclic ring is more preferable since the compound suppresses increasing modulus of a rubber composition during heat aging.  
       [0021] The production methods of these vulcanization accelerators are not particularly restricted, and these accelerators can be easily produced by using, for example, the methods disclosed in Japanese Patent Application Laid-Open (JP-A) No. 49-93361 and the like.  
       [0022] The amount blended of the 2-mercaptobenzothiazole compound containing an alkoxy group which is a vulcanization accelerator used in the present invention is from 0.2 to 10 parts by weight, preferably from 0.5 to 7 parts by weight based on 100 parts by weight of rubber raw materials. When the amount blended is less than 0.2 parts by weight, the effect obtained is insufficient, and when the amount blended is over 10 parts by weight, workability such as the scorch property is lowered, and further effect cannot be obtained.  
       [0023] In addition to these vulcanization accelerators used in the present invention, thiazole-type vulcanization accelerators such as 2-mercaptobenzothiazolyl disulfide, N-t-butylbenzothiazolylsulfenamide, and N-cyclohexylbenzothiazolylsulfenamide, as well as thiuram type vulcanization accelerators such as tetra(2-ethylhexyl) thiuram disulfide and tetramethylthiuram disulfide which are widely-used vulcanization accelerators can be suitably blended.  
       [0024] The reinforcing filler which can be used in the present invention is not particularly restricted, however, at least one compound selected from inorganic fillers such as carbon black and silica is usually used. As the carbon black, for example, SAF, ISAF, HAF, FEF, GPF and the like are preferred. The carbon black is preferably used in an amount from 20 to 150 parts by weight based on 100 parts by weight of rubber raw materials. When the amount of the carbon black is less than 20 parts by weight, the reinforcing effect of the carbon black is insufficient, and when over 150 parts by weight is used, workability is markedly decreased.  
       [0025] In addition to the above-described components, blending agents usually used in the rubber industry such as softening agents, aging preventing agents, vulcanization agents, vulcanization accelerators, silane coupling agents and the like can be suitably blended onto the rubber composition of the present invention as needed.  
       [0026] The rubber composition of the present invention is obtained by kneading using a kneader such as a roll, internal mixer, banbury mixer and the like. After shaping processing, the rubber composition is subjected to vulcanization and used for tire treads and the like.  
       [0027] The reaction mechanism of mercaptobenzothiazole as an antioxidant was studied in detail by G. Scott et al., (Eur. Polym. J., 11,783(1975)), and mercaptobenzothiazole and Zn salt thereof are known to be extremely effective at decomposing peroxides produced by the oxidation of rubber. It is hypothesized that the 2-mercaptobenzothiazole compound containing an alkoxy group used in the present invention obtains higher reactivity with peroxides and grater effectiveness as an antioxidant by the introduction of an alkoxy group having a high electron donating property into an aromatic monocyclic ring. 
     
    
    
     EXAMPLES  
     [0028] The following Examples further illustrate the present invention in detail but are not to be construed as limiting the scope thereof.  
     Preparation and Evaluation of Rubber Composition  
     Examples 1 to 19  
     Comparative Examples 1 to 14  
     [0029] According to basic blending formulations shown in Table 1 and separate blending formulations shown in Tables 2 to 6, the rubber composition was prepared by kneading with a normal banbury mixer. This rubber composition was subjected to vulcanization at 145° C. for a period of time corresponding to 1.5 to 2.0-fold of the T90 value obtained by measurement at 145° C. using a MDR2000 manufactured by US Flexis Corp. (formerly Monsanto Corp.). Initial breakage resistance and breakage resistance after heat aging of this vulcanized material were measured according to the following methods. The results are shown in Tables 2 to 6.  
     Initial Breakage Resistance  
     [0030] A tension test using a sample taken before heat aging, was conducted according to JIS K 6301 (1975) to ascertain tensile strength at break (Tb), elongation at break (Eb) and tensile strength at 200% elongation (M200).  
     Breakage Resistance After Heat Aging  
     [0031] Heat aging was conducted for a prescribed time (24 hours or 72 hours) in a 100° C. gear oven. The aged material was then taken out of the oven and allowed to stand for 6 hours at room temperature. It was then subjected to a tension test to ascertain Tb, Eb and M200. Further, changing ratios of Tb, Eb and M200 after 24 hour and 72 hour heat aging to the initial Tb, Eb and M200 were also ascertained.  
