Patent Publication Number: US-2010120956-A1

Title: Method  for Production of Natural Rubber

Description:
TECHNICAL FIELD 
     The present invention relates to a method for producing natural rubber, more specifically it relates to a method for producing natural rubber, in which solid natural rubber suppressed in the increase of viscosity of the raw rubber during storage by adding a compound having a quaternary ammonium ion and a carboxyl ion in the molecule thereof into a natural rubber latex, followed by drying. 
     BACKGROUND ART 
     Natural rubber is a non-petroleum dependent resource and has superior dynamic physical properties, and therefore, has been increasing in the importance thereof. At the present time, the natural rubber distributed for production of rubber products mainly includes latex grade technical specified rubber (TSR) produced by tapping the trunks of rubber trees ( Hevea brasiliensis ) in the Southeast Asian countries, China, some of the African countries, etc. to obtain latex, coagulating the latex thus obtained by acid, squeezing out the moisture, finely chopping it, then drying it by hot air; general grade TSR produced by collecting harvested latex coagulated by an acid or naturally as a material, finely chopping it up, rinsing it to remove the foreign materials mixed therein, repeating these steps, then drying the crumbs by a dryer by hot air; ribbed smoke sheets (RSS) produced by coagulating harvested latex by an acid, etc., forming the coagulated rubber into sheets by ribbed rolls, naturally drying the sheets in an open air, smoke drying the dried sheets, and visually cutting out the foreign-matter, mixed therein, etc. 
     The present inventors previously proposed in Patent Document 1 to use a pulse wave generated by pulse combustion to dry the natural rubber latex instantaneously directly at a low temperature, without coagulating, proposed in Patent Document 2 to produce natural rubber capable of decreasing the viscosity and remarkably easy to process by not only just drying the latex of natural rubber as it is, but performing various types of chemical treatment in the latex state, and further proposed, in Patent Document 3, a method for producing natural rubber comprising adding a compound having a quaternary ammonium ion in the molecule thereof to a latex of natural rubber to remove the moisture (i.e., water content) and dry the resultant rubber, whereby vulcanized rubber having a low hyesteresis loss can be obtained. 
     Patent Document 1 Japanese Patent Publication (A) No. 2005-194503 
     Patent Document 2 Specification of Japanese Patent Application No. 2006-228149 (Japanese Patent Publication (A) No. 2007-146114) 
     Patent Document 3 Specification of Japanese Patent Application No. 2007-016541 
     DISCLOSURE OF THE INVENTION 
     An object of the present invention is to provide a method for producing natural rubber capable of solving the problem of natural rubber (i.e., raw rubber), i.e., the increase in viscosity during storage. 
     In accordance with the present invention, there is provided a method for producing a solid natural rubber comprising:
         adding a compound having a quaternary ammonium ions and a carboxyl ion in the molecule thereof to a natural rubber latex and;   removing and drying a water content of the latex.       

     According to the present invention, it is possible to obtain a solid natural rubber suppressed in the increase of the viscosity during storage by adding a compound having a quaternary ammonium ion and a carboxyl ion in the molecule thereof to natural rubber in the latex state, followed by and dissolving the mixture stirring, then drying the natural rubber, without coagulating and possible to reduce the mastification costs of the rubber. 
    
    
     BEST MODE FOR CARRYING OUT THE INVENTION 
     The inventors engaged in research to directly produce natural rubber free from curing (or increase in the viscosity) during storage, from a natural rubber latex and, as a result, discovered that a solid natural rubber obtained by adding a compound having a quaternary ammonium ion and a carboxyl ions in the molecule thereof shown by the following formula (I) to a latex state natural rubber, stirring the mixture to dissolve, then drying the natural rubber without coagulating can be suppressed in curing (i.e., increase in the viscosity) during storage, whereby the present invention has been completed. 
     As the compound having a quaternary ammonium ion and a carboxyl ion usable in the present invention, it is possible to mention the compounds having the following formula (I): 
     
