Abstract:
The invention is based on the discovery of useful combinations of fully cross-linked thermoplastic vulcanizates with styrenic block copolymers. The new combinations of the invention can provide a synergistic effect. Specifically, the compositions formed thereby can be both softer and more elastic than would be expected on the basis of the properties of the individual components. Such compositions can be used in numerous applications, including, for example, any application for which a soft material with very good recovery is desired.

Description:
FIELD OF THE INVENTION 
     This invention relates to polymer compositions, and more particularly to polymer compositions that include a thermoplastic vulcanizate and a styrenic block copolymer. 
     BACKGROUND OF THE INVENTION 
     Various compositions of thermoplastic vulcanizates and styrenic block copolymers are known. Nonetheless, a need exists for compositions that are simultaneously softer and more elastic than the existing compositions. 
     SUMMARY OF THE INVENTION 
     The invention is based on the discovery of useful combinations of fully cross-linked thermoplastic vulcanizates with styrenic block copolymers. The new combinations of the invention can provide a synergistic effect. Specifically, the compositions formed thereby can be both softer and more elastic than would be expected on the basis of the properties of the individual components. Such compositions can be used in numerous applications, including, for example, any application for which a soft material with very good recovery is desired. 
     In general, the invention features a composition that includes a styrenic block copolymer (i.e., an “SBC”); and a substantially fully cross-linked thermoplastic vulcanizate (“TPV”). The SBC can have, for example, an A-B-A triblock copolymer structure, an A-B-A-B tetrablock copolymer structure, an A-B-A-B-A pentablock copolymer structure, or a mixture thereof, where, A can be, for example, a hard block made up of vinylarene monomers (e.g., styrene, α-methylstyrene, other styrene derivatives, or mixtures thereof) and B can be, for example, a soft block made up of olefinic monomers (e.g., ethylene, propylene, butylene, isoprene, butadiene, or mixtures thereof). In specific examples, the styrenic block copolymer can have, for instance, a styrene-ethylene butylene-styrene (“SEBS”) structure, a styrene-ethylene propylene-styrene (“SEPS”) structure, or a styrene-ethylene ethylene propylene-styrene (“SEEPS”) structure. The thermoplastic matrix can be, for example, a polyolefin resin. The TPV can be, for example, a dynamically vulcanized blend of polyolefin resin and a rubber (e.g., a dynamically vulcanized blend of a thermoplastic matrix and an ethylene-propylene-diene copolymer (“EPDM”) rubber). The SBC and TPV can be mixed in any proportions; preferably, the SBC/TPV ratio is at least about 5:100 (e.g., between about 5:100 and 400:100, between about 15:100 and 300:100, or intermediate ratios such as 10:100, 20:100, 50:100, 100:100, 150:100, 200:100, 250:100, 300:100, 400:100, 500:100, or 1000:100). The compositions can have a hardness of, for example, less than about 50 Shore A (e.g., 10 to 45 Shore A, 15 to 35 Shore A, or intermediate values such as 20, 25, or 30 Shore A). The compositions can have a 22 hour compression set at 70° C. of, for example, less than about 30% (e.g., about 10% to 25%, about 15% to 23%, or intermediate values such as 5%, 8%, 12%, 18%, or 20%). 
     Optionally, the new compositions can also include mineral oil. When present, the mineral oil can be mixed with the TPV and SBC in any proportions; preferably, when mineral oil is present, the mineral oil/TPV ratio is at least about 10:100 (e.g., between about 20:100 and 800:100, between about 25:100 and 600:100, or intermediate ratios such as 50:100, 100:100, 150:100, 200:100, 250:100, 300:100, 400:100, 500:100, or 1000:100). 
     The invention also features composition that includes (a) an SBC having an SEBS, SEPS, or SEEPS structure and (b) a substantially fully cross-linked blend of polypropylene and an EPDM rubber. Optionally, mineral oil can also be included in the composition. 
     As used herein, a “thermoplastic vulcanizate” (TPV) is a dynamically vulcanized, fully cross-linked mixture of a thermoplastic resin and an elastomer or rubber. 
     As used herein, “dynamic vulcanization” means a vulcanization or curing process for a rubber blended with a thermoplastic resin, where the rubber is vulcanized under conditions of shear at a temperature at which the mixture will flow. The rubber is thus simultaneously cross-linked and dispersed as fine particles within the thermoplastic resin matrix, although other morphologies can also exist. Dynamic vulcanization can be effected by mixing the thermoplastic vulcanizate components at elevated temperatures in conventional mixing equipment such as roll mills, Banbury mixers, Brabender mixers, continuous mixers, mixing extruders and the like. The unique characteristic of dynamically cured compositions is that, notwithstanding the fact that the rubber component is partially or fully cured, the compositions can be processed and reprocessed by conventional plastic processing techniques such as extrusion, injection molding, and compression molding. Scrap or flashing can be salvaged and reprocessed. 
