Patent Publication Number: US-4322319-A

Title: Rubber composition containing crosslinkable processing aid

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to a rubber composition having a good processability and capable of giving a vulcanizate having excellent properties. More particularly, it relates to a rubber composition comprising a diene copolymer, having a relatively low molecular weight, produced by copolymerizing chloromethylstyrene or a glycidyl group-containing monomer, and a cross-linking agent reactive with the glycidyl group or chloromethyl group in which the diene copolymer is difficult to migrate and accordingly the properties of its vulcanizate are not deteriorated. 
     2. Description of Prior Art 
     As a method for improving the processability of rubber, a softening agent such as an extender oil, a petroleum resin or the like has hitherto been blended therewith. However, in such a method for improving the processability of rubber by the use of such softening agents, there are problems that the properties of its vulcanizate are deteriorated, and the softening agent in the vulcanizate bleeds out to cause an insufficient adhesion to other vulcanized rubber compositions contacted with the vulcanizate, or the softening agent migrates into said other vulcanized rubber compositions contacted with the vulcanizate to adversely affect the properties of vulcanized rubber composition, even though the processability of rubber can be improved. Accordingly, it has recently been desired in many fields of rubber industry to develop softening agents which hardly migrate, namely, so-called reactive softening agents. 
     In order to suppress the deterioration of the vulcanizate properties due to softening agents, it is known to use a low molecular weight rubber as a softening agent for the sake of improving the processability and, at the same time, to co-vulcanize the low molecular weight polymer and the rubber. However, this co-vulcanization does not always progress sufficiently, so that the migration of the softening agent is not sufficiently inhibited, and the properties of vulcanizate are not sufficiently stable for a long period of time. 
     The present inventors have conducted extensive studies for obtaining a rubber composition having an improved processability, in which the low molecular weight polymer contained therein as a softening agent does not migrate even in its vulcanizate and hence, the properties of the vulcanizate do not deteriorate. As a result, it has been found that a low molecular weight copolymer containing glycidyl groups or chloromethyl groups acts as a softening agent for the rubber composition at the time of processing and said low molecular weight copolymer is converted into a product having a high molecular weight and a crosslinking structure by the reaction of the glycidyl groups or chloromethyl groups with the crosslinking agent upon vulcanization, so that the rubber composition containing said low molecular weight copolymer exhibits a good processability in the unvulcanized state and the properties of its vulcanizate are excellent. 
     SUMMARY OF THE INVENTION 
     It is an object of this invention to provide a rubber composition having an improved processability. 
     It is another object of this invention to provide a rubber composition having an improved processability, the vulcanizate of which has excellent physical properties and is difficult to migrate. 
     Other objects and advantages of this invention will become apparent from the following description. 
     According to this invention, there is provided a rubber composition comprising (A) 100 parts by weight of a rubber, (B) 5-50 parts by weight of a low molecular weight diene copolymer containing a glycidyl group-containing monomer or chloromethylstyrene, said copolymer comprising 30% by weight or less of copolymerized styrene, and having an intrinsic viscosity of 0.2-1.3 dl/g as measured in toluene at 30° C., (C) a specified crosslinking agent reactive with the glycidyl group or the chloromethyl group in the copolymer (B), and (D) 0.2-7 parts by weight or less, per 100 parts by weight of the rubber (A), of sulfur. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The components constituting the copolymer (B) used in this invention are a glycidyl group-containing monomer or chloromethylstyrene, and a conjugated diene having 4 or 5 carbon atoms, and optionally styrene. The glycidyl group-containing monomer referred to herein includes glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether and the like, among which glycidyl methacrylate is preferable. The chloromethylstyrene referred to herein includes styrenes having a chloromethyl group at the ortho-, meta- or para-position and their mixtures. The content of the glycidyl group-containing monomer in the copolymer (B) is 5-30% by weight. If it is less than 5% by weight the reactivity of the copolymer (B) is low, and hence, said proportion is undesirable. If it exceeds 30% by weight the softening effect decreases, and hence, said proportion is undesirable. 
     The conjugated diene having 4 or 5 carbon atoms which is a constituent of the copolymer (B) includes butadiene, isoprene, piperylene and the like, among which butadiene is preferable. The content of the conjugated diene in the copolymer (B) is preferably 50% by weight or more. It it is less than 50% by weight the softening effect of the copolymer decreases, and hence, said proportion is undesirable. The content of styrene constituting the copolymer (B) is 0-30% by weight. If it exceeds 30% by weight the softening effect of the copolymer (B) decreases, and hence, said proportion is undesirable. 
     The intrinsic viscosity [η] of the copolymer (B) used in this invention must be 0.2 to 1.3 dl/g as measured in toluene at 30° C., preferably 0.3-1.0 dl/g. If [η] is less than 0.2 dl/g, the crosslinkage of the copolymer (B) is insufficient and the migration of the copolymer (B) is not suppressed so that the physical properties of the vulcanizate are deteriorated. On the other hand, if [η] exceeds 1.3 dl/g, the effect of the copolymer (B) as a softening agent for improving the processability decreases, and hence, said intrinsic viscosity is undesirable. Though the copolymer (B) is a viscous liquid or a semi-solid at room temperature, it is liquid at the temperature at which it is blended with the rubber (A) and the blend is processed. 
