Rubber composition
This is a division of application Ser. No. 08/052,742, filed Apr. 27, 1993. 
    
    
     The present invention relates to a rubber composition and in particular, to a rubber composition which keeps at high levels various characteristics required for rubbers, such as tensile strength, elasticity, scorch resistance and processability and is excellent in wear resistance and flame retardance. 
     It is known to improve flame retardance of rubber compositions by adding a hydroxide of magnesium or aluminum. However, there has not yet been provided a rubber composition which keeps various characteristics required for rubbers, such as tensile strength, elasticity, scorch resistance and processability at high levels and is excellent in wear resistance and flame retardance. 
     The object of the present invention is to provide a rubber composition which keeps at high levels various characteristics required for rubbers, such as tensile strength, elasticity, scorch resistance and processability and is excellent in wear resistance and flame retardance. 
     After intensive research, the inventors have accomplished the present invention. 
     One of the present invention relates to a rubber composition comprising 100 parts by weight of the following component (A), 5 to 300 parts by weight of the following component (B) and 0.1 to 50 parts by weight of the following component (C). 
     Component (A): Ethylene-acrylate or methacrylate (herein referred to &#34;(meth)acrylate&#34;) copolymer rubbers and/or ethylene-(meth)acrylate-unsaturated glycidyl ester copolymer rubbers. 
     Component (B): Hydroxides of typical metal elements belonging to Group II or III of the Mendeleev&#39;s periodic table. 
     Component (C): At least one metallic acrylate compound represented by the following formula (I): ##STR1## (wherein R represents a hydrogen atom or an alkyl group of 1 to 8 carbon atoms, M represents a mono- to tri-valent metallic atom, m represents an integer of 1 to 3 and n represents an integer of 0 to 2). 
     Another invention relates to a rubber composition comprising 100 parts by weight of the above component (A), 5 to 300 parts by weight of the above component (B) and 2 to 100 parts by weight of the following component (D). 
     Component (D): Ethylene copolymers containing carboxylic acids or acid anhydrides. 
     Still another invention relates to a rubber composition comprising 100 parts by weight of the above component (A), 5 to 300 parts by weight of the above component (B), 0.1 to 50 parts by weight of the above component (C) and 2 to 100 parts by weight of the above component (D). 
     The present invention will be explained in detail. 
     The component (A) comprises ethylene-(meth)-acrylate copolymer rubbers and/or ethylene-(meth)-acrylate-unsaturated glycidyl ester copolymer rubbers. The (meth)acrylate means an acrylate or a methacrylate. The (meth)acrylates are preferably those which are obtained from alcohols of 1-8 carbon atoms. Examples are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate. These may be used each alone or in combination of two or more. 
     Ratio (molar ratio) of ethylene to (meth)acrylate in the ethylene-(meth)acrylate copolymer rubbers is preferably (50 to 85):(50 to 15), more preferably (58 to 80):(42 to 20). If amount of the (meth)acrylate is too large, brittle point of the copolymer is high and properties as rubbers (elastomers) in low-temperature atmosphere are sometimes inferior. If it is too small, crystallinity of the copolymer is high and a sufficient elasticity for elastomer is not obtained in some case. 
     Examples of the unsaturated glycidyl esters are glycidyl acrylate, glycidyl methacrylate, diglycidyl itaconate, triglycidyl butenetricarboxylate and glycidyl p-styrenecarboxylate. With reference to the proportion of the unsaturated glycidyl ester in the ethylene-(meth)acrylate-unsaturated glycidyl ester copolymers, the molar ratio of (ethylene+(meth)acrylate):(unsaturated glycidyl ester) is preferably 1: (0.0005 to 0.05), more preferably 1:(0.001 to 0.03). When copolymer rubbers containing the unsaturated glycidyl ester in an amount of the above range are used, it becomes possible to vulcanize them with various vulcanizers utilizing the epoxy group of the glycidyl ester. Copolymer rubbers having no unsaturated glycidyl ester are able to be vulcanized with organic peroxides. 
     As the component (A), in addition to those which comprise ethylene and (meth)acrylate or comprise ethylene, (meth)acrylate and unsaturated glycidyl ester, there may be used copolymers comprising other units in addition to the above units so long as advantageous effects of the present invention are not damaged. Other units include, for example, isobutylene, styrene and derivatives thereof, vinyl acetate, and halogenated olefins such as tetrafluoroethylene and hexafluoropropylene. Preferred are those which have a melt index at 190° C. specified in JIS K6791 of 0.5 to 500 g/10 min. and more preferred are those which have the melt index of 0.5 to 50 g/10 min. If the melt index is too large, strength of the copolymers is insufficient and rubber elasticity is inferior. If the melt index is too small, processability of the copolymers is inferior. 