     As used herein, “fully cross-linked” means that the rubber component has been cured or cross-linked to a state in which the elastomeric properties of the cross-linked rubber are similar to those of the rubber in its conventional vulcanized state, apart from the thermoplastic elastomer composition. The degree of cure can be described in terms of gel content, or conversely, extractable components. The rubber component can be described as fully cross-linked when less than about 5%, and preferably less than 3%, of the rubber which is capable of being cured is extractable from the thermoplastic elastomer product by a solvent for that rubber. 
     Dynamic vulcanization processes, including those resulting in fully cross-linked thermoplastic vulcanizates, are known in the art, for example, in U.S. Pat. Nos. 4,104,210, 4,130,534, 4,130,535, and 5,672,660, all of which are incorporated by reference in their entirety. 
     Other features and advantages of the invention will be apparent from the following description and from the claims. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     A composition is provided that includes a substantially fully cross-linked thermoplastic vulcanizate (TPV) and a styrenic block copolymer (SBC). The composition further optionally contains mineral oil and/or other additives. 
     The TPV can be, for example, a fully cross-linked blend of a plastic (e.g., a thermoplastic matrix) and an elastomer or rubber. Examples of thermoplastic matrices include polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate polymers (EVA). 
     Examples of suitable rubbers include ethylene-propylene-diene monomer (EPDM) rubber, ethylene-propylene rubber (EPR), styrene butadiene rubber, butadiene rubber, butyl rubber, and other non-polar or slightly polar rubbers. Both styrenic rubbers and ethylenic rubbers can be useful. Examples of diene monomers include ethylidene norbornene (ENB), dicyclopentadiene (DCPC), hexadiene, and vinyl norbornene (VNB). 
     A preferred TPV is Uniprene® Master Batch™, a 45 Shore A, fully cross-linked TPV available from Teknor Apex. For example, Uniprene® 7100-73, Uniprene® 7100-87, Uniprene® 7100-40D, or Uniprene® 7100-50D can be used. 
     The SBC can be, for example, a fully hydrogenated styrenic block copolymer having a structure such as styrene-ethylene butylene-styrene (SEBS), styrene-ethylene propylene-styrene (SEPS), or styrene-ethylene ethylene propylene-styrene (SEEPS), or a partially or fully unhydrogenated styrenic block copolymer having a structure such as styrene-butadiene-styrene (SBS) or styrene-isoprene-styrene (SIS). Kraton®-G SEBS (Kraton Polymers) products are preferred, with Kraton® G-1651, having the highest molecular weight, being most preferred, and G-1650 and G-1652, having intermediate and lower molecular weights, respectively, being less preferred. 
     Examples of suitable mineral oils include paraffinic, naphthenic, and aromatic types. Paraffinic mineral oils are preferred. A preferred paraffinic mineral oil is Semtol® 500 (Crompton Knowles). 
     The compositions can further contain additives including process aids such as calcium stearate or AC-6A polyethylene; plasticizers; lubricants; process stabilizers such as Irganox® 1010 (Ciba Specialty Chemicals), weathering stabilizers; heat stabilizers; UV protectants such as Tinuvin® 328 or 622 (Ciba Specialty Chemicals), antioxidants; colorants; and/or fillers. Other non-polar or slightly polar additives can also be included to provide desired properties. 
     The compositions are generally prepared according to conventional dry blend or other methods known to those skilled in the art of compounding. 
     The mixtures obtained from the blending process can be further compounded with a mixer such as a Banbury batch mixer, a Farrel Continuous Mixer, or a single- or twin-screw extruder. 
     The compositions are useful in a variety of applications. For example, these compositions are useful in any application in which it is desirable for compositions to have low compression set, high elasticity, and a soft texture, even when subjected to prolonged and/or repeating stretching or other mechanical or thermal stress. Such applications include grips for sporting goods (e.g., golf clubs and tennis rackets), tool handles, toothbrush handles, writing instruments (e.g., pens and pencils), and kitchen utensils (e.g., pan handles, knives, kitchen gadgets such as can openers and vegetable peelers); gaskets; and other seals. The invention also provides for coiled materials that are softer and require less force to stretch than prior art materials having otherwise similar physical properties. 
     In the following examples, the contents and properties of a number of preferred compositions are described. These compositions were prepared as follows, with reference to Table 1. The indicated styrenic block copolymer (SBC) was dry blended with the indicated mineral oil in a dry-blending device (e.g., a pony mixer or ribbon mixer) until the SBC had absorbed the oil and became free flowing. The time required for dry-blending varied from composition-to-composition, depending on the amount of oil added and the formulation. It was generally about five minutes. The dry-blended SBC/oil mixture was then melt-mixed with the indicated thermoplastic vulcanizate (TPV) in a Banbury mixer or twin-screw extruder. The two components (i.e., the SBC/oil mixture and the TPV) were either added to the melt-mixing equipment individually or else dry blended together prior to adding to the melt-mixing equipment. It is noted that the various components can be combined with each other in any order. Additives such as process aids, process stabilizers, weathering stabilizers, and colorants, if desired, can also be added prior to, during, or after the melt-mixing step. 
     