     The rubber (A) which is a constituent of the rubber composition of this invention includes natural rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, nitrile rubber, isobutylene rubber, a rubber having the same constituents as the above-mentioned copolymer (B) containing a glycidyl group-containing monomer or chloromethylstyrene, and the like, among which natural rubber, polyisoprene rubber, polybutadiene rubber and styrene-butadiene rubber are particularly preferable. When the copolymer (B) is incorporated with the rubber (A), 5-50 parts by weight of the copolymer (B) is added to 100 parts by weight of the rubber (A). If the amount of the copolymer (B) is less than 5 parts by weight, the processability of the rubber composition cannot be improved. If it exceeds 50 parts by weight, the properties of the rubber (A) itself are impaired, and hence, said proportion is undesirable. As the process for blending the copolymer (B) with the rubber (A), a direct blending process (dry blend) by means of a Banbury mixer or a roll; a process which comprises blending a latex of the copolymer (B) with a latex of the rubber (A) and a process which comprises blending a solution of the copolymer (B) with a solution of the rubber (A) (wet blend) may be used. Though these processes do not affect the physical properties of the composition, the wet blend is more preferable in view of easy production. 
     The rubber composition of this invention comprising the rubber (A) and the copolymer (B) is subjected to crosslinking through a specific crosslinking agent reactive with the glycidyl group or the chloromethyl group, or subjected simultaneously to the said crosslinking and vulcanization with sulfur. 
     As the crosslinking agent (C) for forming crosslinkages through reaction with the chloromethyl group, there are used metallic oxides (C I ), which are employed as vulcanization accelerators in the sulfur vulcanization process, alone or in combination with amine compounds (C II ) such as polyamines, polyamine salts of carboxylic acids and the like. 
     As the crosslinking agent (C) for forming crosslinkages through reaction with the glycidyl group, there are used such amine compounds (C II ) as in the case of the chloromethyl group, alone or in combination with said metallic oxides (C I ). 
     In order to allow the crosslinking to proceed sufficiently and to inhibit the scorching, it is more preferable to use a metallic oxide and a polyamine salt of carboxylic acid in combination. In the case of the copolymer (B) containing a glycidyl group-containing monomer, however, the crosslinking is insufficient if only a metallic oxide (C I ) is used as a crosslinking agent. As said polyamine, there may be used hexamethylenediamine, N,N&#39;-dimethyl-p-phenylenediamine, secondary amines such as piperazine and the like, and tertiary diamines such as triethylenediamine and the like. Diethylenetriamine, triethylenetetramine, hexamethylenetetramine, polyethyleneimine and the like may also be used. On the other hand, as the carboxylic acid for forming said salt, there may be used monocarboxylic acids such as acetic acid, propionic acid, octanoic acid, stearic acid, benzoic acid and toluic acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, phthalic acid and the like; carboxylic acids having a hydroxyl group such as glycolic acid, malic acid, lactic acid, p-oxybenzoic acid and the like; and carboxylic acids having a thiol group such as thioglycolic acid and the like. Among the salts of amine compounds with carboxylic acids, preferred are piperazine oxalate, piperazine glycolate, piperazine malate, piperazine lactate, piperazine p-oxybenzoate, piperazine stearate, hexamethylenediamine succinate (6,4-Nylon salt), and hexamethylenediamine sebacate (6,10-Nylon salt). 
     As said metallic oxide (C I ), there may be used zinc oxide, lead oxide, magnesium oxide and the like, among which zinc oxide and lead oxide are preferable. Since zinc oxide is used more generaly in the case of sulfur vulcanization, it is particularly preferable when vulcanization is carried out simultaneously. 
     The amount of said metallic oxide is 0.5 to 10 parts by weight per 100 parts by weight of the rubber (A). Although a metallic oxide serves also as an adjuvant for vulcanization and processing, its action as an adjuvant is too small and the crosslinkage with the copolymer (B) cannot be formed sufficiently if the amount of the metallic oxide is less than 0.5 parts by weight and, if its amount exceeds 10 parts by weight, blooming or the like occurs, which are both undesirable. 
     When an amine compound is incorporated, its amount is 1 to 40 parts by weight per 100 parts by weight of the copolymer (B) containing a glycidyl group-containing monomer or chloromethylstyrene, and preferably 1.5 to 20 parts by weight on the same basis. If the amount is less than 1 part by weight, the reaction between the amine commpound and the copolymer (B) cannot progress sufficiently and, consequently the modulus is not increased, and if it exceeds 40 parts by weight, there occurs undesirable blooming or the like. 
     The rubber composition of this invention is crosslinked through the above-mentioned crosslinking agent (amine compound or metallic oxide) and, in addition, vulcanized with sulfur (including organic sulfur compounds). The rubber composition of this invention is crosslinked by heating it at a temperature of, for example 60° to 200° C., preferably at 100° to 170° C., for a period of 10 minutes to 5 hours. As the means of the heating, either open system or press system may be selected depending upon the shape of object to be heated. The amount of sulfur blended is 0.2 to 7 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the rubber (A). If it exceeds 7 parts by weight, scorch, blooming and the like occur. And if the amount is less than 0.2 part by weight vulcanization is not sufficient. This is undesirable. When the rubber (A) contains glycidyl groups, crosslinking is possible even if sulfur is not used. However, the properties of vulcanized rubber are more excellent when sulfur is used. 
     Additives which are usually blended with rubber, such as a reinforcing material, a filler, a processing adjuvant, an antioxidant and the like, may be added to the rubber composition of this invention. These additives can be mixed by means of a roll or a Banbury mixer or they may also be added in the course of producing the polymer. However, it is undesirable to add any other additives reactive with the glycidyl group or the chloromethyl group than the above-mentioned crosslinking agent over the whole process of production including the polymerization step. 
     The rubber composition of this invention is excellent in processability, and the adverse effect of the addition of the copolymer (B) on the vulcanizate properties is only small and the copolymer (B) used as a softening agent is hardly extracted with a solvent or the like. Therefore, when the rubber composition of this invention is used as a part of composite material, it causes neither an insufficient adhesion to other vulcanized rubbers nor deterioration of the properties of other parts due to the migration of the copolymer (B) into said other parts. 
     If a diene rubber containing at least 40% by weight of natural rubber or polyisoprene rubber is used as the rubber (A), there can be obtained excellent vibration-proof characteristics, so that it can be used effectively as a vibration insulator for preventing noises and vibrations in transport facilities such as automobile and the like, as well as in industrial machines. 
    
