Patent Publication Number: US-2015073087-A1

Title: Process oil and rubber composition

Description:
TECHNICAL FIELD 
     The present invention relates to a process oil and a rubber composition formed by applying the process oil to a natural rubber and a synthetic rubber. 
     BACKGROUND ART 
     A rubber used in various fields such as for machinery and electric products typically contains a process oil to improve mechanical property and processability. The process oil is used as constituents of a plasticizer for a thermoplastic resin and a printing ink and as lubricant or a solvent component used for a softener or the like for a recycle asphalt, as well as being added to a rubber material such as a natural rubber and a synthetic rubber. 
     In recent years, there have been increasing demands for a rubber composition containing an EPDM (Ethylene-Propylene-Diene Monomer), an olefin thermoplastic elastomer or a styrenic thermoplastic elastomer, the rubber composition being used as an automobile interior material. 
     Since the rubber composition is required to have heat resistance and weather resistance to be used as the automobile interior material, a white paraffin process oil with a high purity is typically employed. For instance, a process oil exhibiting a Saybolt color of +28 or more and excellent heat resistance and weather resistance is known (see Patent Literature 1). 
     CITATION LIST 
     Patent Literature(S) 
     Patent Literature 1: JP-A-2007-112824 
     SUMMARY OF THE INVENTION 
     Problem(s) to be Solved by the Invention 
     In recent years, the rubber material, for instance, used for the automobile interior material, has been required to have a higher weather resistance. In general, the thermoplastic elastomer is gradually degraded as being exposed to sunlight. Specifically, in the thermoplastic elastomer, surface crack or brittleness is caused by polymer molecular chains cutting or gelation caused by ultraviolet ray contained in the sunlight, so that the thermoplastic elastomer is no longer suitable for practical use. The process oil contained in rubber significantly influences a shape change due to such a degradation phenomenon. 
     When a so-called oil extended rubber using the process oil is exposed to the sunlight for a short time, the rubber is only discolored but a shape of the rubber is not changed (e.g., deformed) However, when the rubber is exposed to the sunlight for a long time, the shape change (e.g., deformation, surface crack) of the rubber occurs. Accordingly, such an oil extended rubber may be not suitable for use. 
     Even the process oil of Patent Literature 1 is not necessarily sufficient for the weather resistance of the oil extended rubber. For instance, when the rubber is exposed to the sunlight for a long time, in addition to the discoloration of the rubber, the shape change (e.g., deformation, surface crack) of the rubber may occur. 
     An object of the invention is to provide a process oil having an excellent weather resistance and being unlikely to cause a shape change such as deformation of a rubber product when the rubber product is degraded, and to provide a rubber composition using the process oil. 
     Means for Solving the Problem(s) 
     As a process oil, a paraffinic mineral oil or a naphthenic mineral oil have typically widely been used. The inventor found that a shape change (e.g., deformation and surface crack) of an oil extended rubber is preventable by setting a content of a specific aromatic component in an oil substantially at a predetermined level or less with reference to ultraviolet absorbances of two specific wavelengths, even when the rubber is exposed to sunlight for a long time. The invention is completed based on this finding. Specifically, the invention provides a process oil and a rubber composition as follows. 
     (1) According to an aspect of the invention, a process oil has properties (a) to (c) below: (a) an ultraviolet absorbance at 198 nm of 3 or less; (b) an ultraviolet absorbance at 228 nm of 1 or less; and (c) a kinematic viscosity at 40 degrees C. in a range of 25 mm 2 /s to 450 mm 2 /s. 
     (2) According to another aspect of the invention, a rubber composition contains the above-described process oil. 
     (3) In the rubber composition according to the above aspect of the invention, a rubber material of the rubber composition is at least one selected from an EDPM, an olefin thermoplastic elastomer and a styrenic elastomer. 
     Because of an excellent weather resistance, when used for the rubber product, the process oil of the invention is unlikely to cause a shape change such as deformation due to degradation of the rubber product. Accordingly, an appearance and a performance of the rubber product are preventable from being deteriorated, so that a lifetime of the rubber product can be prolonged. 
    