     [0032] Then, using treads made of the rubber compositions of Examples 2, 6 and Comparative Example 2, tires of size 205/50R16 were made experimentally, and the chunk property of each tire at an internal pressure of 2 kg/cm 2  was measured by the following methods. The results are shown in Tables 2 and 3.  
     Chunk Property  
     [0033] The test was performed by driving the tires for 15 laps around the Bridgestone Company test course and then looking for chips of the tire tread portion with the naked eye. The value is expressed against an index whereby the new tire in 1 Comparative Example 2 has the value of 100. Further, the tires used in the evaluation were those which showed 50% abrasion of treads under normal driving conditions.  
                           TABLE 1                                   Blending component   Parts by weight                                                    Rubber raw material   100           Carbon black 1)     Variable           Aromatic oil   25           Stearic Acid   2           Zinc oxide   3           Antioxidant 2)     2           Vulcanization accelerator   Variable           Sulfur   1.5                                              
 
     [0034]                           TABLE 2                                  Comparative example   Example                                                             1   2   3   4   1   2   3   4                                                             Formulation   SBR   100   100   100   100   100   100   100   100       (parts by   NR   —   —   —   —   —   —   —   —       weight)   BR   —   —   —   —   —   —   —   —           Carbon black   50   50   50   50   50   50   50   50           Known   1.5   3   5   7   —   —   —   —           vulcanization           accelerator X           Known   —   —   —   —   —   —   —   —           vulcanization           accelerator Y           Vulcanization   —   —   —   —   1.5   3   5   7           accelerator A           of the present           invention           Vulcanization   —   —   —   —   —   —   —   —           accelerator B           of the present           invention           Vulcanization   —   —   —   —   —   —   —   —           accelerator C           of the present           invention           Known   —   —   —   —   —   —   —   —           vulcanization           accelerator Z           Vulcanization   —   —   —   —   —   —   —   —           accelerator D           of the present           invention           Vulcanization   —   —   —   —   —   —   —   —           accelerator E           of the present           invention           Vulcanization   —   —   —   —   —   —   —   —           accelerator F           of the present           invention       Physical   Initial       properties   Tb(MPa)   22   24.2   21.7   20.2   24.6   24.7   22.9   20.1           Eb(%)   600   550   480   451   631   581   510   472           M200(MPa)   4.2   5.2   6.4   7.6   3.9   5.4   6.3   7.5           After aging for           24 hours at           100° C.           Tb(MPa)   20.2   21.7   20   18.6   23.1   23.3   22.8   19.8           Eb(%)   560   460   400   360   610   570   530   460           M200(MPa)   4.9   7   7.9   8.9   4.2   5.3   5.9   7.6           Change ratio (%)           Tb(MPa)   92   90   92   92   94   94   100   99           Eb(%)   93   84   83   80   97   98   104   97           M200(MPa)   117   135   123   117   108   98   94   101           After aging for           72 hours at           100° C.           Tb(MPa)   18   19.7   18   16.5   21   21.2   21.4   18.7           Eb(%)   450   390   320   305   578   510   480   432           M200(MPa)   5.8   8.8   10   11   5   6.5   7.1   8.2           Change ratio (%)           Tb(MPa)   82   81   83   82   85   86   93   93           Eb(%)   75   71   67   68   92   88   94   92           M200(MPa)   138   169   156   145   128   120   113   109       Tire ability       Chunk property   new article   —   100   —   —   —   100   —   —           driven article   —   75   —   —   —   90   —   —                    
     [0035]                               TABLE 3                                  Example   *C.E.   Example                                                         5   6   7   8   5   9   10                                                         Formula-   SBR   100   100   100   100   100   100   100       tion   NR   —   —   —   —   —   —   —       (parts by   BR   —   —   —   —   —   —   —       weight)   Carbon   50   50   50   50   50   50   50           black           Known   —   —   —   0.5   —   —   —           vulcaniza-           tion           accelerator           X           Known   —   —   —   —   —   —   —           vulcaniza-           tion ac-           celerator           Y           Vulcaniza-   —   —   —   1   —   —   —           tion           accelerator           A of the           present           invention           Vulcaniza-   3   5   —   —   —   —   —           tion           accelerator           B of the           present           invention           