       
         
         
             
             
         
       
     
     wherein R 1 , R 2  and R 3  independently indicate an organic groups selected from C 1  to C 20 , preferably C 1  to C 10  alkyl groups, C 6  to C 20 , preferably C 6  to C 16  aryl groups, and C 7  to C 20 , preferably C 7  to C 17  aralkyl groups, may include an ester bond and/or an amide bond, and R 4  indicates a C 1  to C 12 , preferably C 1  to C 6  alkylene group. 
     The addition amount of the compound having a quaternary ammonium ion and a carboxyl ion is preferably 0.001 to 0.1 mol %, more preferably 0.008 to 0.08 mol %, based upon to the 1.0 kg in terms of the solid content of the natural rubber latex. If this amount is small, the increase in the viscosity during storage is liable not to be suppressed, while if conversely large, an effect commensurate with the amount is liable not to be obtained and the cost is liable to rise. 
     According to the present invention, the natural rubber latex including a compound having a quaternary ammonium ion and a carboxyl ions in the molecule thereof can be prepared by any method. For example, it is produced by adding a predetermined amount of said compound into a natural rubber latex at ordinary temperature in the atmosphere, while stirring. In a preferable aspect of the present invention, the natural rubber latex is dried by removing the moisture (i.e., water content). As the method for removing the moisture for drying, it is possible to use a generally known method, but the method of spraying the natural rubber latex in a pulse atmosphere to dry it enables drying at a relatively low temperature in a short time, and therefore, can be preferably used. Pulse drying can dry a natural rubber latex to produce rubber using, for example, a pulse burner generating pulse shock waves described in Japanese Patent Publication (A) No. 7-71875 etc. In the present invention, this sort of pulse drier is used to spray dry a latex with preferably a solid content of 70% by weight or less in a drying chamber under conditions of preferably a frequency of 250 to 1200 Hz, more preferably 300 to 1000 Hz, preferably a temperature 140° C. or less, more preferably 40 to 100° C., and 100 to 200 dB (decibel). 
     It is generally known in the art that natural rubber increases in viscosity along with time. For this reason, in the past, sometimes a viscosity stabilizer is included in natural rubber to suppress the increase in the viscosity of the natural rubber. In the present invention as well, if necessary, it is possible to include a viscosity stabilizer in the natural rubber latex spray dried in an atmosphere of shock waves caused by pulse combustion. 
     As the viscosity stabilizer usable in the present invention, it is possible to use any viscosity stabilizer generally used in the past not liable to break down under the above pulse drying conditions. Specifically, for example, at least one of hydroxylamine sulfate ((NH 2 OH) 2 .H 2 SO 4 ), semicarbazide (NH 2 CONHNH 2 ), dimedone (1,1-dimethylcyclohexane-3,5-dione), etc. may be used. 
     The natural rubber produced in the present invention, for example, may be blended with a conventional diene-based rubber, carbon black or silica or the other fillers, a vulcanization or cross-linking agent, a vulcanization or cross-linking accelerator, various types of oils, an antioxidant, plasticizer, and various other types of additives generally compounded for tire use or other rubber composition use so as to obtain a rubber composition. The additives may be mixed by a general method to obtain a composition for use for vulcanization or cross-linking. The amounts of these additives may be made the conventional general amounts so long as the object of the present invention is not adversely affected. 
     EXAMPLES 
     Examples will now be used to further illustrate the present invention, but the scope of the present invention is by no means limited to these Examples. 
     Standard Example 1 
     Examples 1 to 2 and Comparative Examples 1 to 5 
     (1) Treatment of Latex 
     To untreated field latex (made in Thailand, ammonia concentration=0.5 wt %, solid content concentration=about 30 wt %), the treatment chemical shown in Table I was added, based upon the solid content, and the mixture stirred at room temperature for about 6 hours. The mixture was allowed to stand for a while and the state after addition (i.e., presence or absence of any coagulation) was confirmed (see Table I). The precipitate was removed, then the resultant mixture was processed by a centrifuge at 12000 rpm for 30 minutes. Distilled water was added to the creamy substance thus obtained to be dispersed to a DRC (i.e., dry rubber content) of about 60%. 
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE I 
               