    
     DESCRIPTION OF EMBODIMENT(S) 
     A process oil according to an exemplary embodiment of the invention has properties (a) to (c) below: 
     (a) an ultraviolet absorbance at 198 nm of 3 or less; 
     (b) an ultraviolet absorbance at 228 nm of 1 or less; and 
     (c) a kinematic viscosity at 40 degrees C. in a range of 25 mm 2 /s to 450 mm 2 /s. 
     Ultraviolet Absorbance 
     It is well known that, when a process oil is contained in rubber, an oil extended rubber gelates or the like by ultraviolet ray due to an influence of an aromatic component in the process oil, thereby causing discoloration. Moreover, since an absorbed amount of the ultraviolet ray represents a content of the aromatic component in the process oil, it is assumable that the larger ultraviolet absorbance indicates the larger content of the aromatic component. Accordingly, in a simple consideration, in order to improve the weather resistance of the process oil, the following is easily conceivable: in order to avoid the influence by the ultraviolet ray, it is only necessary to reduce the content of the aromatic component that is a cause of ultraviolet absorption; in other words, it is only necessary to reduce a value of the ultraviolet absorbance as an index of the content of the aromatic component. 
     However, since compatibility between the process oil and the rubber is crucial for blending the process oil in the rubber, it is not sufficient to simply reduce the content of the aromatic component. Accordingly, an index for a specific minute content of the aromatic component that would adversely affect the weather resistance is required. However, there have been no findings about the minute content of the aromatic component that affects the shape change of the oil extended rubber left in severe conditions. 
     The invention disclosed in JP-A-2007-112824 defines an ultraviolet absorbance at a wavelength of 198 nm as an index for weather resistance of the oil extended rubber. However, this index is not always sufficient to prevent the shape change (e.g., deformation) due to an insufficient weather resistance of the oil extended rubber. Although a % CA value by a ring analysis is an index of the aromatic component, the % CA value is not an index for the weather resistance of the oil extended rubber (because the % CA value exceeds 0.1). 
     In the process oil according to the exemplary embodiment, two ultraviolet absorbances are defined at the wavelengths of 198 nm and 228 nm, whereby not only a hue change of the oil extended rubber but also a shape change thereof when the oil extended rubber is degraded by the ultraviolet ray are controllable. 
     The process oil according to the exemplary embodiment has (a) an ultraviolet absorbance (at 198 nm) of 3 or less, preferably 2 or less, and (b) an ultraviolet absorbance (at 228 nm) of 1 or less, preferably 0.5 or less. When the two ultraviolet absorbances defined by the above (a) and (b) exceed the respective upper limit values, since the content of the specific aromatic component that adversely affects the weather resistance is large, the weather resistance is likely to be deteriorated to particularly cause the shape change of the oil extended rubber. 
     Note that it is only necessary to measure the ultraviolet absorbance in accordance with JIS K 0115. Specifically, 2.00 g of a sample is diluted with hexane to be 50 ml, which is then placed in a 10-mm cell and irradiated with the wavelengths of 198 nm and 228 nm for measurement. The hexane is provided as a blank in the measurement. 
     For a favorable performance of the process oil, a kinematic viscosity at 40 degrees C. of the process oil is in a range of 25 mm 2 /s to 450 mm 2 /s, preferably in a range of 85 mm 2 /s to 400 mm 2 /s. 
     The process oil according to the exemplary embodiment is exemplarily obtainable by performing hydrocracking, solvent dewaxing, hydrodewaxing, hydrofinishing, hydro-reformation, hydrorefining and the like to an atmospheric distillation residual oil of paraffin crude, a vacuum distillation fraction of the atmospheric distillation residual oil and a bottom oil obtained from a hydrocracker (fuel oil manufacturing device). Specifically, the process oil according to the exemplary embodiment only need to be a mineral oil satisfying the predetermined requirements in terms of the ultraviolet absorbances at the two wavelengths of 198 nm and 228 nm and the kinematic viscosity. 
     Since the thus obtained process oil of the exemplary embodiment has the properties (a) to (c) described above, the process oil exhibits a low evaporativity and an excellent weather resistance. 
     By blending the process oil to the rubber material which is at least one selected from EPDM, olefin thermoplastic elastomer and styrenic elastomer, various rubber compositions can be suitably provided. Moreover, the obtained rubber compositions can be suitably used especially as the automobile interior material that requires weather resistance. 
     When a rubber (rubber composition) is manufactured using the process oil of the exemplary embodiment, a content of the process oil may be, for instance, 10 mass parts to 50 mass parts, preferably 20 mass parts to 40 mass parts relative to 100 mass parts of the rubber component. 