Vulcaniza-   —   —   3   —   —   —   —           tion           accelerator           C of the           present           invention           Known   —   —   —   —   1.5   —   —           vulcaniza-           tion           accelerator           Z           Vulcaniza-   —   —   —   —   —   1.5   —           tion           accelerator           D of the           present           invention           Vulcaniza-   —   —   —   —   —   —   1.5           tion           accelerator           E of the           present           invention           Vulcaniza-   —   —   —   —   —   —   —           tion           accelerator           F of the           present           invention       Physical   Initial       properties   Tb(MPa)   24.9   24.4   22.3   24.3   24.7   24.6   24.5           EB(%)   630   610   610   600   580   580   600           M200   4.1   4.5   4.2   4.2   5.6   5.3   4.2           (MPa)           After           aging           for 24           hours           at 100° C.           Tb(MPa)   22.9   23.5   20.1   23   22.2   23.4   23           Eb(%)   570   580   537   605   560   580   585           M200   4.4   4.7   4.5   4.5   5.8   5.4   4.5           (MPa)           Change           ratio(%)           Tb(MPa)   92   96   90   95   90   95   94           Eb(%)   90   95   88   101   97   100   98           M200   107   104   107   107   104   102   108           (MPa)           After           aging for           72 hours           at 100° C.           Tb(MPa)   22.4   22.7   19.6   20.9   21   22.1   22.2           Eb(%)   520   510   506   560   480   530   522           M200   5.9   6.4   6.1   5.6   7.1   6.5   5.8           (MPa)           Change           ratio(%)           Tb(MPa)   90   93   88   86   85   90   91           Eb(%)   83   84   83   93   83   91   87           M200   144   142   145   133   127   123   138           (MPa)       Tire       ability       Chunk   new   —   100   —   —   —   —   —       property   article           driven   —   90   —   —   —   —   —           article                            
     [0036]                                       TABLE 4                                  *C.E.   *C.E.   Example   *C.E.   Ex.                                                         6   7   11   12   8   9   13                                                         Formula-   SBR   —   —   —   —   50   50   50       tion   NR   100   100   100   100   50   50   50       (parts by   BR   —   —   —   —   —   —   —       weight)   Carbon   50   50   50   50   50   50   50           black           Known   1.5   —   —   —   1.5   —   —           vulcaniza-           tion           accelerator           X           Known   —   1.5   —   —   —   1.5   —           vulcaniza-           tion           accelerator           Y           Vulcaniza-   —   —   1.5   —   —   —   1.5           tion           accelerator           A of the           present           invention           Vulcaniza-   —   —   —   1.5   —   —   —           tion           accelerator           B of the           present           invention           Vulcaniza-   —   —   —   —   —   —   —           tion           accelerator           C of the           present           invention           Known   —   —   —   —   —   —   —           vulcaniza-           tion           accelerator           Z           Vulcaniza-   —   —   —   —   —   —   —           tion           accelerator           D of the           present           invention           Vulcaniza-   —   —   —   —   —   —   —           tion           accelerator           E of the           present           invention           Vulcaniza-   —   —   —   —   —   —   —           tion           accelerator           F of the           present           invention       Physical   Initial       proper-   Tb(MPa)   27.6   27.8   28   26.5   24.8   24.5   25.4       ties   Eb(%)   515   505   510   580   560   565   570           M200   6.9   7   7.1   5.4   5.6   5.4   5.2           (MPa)           After           aging for           24 hours           at 100° C.           Tb(MPa)   21.5   20.9   23   24   20.9   20.3   22.6           Eb(%)   330   345   450   430   445   460   485           M200   12.0   9.7   10.4   9.5   8.5   6.6   7           (MPa)           Change           ratio (%)           Tb(MPa)   78   75   82   91   84   83   69           Eb(%)   64   68   88   74   79   81   85           M200   174   138   146   175   152   122   135           (MPa)           After           aging for           72 hours           at 100° C.           Tb(MPa)   18.9   14.4   20.6   21.8   18.5   16.4   19.4           Eb(%)   275   220   360   360   360   350   420           M200   12.5   10.1   11.2   9.9   9.2   7.3   7.5           (MPa)           Change           ratio(%)           Tb(MPa)   68   52   74   82   75   67   76           Eb(%)   53   44   71   62   64   62   74           M200   181   144   158   183   164   135   144           (MPa)                            