               
                   
               
               
                   
                 Stand. Ex. 1 (NR1) 
                 Comp. Ex. 1 (NR2) 
                 Comp. Ex. 2 (NR3) 
                 Comp. Ex 3 (NR4) 
                 Comp. Ex. 4 (NR5) 
                 Ex. 1 (NR6) 
                 Ex. 2 (NR7) 
                 Comp. Ex. 5 (NR8) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
            
               
                 Latex used 
                 Field latex (solid content 30 wt %) 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Latex treatment 
                 HYDA* 1   
                 SDS* 2   
                 TR-701* 3   
                 TR-913* 4   
                 DM-30A *5   
                 PB-30L* 6   
                 AB-35L* 7   
                 MD-100* 8   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 chemical 
                   
                   
                   
                   
                   
                   
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Amount added: 
                 0.008 
                 0.008 
                 0.008 
                 0.008 
                 0.008 
                 0.008 
                 0.008 
                 0.008 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 mol/kg rubber 
                   
                   
                   
                   
                   
                   
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 State after 
                 No 
                 No 
                 Partial 
                 Partial 
                 Coagulation 
                 No 
                 No 
                 Partial 
               
               
                 addition 
                 coagulation 
                 coagulation 
                 coagulation 
                 coagulation 
                   
                 coagulation 
                 coagulation 
                 coagulation 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Mooney 
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 viscosity (Note)   
                   
                   
                   
                   
                   
                   
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 After 24 hours 
                 82 
                  86 
                 — 
                 — 
                 — 
                 90 
                 92 
                 — 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 after drying 
                   
                   
                   
                   
                   
                   
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 After elapse of 48 
                 86 
                 103 
                 — 
                 — 
                 — 
                 97 
                 96 
                 — 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 hours at 60° C. 
                   
                   
                   
                   
                   
                   
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Rate of change (%) 
                 +5 
                 +20 
                 — 
                 — 
                 — 
                 +8 
                 +4 
                 — 
               
               
                   
               
               
                   (Note) Mooney viscosity according to JIS K6300, determined after drying natural rubber for 24 hours and after 60° C. × 48 hours (after holding in gear oven). 
               
               
                 Note of Table I 
               
               
                 * 1 HYDA (hydroxylamine sulfate made by Tokyo Kasei Industry Co., Ltd.) 
               
               
                 * 2 SDS (sodium dodecyl benzenesulfonate made by Tokyo Kasei Industry Co., Ltd.) 
               
               
                 * 3  to * 8 All made by ADEKA and having the following chemical structrures: 
               
               
                 * 3 TR-701 (made by ADEKA) 
               
               
                                   
* 4 TR-913R (made by ADEKA) 
               
               
                                   
* 5 DM-30A (made by ADEKA) 
               
               
                                   
* 6 PB-30L (made by ADEKA) 
               
               
                                   
* 7 AB-35L (made by ADEKA) 
               
               
                                   
* 8 MD-100 (made by ADEKA) 
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
            
           
         
       
     