     Moreover, when the rubber composition is manufactured, a carbon black, a reinforcer such as a silica, a vulcanizing agent, a vulcanizing accelerator, a filler, a degradation preventing agent such as waxes, a softener other than the process oil of the exemplary embodiment, a plasticizer, etc., which is generally used in rubber industry, may appropriately be blended. 
     Note that the embodiment described above is only an exemplary embodiment illustrating the invention, and the invention is not limited to the above exemplary embodiment but includes modifications and improvements as long as an object of the invention can be achieved. 
     For instance, as long as the process oil has the properties (a) to (c), the procedure to obtain the process oil may appropriately be adjusted. 
     EXAMPLES 
     The invention will be described in more detail with reference to Examples and Comparatives, However, it should be appreciated that the scope of the invention is by no means limited by the Examples and the like. 
     Manufacturing Example 1 
     Example 1 
     A paraffin crude was subjected to atmospheric distillation and then the obtained residual oil was subjected to vacuum distillation to provide a fraction. The fraction was subjected to a two-stage hydrogenation process, so that a mineral oil A having a boiling point at an ambient pressure in a range of 335 degrees C. to 491 degrees C. was obtained. The mineral oil A was provided as a sample oil of Example 1. Properties of the mineral oil A are shown in Table 1. 
     Manufacturing Example 2 
     Example 2 
     A paraffin crude was subjected to atmospheric distillation and the obtained residual oil was subjected to vacuum distillation to provide a fraction. The fraction was subjected to a two-stage hydrogenation process, so that a mineral oil B having the boiling point at the ambient pressure in a range of 367 degrees C. to 627 degrees C. was obtained. The mineral oil B was provided as a sample oil of Example 2. Properties of the mineral oil B are shown in Table 1. 
     Manufacturing Example 3 
     Example 3 
     A paraffin crude was subjected to atmospheric distillation and the obtained residual oil was subjected to vacuum distillation to provide a fraction. The fraction was subjected to a two-stage hydrogenation process, so that a mineral oil C having the boiling point at the ambient pressure in a range of 409 degrees C. to 700 degrees C. was obtained. The mineral oil C was provided as a sample oil of Example 3. Properties of the mineral oil C are shown in Table 1. 
     Manufacturing Example 4 
     Comparative 4 
     A paraffin crude was subjected to atmospheric distillation and the obtained residual oil was subjected to vacuum distillation to provide a fraction. The fraction was subjected to a one-stage hydrogenation process, so that a mineral oil D having the boiling point at the ambient pressure in a range of 353 degrees C. to 513 degrees C. was obtained. The mineral oil D was provided as a sample oil of Comparative 4. Properties of the mineral oil D are shown in Table 2. 
     Manufacturing Example 5 
     Comparative 5 
     A paraffin crude was subjected to atmospheric distillation and the obtained residual oil was subjected to vacuum distillation to provide a fraction. The fraction was subjected to a one-stage hydrogenation process, so that a mineral oil E having the boiling point at the ambient pressure in a range of 405 degrees C. to 610 degrees C. was obtained. The mineral oil E was provided as a sample oil of Comparative 5. Properties of the mineral oil E are shown in Table 2. 
     Manufacturing Example 6 
     Comparative 6 
     A paraffin crude was subjected to atmospheric distillation and the obtained residual oil was subjected to vacuum distillation to provide a fraction. The fraction was subjected to a one-stage hydrogenation process, so that a mineral oil F having the boiling point at the ambient pressure in a range of 423 degrees C. to 732 degrees C. was obtained. The mineral oil F was provided as a sample oil of Comparative 6. Properties of the mineral oil F are shown in Table 2. 
     Manufacturing Example 7 
     Example 7 
     A bottom oil obtained from a hydrocracking device (fuel oil manufacturing device) was subjected to hydrodewaxing, hydrofinishing and vacuum distillation, so that a mineral oil G having the boiling point at the ambient pressure in a range of 446 degrees C. to 598 degrees C. was obtained. The mineral oil G was provided as a sample oil of Example 7. Properties of the mineral oil G are shown in Table 1. 
     Examples 4 to 6, Comparatives 1 to 3 
     The mineral oils A to F manufactured in the above Manufacturing Examples were mixed in a predetermined mass ratio to provide sample oils. Properties of the sample oils are shown in Tables 1 and 2. 
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 Example 1 
                 Example 2 
                 Example 3 
                 Example 4 
                 Example 5 
                 Example 6 
                 Example 7 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Base Oil 
                 Mineral 
                 Mineral 
                 Mineral 
                 Mineral  
                 Mineral 
                 Mineral 
                 Mineral 
               