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 Composition 1 
                 Composition 2 
                 Composition 3 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 SBC 
                 Kraton ® G-1651 
                 Kraton ® G-1651 
                 Kraton ® G-1651 
               
               
                   
                 20 parts (12.5%) 
                 40 parts (22.2%) 
                 40 parts (18.2%) 
               
               
                 Mineral Oil 
                 Semtol ® 500 
                 Semtol ® 500 
                 Semtol ® 500 
               
               
                   
                 40 parts (25%) 
                 40 parts (22.2%) 
                 80 parts (36.3%) 
               
               
                 TPV 
                 Uniprene ® 
                 Uniprene ® 
                 Uniprene ® 
               
               
                   
                 Master Batch ™ 
                 Master Batch ™ 
                 Master Batch ™ 
               
               
                   
                 100 parts (62.5%) 
                 100 parts (55.6%) 
                 100 parts (45.5%) 
               
               
                   
               
             
          
         
       
     
     The properties of the compositions, including specific gravity (ASTM D792), hardness (ASTM D2240), tensile strength (ASTM D412), elongation at break (ASTM D412), 100% modulus (ASTM D412), tear strength (ASTM D624), percent weight change (ASTM D471), compression set (ASTM D395, method B), melt index (ASTM D1238), and viscosity (16/1 die, 200° C.) are indicated in Table 2. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Composition 
                 Composition 
                 Composition 
                   
               
               
                   
                 1 
                 2 
                 3 
                 Units 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 Specific Gravity 
                 0.91 
                 0.91 
                 0.91 
                 — 
               
               
                 Hardness (5 s 
                 30 
                 32 
                 23 
                 Shore A 
               
               
                 delay) 
               
               
                 Tensile Strength 
                 378 
                 373 
                 319 
                 psi 
               
               
                 Elongation at 
                 369 
                 345 
                 407 
                 % 
               
               
                 break 
               
               
                 100% Modulus 
                 114 
                 118 
                 78 
                 psi 
               
               
                 Tear strength, 
                 60 
                 78 
                 57 
                 pli 
               
               
                 Die C 
               
               
                 Weight change 
                 105 
                 152 
                 106 
                 % 
               
               
                 Compression set 
               
               
                 22 h, 23° C. 
                 9.8 
                 9.5 
                 8.0 
                 % 
               
               
                 22 h, 70° C. 
                 18.5 
                 17.8 
                 17.6 
                 % 
               
               
                 70 h, 125° C. 
                 52.3 
                 53.0 
                 66.4 
                 % 
               
               
                 Viscosity 
               
               
                 (shear rate) 
               
               
                 100 1/s 
                 329 
                 617 
                 322 
                 Pa-s 
               
               
                 500 1/s 
                 100 
                 173 
                 99 
                 Pa-s 
               
               
                 1000 1/s 
                 59 
                 97 
                 58 
                 Pa-s 
               
               
                   
               
             
          
         
       
     
     Seven additional compositions of the invention were prepared (Compositions 4–10) as described above using the compositions specified in Table 3, and compared with three controls: Uniprene® 7100-87 alone, Uniprene® 7100-40D alone, and Pebax® 3533. Each of these compositions of the invention and control compositions was fashioned into a rod having an outer diameter of 3/16″. Each rod was then made into a coil with a length of 8″ and an outer diameter of about 1″. The force required to stretch each article to four times its original length (i.e., to 32″) was measured, and is reported in Table 3. After 300 stretching cycles to 32″, the length of each article was measured. This procedure was repeated once, and the average measurements obtained are indicated in Table 3. Other physical properties were also measured and are shown in Table 3. 
     
