Polybutylene terephthalate molding compositions and articles molded therefrom
The present invention relates to polybutylene terephthalate molding composition containing one or more vinyl polymers as adjuvants to provide moldings of improved impact resistance and lower specific gravity, without more than negligible loss of other properties. The invention includes articles molded from the compositions. 
     BACKGROUND OF THE INVENTION 
     It is known that high molecular weight polybutylene terephthalate resins are uniquely useful as the principal components of compositions for the production of molded articles by the blow mold, injection molding and extrusion methods; see Winfield U.S. Pat. No. 2,465,319. The compositions find principal use in the production of television and radio sets, housings for kitchen appliances and hand tools, bottles, and parts for electric motors and automobile engines. Much effort has been expended in improving these compositions to improve the impact resistance of articles molded therefrom; see Lane U.S. Pat. No. 4,034,013; Baron et al. U.S. Pat. Nos. 4,034,016 and 4,044,072; and Farnharm et al. U.S. Pat. No. 4,096,202. Efforts have also been made to improve these compositions for electrical insulating purposes, and Seydl et al. U.S. Pat. No. 3,937,757 discloses that the &#34;tracking&#34; resistance of articles molded from polybutylene terephthalate molding compositions is improved when the compositions have a content of 5% to 50% by weight of a polyolefin component, which can be polyethylene, a poly(ethylene-vinyl acetate), a poly (ethylene-acrylate), and mixtures thereof. &#34;Tracking resistance&#34; is the ability of a molded article to resist formation of conductive tracks of carbonized material when an electrical arc is established on the surface of an article. Abolins U.S. Pat. No. 4,013,613 discloses similar compositions which, however, require a reinforcing filler. 
     The discovery has now been made that polybutylene terephthalate molding compositions which contain a small amount of an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer, or a mixture of the two copolymers, and optionally polyethylene, the total weight of said copolymer or copolymers and said polyethylene (when present) being less than 5% but more than 0.1% of the weight of said composition, provide molded articles which in preferred embodiments possess greatly improved impact resistance and lower specific gravity, without more than negligible sacrifice of other properties. 
     The polybutylene terephthalate which is the principal polymeric component in the compositions of the present invention can be any of the polymers of this group or mixtures thereof. The polybutylene terephthalate which is present in the compositions of the present invention is preferably of such high molecular weight that it has an intrinsic viscosity of at least 0.6 and preferably about 0.8 dl./g. measured in a mixture of phenol and sym-tetrachloroethane in 3:2 by weight ratio at 30° C. and a maximum viscosity of about 1.5 dl./g. Polymers having an intrinsic viscosity in the range of 0.8 to 1.2 dl./g. are preferred for injection molding applications since these polymers provide molded articles of excellent toughness and impact resistance. 
     The ethylene-ethyl acrylate and ethylene-vinyl acetate copolymers which are present in the compositions of the present invention are composed of ethylene and ethyl acrylate (or vinyl acetate) units in 10:1 to 1:10 molar ratio and preferably in 3:1 to 1:3 molar ratio. The polymers have molecular weights in the range where they are spinnable on the one hand and extrudable at ordinary temperatures on the other hand, that is, molecular weights between about 100,000 and 1,000,000. 
     The optional polyethylene is likewise of high molecular weight, in the range of 50,000 to 500,000. 
     The compositions of the present invention can and advantageously do contain some or all of the supplementary components which are customarily present in thermoplastic polyester molding compositions. 
     Thus they can advantageously contain one or more fibrous reinforcing agents, for example asbestos fibers, graphite fibers, cotton, silk, metal &#34;whiskers&#34; and the like. Because of their ready availability and the excellent increase in impact resistance which they impart, glass fibers (chopped to about 1/4&#34; or less) are preferred. In addition, the composition can contain one or more pigments, for example titanium dioxide and barium sulfate whites, ultramarine and phthalocyanine blues, chrom green, carbon black and nigrosine black; mineral fillers for example talc, mica and, preferably, clay; flame retardants such as decabromodiphenyl ether and the other fully brominated aryl compounds disclosed in U.S. Pat. No. 3,751,396 alone or in admixture with Sb 2  O 3  and similar compounds as disclosed in U.S. Pat. Nos. 3,833,685 and 4,035,333; blowing agents; mold release agents; and stabilizers. 
     With regard to the proportions of the supplementary additives, the amount of fibrous reinforcing agent which is present can be as little as 1% or as much as 60% or more of the weight of the composition, amounts in the range of 5% to 50% being preferred. The fire retardant (or combination of fire retardants) is preferably present in amount between 1% and 20% of the weight of the composition as larger amounts detract from the properties of the moldings, and less than 1% confers little or no benefit. The remaining additives are present in customary minor amount. 
     The compositions of the present invention can be prepared in any conventional manner as, for example, by dry mixing the components in granular or powder form. The mixture can be extruded in the form of strands which after cooling can be chopped or otherwise comminuted into granular or powder form. The last procedure is specially advantageous because the particles so produced are uniform and remain uniform in composition on storage and transportation, so that differential settling during transportation does not occur. 
     Shaped articles can be molded from the compositions by any of the techniques heretofore used for the purpose. Temperatures and molding cycles in general conform with those presently employed for the production of moldings from polybutylene terephthalate based compositions. The most suitable temperature in any instance, however, is best determined by laboratory trial as this temperature varies with the molecular weights of the particular polybutylene terephthalate resin (and other resins) which are present, the presence of cross linkages and branching components as is shown in Cohen et al., copending U.S. application Ser. No. 957,801, and the flow characteristics which are desired, taking into account the dimensions and complexity of the mold. In most instances the compositions can be injection molded in an injection molding machine at a cylinder temperature of 250° C. and a mold temperature of 75° C. with a 60-second molding cycle. 
    