               
                   
                 Oil A 
                 Oil B 
                 Oil C 
                 oil A/ 
                 oil B/ 
                 oil C/ 
                 oil G 
               
               
                   
                   
                   
                   
                 Mineral 
                 Mineral 
                 Mineral oil F 
               
               
                   
                   
                   
                   
                 oil D 
                 oil E 
               
               
                   
                   
                   
                 (98/2) 
                 (98/2) 
                 (96/4) 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 Properties 
                 Viscosity at 40° C. 
                 [mm 2 /s] 
                 30.91 
                 91.41  
                 388.6 
                 30.88  
                 91.60  
                 388.5   
                 104.9 
               
               
                   
                 Viscosity at 100° C. 
                 [mm 2 /s] 
                 5.324 
                 10.89 
                 29.49 
                 5.321 
                 10.89  
                 29.47  
                 12.21 
               
               
                   
                 Viscosity Index 
                 — 
                 105 
                 104 
                 105 
                 105     
                 103     
                 105     
                 108 
               
               
                   
                 UV Absorbance 
                 Abs 
                 1.503 
                 1.553 
                 0.880 
                 2.591 
                 2.736 
                 2.685 
                 0.089 
               
               
                   
                 (198 nm) 
               
               
                   
                 UV Absorbance 
                 Abs 
                 0.243 
                 0.265 
                 0.174 
                 0.480 
                 0.551 
                 0.561 
                 0.019 
               
               
                   
                 (228 nm) 
               
               
                 Evaluation 
                 Hue (Saybolt) 
                 Before weather 
                 +30 
                 +30 
                 +30 
                 +27     
                 +12     
                 −4    
                 +30 
               
               
                 Results 
                   
                 resistance test 
               
               
                   
                   
                 After weather 
                 +22 
                 +16 
                 +15 
                 −16&gt;    
                 −16&gt;    
                 −16&gt;    
                 +25 
               
               
                   
                   
                 resistance test 
               
               
                   
                   
                 (xenon  
               
               
                   
                   
                 BP65° C. × 
               
               
                   
                   
                 10H) 
               
               
                   
                 Appearance of Oil 
                 Discoloration 
                 A 
                 A 
                 A 
                 A 
                 A 
                 A 
                 A 
               
               
                   
                 extended rubber 
                 Shape change 
                 none 
                 none 
                 none 
                 none 
                 none 
                 none 
                 none 
               
               
                   
                 (after weather 
                 (e.g.,  
               
               
                   
                 resistance test, 
                 deformation) 
               
               
                   
                 xenon P65° C. × 
               
               
                   
                 500H) 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
             
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Comparative 
                 Comparative 
                 Comparative 
                 Comparative 
                 Comparative 
                 Comparative 
               
               
                   
                 1 
                 2 
                 3 
                 4 
                 5 
                 6 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Base Oil 
                 Mineral oil A/ 
                 Mineral oil B/ 
                 Mineral oil C/ 
                 Mineral oil D 
                 Mineral oil E 
                 Mineral oil F 
               
               
                   
                 Mineral oil D 
                 Mineral oil E 
                 Mineral oil F 
               
               
                   
                 (90/10) 
                 (90/10) 
                 (87/13) 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Properties 
                 Viscosity at 40° C. 
                 [mm 2 /s] 
                 30.75  
                 91.72 
                 387.8  
                 29.98 
                 90.38 
                 380.6  
               
               
                   
                 Viscosity at 100° C. 
                 [mm 2 /s] 
                 5.301 
                 11.01 
                 29.41 
                  5.193 
                 10.86 
                 29.19 
               
               
                   
                 Viscosity Index 
                 — 
                 104     
                 105    
                 105    
                 102    
                 105    
                 106    
               
               
                   
                 UV Absorbance 
                 Abs 
                 3.367 
                  3.583 
                  3.462 
                 10&lt;   
                 10&lt;   
                 10&lt;   
               
               
                   
                 (198 nm) 
               
               
                   