     Test of Increase in Viscosity of Raw Rubber During Storage 
     The extents of the increase in the viscosity of the samples of the Examples and Comparative Examples were investigated by comparing the initial Mooney viscosities and the Mooney viscosities after standing at 60° C. for 48 hours in a drying atmosphere. The results are shown in Table I. It is clear that the Examples of the present invention have smaller changes in the viscosities. Note that the change in the viscosity of the Standard Example using HYDA (hydroxylamine sulfate) is also small, but HYDA is not preferable in terms of the safety and health, and, therefore, is preferably not used. 
     Method of Evaluation and Testing of Rubber Physical Properties 
     The rubber physical properties of the natural rubbers obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were compared. In each of the formulations shown in Table II, the ingredients other than the vulcanization accelerator and sulfur were kneaded by a 1.7 liter Banbury mixer (Trademark) for 5 minutes. The mixture was discharged when reaching 140° C. to obtain a master batch. The vulcanization accelerator and sulfur were kneaded to this master batch by an 8-inch open roll to obtain a rubber composition. The results are shown in Table II. It is learned that the Examples of the present invention exhibit physical properties with no different compared with the natural rubber usually used as vulcanized rubber (see Reference Examples 1 to 5). 
     Mooney viscosity: Determined according to a JIS K6300 method 
     Rheometer: Determined according to an ASTM D2084 method 
     Tensile test: Determined according to a JIS K6251 method 
     Rupke resilience: Resilience at temperature of 20° C. determine according to a JIS K6255 method 
     Abrasion: A Lambourn abrasion tester was used to determine the abrasion according to a JIS K6264 method under conditions of a load of 4.0 kg and a slip rate of 30%. The results were shown, as indexed to the amount of abrasion of Reference Example 2 as 100. The larger the index, the better the abrasion resistance. 
     
       
         
           
               
               
             
               
                 TABLE II 
               
               
                   
               
               
                   
                 Parts by 
               
               
                 Compounding Ingredients 
                 weight 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 Natural rubber 
                 See Table I 
                 100 
               
               
                 Carbon black 
                 Shoblack N330 (made by Showa Cabot) 
                 45 
               
               
                 (N330) 
               
               
                 Zinc white 
                 Zinc white JIS No. 3 (Seido Chemical 
                 5 
               
               
                   
                 Ind.) 
               
               
                 Stearic acid 
                 Kogyouyou stearic acid (ADEKA) 
                 3 
               
               
                 Antioxidant 
                 Nocrac 6C (Ouchi Shinko Chemical Ind.) 
                 1 
               
               
                 (6PPD) 
               
               
                 Vulcanization 
                 Sancelar NS (Sanshin Chemical Ind.) 
                 0.7 
               
               
                 accelerator 
               
               
                 (TBBS) 
               
               
                 Powdered sulfur 
                 Powdered sulfur (Karuizawa Refinery) 
                 2 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                 TABLE III 
               
               
                   
               
             
            
               
                   
                 Ref. 
                 Ref. 
                 Ref. 
                 Ref. 
                 Ref. 
                 Stand. 
                 Comp. 
               
               
                   
                 Ex. 1 
                 Ex. 2 
                 Ex. 3 
                 Ex. 4 
                 Ex. 5 
                 Ex. 1 
                 Ex. 1 
               
               
                 Natural rubber 
                 CV60 
                 STR20 
                 SIR20 
                 RSS#1 
                 RSS#3 
                 (NR1* 1 ) 
                 (NR2* 1 ) 
               
               
                   
               
            
           
           
               
            
               
                 Mooney viscosity 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Test temp./100° C. 
                 INT [Mooney] 
                 100 
                 109 
                 106 
                 175 
                 136 
                 137 
                 165 
               
               
                 Rotor/L 
                 Vis [Mooney] 
                 57 
                 53 
                 57 
                 71 
                 66 
                 56 
                 62 
               
            
           
           
               
            
               
                 Rheometer 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Test temp./148° C. 
                 T30 [min] 
                 7.3 
                 6.4 
                 6.9 
                 5.8 
                 7.2 
                 5.2 
                 5.2 
               
               
                   
                 T95 [min] 
                 14.8 
                 13.7 
                 14.1 
                 13.6 
                 15.2 
                 11.1 
                 11.8 
               
               
                   
                 MH [N · m] 
                 1.484 
                 1.474 
                 1.517 
                 1.55 
                 1.54 
                 1.44 
                 1.44 
               
            
           
           
               
            
               
                 Tensie test (vulcanization 148° C. × 30 min) 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 M100 [MPa] 
                 3.1 
                 3.0 
                 3.0 
                 3.2 
                 3.1 
                 3.1 
                 3.1 
               