    
     The invention is further illustrated by the examples which follow. These examples represent best embodiments of the invention and are not to be construed in limitation thereof. Parts are by weight except where otherwise stated. 
     EXAMPLE 1 
     The following illustrates the effect of a small amount of a poly(ethylene-ethyl acrylate) as modifier which improves the impact resistance of a polybutylene terephthalate molding. 
     A. A molding composition is prepared by co-extrusion and pelletization the following components in finely-divided form: 
     
         ______________________________________                                    
Components             Parts                                              
______________________________________                                    
Poly-(1,4-butylene terephthalate).sup.1                                   
                       95.3                                               
Poly(ethylene-ethyl acrylate) copol..sup.2                                
                       4.5                                                
Stabilizers            0.2                                                
______________________________________                                    
 .sup.1 VALOX 310 of General Electric Co.                                 
 .sup.2 PT-3085 of Union Carbide Co.                                      
 
    
     The extruded pellets are injection molded into 1/8&#34; thick test specimens that are tested to determine the impact resistance by the Izod and Gardner methods. 
     B. Procedure A is repeated except that the poly(ethylene-ethyl acrylate) is omitted and the amount of the poly(1,4-butylene terephthalate) is increased to 99.8 parts. 
     Results are as follows. 
     
         ______________________________________                                    
           Izod (ft.-lb./in.                                              
Run  Modifier    Notched    Unnotched                                     
                                    Gardner                               
______________________________________                                    
A    Poly(ethylene-                                                       
                 1.4        No break                                      
                                    430                                   
     ethyl acrylate)                                                      
B    None        1.0        No break                                      
                                    300                                   
______________________________________                                    
 
    
     EXAMPLE 2 
     A molding composition is prepared from 80 parts of the molding composition of Example 1-A and 20 parts of chopped glass fibers as reinforcing component. Tests samples are molded by the method of Example 1, which show improved impact resistance. 
     EXAMPLE 3 
     A molding composition is prepared from 85 parts composition of Example 1-A, 15 parts of chopped glass fibers, and 15 parts of a 1:2 mixture of Sb 2  O 3  and decabromodiphenyl ether as fire retardant. Test strips are extruded by the method of Example 1, which show improved impact resistance and satisfactory combustion resistance. 
     EXAMPLE 4 
     The following illustrates the improved impact resistance of moldings based on polybutylene terephthalate and containing a small amount of poly(ethylene-vinyl acetate) and reinforcing glass fibers. 
     A. The following materials in granular form are dry co-extruded and pelletized to form a molding composition: 
     
         ______________________________________                                    
Component                Parts                                            
______________________________________                                    
Poly(1,4-butylene terephthalate) -                                        
General Electric Co.     80                                               
Poly(ethylene-vinyl acetate) - Alathon 3892                               
                          3                                               
Polyethylene (Microthene FN 310)                                          
                          2                                               
Glass fibers (chopped)   15                                               
______________________________________                                    
 
    
     The compositions are injection molded into test specimens 1/8&#34; thick, after which their impact resistance is determined by the Izod method. 
     B. The procedure is repeated except that the poly(ethylene-vinyl acetate) and the polyethylene are omitted, and the amount of the poly(1,4-butylene terephthalate) is increased to 85 parts. Results are as follows. 
     