                 UV Absorbance  
                 Abs 
                 0.964 
                  1.552 
                  1.341 
                 5&lt;   
                 5&lt;   
                 5&lt;   
               
               
                   
                 (228 nm) 
               
               
                 Evaluation 
                 Hue (Saybolt) 
                 Before weather 
                 +5    
                 −16&gt;   
                 −16&gt;   
                 −16&gt;   
                 −16&gt;   
                 −16&gt;   
               
               
                 Results 
                   
                 resistance test 
               
               
                   
                   
                 After weather 
                 −16&gt;    
                 −16&gt;   
                 −16&gt;   
                 −16&gt;   
                 −16&gt;   
                 −16&gt;   
               
               
                   
                   
                 resistance test 
               
               
                   
                   
                 (xenon BP65° C. × 
               
               
                   
                   
                 10H) 
               
               
                   
                 Appearance of Oil 
                 Discoloration 
                 B 
                 B 
                 B 
                 B 
                 B 
                 B 
               
               
                   
                 extended rubber 
                 Shape change 
                 changed 
                 changed 
                 changed 
                 changed 
                 changed 
                 changed 
               
               
                   
                 (after weather 
                 (e.g., deformation) 
               
               
                   
                 resistance test,  
               
               
                   
                 xenon BP65° C. × 
               
               
                   
                 500H) 
               
               
                   
               
            
           
         
       
     
     Test Example 1 
     For the sample oils of Examples 1 to 7 and Comparatives 1 to 6, the Saybolt colors after the weather resistance test were measured. Properties and the test results of the process oils are shown in Tables 1 and 2. Note that the following test method was employed. 
     Weather Resistance Test 
     50 mL of each of the sample oils was put in a 50-m1 glass bottle and was irradiated with light by a xenon lamp at 65 degrees C. for 10 hours. Subsequently, a hue (Saybolt) of each of the sample oils was checked (in accordance with JIS K 2580). Note that the time corresponds to a condition in which the sample oils are exposed outdoors for one month in summer. 
     Evaluation Results 
     It is understood from Table 1 that the sample oils of Examples 1 to 7 show the ultraviolet absorbance equivalent to or less than a predetermined value in each of two wavelengths of 198 nm and 228 nm, which indicates that the content of the aromatic component having an adverse effect on the weather resistance is small, so that the Saybolt colors after the weather resistance tests are less changed, which means that the sample oils of Examples 1 to 7 have excellent weather resistance. 
     On the other hand, as shown in Table 2, the sample oils of Comparatives 1 to 6 exceed the ultraviolet absorbance of at least one of the above two wavelengths, which indicates that the sample oils of Comparatives 1 to 6 have a poor weather resistance, so that all of the sample oils of Comparatives 1 to 6 clearly showed discoloration after the weather resistance test. 
     Test Example 2 
     Using the above-described sample oils, styrene rubber was manufactured as follows. 
     500 mass parts of each of the sample oils was blended and kneaded with 100 mass parts of styrenic thermoplastic elastomer (manufactured by KURARAY CO., LTD: SEPTON 4033) to provide a rubber composition. The rubber composition was heated into a fluid condition, put into a stainless steel container, and cooled to the room temperature into a solid condition. Subsequently, the obtained oil-extended rubber was cut into a 3-cm cube. 
     The obtained cubic rubber piece was subjected to a weather resistance test in which the rubber piece was irradiated with light using a xenon lamp at a temperature of 65 degrees for 500 hours. A discoloration of the rubber and presence or absence of a shape change (e.g., deformation) thereof were visually observed. The discoloration of the rubber was evaluated according to the following standard. 
     A: not discolored 
     B: discolored 
     Evaluation Results 
     When the sample oils of Examples 1 to 7 were used as the process oil as shown in Table 1, it was confirmed that the rubber was not discolored and a shape change (e.g., deformation) of the rubber was not generated. Accordingly, the process oil of the invention can prolong a substantial lifetime of the rubber product. 
     In contrast, when the sample oils of Comparatives 1 to 6 were used, the rubber was discolored and a shape change (e.g., deformation) of the rubber was severely generated as the process oil as shown in Table 2, so that the sample oils of Comparatives 1 to 6 have difficulty in practical use. 
     INDUSTRIAL APPLICABILITY 
     A process oil of the invention is suitably applicable to a process oil for manufacturing a rubber product used as an automobile interior material and the like.