Abstract:
Rubber compositions are disclosed for use in tread portions of automotive tires. A selected class of starting rubbers are combined with specified amounts of a selected type of carbon black having well balanced N 2  SA, DBP, ΔDBP and ΔDst properties. The use of this carbon black is conducive to enhanced driving stability and other important physical characteristics.

Description:
This application is a continuation, of application Ser. No. 07/287,372, now abandoned filed Dec. 21, 1988. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to rubber compositions suitable for use in tread portions of automobile tires. More particularly, the invention is directed to the provision of such a composition comprised of a selected rubber combined with a selected type of carbon black of specified particle characteristics. 
     2. Description of the Prior Art 
     Tires for use in highly sophisticated sports cars should meet various physical and mechanical properties and driving stability in particular. An approach has been proposed to cope with this trend with the use of a tread rubber of high tan δ at 60° C. This quality is closely associated with the gripping force of the tire on the road surface. 
     To attain increased tan δ at 60° C., polymeric rubbers of high glass transition temperatures (Tg) have been used which are selected for instance from styrene-butadiene copolymer rubbers abundant in styrene content or in 1,2-vinyl content. Alternatively, large amounts of carbon black have been incorporated with a given starting rubber. 
     High Tg rubbers, however, are not wholly satisfactory as they are rather dependent on temperature, insufficiently hard and rigid at elevated temperature and inadequate in gripping force. Too much carbon black fails to get homogeneously dispersible, rendering the finished rubber composition susceptible to great hysteresis loss and hence objectionable heat buildup and poor mechanical strength. 
     SUMMARY OF THE INVENTION 
     With the foregoing difficulties of the prior art in view, the present invention seeks to provide an improved rubber composition for use in treads of automobile tires which excels in tan δ at 60° C., hardness and abrasion resistance at high temperature and other important physical characteristics desired to run at high speed, thus contributing to efficient, safe driving. 
     Other objects and advantages of the invention will be better understood from the following description. 
     More specifically, the invention provides a rubber composition for use in automotive tire treads, which comprises: (a) 100 parts by weight of a starting rubber; and (b) 50-150 parts by weight of carbon black having an N 2  SA in the range of 140-160 m 2  /g as defined by nitrogen adsorption surface area, a DBP of more than 120 ml/100 g as defined by dibutyl phthalate adsorption, a ΔDBP of greater than 30 ml/100 g as determined from the DBP-24 M4 DBP equation and a ΔDst of smaller than 50 mμ as defined by the half value width of a centrifugally classified aggregate size distribution. 
     DETAILED DESCRIPTION OF THE INVENTION 
     Rubber compositions according to the present invention are essentially comprised of a selected class of starting rubbers hereafter referred to as &#34;component (I)&#34; and a selected type of carbon black hereafter referred to as &#34;component (II)&#34;. 
     Component (I) is not particularly limited in the practice of the invention. Typical examples of this component include natural rubber, styrene-butadiene copolymer rubber, butadiene rubber, polyisoprene rubber, butyl rubber and similar tread rubbers in common use. These rubbers may be used alone or in combination. 
     Component (II) suitable for the purpose of the invention should meet certain physical characteristics determined by the following methods. 
     Nitrogen Adsorption Surface Area (N 2  SA)(m 2  /g) 
     ASTM D-3037-78 is followed by &#34;Standard Method of Testing Carbon Black-Surface Area by Nitrogen Adsorption&#34;, Method C. 
     Dibutyl Phthalate Adsorption (DBP)(ml/100 g) 
     JIS K-6221 (1982) is followed by &#34;Method of Testing Carbon Black for Rubber&#34;, Section 6.1.2(1), Method A. 24 M4 DBP Adsorption (ml/100 g) 
     Measurement is made as stipulated in ASTM D-3493. 
     ΔDBP (ml/100 g) 
     This adsorptivity is determined by subtracting 24 M4 DBP from DBP. 
     Half Value Width of Aggregate Size Distribution (ΔDst)(mμ) 
     Centrifugal classification is effected with the use of a disc centrifuge manufactured by Joyce Loebl Co., England. A carbon black sample is accurately weighed and then added with a 20% aqueous ethanol solution and a surfactant, followed by ultrasonic dispersion to provide a dispersion concentrated to 5 mg/100 cc. The resulting dispersion is subjected to the above centrifuge set at 8,000 rpm. Into the centrifuge are put 10 ml of a spin liquid in distilled water, subsequently 0.5 ml of a buffer in 20% by volume of ethanol and finally 0.5 to 1.0 ml of the carbon black dispersion through a syringe. Centrifugation is initiated and a photoelectric recorder switched on to draw a distribution curve of aggregates converted by Stock&#39;s mode of diameter. ΔDst is determined from the half value width of the maximum absorbance on the histogram. 
     Importantly, component (II) should have an N 2  SA in the range of 140-160 m 2  /g, a DBP of more than 120 ml/100 g, a ΔDBP of greater than 30 ml/100 g and a ΔDst of smaller than 50 mμ. 
     Carbon black if smaller than 140 m 2  /g in N 2  SA would invite inadequate abrasion resistance and if larger than 160 m 2  /g would lead to objectionable heat generation. Less DBP would result in a rubber mix being less resistant to abrasion and less stable in driveability. ΔDBP not exceeding 30 ml/100 g would fail to improve tan δ at elevated temperature, giving rise to inadequate driving stability. Excess ΔDst should be avoided to preclude a decline in abrasion resistance and hence driving stability. 
     The amount of component (II) to be added with component (I) should be between 50 and 150 parts by weight. Smaller amounts would not be effective in attaining sufficient abrasion resistance, whereas larger amounts would become difficult to disperse into the starting rubber. 
     Various other additives may be employed, if necessary, in which are included vulcanization agents such as sulfur, vulcanization accelerators, vulcanization activators, antioxidants, tackifiers, softeners, fillers and the like. 
    