     The ethylene-(meth)acrylate copolymer rubbers or the ethylene-(meth)acrylate-unsaturated glycidyl ester copolymer rubbers are obtained by known polymerization methods such as free-radical initiated bulk polymerization, emulsion polymerization and solution polymerization. As an example, mention may be made of the method mentioned in Japanese Patent Kokoku No. 46-45085, namely, the method of preparation under a pressure of 500 kg/cm 2  or higher and a temperature of 40 to 300° C. in the presence of a polymerization initiator which produces free radicals. 
     The component (B) comprises hydroxides of typical metallic elements belonging to Group II or III of the Mendeleev&#39;s periodic table. Examples are magnesium hydroxide and aluminum hydroxide. These may be used each alone or in combination of two or more. 
     The component (C) comprises at least one metallic acrylate compound represented by the above formula (I). In the formula, R represents a hydrogen atom or an alkyl group of 1 to 8 carbon atoms, preferably a hydrogen atom or a methyl group, M represents a mono- to tri-valent metallic atom, m represents an integer of 1 to 3 and n represents an integer of 0 to 2. Examples of M are lithium, sodium, potassium, magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel, copper, silver, zinc and aluminum. Examples of the metallic acrylate compounds are zinc acrylate, magnesium acrylate, aluminum hydroxyacrylate, zinc methacrylate, magnesium methacrylate and aluminum hydroxymethacrylate. These may be used each alone or in combination of two or more. Furthermore, metallic polyacrylates may also be used as the compound represented by the formula (I). 
     The component (D) comprises ethylene copolymers containing carboxylic acids or acid anhydrides. Examples of the ethylene copolymers containing carboxylic acids or acid anhydrides are ethylene-maleic anhydride copolymer, ethylene-acrylate-maleic anhydride copolymer and ethylene-acrylate-maleic anhydride half ester copolymer. The ethylene-maleic anhydride copolymer may be a copolymer obtained by radical polymerization of ethylene and maleic anhydride under high pressures and a copolymer containing a radical copolymerizable monomer such as vinyl acetate, methyl methacrylate, ethyl acrylate or butyl acrylate in addition to ethylene and maleic anhydride. 
     The rubber composition of the present invention comprises components (A), (B) and (C), components (A), (B) and (D) or components (A), (B), (C) and (D). 
     Content of the component (B) is in the range of 5 to 300 parts by weight, preferably 10 to 200 parts by weight every 100 parts by weight of the component (A). If the content is too small, the composition is inferior in flame retardance and if it is too large, the composition is inferior in processability. 
     Content of the component (C) in the rubber compositions comprising components (A), (B) and (C) is in the range of 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight every 100 parts by weight of the component (A). If the content is too small, the composition is inferior in wear resistance and if it is too large, the composition is inferior in processability. 
     Content of the component (D) in the rubber compositions comprising components (A), (B) and (D) is in the range of 2 to 100 parts by weight, preferably 5 to 50 parts by weight every 100 parts by weight of the component (A). If the content is too small, the composition is inferior in wear resistance and if it is too large, the composition is inferior in rubber elasticity and scorch resistance. 
     The rubber compositions of the present invention may comprise 100 parts by weight of the component (A), 5 to 300 parts by weight, preferably 10 to 200 parts by weight of the component (B), 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight of the component (C) and 2 to 100 parts by weight, preferably 5 to 50 parts by weight of the component (D). When the rubber compositions contain all of the components (A), (B), (C) and (D) as above, wear resistance and tensile strength are further conspicuously improved. 
     Two or more ingredients in each of the components (A) to (D) may be used in combination. In this case, the total amount of them in each component must satisfy the range of the content of the component. 
     Method for production of the rubber compositions of the present invention and method for use thereof are as follows. The respective components and, if necessary, carbon black, organic peroxides, anti-oxidants, vulcanizing accelerators, processing aids, stearic acid, reinforcing agents, fillers, plasticizers, softening agents and others are mixed by usual kneaders such as roll mills and Banbury mixer to make a vulcanizable rubber composition. The resulting rubber composition is molded into a desired shape and subjected to vulcanization to make a vulcanized rubber composition which is a molded final article. The vulcanization is usually carried out at a temperature of 120° C. or higher, preferably 150° to 220° C. for about 1 to 30 minutes. 
     When copolymer rubbers having unsaturated glycidyl esters are used as component (A), the epoxy group is able to be a crosslinking site. Examples of the vulcanizers reactable with the epoxy group are combinations of quaternary ammonium salts, quaternary phosphonium salts and organic phosphorus compounds with organic acids and polyfunctional amine compounds. 