     [0037]                                   TABLE 5                                  *C.E.   Example   *C.E.   Example                                                         10   14   15   11   12   16   17               Formu-   SBR   —   —   —   —   —   —   —       lation   NR   100   100   100   100   100   100   100       (parts   BR   —   —   —   —   —   —   —       by   Carbon black   50   50   50   30   70   30   70       weight)   Known   —   —   —   1.5   1.5   —   —           vulcanization           accelerator X           Known   —   —   —   —   —   —   —           vulcanization           accelerator Y           Vulcaniza-   —   —   —   —   —   1.5   1.5           tion           accelerator A           of the           present           invention           Vulcaniza-   —   —   —   —   —   —   —           tion           accelerator B           of the           present           invention           Vulcaniza-   —   —   —   —   —   —   —           tion           accelerator C           of the           present           invention           Known   0.8   —   —   —   —   —   —           vulcanization           accelerator Z           Vulcaniza-   —   0.8   —   —   —   —   —           tion           accelerator D           of the           present           invention           Vulcaniza-   —   —   —   —   —   —   —           tion           accelerator E           of the           present           invention           Vulcaniza-   —   —   0.8   —   —   —   —           tion           accelerator F           of the           present           invention       Physical   Initial       proper-   Tb(MPa)   28   28.2   27.9   27.8   26.7   27.6   25.9       ties   Eb(%)   495   515   505   620   390   630   410           M200(MPa)   6.8   6.5   6.6   4.7   8.9   4.5   8.5           After aging           for 24 hours           at 100° C.           Tb(MPa)   23.2   24.5   24.3   21.1   19.2   22.9   21.5           Eb(%)   345   405   405   385   230   555   335           M200(MPa)   10.2   9.5   9.5   7.9   14.8   6.7   13           Change ratio           (%)           Tb(MPa)   83   87   87   76   72   83   83           Eb(%)   70   79   80   62   59   88   82           M200(MPa)   150   146   144   168   166   149   153           After aging           for 72 hours           at 100° C.           Tb(MPa)   19.6   21.7   21.2   19.2   17.4   20.1   19.2           Eb(%)   305   370   360   340   190   440   295           M200(MPa)   11.2   10.1   10.3   8.4   —   7.2   14           Change ratio           (%)           Tb(MPa)   70   77   76   69   65   73   74           Eb(%)   62   72   71   55   49   70   72           M200(MPa)   165   155   156   179   —   138   165                            
     [0038]                                   TABLE 6                                   *C.E.   Example   *C.E.   Example           13   18   14   19                                                            Formu-   SBR   70   70   50   50       lation   NR   30   30   30   30       (parts by   BR   —   —   20   20       weight)   Carbon black   50   50   50   50           Known   1.5   —   1.5   —           vulcanization           accelerator X           Known   —   —   —   —           vulcanization           accelerator Y           Vulcanization   —   1.5   —   1.5           accelerator A           of the present           invention           Vulcanization   —   —   —   —           accelerator B           of the present           invention           Vulcanization   —   —   —   —           accelerator C           of the present           invention           Known   —   —   —   —           vulcanization           accelerator Z           Vulcanization   —   —   —   —           accelerator D           of the present           invention           Vulcanization   —   —   —   —           accelerator E           of the present           invention           Vulcanization   —   —   —   —           accelerator F           of the present           invention       Physical   Initial       properties   Tb(MPa)   24.8   25.3   25.1   24.6           Eb(%)   570   580   580   570           M200(MPa)   4.7   4.4   4.6   4.5           After aging for           24 hours at           100° C.           Tb(MPa)   21.3   22   21   20.7           Eb(%)   460   490   480   485           M200(MPa)   7.0   5.9   7.3   6.7           Change ratio           (%)           Tb(MPa)   86   87   84   84           Eb(%)   81   84   83   85           M200(MPa)   149   134   159   149           After aging for           72 hours at           100° C.           Tb(MPa)   18.2   19.2   19.1   19.2           Eb(%)   320   360   310   340           M200(MPa)   9.7   8.1   10.0   8.0           Change ratio           (%)           Tb(MPa)   73   76   76   78           Eb(%)   56   62   53   60           M200(MPa)   206   185   217   178                            
     [0039] Explanation of the rubber raw materials and blending agents in Tables 2 to 6:  
     [0040] 1) SBR: SBR1500 (manufactured by Japan Synthetic Rubber Co., Ltd.)  
     [0041] 2) BR: BR01 (manufactured by Japan Synthetic Rubber Co., Ltd.)  