         ______________________________________                                    
Modifiers          Izod (Ft.-lb./in.)                                     
Run     PEVA*    PE**      Notched                                        
                                  Unnotched                               
______________________________________                                    
A       3%       2%        1.8    12.0                                    
B       None     None      0.8     6.6                                    
______________________________________                                    
 *Poly(ethylene-vinyl acetate).                                           
 **Polyethylene.                                                          
 
    
     EXAMPLE 5 
     The procedure of Example 4-A is repeated except that 10 parts of the poly(1,4-butylene terephthalate) are replaced by 10 parts of poly(ethylene terephthalate). Results are substantially the same. 
     EXAMPLE 6 
     The following molding compositions are prepared. 
     
         ______________________________________                                    
Parts                                                                     
                      Stabi-                                              
Run  PBT.sup.(1)                                                          
             PEVA.sup.(2)                                                 
                      lizers.sup.(3)                                      
                            PEEA.sup.(4)                                  
                                   PEEA.sup.(5)                           
                                          PEEA.sup.(6)                    
______________________________________                                    
A    95.3    4.5      0.2   --     --     --                              
B    95.3    --       0.2   4.5    --     --                              
C    95.3    --       0.2   --     4.5    --                              
D    95.3    --       0.2   --     --     4.5                             
______________________________________                                    
 .sup.(1) Poly(1,4-butylene terephthalate) Valox 310, General Electric Co.
 .sup.(2) Poly(ethylene-vinyl acetate)  Alathon 3892                      
 .sup.(3) Conventional antioxidantstabilizer combination                  
 .sup.(4) Poly(ethylene-ethyl acrylate) copolymerP7967  Union Carbide     
 .sup.(5) Poly(ethylene-ethyl acrylate) copolymerPT 7709  Union Carbide   
 .sup.(6) Poly(ethylene-ethyl acrylate) copolymer Pt3085 Union Carbide    
 
    
     The compositions are injection molded by standard laboratory procedure to provide test pieces, which have the following properties. 
     
         ______________________________________                                    
Property       A       B       C     D                                    
______________________________________                                    
Impact resistance:                                                        
Izod, notched, ft.-lb./in.                                                
               1.4     1.2     1.2   1.4                                  
Izod, unnotched, ft.-lbs./in.                                             
               5NB.sup.1                                                  
                       5NB.sup.1                                          
                               5NB.sup.1                                  
                                     41.3;2NB.sup.1                       
Gardner, dislodge, in.-lb.                                                
               430     450     390   395                                  
Strength:                                                                 
Flexural strength, psi                                                    
               12,000  12,500  12,400                                     
                                     12,4000                              
Flexural modulus, psi                                                     
               324,000 333,000 329,000                                    
                                     328,000                              
Tensile strength, psi                                                     
               6830    6960    7200  7380                                 
Specific gravity                                                          
               1.284   1.284   1.283 1.284                                
Melt viscosity, Pell,                                                     
               5,690   5,910   5,710 5,600                                
250° C.                                                            
Tensile Elongation, %                                                     
               355     334     306   283                                  
DTUL.sup.2, °F., 264 psi                                           
               124     126     122   132                                  
______________________________________                                    
 .sup.1 Not broken.                                                       
 .sup.2 Deflection temperature under load.                                
 
    
     EXAMPLE 7 
     
         ______________________________________                                    
Components           Parts                                                
______________________________________                                    
Poly(1,4-butylene terephthalate                                           
                     84.8                                                 
Glass fibers, chopped                                                     
                     15.0                                                 
Stabilizers           0.2                                                 
______________________________________                                    
 
    
     Aliquots of this batch are taken. One aliquot is not modified, and is processed as control (column A below). The remaining aliquots are modified by addition of poly(ethylene-vinyl acetate), polyethylene, or a mixture of the two, as shown in columns B-F below. 
     The compositions are in a 13/4&#34; Sterling extruder and then are molded in a 3-oz. Van Dorn molding machine extruder to form test pieces which are tested according to standard laboratory procedure. 
     The procedure is repeated starting with a different master batch of the same materials obtained at a different time, providing the results shown in columns AA, BB and CC below. 
     Results are as follows. 
     