    
     DESCRIPTION OF PREFERRED EMBODIMENTS 
     This invention will be illustrated below more specifically with reference to Examples and Comparative Examples. The Examples are not by way of limitation but by way of illustration. 
     (1) PRODUCTION OF COPOLYMER (B) 
     Example 1 
     A copolymer (B) was produced by polymerizing 72% by weight of butadiene, 8% by weight of styrene and 20% by weight of glycidyl methacrylate by a conventional free radical emulsion polymerization method at a reaction temperature of 5° C. with tert-dodecylmercaptan as a molecular weight regulator. The conversion was 80%. 
     Example 2 
     The same procedure as in Example 1 was repeated, except that styrene was not used and 90% by weight of butadiene and 10% by weight of glycidyl methacrylate were used. The conversion was 80%. 
     Examples 3 to 9 
     The same procedure as in Example 1 was repeated except that 72% by weight of butadiene, 18% by weight of styrene and 10% by weight of glycidyl methacrylate were used and the amount of tert-dodecylmercaptan as a molecular weight regulator was varied, to obtain polymers having different [η] values as shown in Table 1. The conversion was 80%. 
     In the case of Example 4, the polymer obtained had the following composition and [η]: 
     
         ______________________________________                                    
[η] as measured in toluene at 30° C.                           
                        0.33 dl/g                                         
Glycidyl methacrylate   8.8% by weight                                    
Styrene                11.3% by weight                                    
Butadiene              79.9% by weight                                    
______________________________________                                    
 