    
     EXAMPLES 
     The present invention will now be described by way of the following examples which are provided for illustrative purposes but should not be construed as limiting the invention. 
     Different rubber compositions were formulated, as shown in Tables 3 and 4, with the use of three SBR rubbers of Table 1 and of ten carbon blacks of Table 2, followed by kneading and subsequent vulcanization at 160° C. for 20 minutes. The resulting vulcanizates were examined for their gripping force (tan δ), dynamic modulus (E&#39;), Pico type abrasion, tensile strength (T B ), 300% tensile stress (M 300 ) and hardness (H S ) under the conditions given below and with the results shown in Tables 3 and 4. 
     Gripping Force (tan δ) and Dynamic Modulus (E&#39;) 
     Viscoelastic spectrometer manufactured by Iwamoto Seisakusho Co., Ltd. was used at 60° C., at 10±2% strain and at 20 Hz. The greater tan δ, the higher in gripping force. 
     Dynamic modulus was taken as a measure of hardness. The larger E&#39;, the harder. 
     Pico Type Abrasion 
     The method of JIS K-6301 was followed. The greater value, the more resistant to abrasion. 
     Tensile Strength (T B ) 
     Measurement was made in accordance with JIS K-6301. The larger T B , the higher in tensile strength. 
     Elongation (E B ) 
     As stipulated in JIS K-6301, elongation was determined. The larger E B , the greater in this quality. 
     300% Tensile Stress (M 300 ) 
     JIS K-6301 was followed. The larger M 300 , the greater tensile stress. 
     Hardness (H S ) 
     Hardness was determined by the method of JIS K-6301. The greater H S , the harder. 
     As appears clear from Tables 3 and 4, the rubber compositions representing the invention excel in tan δ at 60° C. compared to Comparative Examples 1 to 11, meaning improved driving stability. 
     The compositions of Inventive Examples 1 and 2 and Comparative Examples 1 and 10 were employed as tread rubbers to produce car tires of 225/50 VR16. These tires were assessed for driveability by a feeling test in which comparison was made by taking the rubber of Comparative Example 1 as an index of 3.0. The greater value, the more safe driving. The inventive rubber compositions are highly satisfactory in respect of driveability as is evident from Table 5. 
     Although the invention has been described in connection with certain preferred embodiments, it will be noted as apparent to those skilled in the art that many changes and modifications may be made without departing from the scope of the appended claims. 
     