     As the organic peroxides, there may be used those which are generally used for crosslinking of rubbers. Examples of the organic peroxides are di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α-bis(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane and 2,2-bis(t-butylperoxy)octane. 
     Amount of the organic peroxide is preferably in the range of 1 to 10 parts by weight, more preferably in the range of 2 to 6 parts by weight every 100 parts by weight of the copolymer. If the amount is too small, crosslinking density is low and mechanical strength of the vulcanized rubber compositions is insufficient. If it is too large, problems such as blowing often occur at the time of vulcanization and molding. Furthermore, known crosslinking aids such as p,p&#39;-dibenzoylquinone dioxime, quinone dioxime, triallyl cyanurate, sulfur, ethylene dimethacrylate, N,N&#39;-m-phenylenebismaleimide, triallyl isocyanurate and trimethylolpropane trimethacrylate may be used for improving crosslinking efficiency in vulcanization with organic peroxides. 
     The rubber compositions of the present invention are able to be used in a wide field taking advantage of the excellent properties. Especially, they are suitable as covering materials for electric wires and cables used in multistory buildings, power stations, ships and various plants. 
    
    
     The present invention will be explained by the following Examples and Comparative Examples. 
     Examples 1-18 and Comparative Examples 1-5 
     The components shown in Table 1 (excluding peroxide and triallyl isocyanurate) were kneaded with a Brabender plastomill of 350 cc adjusted to 90° C. at a rotor velocity of 60 rpm for 5 minutes. Thereafter, peroxide and triallyl isocyanurate were added thereto and kneaded with an open roll mill of 6 inches to obtain a rubber composition. Then, the rubber composition was press vulcanized to obtain a vulcanized rubber. This vulcanized rubber was evaluated on properties in accordance with JIS K6301 except for the annotated properties. 
     Measurement of abrasion wear was conducted in the following manner. That is, the sample vulcanized rubber was subjected to preliminary abrasion of 500 times using a Taber machine (using a whetstone of H-18 and a load of 500 g) and was further subjected to abrasion of 1000 times and thereafter weight change of the sample was measured and the decrement in weight was taken as abrasion wear. The measurement was carried out 3 times and the average value was used for evaluation. Measurement of oxygen index (O.I.) was conducted in accordance with JIS K7201. 
     Results of the all evaluations are shown in Table 1. 
     From the results, the following are recognized. 
     That is, all of the Examples of the present invention show satisfactory results of evaluations. On the other hand, the samples of Comparative Examples 1-4 in which neither the component (C) nor the component (D) of the present invention were used were infrior in wear resistance. The sample of Comparative Example 2 was further inferior in tensile strength. Considerable scorching occurred in Comparative Example 5 where the component (A) was not used. 
     
                                           TABLE 1                                 
__________________________________________________________________________
Components *1                                                             
(Part by Example                                                          
               Example                                                    
                     Example                                              
                           Example                                        
                                 Example                                  
weight)  1     2     3     4     5                                        
__________________________________________________________________________
Component (A)                                                             
Kind *2  A1    A1    A1    A1    A1                                       
Amount   100   100   100   100   100                                      
Component (B) *3                                                          
         100   100   100   100   100                                      
Component (C)                                                             
C1 *4    1     3     0     0     0                                        
C2       0     0     0     0     0                                        
Component (D)                                                             
Kind *5  --    --    D1    D1    D1                                       
Amount   0     0     5     10    20                                       
LDPE *6  0     0     0     0     0                                        
Evaluation                                                                
Mooney scorch                                                             
125° C.                                                            
Vm       16.3  18.5  13.4  15.7  21.2                                     
t5 minute                                                                 
         14.3  11.0  27.6  30.0  30.8                                     
t35 minute                                                                
         52.1  17.0  &gt;60   &gt;60   &gt;60                                      
Properties of                                                             
vulcanized                                                                
product *7                                                                
Tensile strength                                                          
         68    107   68    75    86                                       
Kgf/cm.sup.2                                                              
Elongation                                                                
         310   210   390   390   370                                      
Hardness JIS-A                                                            
         74    79    72    76    81                                       
Taber abrasion                                                            
         0.3031                                                           
               0.2278                                                     
                     0.5297                                               
                           0.4791                                         
                                 0.3578                                   
wear                                                                      
g/1000 times                                                              
Oxygen index                                                              
         30.0  30.0              28.0                                     
(O.I.)                                                                    
__________________________________________________________________________
Components *1                                                             
(Part by Example                                                          
               Example                                                    
                     Example                                              
                           Example                                        
                                 Example                                  
weight)  6     7     8     9     10                                       
__________________________________________________________________________
Component (A)                                                             
Kind *2  A1    A1    A1    A1    A1                                       
Amount   100   100   100   100   100                                      
Component (B) *3                                                          
         100   100   100   100   100                                      
Component (C)                                                             
C1 *4    0     0     0     0     0                                        
C2       0     0     0     0     0                                        
Component (D)                                                             
Kind *5  D2    D2    D2    D3    D3                                       
Amount   5     10    20    10    20                                       
LDPE *6  0     0     0     0     0                                        
Evaluation                                                                
Mooney scorch                                                             
125° C.                                                            
Vm       11.7  12.9  18.9  15.9  17.9                                     
t5 minute                                                                 
         24.0  25.8  28.1  17.2  18.9                                     
t35 minute                                                                
         &gt;60   &gt;60   &gt;60   45.5  45.9                                     
Properties of                                                             
vulcanized                                                                
product *7                                                                
Tensile strength                                                          
         72    71    75    80    86                                       
Kgf/cm.sup.2                                                              
Elongation                                                                
         430   400   410   320   330                                      
Hardness JIS-A                                                            
         70    72    73    71    72                                       
Taber abrasion                                                            
         0.5127                                                           
               0.4780                                                     
                     0.3977                                               
                           0.3910                                         
                                 0.2807                                   