    
     The glycidyl methacrylate content and the styrene content were determined by infrared absorption spectrometry. 
     The butadiene content was calculated by deducting the total contents of the above two components from 100%. 
     Example 10 
     The same procedure as in Example 1 was repeated, except that 72% by weight of isoprene, 18% by weight of styrene and 10% by weight of glycidyl methacrylate were used. The conversion was 80%. 
     (2) COMPOUNDING AND VULCANIZATION 
     Mixtures were prepared by blending the abovementioned copolymer (B) with a rubber (A) by a wet blend method in the case of Run Nos. 1 and 4 in Table 2 and by a dry blend method in the other cases. The mixtures were then compounded according to the recipe shown in Table 1 and vulcanized under the conditions shown in Table 1. 
     (3) PHYSICAL PROPERTIES OF VULCANIZATE, MIGRATION PROPERTY AND PROCESSABILITY 
     Tensile test was carried out according to JIS K 6301. 
     Though there is no recognized method for measuring the copolymer (B) (softening agent) in the vulcanized rubber composition, the degree of extraction with a solvent as measured by the following method was adopted as a measure. 
     About 1 g of the vulcanized product was twice extracted with 100-ml portions of toluene at 80° C. each for 5 hours, and the degree of extraction was calculated from the weight loss after the extraction. That is, it can be said that a smaller degree of extraction means a smaller migration property. 
     The processability was evaluated by measuring compound Mooney viscosity (a lower compound Mooney viscosity as compared with that of the rubber (A) containing neither copolymer (B) nor softening agent means a better processability). Further, the exothermic temperature was measured by means of Brabender Plastograph, and a lower exothermic temperature was regarded as a better processability (a lower exothermic temperature as compared with that of the rubber (A) containing neither copolymer (B) nor softening agent means a better processability). 
     The results obtained were as shown in Table 2. In Table 2, the comparative examples show the data of the following materials: 
     Comparative Example 1: the rubber itself obtained by coagulating SBR #1500 latex with methanol (it contains none of the compounding materials shown in Table 1 at all). 
     Comparative Example 2: a composition obtained by blending 20 parts by weight of a high-aromatic extender oil (JSR AROMA) as a softening agent with 100 parts by weight of the rubber of Comparative Example 1. 
     Comparative Example 3: a composition having the recipe of Table 1, wherein the copolymer (B) is replaced with 20 parts by weight of a liquid styrene-butadiene rubber obtained by copolymerizing 72 parts by weight of butadiene and 28 parts by weight of styrene by the same process as used for producing the copolymer (B) in Example 1. 
     Comparative Example 4: a composition having the recipe of Table 1, wherein the copolymer (B) is replaced with a copolymer having a glycidyl group-containing monomer and a small [η] value which has been obtained using the same monomers in the same ratios as in Example 3 with a larger amount of tert-dodecylmereaptan under the same polymerization conditions as in Example 3. 
     As shown in Table 2, Run Nos. 1-10 are lower in compound Mooney viscosity and exothermic temperature and more excellent in processability than Run No. 11. It is also shown that Run Nos. 1, 3, 4 and 6-9 are greatly improved in properties of vulcanizate (M 100 ) and migration property (degree of extraction) as compared with Run Nos. 12 and 13. On the other hand, in Run No. 14 in which a copolymer (B) having a glycidyl group-containing monomer, having an [η] value of 0.2 dl/g or less, was used, the properties of vulcanizate are low and the degree of extraction is high though the processability is good. 
     As is apparent from the comparison of Run Nos. 1 and 4 with Run Nos. 2 and 5, in the cases where an amine compound (C II ) reactive with the glycidyl group was used, there are advantages that modulus (M 100 ) in properties of vulcanizate is greater and the degree of extraction of the copolymer (B) is smaller than where said amine compound was not used. 
     
                       TABLE 1                                                     
______________________________________                                    
 Recipe and Vulcanization Conditions                                      
______________________________________                                    
Rubber (A) (styrene-butadiene rubber*)                                    
                       100 parts                                          
Copolymer (B)          20 parts                                           
ISAF Carbon Black      50 parts                                           
Zinc oxide (C.sub.I)    5 parts                                           
Stearic acid            3 parts                                           
Vulcanization accelerator NOBS                                            
                         1.5 parts                                        
Sulfur                   2.5 parts                                        
Amine compound (C.sub.II)                                                 
                       Varied                                             
Vulcanization temperature                                                 
                       145° C.                                     
Vulcanization time     60 min                                             
______________________________________                                    
 Note:                                                                    
 *SBR #1500 manufactured by Japan Synthetic Rubber Co. (combined styrene  
 23.5%, Mooney viscosity ML.sub.1+4.sup.100° C. 52).               
 
    
     