                       TABLE 1______________________________________SBR-1       polymerization: emulsion       styrene content:                       35%       oil extension:  50 wt. partsSBR-2       polymerization: emulsion       styrene content:                       45%       oil extension:  50 wt. partsSBR-3       polymerization: solution       styrene content:                       15%       1,2-vinyl content:                       80%       not oil-extended______________________________________ 
    
     
                       TABLE 2______________________________________carbon N.sub.2 SA         DBP       24M4DBP  ΔDPB                                    ΔDstblack (m.sup.2 /g)         (ml/100 g)                   (ml/100 g)                            (ml/100 g)                                    (mμ)______________________________________CB-1  143     116       99       17      76CB-2  145     118       94       24      46CB-3  131     130       99       31      47CB-4  130     128       92       36      47CB-5  148     113       101      12      46CB-6  133      87       81        6      73CB-7  131     149       116      33      57CB-8  211      82       66       16      48CB-9  122     121       100      21      70 CB-10 152     135       98       37      40______________________________________ CB-1: Dia Black A, Mitsubishi Chemical Industries Ltd. CB2: Seast 9, Tokai Carbon Co., Ltd. CB3-CB9: test carbon blacks not meeting the parameters of the invention CB10: carbon black according to the invention 
    
     
                                           TABLE 3__________________________________________________________________________     Comparative Examples                           InventiveRun       1    2    3    4    5    6     7    8     9    Example__________________________________________________________________________                                                    1FormulationsSBR-1     150  150  150  150  150  150   150  150   150  150CB-1      100CB-2           100CB-3                100CB-4                     100CB-5                          100CB-6                               100CB-7                                     100CB-8                                          100CB-9                                                100CB-10                                                    100zinc oxide      3    3    3    3    3    3     3    3     3    3stearic acid      2    2    2    2    2    2     2    2     2    2antioxidant 6C      3    3    3    3    3    3     3    3     3    3wax           0.5             0.5                  0.5                       0.5                            0.5                                 0.5                                       0.5                                            0.5                                                  0.5                                                       0.5accelerator CZ        1.5             1.5                  1.5                       1.5                            1.5                                 1.5                                       1.5                                            1.5                                                  1.5                                                       1.5sulfur       2.5             2.5                  2.5                       2.5                            2.5                                 2.5                                       2.5                                            2.5                                                  2.5                                                       2.5Propertiestan δ at 60° C.        0.50             0.54                  0.54                       0.51                            0.49                                 0.51                                       0.50                                            0.52                                                  0.45                                                       0.56E&#39; (MPa) at 60° C.        6.9             7.4                  7.3                       6.4                            7.7                                  5.5                                       9.2                                            5.9                                                  6.6                                                       7.6Pico type   27.2            27.3                 25.1                      26.2                           25.9                                35.7                                      23.1                                           51.6                                                 24.1                                                      26.9abrasion (μl)T.sub.B   189  205  205  219  217  204   213  204   199  205E.sub.B   440  440  420  450  410  510   340  510   400  460M.sub.300 136  143  154  150  158  113   190  107   155  137H.sub.S    75   75   76   75   78   72    84   73    75   75__________________________________________________________________________ Comparative Example 1: control antioxidant 6C: Nphenyl-N(1,3-dimethylbutyl)-p-phenylenediamine accelerator CZ: Ncyclohexyl-2-benzotiazole sulfenamide 
    
     
                                           TABLE 4__________________________________________________________________________    Comparative           Inventive                 Comparative                        Inventive ExamplesRun      Example 10           Example 2                 Example 11                        3    4__________________________________________________________________________FormulationsSMR-20                10     10SBR-1    60     60    135    135  56.25SBR-2    60     60                56.25SBR-3                             25BR 1441  27.5   27.5CB-1     95           100CB-10           95           100  95aromatic oil    2.5    2.5   5      5    12.5zinc oxide    3      3     3      3    3stearic acid    2      2     2      2    2antioxidant 6C    3      3     3      3    3wax      0.5    0.5   0.5    0.5  0.5accelerator CZ    1.6    1.6   1.6    1.6  1.6sulfur   2.5    2.5   2.5    2.5  2.5Propertiestan δ at 60° C.    0.56   0.60  0.50   0.55 0.63E&#39;(MPa) at 60° C.    6.2    6.5   6.6    7.0  6.4Pico type    29.4   28.8  30.5   30.0 29.5abrasion (μl)T.sub.B  187    200   196    205  185E.sub.B  540    550   460    470  500M.sub.300    102    105   133    135  104H.sub.S  72     72    75     75   73__________________________________________________________________________ SMR-20: natural rubber 
    
     
                       TABLE 5______________________________________  Comparative             Inventive Comparative                                InventiveRun    Example 1  Example 1 Example 10                                Example 2______________________________________gripping  3.0        3.5       3.0      3.5strength______________________________________