wear                                                                      
g/1000 times                                                              
Oxygen index         28.0                                                 
(O.I.)                                                                    
__________________________________________________________________________
Components *1                                                             
(Part by Example                                                          
               Example                                                    
                     Example                                              
                           Example                                        
                                 Example                                  
weight)  11    12    13    14    15                                       
__________________________________________________________________________
Component (A)                                                             
Kind *2  A2    A1    A1    A1    A1                                       
Amount   100   100   100   100   100                                      
Component (B) *3                                                          
         100   100   100   100   100                                      
Component (C)                                                             
C1 *4    0     1     2     3     0                                        
C2       0     0     0     0     3                                        
Component (D)                                                             
Kind *5  D1    D1    D1    D1    D3                                       
Amount   10    20    20    20    20                                       
LDPE *6  0     0     0     0     0                                        
Evaluation                                                                
Mooney scorch                                                             
125° C.                                                            
Vm       18.0  24.9  25.1  27.2  22.2                                     
t5 minute                                                                 
         14.2  21.4  13.0  15.0  23.2                                     
t35 minute                                                                
         50.7  &gt;60   39.5  24.5  &gt;60                                      
Properties of                                                             
vulcanized                                                                
product *7                                                                
Tensile strength                                                          
         70    97    112   126   87                                       
Kgf/ cm.sup.2                                                             
Elongation                                                                
         340   280   220   210   330                                      
Hardness JIS-A                                                            
         75    81    82    84    81                                       
Taber abrasion                                                            
         0.4152                                                           
               0.2504                                                     
                     0.1904                                               
                           0.2109                                         
                                 0.2343                                   
wear                                                                      
g/1000 times                                                              
Oxygen index         28.0  28.0                                           
(O.I.)                                                                    
__________________________________________________________________________
Components *1                                                             
(Part by Example                                                          
               Example                                                    
                     Example                                              
                           Example                                        
weight)  16    17    18    19                                             
__________________________________________________________________________
Component (A)                                                             
Kind *2  A1    A1    A1    A2                                             
Amount   100   100   100   100                                            
Component (B) *3                                                          
         100   100   100   100                                            
Component (C)                                                             
C1 *4    0     0     1     1                                              
C2       4     5     3     3                                              
Component (D)                                                             
Kind *5  D1    D1    D1    D1                                             
Amount   20    20    20    20                                             
LDPE *6  0     0     0     0                                              
Evaluation                                                                
Mooney scorch                                                             
125° C.                                                            
Vm       23.2  24.5  23.1  31.8                                           
t5 minute                                                                 
         23.1  21.3  13.8  8.1                                            
t35 minute                                                                
         &gt;60   &gt;60   54.5  39.8                                           
Properties of                                                             
vulcanized                                                                
product *7                                                                
Tensile strength                                                          
         89    94    102   96                                             
Kgf/cm.sup.2                                                              
Elongation                                                                
         290   270   270   260                                            
Hardness JIS-A                                                            
         82    83    82    80                                             
Taber abrasion                                                            
         0.2340                                                           
               0.2497                                                     
                     0.2098                                               
                           0.2324                                         
wear                                                                      
g/1000 times                                                              
Oxygen index   28.0  28.0  28.0                                           
(O.I.)                                                                    
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         Compara-                                                         
               Compara-                                                   
                     Compara-                                             
                           Compara-                                       
                                 Compara-                                 
Components *1                                                             
         tive  tive  tive  tive  tive                                     
(Part by example                                                          
               example                                                    
                     example                                              
                           example                                        
                                 example                                  
weight)  1     2     3     4     5                                        
__________________________________________________________________________
Component (A)                                                             
Kind *2  A1    A2    A1    A1    --                                       
Amount   100   100   100   100   0                                        
Component (B) *3                                                          
         100   100   100   100   100                                      
Component (C)                                                             
C1 *4    0     0     0     0     0                                        
C2       0     0     0     0     0                                        
Component (D)                                                             
Kind *5  --    --    --    --    D3                                       
Amount   0     0     0     0     100                                      
LDPE *6  0     0     5     10    0                                        
Evaluation                                                                
Mooney scorch                                                             
125° C.                                                            
Vm       8.6   19.5  11.7  10.9                                           
t5 minute                                                                 
         26.0  21.5  30.2  28.1  *8                                       
t35 minute                                                                
         &gt;60   &gt;60   &gt;60   &gt;60   Measur-                                  
Properties of                    ement                                    
vulcanized                       was                                      
product *7                       impos-                                   
Tensile strength                                                          
         70    64    76    69    sible.                                   
