Patent Publication Number: US-4317888-A

Title: Process for manufacturing an olefin resin foam

Description:
Polyolefin resin foams, because of their closed-cell structure, flexibility and other features, have utility in a wide range of industrial applications such as for use as cushioning materials, etc. However, since the polyolefin resin is crystalline in nature, its cell size has not been easily controllable in the extrusion-expansion process. Generally, in manufacturing an extruded polyolefin resin foam, a small quantity of inorganic fine powder (such as talc) is added to a polyolefin resin before being extrusion-expanded into a foam in order to produce small, uniform cells. However, such fine powder of a conventional type is highly susceptible to conditions such as extrusion-expanding temperature, the quantity of a volatile blowing agent used and other factors and, thus, even the smallest fluctuations of these conditions in the extrusion-expanding process may cause the cell size to vary so remarkably that the resultant foam does not have a desired thickness and appearance. Also, it has been difficult to accurately correct or compensate varying factors and conditions. Further, it requires rather complicated operations and equipment to suitably control the quantity of the cell control agent correspondingly to the specific conditions involved for otherwise correcting or preventing the variation in the quality of the resultant foam. Besides, in such a method as cited immediately above, defective or unacceptable products produced until the quantity of the cell control agent is properly adjusted to the specific conditions may often amount to a large loss of product. 
     The present invention provides an improved process for manufacturing a polyolefin resin foam by adding to and mixing with a base polyolefin resin a cell control agent and a voltaile blowing agent and extrusion-expanding the resultant mixture in which process the cell control agent employed comprises amorphous silica having a pH of from 3.5 to 4.5 in the form of nonporous microspheres with an average particle size of from about 5 to about 100 mμ and wherein said amorphous silica is added in an amount in the range of from about 0.1 to about 5 percent by weight of the base polyolefin resin. 
     If the content of the amorphous silica cell control agent is lower than about 0.1 percent by weight or exceeds about 5.0 percent by weight, it is difficult to obtain a foamed product having small, uniform cells. 
     The pH of the unique cell control agent herein referred to is measured by the method in accordance with ASTM E-70-52T. Preferably the cell control agent contains at least 98 percent by weight of silicon dioxide. The amorphous silica usable in the present invention is obtained by a method which is generally known as the dry process. The object of the present invention cannot be achieved by using porous, nonspherical silica such as that which is generally used in the art, nor by using silica having an average particle size outside the range of about 5 to about 100 mμ. Moreover, such object is also difficult to obtain with any silica other than amorphous silica containing at least 98 percent by weight of silicon dioxide. The reason for this is not known, but this technical breakthrough may possibly be attributed to dispersibility of the cell control agent, the spherical surface conditions of the agent and compatibility of the volatile blowing agent with the base resin at the time when the resin, the blowing agent and the cell control agent are kneaded with each other within an extruder at a high temperature under high pressure. 
     To add the cell control agent of the present invention to the base resin, it may be either dryblended or masterbatched with the latter. 
     The polyolefin resin herein referred to includes, for example, low-density, medium-density and high-density polyethylene, polypropylene, polyethylene-propylene copolymer, polyethylene-vinyl acetate copolymer, polyethylene-acrylic acid copolymer and metal salts of polyethylene-acrylic acid copolymer. These may be used either singly or in mixture. 
     Useful volatile organic blowing agents include those having a boiling point equal to or lower than the Vicat softening point of the base resin as, for example, propane, butane, dichlorodifluoromethane, dichlorotetrafluoroethane, dichlorofluoromethane, trichlorofluoromethane, chlorodifluoroethane, difluoroethane and the like. These may be used either singly or in mixture. The use of chemical blowing agents is not desirable for the present invention because the proportion of closed cells in the extrusion-expanded foam will be lowered thereby. 
     The method of the present invention is applicable particularly advantageously to the manufacture of extruded foams having a density ranging from 15 to 100 kg/m 3 . Also, in the method according to the present invention, known additives such as thermal stabilizers, lubricants, antistatic agents, flame retardants, etc. may be used in the normal fashion and in the conventionally employed amounts thereof (e.g., typically in the range of from about 0.1 to about 5 weight percent based upon the total composition weight). 
     The present invention is further described in detail by way of the preferred embodiments and comparative examples thereof, in which the cell control agents as listed in Table I below were used. 
     
                                           TABLE I                                 
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Cell Control                               Average                        
Agents                              SiO.sub.2                             
                                           particle                       
in Trade Names                                                            
            Manufacturer                                                  
                       Surface Profile                                    
                               pH   Content (%)                           
                                           size (mμ)                   
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Preferred Embodiments:                                                    
Aerosil 300 NIPPON AEROSIL                                                
            CO., LTD.  Nonporous                                          
                               3.6 ˜ 4.3                            
                                    99.8&lt;  Approx. 7                      
Aerosil OX-50                                                             
            NIPPON AEROSIL                                                
            CO., LTD.  Nonporous                                          
                               3.8 ˜ 4.5                            
                                    99.8&lt;  Approx. 40                     
Comparative Examples:                                                     
Silene EF   FUJI TALC                                                     
            CO., LTD.  Porous  9 ˜ 10                               
                                    64     Approx. 30                     
Bitasil 220 TAGI FERTILIZER                                               
            MANUFACTURING                                                 
            CO., LTD.  Porous  8 ˜ 9                                
                                    81 ˜ 85                         
                                           Approx. 30                     
Silmos T    SHIRAISHI KOGYO                                               
            KAISHA LTD.                                                   
                       Porous  9 ˜ 9.5                              
                                    57.5   Approx. 50                     
Talc LMR    FUJI TALC                                                     
            CO., LTD.  Porous  9 ˜ 10                               
                                    61.7   Approx. 1 × 10.sup.3     
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     In the drawings, FIG. 1 is a chart plotting the average cell size obtained by a cell control agent of the present invention and by another cell control agent against the density thereof; 
     and FIG. 2 is a chart plotting the average cell size and against the content of the specific cell control agents used. 
    