         __________________________________________________________________________
            Run                                                           
            A  B  C  D  E  F  AA BB CC                                    
__________________________________________________________________________
Composition, parts                                                        
PBT master batch.sup.1                                                    
            100                                                           
               98 93 93 91 91 100                                         
                                 96 95                                    
PEVA.sup.2  0  0  5  7  9  7  0  2  3                                     
PE.sup.3    0  2  2  0  0  2  0  2  2                                     
Properties                                                                
Impact strength:                                                          
Izod, notched, ft.-lb./in.                                                
            0.77                                                          
               1.17                                                       
                  1.60                                                    
                     1.91                                                 
                        1.94                                              
                           2.11                                           
                              0.80                                        
                                 1.31                                     
                                    1.79                                  
Izod, unnotched, ft.                                                      
            6.6                                                           
               11.0                                                       
                  11.3                                                    
                     11.2                                                 
                        11.3                                              
                           11.8                                           
                              6.6                                         
                                 9.6                                      
                                    12.0                                  
lb./in                                                                    
Gardner, in. lbs.                                                         
Bottom      12 12 20 16 24 16 12 20 16                                    
Top         32 40 60 64 80 64 28 40 64                                    
Dislodge    32 68 72 92 96 100                                            
                              32 64 88                                    
Tensile strength, 10.sup.3 psi                                            
            12.6                                                          
               13.2                                                       
                  12.4                                                    
                     11.9                                                 
                        11.3                                              
                           11.9                                           
                              13.0                                        
                                 13.0                                     
                                    13.3                                  
Flexural:                                                                 
Strength, 10.sup.3 psi                                                    
            19.3                                                          
               19.8                                                       
                  18.4                                                    
                     16.7                                                 
                        16.2                                              
                           17.1                                           
                              20.9                                        
                                 20.0                                     
                                    20.1                                  
Modulus, 10.sup.3 psi                                                     
            583                                                           
               599                                                        
                  562                                                     
                     526                                                  
                        491                                               
                           510                                            
                              597                                         
                                 565                                      
                                    581                                   
Tensile Elongation, %                                                     
            -- -- -- -- -- -- 6.5                                         
                                 6.1                                      
                                    6.0                                   
Specific gravity                                                          
            1.413                                                         
               1.404                                                      
                  1.383                                                   
                     1.373                                                
                        1.358                                             
                           1.370                                          
                              1.414                                       
                                 1.390                                    
                                    1.392                                 
DTUL.sup.1, °F., 264 psi                                           
            378                                                           
               388                                                        
                  393                                                     
                     392                                                  
                        378                                               
                           390                                            
                              383                                         
                                 392                                      
                                    398                                   
 66 psi     -- -- -- -- -- -- 424                                         
                                 430                                      
                                    427                                   
Melt viscosity, poises                                                    
            7,240                                                         
               7,870                                                      
                  8,050                                                   
                     8,080                                                
                        7,180                                             
                           8,480                                          
                              6,720                                       
                                 7,090                                    
                                    6,890                                 
Shrink, mils/in.,                                                         
            11 11 11 11 11 11 -- -- --                                    
4&#34; × 1/8&#34; disc                                                      
__________________________________________________________________________
 .sup.1 See text above.                                                   
 .sup.2 Poly(ethylene-vinyl acetate).                                     
 .sup.3 Polyethylene (Microthene FN510).                                  
 .sup.4 Deflection temperature under load.                                
 
    
     In the above example, Runs D, E, and F contain amounts of modifiers beyond the scope of the invention, and are included for control purposes. While amounts of the ethylene-vinyl acetate copolymer in excess of 5% have a beneficial effect on the impact strength of the compositions, compositions containing such larger amounts have significantly reduced flexural strength and modulus. 
     On the other hand, a comparison of Runs BB and CC with the control Run AA shows that compositions within the scope of the invention have significantly improve impact strength yet retain to a significant degree the excellent flexural strength and modulus of the control composition Run AA. 
     All of the above-mentioned patents and/or patent applications are incorporated herein by reference. Obviously, other modifications and variations of the present invention are possible, in the light of the above teachings. For example, as flame retardant components there can be used tetrabromobisphenol A/ bisphenol A copolycarbonate and antimony oxide; tetrabromobisphenol A carbonate oligomer capped with tribromophenol and antimony oxide, and the like. It is therefore to be understood that changes may be made in the particular embodiments of the invention described which are within the full intended scope of the invention as defined by the appended claims.