Kgf/cm.sup.2                                                              
Elongation                                                                
         380   440   410   390                                            
Hardness JIS-A                                                            
         65    61    72    73                                             
Taber abrasion                                                            
         0.5937                                                           
               0.5321                                                     
                     0.6044                                               
                           0.5863                                         
wear                                                                      
g/1000 times                                                              
Oxygen index                                                              
         30                                                               
(O.I.)                                                                    
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 *1 Components                                                            
 The following common components were used in addition to those shown in  
 Table 1: 15 parts by weight of SEAST SO (FEF carbon black manufactured by
 Tokai Carbon Co.); 1 part by weight of stearic acid; 1 part by weight of 
 stearylamine (0.5 part by weight in Examples 3 to 11 and Comparative     
 Examples 1 to 5); 2 parts by weight of NOGUARD 445 (aging inhibitor      
 manufactured by Uniroyal Co.); 8.8 parts by weight of DCP40 (dicumyl     
 peroxide manufactured by Nippon Oil &amp; Fats Co., Ltd.); and 1 part by     
 weight of triallyl isocyanurate.                                         
 *2 Component (A)                                                         
 A1: Ethylene (66.3 mol %)methyl acrylate (33.0 mol %)glycidyl methacrylat
 (0.7 mol %) copolymer rubber.                                            
 A2: Ethylene (67.0 mol %)methyl acrylate (33.0 mol %) copolymer rubber.  
 *3 Component (B)                                                         
 KISUMA 5B (magnesium hydroxide manufactured by Kyowa Chemical Co.)       
 *4 Component (C)                                                         
 C1: Compound of the formula (1) where R =  hydrogen atom, M = Zn, m = 2, 
 and n = 0 (zinc acrylate).                                               
 C2: Compound of the formula (1) where R = hydrogen atom, M = A1, m = 2,  
 and n = 1 (aluminum acrylate).                                           
 *5 Component (D)                                                         
 D1: BONDINE TX8030 [Ethylene (85.0% by weight)maleic anhydride (3.5% by  
 weight)ethyl acrylate (11.5% by weight) copolymer having a melting point 
 of 95° C. and an MFR (190° C.) of 3.0 g/10 min and         
 manufactured by Sumitomo Chemical Co.,                                   
 D2: BONDINE TX8390 [Ethylene (68% by weight)maleic anhydride (2% by      
 weight)ethyl acrylate (30% by weight) copolymer having a melting point of
 67° C. and an MFR (190° C.) of 7.0 g/10 min and manufacture
 by Sumitomo Chemical Co., Ltd.                                           
 D3: VamacG (Ethylenemethyl acrylatemaleic anhydride half ester copolymer 
 manufactured by DuPont Co.)                                              
 *6 LDPE                                                                  
 SUMIKASEN F7023 (Lowdensity polyethylene having a melting point of       
 107° C. and an MFR (190° C.) of 6.7 g/10 min and           
 manufactured by Sumitomo Chemical Co., Ltd.)                             
 *7 Properties of vulcanized products                                     
 Properties of products vulcanized at 170° C. for 20 minutes.      
 *8 Scorch occurred and measurement of the properties was impossible.     
 
    
     As explained above, the present invention provides a rubber composition which keeps various properties required for rubbers such as tensile strength, elasticity, scorch resistance and processability at high levels and is excellent in wear resistance and flame retardance.