    
     Preferred Embodiment No. 1 and Comparative Example No. 1 
     100 Parts by weight of low-density polyethylene (F-2130 with MI of 3.0, produced by Asahi-Dow Limited), a varied amount of a volatile blowing agent, namely, 21˜32 parts by weight of dichlorotetrafluoroethane, 0.3 part by weight of barium stearate as lubricant and 0.6 part by weight of Aerosil OX-50 or Talc LMR as a cell control agent were fed, respectively, into an extruder with an inside barrel diameter of 65 mm heated at 200° C. and evenly kneaded therein. The thus kneaded mixtures were cooled down to 100° C. by a cooler succeeding to the extruder, and then extruded into foams 2 mm thick, respectively. Properties and qualities of the resultant foams are summarized in Table II. Also, the average cell size of the resultant foams are plotted against the density thereof in FIG. 1. 
     
                                           TABLE II                                
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               Density of                                                 
                       Average                                            
Cell Control Agent                                                        
               foam (Kg/m.sup.3)                                          
                       cell size (mm)                                     
                               Quality of Foam                            
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Preferred Embodiment No. 1:    No thickness variation, evenly             
Aerosil OX-50  26.0    1.15    distributed cells, good appearance         
               31.5    1.10    No thickness variation, evenly             
                               distributed cells, good appearance         
               36.0    1.10    No thickness variation, evenly             
                               distributed cells, good appearance         
               41.0    1.10    No thickness variation, evenly             
                               distributed cells, good appearance         
Comparative Example No. 1:                                                
Talc LMR       26.0    0.1 or below                                       
                               Heavy corrugate marks and                  
                               thickness variation in lateral             
                               direction, uneven cell distri-             
                               bution, inferior appearance                
               33.5    Approx. 0.62                                       
                               Heavy corrugate marks and                  
                               thickness variation in lateral             
                               direction, uneven cell distri-             
                               bution, inferior appearance                
               35.0    Approx. 0.82                                       
                               Light corrugate marks and                  
                               thickness variation, rather                
                               uneven cell distribution and               
                               inferior appearance                        
               41.0    1.19    No corrugate mark or thickness             
                               variation, good appearance with            
                               evenly distributed cells                   
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     As obviously understood from the observations of preferred embodiment No. 1 and comparative example No. 1 shown in Table II, the method of the present invention is much improved in that the average cell size of the resultant foam does not change even if the content of a volatile blowing agent is varied and, therefore, foamed sheets of consistent quality can be easily obtained according to the present invention. 
     Preferred Embodiment No. 2 and Comparative Example No. 2 
     Except that 24 parts by weight of chlorodifluoroethane were used as a volatile blowing agent instead of dichlorotetrafluoroethane, the same formulations as those of the preferred embodiment No. 1 and comparative example No. 1 were subjected to extrusion-expansion, respectively, in the same manner as in the preferred embodiment No. 1 and comparative example No. 1 but the extrusion-expansion temperature at a point just preceding to the circular die was set at three levels of 102° C., 104° C. and 106° C., respectively. 
     The resultant foams were 2 mm thick, respectively, and showed properties and qualities as summarized in Table III below. Table III also shows that, in the method according to the present invention, the average cell size of the resultant foam does not change even if the extrusion-expansion temperature is varied to a small extent and that foamed sheet of uniform quality can therefore be obtained even in spite of such extrusion-expansion temperature variations. 
     
                                           TABLE III                               
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               Extrusion-                                                 
               expansion                                                  
                      Average                                             
               temperature                                                
                      cell  Density                                       
Cell Control Agent                                                        
               (°C.)                                               
                      size (mm)                                           
                            (Kg/m.sup.3)                                  
                                 Quality of foam                          
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Preferred Embodiment No. 2:                                               
Aerosil OX-50  102    1.13  35   No thickness variation,                  
                                 evenly distributed cells,                
                                 good appearance                          
               104    1.15  36   No thickness variation,                  
               106    1.15  36   evenly distributed cells,                
                                 good appearance                          
Comparative Example No. 2:                                                
Talc LMR       102    0.80  35   Light corrugate mark and                 
                                 thickness variation in                   
                                 lateral direction, rather                
                                 uneven cell distribution                 
                                 and inferior appearance                  
               104    1.16  36   No thickness variation,                  
                                 evenly distributed cells                 
                                 and good appearance                      
               106    1.45  36   No thickness variation,                  
                                 evenly distributed cells,                
                                 but appearance lacked                    
                                 smooth feeling                           
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     Preferred Embodiment No. 3 and Comparative Example No. 3 
     The same procedure as described in preferred embodiment No. 1 and comparative example No. 1 was repeated except that 24 parts by weight of dichlorodifluoroethane was used as volatile blowing agent and except that Aerosil 300, Bitasil 220, Silene EF, Silmos T and Talc LMT are added individually in the quantities of 0.3, 0.6 and 0.9 parts by weight to obtain mixtures for extrusion-expansion, without using any lubricant. The resultant foams showed properties as shown in FIG. 2, respectively. As obviously understood from the observations of the preferred embodiment No. 3 and comparative example No. 3 plotted in FIG. 2, the average cell size of the resultant foams is hardly affected by small variations in the quantity of a cell control agent as appearing in the preferred embodiment No. 3, so long as the unique cell control agent according to the present invention is used. In the observations as summarized in Table II and III and shown in FIGS. 1 and 2, cell sizes were measured on the cross-section of a foam magnified by 20 times and the algebraic mean of their maximum diameters was given as their average cell size.