               
                   
                 M300 [MPa] 
                 15.9 
                 15.5 
                 15.1 
                 16.4 
                 16.2 
                 15.9 
                 16.2 
               
               
                   
                 T B  [MPa] 
                 30.6 
                 29.7 
                 27.6 
                 30.4 
                 29.7 
                 30.1 
                 29.9 
               
               
                   
                 E B  [%] 
                 506 
                 502 
                 478 
                 499 
                 483 
                 485 
                 491 
               
            
           
           
               
            
               
                 Rupke resilience (vulcanization 148° C. × 30 min) 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Test temp./20° C. 
                 Resilience 
                 60 
                 63 
                 62 
                 62 
                 65 
                 64 
                 66 
               
            
           
           
               
            
               
                 Lambourn abrasion test (vulcanization 148° C. × 30 min) 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 Abrasion index 
                 105 
                 100 
                 102 
                 104 
                 109 
                 102 
                 102 
               
               
                   
                 [%] 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 Comp. 
                 Comp. 
                 Comp. 
                   
                   
                 Comp. 
               
               
                   
                 Ex. 2 
                 Ex. 3 
                 Ex. 4 
                 Ex. 1 
                 Ex. 2 
                 Ex. 5 
               
               
                 Natural rubber 
                 (NR3* 1 ) 
                 (NR4* 1 ) 
                 (NR5* 1 ) 
                 (NR6* 1 ) 
                 (NR7* 1 ) 
                 (NR8* 1 ) 
               
               
                   
               
            
           
           
               
            
               
                 Mooney viscosity 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Test temp./100° C. 
                 INT [Mooney] 
                 137 
                 136 
                 126 
                 152 
                 150 
                 156 
               
               
                 Rotor/L 
                 Vis [Mooney] 
                 55 
                 56 
                 53 
                 59 
                 56 
                 59 
               
            
           
           
               
            
               
                 Rheometer 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Test temp./148° C. 
                 T30 [min] 
                 4.2 
                 4.9 
                 4.5 
                 4.6 
                 4.9 
                 4.7 
               
               
                   
                 T95 [min] 
                 10.4 
                 11.1 
                 11.0 
                 11.0 
                 11.2 
                 10.9 
               
               
                   
                 MH [N · m] 
                 1.45 
                 1.47 
                 1.47 
                 1.46 
                 1.46 
                 1.46 
               
            
           
           
               
            
               
                 Tensile test (vulcanization 148° C. × 30 min) 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                 M100 [MPa] 
                 3.1 
                 3.1 
                 3.4 
                 3.3 
                 3.1 
                 3.2 
               
               
                   
                 M300 [MPa] 
                 15.4 
                 15.9 
                 16.7 
                 16.2 
                 16.2 
                 16.3 
               
               
                   
                 T B  [MPa] 
                 30.2 
                 30.7 
                 29.7 
                 29.7 
                 30.9 
                 30.0 
               
               
                   
                 E B  [%] 
                 517 
                 512 
                 483 
                 493 
                 504 
                 502 
               
            
           
           
               
            
               
                 Rupke resilience (vulcanization 148° C. × 30 min) 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Test temp./20° C. 
                 Resilience 
                 65 
                 67 
                 66 
                 65 
                 68 
                 65 
               
            
           
           
               
            
               
                 Lambourn abrasion test (vulcanization 148° C. × 30 min) 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                 Abrasion index 
                 106 
                 99 
                 108 
                 102 
                 107 
                 106 
               
               
                   
                 [%] 
               
               
                   
                   
               
               
                   
                 * 1 See Table I 
               
            
           
         
       
     
     INDUSTRIAL APPLICABILITY 
     According to the method of the present invention, it is possible to produce natural rubber suppressed in the increase of the viscosity during storage from a natural rubber latex, and therefore, the present invention is useful for utilization as tires, conveyor belts, rubber supports, and other various rubber products.