                                           TABLE 2                                 
__________________________________________________________________________
                                    Properties of                         
                                    vulcanized                            
                                             Migration                    
                                                   Exo-                   
             Kind                                                         
                 Amine compound (C.sub.II)                                
                              Compound.sup.2                              
                                    product  property.sup.5               
                                                   thermic                
             of          Amount.sup.3                                     
                              Mooney                                      
                                    M.sub.100                             
                                       T.sub.B                            
                                             (Degree of                   
                                                   temper-                
Run                                                                       
   Copolymer (B)                                                          
             rubber      (parts                                           
                              viscosity                                   
                                    (kg/                                  
                                       (kg/                               
                                          E.sub.B                         
                                             extraction)                  
                                                   ature                  
No.                                                                       
   Kind   [η].sup.1                                                   
             (B) Kind    by wt.                                           
                              ML.sup.100° C. .sub.1+4              
                                    cm.sup.2)                             
                                       cm.sup.2)                          
                                          (%)                             
                                             (%)   (°C.)           
                                                        Remarks           
__________________________________________________________________________
1  Example 1                                                              
          0.69                                                            
             SBR Piperazine                                               
                         14   58.5  53 181                                
                                          296                             
                                             8     119  Present           
                 glycolate                              invention         
2  Example 1                                                              
          0.69                                                            
             &#34;   --      0    58.5  24 193                                
                                          467                             
                                             24    119  Comparison        
3  Example 2                                                              
          0.52                                                            
             &#34;   Piperazine                                               
                         14   53.5  49 177                                
                                          280                             
                                             6     117  Present           
                 glycolate                              invention         
4  Example 3                                                              
          0.50                                                            
             &#34;   Piperazine                                               
                         14   51.5  40 199                                
                                          339                             
                                             7     115  Present           
                 glycolate                              invention         
5  Example 3                                                              
          0.50                                                            
             &#34;   --      0    51.5  24 240                                
                                          512                             
                                             22    115  Comparison        
6  Example 4                                                              
          0.33                                                            
             &#34;   Piperazine                                               
                         14   48.5  47 174                                
                                          313                             
                                             11    115  Present           
                 glycolate                              invention         
7  Example 5                                                              
          0.70                                                            
             &#34;   Hexamethylene-                                           
                         14   55.0  34 196                                
                                          344                             
                                             9     118  Present           
                 diamine                                invention         
                 sebacate                                                 
8  Example 6                                                              
          0.70                                                            
             &#34;   Hexamethylene-                                           
                         10   55.0  34 176                                
                                          358                             
                                             12    118  Present           
                 diamine                                invention         
                 succinate                                                
9  Example 7                                                              
          0.70                                                            
             &#34;   Hexamethylene-                                           
                         8    55.0  36 167                                
                                          329                             
                                             14    118  Present           
                 diamine                                invention         
                 succinate                                                
10 Example 10                                                             
          0.70                                                            
             &#34;   Piperazine                                               
                         14   53.0  35 185                                
                                          320                             
                                             6     116  Present           
                 glycolate                              invention         
11 Comparative                                                            
          -- &#34;   --      0    88.0  50 247                                
                                          299                             
                                             --    132  Comparison        
   Example 1                                                              
12 Comparative                                                            
          --.sup.4                                                        
             &#34;   --      0    49.5  26 174                                
                                          403                             
                                             93    118  &#34;                 
   Example 2                                                              
13 Comparative                                                            
          0.44                                                            
             &#34;   --      0    48.5  23 206                                
                                          474                             
                                             44    118  &#34;                 
   Example 3                                                              
14 Comparative                                                            
          0.14                                                            
             &#34;   Piperazine                                               
                         14   48.5  31 219                                
                                          419                             
                                             42    113  &#34;                 
   Example 4     glycolate                                                
__________________________________________________________________________
 Note:                                                                    
 .sup.1 Measured in toluene at 30° C.                              
 .sup.2 Values given by compositions not containing accelerator, sulfur no
 amine compound (C.sub.II).                                               
 .sup.3 Based on 100 parts by weight of the copolymer (B).                
 .sup.4 In place of the copolymer (B), 20 parts by weight of higharomatic 
 extender oil was added to 100 parts by weight of the rubber (A).         
 .sup.5 Degree of extraction of the copolymer (B) or extender oil.        
 M.sub.100 : modulus of elasticity. T.sub.B : tensile strength at break   
 E.sub.B : elongation at break                                            
 
    
     (4) PRODUCTION OF COPOLYMER (B) 
     Examples 11-14 and Comparative Example 7 
     72 parts by weight of butadiene, 18 parts by weight of styrene and 10 parts by weight of chloromethylstyrene were compolymerized by a conventional free radical emulsion polymerization process at 5° C. with a varying quantity of tert-dodecylmercaptan as a molecular weight regulator. The conversion was 80%, and the [η] values of the copolymers obtained were as shown in Table 4. The result of, for example, Example 11 was as follows: 
     
         ______________________________________                                    
[η] as measured in toluene at 30° C.                           
                            0.78 dl/g                                     
Chloromethylstyrene content (% by weight)                                 
                            9.5                                           
Styrene content (% by weight)                                             
                           16.8                                           
Butadiene content (% by weight)                                           
                           73.7                                           
______________________________________                                    
 