       
         
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 3 
               
               
                   
                   
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 TPV 
                 TPV 
                 Pebax 
               
               
                   
                 Comp. 4 
                 Comp. 5 
                 Comp. 6 
                 Comp. 7 
                 Comp. 8 
                 Comp. 9 
                 Comp. 10 
                 Control 1 
                 Control 2 
                 Control 3 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 SBC 
                 10 parts 
                 20 parts 
                 20 parts 
                 20 parts 
                 25 parts 
                 25 parts 
                 25 parts 
                 n/a 
                 n/a 
                 n/a 
               
               
                   
                 Kraton 
                 Kraton 
                 Kraton 
                 Kraton 
                 Kraton 
                 Kraton 
                 Kraton 
               
               
                   
                 G-1651 
                 G-1651 
                 G-1650 
                 G-1652 
                 G-1651 
                 G-1650 
                 G-1652 
               
               
                 TPV 
                 90 parts 
                 100 parts 
                 100 parts 
                 100 parts 
                 100 parts 
                 100 parts 
                 100 parts 
                 100 parts 
                 100 parts 
                 n/a 
               
               
                   
                 Uniprene 
                 Uniprene 
                 Uniprene 
                 Uniprene 
                 Uniprene 
                 Uniprene 
                 Uniprene 
                 Uniprene 
                 Uniprene 
               
               
                   
                 7100-40D 
                 7100-40D 
                 7100-40D 
                 7100-40D 
                 7100-50D 
                 7100-50D 
                 7100-50D 
                 7100-87 
                 7100-40D 
               
               
                 Length after 
                 8.3″ 
                 8.0″ 
                 8.0″ 
                 8.0″ 
                 8.0″ 
                 8.0″ 
                 8.0″ 
                 9.1″ 
                 8.0″ 
                 8.0″ 
               
               
                 300 cycles 
               
               
                 Immed. 
               
               
                 30 min. 
                 8.0″ 
                 8.0″ 
                 8.0″ 
                 8.0″ 
                 8.0″ 
                 8.0″ 
                 8.0″ 
                 8.0″ 
                 8.0″ 
                 8.0″ 
               
               
                 Force to extend 
                 980 parts 
                 820 parts 
                 765 parts 
                 560 parts 
                 1150 parts 
                 1410 parts 
                 1375 parts 
                 435 parts 
                 1250 parts 
                 665 parts 
               
               
                 ×4 
               
               
                 Spec. Grav. 
                 0.96 
                 0.97 
                 0.96 
                 0.96 
                 0.96 
                 0.95 
                 0.96 
                 0.97 
                 0.97 
               
               
                 Hardness 
                 42/33 
                 40/32 
                 41/33 
                 42/32 
                 48/40 
                 49/40 
                 51/42 
                 35/28 
                 47/38 
               
               
                 Shore D (inst/10 
               
               
                 sec) (ASTM 
               
               
                 D2240) 
               
               
                 Tensile strength 
                 2090 psi 
                 2250 psi 
                 2140 psi 
                 1740 psi 
                 2760 psi 
                 2740 psi 
                 2130 psi 
                 1390 psi 
                 1950 psi 
               
               
                 (MOLDs) 
               
               
                 Elongation at 
                 630% 
                 650% 
                 620% 
                 0590% 
                 670% 
                 640% 
                 600% 
                 480% 
                 580% 
               
               
                 break (MOLDs) 
               
               
                 Melt index (g/10 
                 11.5 
                 6.8 
                 5.1 
                 10.8 
                 7.1 
                 5.8 
                 9.9 
                 48.0 
                 11.0 
               
               
                 min) 
               
               
                 (190° C./10 kg) 
               
               
                   
               
             
          
         
       
     
     A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.