     [0042] 3) Accelerator X: 2-benzothiazolyl disulfide  
     [0043] 4) Accelerator Y: 4-methyl-2-benzothiazolyl disulfide  
     [0044] 5) Accelerator A: di-4-ethoxy-2-benzothiazolyl disulfide  
     [0045] 6) Accelerator B: di-6-ethoxy-2-benzothiazolyl disulfide  
     [0046] 7) Accelerator C: di-6-methoxy-2-benzothiazolyl disulfide  
     [0047] 8) Accelerator Z: N-tert-butyl-2-benzothiazolylsulfenamide  
     [0048] 9) Accelerator D: N-tert-butyl-4-ethoxy-2-benzothiazolylsulfenamide  
     [0049] 10) Accelerator E: N-tert-butyl-6-ethoxy-2-benzothiazolylsulfenamide  
     [0050] 11) Accelerator F: N,N-tert-butyl-4-ethoxy-2-benzothiazolylsulfenimide  
     [0051] The results when the amount of conventional 2-benzothiazolyl disulfide was changed are shown in Comparative Examples 1 to 4, and the results when the amounts of di-4-ethoxy-2-benzothiazolyl disulfide and di-6-ethoxy-2-benzothiazolyl disulfide were changed are shown in Examples 1 to 6. It is known that lowering of breaking strength (Tb) after heat aging (especially when aging is over a long period) is suppressed by introduction of an ethoxy group into a benzothiazole ring. Di-4-ethoxy-2-benzothiazolyl disulfide markedly improves elongation at break (Eb) after heat aging, since it also suppresses increase of modulus during heat aging. Di-6-methoxy-2-benzothiazolyl disulfide can also provide an approximately the same effect as di-6-ethoxy-2-benzothiazolyl disulfide (Example 7). Further, conventional 2-benzothiazolyl disulfide can also be used together with di-4-ethoxy-2-benzothiazolyl disulfide, although the effect is reduced (Example 8). The results when conventional N-tert-butyl-2-benzothiazolylsulfenamide was used are shown in Comparative Example 5, and the results when N-tert-butyl-4-ethoxy-2-benzothiazolylsulfenamide and N-tert-butyl-6-ethoxy-2-benzothiazolylsulfenamide were used are shown in Examples 9 and 10. When the sulfenamide type compound is used, superiority is maintained although the effect of the ethoxy group is reduced as compared with the disulfide type compound.  
     [0052] Next, the results when the amount of NR was 100 parts by weight are explained. When conventional 2-benzothiazolyl disulfide (Comparative Example 6) is replaced by an equivalent amount of conventional 4-methyl-2-benzothiazolyl disulfide (Comparative Example 7), curing after heat aging is suppressed, however, especially after aging at 100° C. for 72 hours, elongation at break is also reduced due to the extreme reduction of breaking strength. On the other hand, when di-4-ethoxy-2-benzothiazolyl disulfide (Example 11) or di-6-ethoxy-2-benzothiazolyl disulfide (Example 12) is used, reduction of breading strength is low, and physical properties after aging which are better than those of Comparative Example 6 are obtained. Also in the formulation of NR/SBR=50/50, the superiority of di-4-ethoxy-2-benzothiazolyl disulfide is apparent (Comparative Examples 8, 9 and Example 13).  
     [0053] In the same way, when conventional N-tert-butyl-2-benzothiazolylsulfenamide (Comparative Example 10) in an NR formulation is replaced with equivalent amounts of N-tert-butyl-4-ethoxy-2-benzothiazolylsulfenamide (Example 14) and N,N-tert-butyl-4-ethoxy-2-benzotrthiazolylsulfenimide (Example15), breaking strength after heat aging increases. It is learned that even if the amount of carbon black was changed (Comparative Examples 11, 12 and Examples 16 and 17), or if a mixture of NR/SBR of 30/70 is used (Comparative Example 13 and Example 18), or even if a blend of NR/SBR/BR was used (Comparative Example 14 and Example 19) then di-4-ethoxy-2-benzothiazolyl disulfide had superior breaking properties after heat aging than the conventional 2-benzothiazolyl sulfide.  
     [0054] As described above, it was learned that the rubber composition of the present invention has excellent breaking properties after heat aging. The superiority of the breaking properties after driving is also confirmed by the fact that there is a lower occurrence of chunking after driving in the tires using the rubber compositions of the present invention compared to the tires in the comparative examples.