    
     The chloromethylstyrene content was determined from the elementary analysis of halogen. 
     The styrene content was determined by infrared absorption spectrometry. 
     The butadiene content was calculated by deducting the total contents of the above two components from 100%. 
     Example 15 
     The reaction was carried out in the same manner as in Example 11, except that 72 parts by weight of butadiene, 23 parts by weight of styrene and 5 parts by weight of chloromethylstyrene were used. The conversion was 80%. 
     Example 16 
     The reaction was carried out in the same manner as in Example 11, except that 72 parts by weight of butadiene, 13 parts by weight of styrene and 15 parts by weight of chloromethylstyrene were used. The conversion was 80%. 
     Example 17 
     The reaction was carried out in the same manner as in Example 11, except that 72 parts by weight of butadiene, 8 parts by weight of styrene and 20 parts by weight of chloromethylstyrene were used. The conversion was 80%. 
     Example 18 
     The reaction was carried out in the same manner as in Example 11, except that 90 parts by weight of butadiene and 10 parts by weight of chloromethylstyrene were used. The conversion was 80%. 
     Example 19 
     The reaction was carried out in the same manner as in example 11, except that 72 parts by weight of isoprene, 18 parts by weight of styrene and 10 parts by weight of chloromethylstyrene were used. The conversion was 80%. 
     (5) COMPOUNDING AND VULCANIZATION 
     Mixtures were prepared by blending the abovementioned copolymer (B) with a rubber (A) by a wet blend method in the case of Run No. 15 in Table 3 and by a dry blend method in the other cases. Then they were compounded according to the recipe shown in Table 1 and the compounds obtained were vulcanized under the conditions shown in Table 1, provided that a press-vulcanization was carried out at 160° C. for 60 minutes in case of Run Nos. 15, and 17-24 in Table 3. 
     (6) PHYSICAL PROPERTIES OF VULCANIZATE, MIGRATION PROPERTY AND PROCESSABILITY 
     By the same procedures as in above item (3), the properties of vulcanizates, the migration property of the copolymer (B) and the processabilities of the compositions were measured to obtain the results shown in Table 3. 
     
                                           TABLE 3                                 
__________________________________________________________________________
                                    Properties of                         
                                             Migration                    
                                                   Exo-                   
             Kind                                                         
                 Amine compound (C.sub.II)                                
                              Compound.sup.2                              
                                    vulcanizate                           
                                             property.sup.5               
                                                   thermic                
             of          Amount.sup.3                                     
                              Mooney                                      
                                    M.sub.100                             
                                       T.sub.B                            
                                             (Degree of                   
                                                   temper-                
Run                                                                       
   Copolymer (B)                                                          
             rubber      (parts                                           
                              viscosity                                   
                                    (kg/                                  
                                       (kg/                               
                                          E.sub.B                         
                                             extraction)                  
                                                   ature                  
No.                                                                       
   Kind   [η].sup.1                                                   
             (A) Kind    by wt.)                                          
                              ML.sup.100° C. .sub.1+4              
                                    cm.sup.2)                             
                                       cm.sup.2)                          
                                          (%)                             
                                             (%)   (°C.)           
                                                        Remarks           
__________________________________________________________________________
15 Example 11                                                             
          0.78                                                            
             SBR --      0    58.5  51 176                                
                                          229                             
                                             5     119  Present           
                                                        invention         
16 Example 12                                                             
          0.78                                                            
             &#34;   Piperazine                                               
                         14   62.5  55 197                                
                                          242                             
                                             3     119                    
                 glycolate                                                
17 Example 13                                                             
          0.53                                                            
             &#34;   --      0    48.5  50 219                                
                                          265                             
                                             8     114                    
18 Example 15                                                             
          0.67                                                            
             &#34;   --      0    53.5  48 221                                
                                          234                             
                                             15    116                    
19 Example 16                                                             
          0.59                                                            
             &#34;   --      0    50.5  52 197                                
                                          224                             
                                             7     115                    
20 Example 17                                                             
          0.48                                                            
             &#34;   --      0    48.0  54 184                                
                                          234                             
                                             4     113                    
21 Example 18                                                             
          0.50                                                            
             &#34;   --      0    50.5  47 180                                
                                          249                             
                                             8     115                    
22 Example 19                                                             
          0.41                                                            
             &#34;   --      0    47.0  46 182                                
                                          250                             
                                             5     113                    
23 Example 14                                                             
          0.78                                                            
             &#34;   Piperazine                                               
                         12   61.5  49 175                                
                                          242                             
                                             4     119                    
                 maleate                                                  
24 Comparative                                                            
          0.16                                                            
             &#34;   --      --   45.0  40 198                                
                                          252                             
                                             26    36   Comparison        
   Example 7                                                              
11 Comparative                                                            
          -- &#34;   --      --   88.0  50 247                                
                                          299                             
                                             --    132                    
   Example 1                                                              
12 Comparative                                                            
          --.sup.4                                                        
             &#34;   --      --   49.5  26 174                                
                                          403                             
                                             93    118                    
   Example 2                                                              
13 Comparative                                                            
          0.44                                                            
             &#34;   --      --   48.5  23 206                                
                                          474                             
                                             44    118                    
   Example 3                                                              
__________________________________________________________________________
 Note:                                                                    
 .sup.1 Measured in toluene at 30° C.                              
 .sup.2 Values given by compositions free from accelerator, sulfur and    
 amine compound (C.sub.II).                                               
 .sup. 3 Based on 100 parts by weight of the copolymer (B).               
 .sup.4 In place of the copolymer (B), 20 parts by weight of higharomatic 
 extender oil was added to 100 parts by weight of the rubber (A).         
 .sup.5 Degree of extraction of the copolymer (B) or extender oil.        
 M.sub.100, T.sub.B and E.sub.B : the same as in Table 2.                 
 
    
     It is apparent that Run Nos. 15-23 are lower in Mooney viscosity of formulated rubber and exothermic temperature and more excellent in processability than Run No. 11. It is also apparent that Run Nos. 15-23 are greatly improved in physical properties of vulcanizates (M 100 ) and migration property (degree of extraction) as compared with Run Nos. 12 and 13. On the other hand, in Run No. 24 in which a chloromethylstyrene-containing copolymer (B) having an [η] value of 0.2 dl/g or less (the copolymer of Comparative Example 7) was used, the properties of vulcanized product (M 100 ) are low and the rate of extraction is high through the processability is good. It is apparent from the Run Nos. 15 and 17-22 that when chloromethylstyrene-containing copolymer (B) is used, metallic oxide (C I ) alone is enough to exhibit an effect as a crosslinking agent for the copolymer (B). 
     Example 20 
     By using the copolymers (B) obtained in Examples 8 and 9, compositions were prepared by the same procedure as in above items (2) and (3) according to the recipe of Table 4, and the compositions were vulcanized under the conditions shown in Table 4. The properties of vulcanizate, the migration property and the processability were measured to obtain the results shown in Table 5. In Table 5, the case in which the copolymer (B) was replaced by a high-aromatic extender oil is also shown for comparison. The compositions prepared from the copolymers (B) of Examples 8 and 9 exhibit good properties of vulcanizate and good processability and, furthermore, are much lower in degree of extraction than the compositions containing the extender oil (Run Nos. 26 and 28). 
     
                       TABLE 4                                                     
______________________________________                                    
Recipe and vulcanization conditions                                       
               Run No.                                                    
               (parts by weight)                                          
               25    26      27      28                                   
______________________________________                                    
Polybutadiene rubber.sup.1                                                
(rubber (A))     100     100     --    --                                 
Polyisoprene rubber.sup.2                                                 
(rubber (A))     --      --      100   100                                
Copolymer (B) of Example 8                                                
                 20      --      --    --                                 
Copolymer (B) of Example 9                                                
                 --      --      20    --                                 
High-aromatic extender oil                                                
                 --      20      --    20                                 
ISAF Carbon Black                                                         
                 50      50      50    50                                 
Zinc oxide (C.sub.I)                                                      
                 5       5       5     5                                  
Stearic acid     3       3       3     3                                  
Vulcanization accelerator                                                 
NOBS             1.5     1.5     0.5   0.5                                
Sulfur           2.5     2.5     2.5   2.5                                
Amine compound (C.sub.II)                                                 
(piperazine stearate)                                                     
                 14.sup.3                                                 
                         0       14.sup.3                                 
                                       0                                  
Vulcanization temperature                                                 
(°C.)     145     145     145   145                                
Vulcanization time (min)                                                  
                 30      30      30    30                                 
______________________________________                                    
 Note:                                                                    
 .sup.1 BR01, a trade name of Japan Synthetic Rubber Co., Ltd. (cis       
 content: 97%, Mooney viscosity ML.sub.1+4.sup.100° C.: 44).       
 .sup.2 IR 2200, a trade name of Japan Synthetic Rubber Co., Ltd. (cis    
 content: 98%, Mooney viscosity ML.sub.1+4.sup.100° C.: 82).       
 .sup.3 Based on 100 parts by weight of the copolymer (B).                
 
    
     
                                           TABLE 5                                 
__________________________________________________________________________
                                    Migration                             
                 Compound.sup.2                                           
                       Physical properties.sup.3                          
                                    property                              
                 Mooney                                                   
                       of vulcanizate                                     
                                    (Degree of                            
Run                                                                       
   Copolymer (B)                                                          
            Rubber                                                        
                 viscosity                                                
                       M.sub.100                                          
                            T.sub.B                                       
                                 E.sub.B                                  
                                    extraction)                           
No.                                                                       
   Kind  [η].sup.1                                                    
            (A)  ML .sub.1+4.sup.100° C.                           
                       (kg/cm.sup.2)                                      
                            (kg/cm.sup.2)                                 
                                 (%)                                      
                                    (%)                                   
__________________________________________________________________________
25 Example 8                                                              
         0.70                                                             
            BR   59.5  44   131  277                                      
                                    33                                    
26 --    --.sup.3                                                         
            BR   55.5  21   136  448                                      
                                    97                                    
27 Example 9                                                              
         0.70                                                             
            IR   44.5  34   152  347                                      
                                    37                                    
28 --    --.sup.3                                                         
            IR   46.5  15   142  484                                      
                                    98                                    
__________________________________________________________________________
 Note:                                                                    
 .sup.1 Measured in toluene at 30° C.                              
 .sup.2 Values given by compositions free from accelerator, sulfur and    
 amine compound (C.sub.II).                                               
 .sup.3 20 parts by weight of higharomatic extender oil was added to 100  
 parts by weight of the rubber (A).                                       
 M.sub.100, T.sub.B and E.sub.B : the same as in Table 2.                 
 
    
     Examples 21 and 22 and Comparative Examples 8 and 9 
     Compounding and vulcanization were carried out by employing the recipe and vulcanization conditions shown in Table 6. 
     The results are shown in Table 7. It is apparent that the rubber compositions comprising mainly natural rubber or polyisoprene rubber as the rubber (A) are particularly excellent in vibration-proof characteristics. 
     As a measure of processability, compound Mooney viscosity ML 1+4   100 ° C. was employed. Hardness and compression set were measured according to JIS K 6301, wherein the conditions of compression set were at 70° C. for 22 hours. Static-dynamic ratio and static spring constant and were expressed by the value of Young&#39;s modulus measured with Viscoelastic Spectrometer manufactured by Iwamoto Seisakusho. The repeated extension fatigue characteristic was determined as follows: Repeated extensions were applied to each sample at an extension degree giving a tensile stress of 100 kgf/cm 2 , measuring the number of repeated extensions N at break, and the product of N and 10 -4  was employed as the repeated fatigue characteristic. Accordingly, the greater the value the better. 
     
                       TABLE 6                                                     
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                          Comparative                                     
                  Example Example                                         
                  21   22     8      9                                    
______________________________________                                    
Natural rubber (part by wt.)                                              
                    50     50     50   50                                 
cis-1,4-Polybutadiene (part by wt.)                                       
                    50     50     50   50                                 
Plasticizer*.sup.1 (part by wt.)                                          
 A                  20                                                    
 B                         20                                             
 C                                20                                      
 D                                     20                                 
ISAF Carbon Black (part by wt.)                                           
                    60     60     60   60                                 
Piperazine glycolate (part by wt.)                                        
                    1.7    --     --   --                                 
NOBS*.sup.2 (part by wt.)                                                 
                    0.6    0.6    0.6  0.6                                
MBTS*.sup.3 (part by wt.)                                                 
                    0.15   0.15   0.15 0.15                               
Zinc oxide (part by wt.)                                                  
                    4.0    4.0    4.0  4.0                                
Stearic acid (part by wt.)                                                
                    2.0    2.0    2.0  2.0                                
Sulfur (part by wt.)                                                      
                    2.0    2.0    2.0  2.0                                
Vulcanization conditions                                                  
                    at 150° C. for 30 min.                         
______________________________________                                    
 Note:                                                                    
 *.sup.1 A: Liquid glycidyl groupcontaining styrenebutadiene copolymer    
 (styrene 23.3% by wt., glycidyl methacrylate 9.6% by wt.,                
 [η].sub.30° C..sup.toluene = 0.56 dl/g)                       
 B: Liquid chloromethylstyrenecontaining styrenebutadiene copolymer       
 (chloromethylstyrene 5.8% by weight, total styrene 27.0% by weight, [.eta
 ].sub.30° C..sup.toluene = 0.80 dl/g)                             
 C: Liquid polybutadiene ([η].sub.30° C..sup.toluene = 0.7 dl/g
 D: Higharomatic extender oil, JSRAROMA, a trade name of Japan Synthetic  
 Rubber Co., Ltd.                                                         
 *.sup.2 NOBS: A mixture of Noxydiethylene-2-benzothiazylsulfenamide and  
 dibenzothiazyl disulfide.                                                
 *.sup.3 MBTS: Dibenzothiazyl disulfide                                   
 
    
     
                       TABLE 7                                                     
______________________________________                                    
                           Comparative                                    
                   Example Example                                        
                   21   22     8      9                                   
______________________________________                                    
Compound Mooney viscosity ML .sub.1+4.sup.100° C.                  
                     58     60     62   51                                
Hardness (JIS-A)     71     68     60   61                                
Static spring constant                                                    
E&#39; × 10.sup.-8 (dyne/cm.sup.2)                                      
                     1.32   1.39   0.91 0.99                              
Static-dynamic ratio                                                      
E&#39;.sub.100HZ /E&#39;.sub.5HZ                                                  
                     1.27   1.30   1.30 1.30                              
Compression set (%)  26     23     31   29                                
Repeated extension fatigue                                                
characteristic (N × 10.sup.-4)                                      
                     7.2    4.0    1.2  1.8                               
______________________________________