Patent Publication Number: US-2009239984-A1

Title: Polyvinyl halide-uncrosslinked elastomer alloy

Description:
CLAIM OF PRIORITY 
     This application claims priority from U.S. Provisional Patent Application Ser. No. 60/754,078 bearing Attorney Docket Number 12005015 and filed on Dec. 27, 2005, which is incorporated by reference. 
    
    
     FIELD OF THE INVENTION 
     The present invention relates to a thermoplastic alloy of a polyvinyl halide, particularly polyvinyl chloride (PVC), and an elastomer that exhibits thermoplastic properties because it is not crosslinked. 
     BACKGROUND OF THE INVENTION 
     U.S. Patent Application Publication 20040054085 (Tansey) describes a problem in the art of making instrument panel coverstocks that are designed to tear at specific locations in order to permit release of airbags from their compartments. Low temperatures can embrittle PVC or PVC alloys used as such coverstock for instrument panels, creating the possibility of fragments of coverstock causing injury to passengers during deployment of an airbag. 
     Tansey attempts to solve the embrittlement problem by dispersing a melt processible partially crosslinked rubber into a PVC matrix. However, the dispersion of a partially crosslinked rubber into a polymer does not assist the overall thermoplastic nature of the alloy. Indeed, a crosslinked elastomer; i.e., a rubber can inhibit melt processibility of the alloy during the formation of the final form of the thermoplastic product. Also, a rubber can reduce the cold temperature performance of the alloy and elevate the melt viscocity of the polymer. 
     SUMMARY OF THE INVENTION 
     The present invention solves the embrittlement problem without creating the problems associated with using crosslinked elastomers even those characterized as melt processible rubbers. 
     One aspect of the present invention is a slush molded article made from a thermoplastic alloy comprising poly(vinyl halide), plasticizer, and an olefin-based uncrosslinked elastomer having thermoplastic properties. 
     One advantage of the invention is that the thermoplastic alloy can be processed to form a polymeric skin using slush molding techniques. 
     EMBODIMENTS OF THE INVENTION 
     Poly(Vinyl Halide) 
     Polyvinyl halides are polymers containing a vinyl moiety and one or more halides bonded thereto. Commercially accepted polyvinyl halides are poly(vinyl chloride) (“PVC”) and chlorinated poly(vinyl chloride) (“CPVC”) due to availability and cost. 
     PVC or CPVC are essentially homopolymers of vinyl chloride with minor amounts of other co-monomers, if any. CPVC is chlorinated PVC where PVC containing approximately 57% chlorine is further reacted with chlorine radicals produced from chlorine gas dispersed in water and irradiated to generate chlorine radicals dissolved in water to produce CPVC, a polymer with a higher Tg and heat distortion temperature. Commercial CPVC typically contains by weight from about 58% to about 70% and preferably from about 63% to about 68% chlorine. 
     Poly(vinyl chloride) comprises polymerized vinyl chloride monomer where preferred polymers are essentially homopolymerized vinyl chloride with little or no copolymerized co-monomers. Useful co-monomers if desired include mono-unsaturated ethylenically unsaturated monomer copolymerizable with vinyl chloride monomer by addition polymerization. Useful co-monomers include other vinyl monomers such as vinyl acetate, ethers, and vinylidene chloride. Other useful co-monomers comprise mono-ethylenically unsaturated monomers including acrylics such as lower alkyl acrylates or methacrylates, acrylic and methacrylic acid, lower alkenyl olefins, vinyl aromatics such as styrene and styrene derivatives, and vinyl esters and ethers. Typical useful commercial co-monomers include acrylonitrile, 2-ethylhexyl acrylate, vinylidene chloride, and isobutyl ether. Useful PVC copolymers can contain from about 0.1% to about 10% or 15%, preferably from about 0.5% to about 5%, by weight of copolymerized co-monomer. 
     Chlorinated PVC copolymers can be obtained by chlorinating such PVC copolymers using conventional methods such as that described in U.S. Pat. No. 2,996,489. 
     Preferred PVCs are suspension polymerized vinyl chloride although less preferred mass (bulk) polymerized can be useful. 
     The PVCs of this invention have a K-value from about 50 to about 90 and preferably from about 60 to about 80, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. by ASTM D 1243. 
     Plasticizer 
     The poly(vinyl halide) used in the present invention needs to be flexible. Plasticizers are added to poly(vinyl halide) to form flexible thermoplastic polymers. Any conventional plasticizer known to those skilled in the art for poly(vinyl halide) is suitable for use in the present invention. When PVC is used, the most common plasticizer is a phthalate plasticizer. 
     Non-limiting examples of plasticizers are a phthalate plasticizer (such as di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, dibutyl phthalate or dihexyl phthalate); a straight chain dibasic acid ester plasticizer (such as dioctyl adipate, or dioctyl sebacate); a trimellitate plasticizer; a polyester polymer plasticizer; an epoxy plasticizer (such as epoxidized soybean oil, epoxidized linseed oil or an epoxy resin); a phosphate plasticizer (such as triphenyl phosphate, trixylyl phosphate or tricresyl phosphate). These plasticizers can be used alone or in combination as a mixture of two or more of them. 
     Commercially available plasticizers are Palatinol 11P-E from BASE Corporation, Palatinol TOTM from BASF Corporation, Plas-chek 775 from Ferro Corporation, and Synplast NOTM from PolyOne Corporation, among others. 
     Uncrosslinked Elastomer Having Thermoplastic Properties 
     A partially or fully crosslinked thermoplastic elastomer is also known as a thermoplastic vulcanizate because the elastomer is partially or fully vulcanized, as is a thermoset rubber. Once vulcanization has occurred, there is less flexibility in processing the form of the thermoplastic vulcanizate because the vulcanizate has become thermoset. 
     Unlike the teaching of U.S. Patent Application Publication 20040054085, the present invention does not desire any crosslinking in the elastomer. Thus, the elastomer remains fully thermoplastic, exhibits thermoplastic properties, and is capable of multiple thermoplastic processing steps without complications associated with partial or full crosslinking of the material. 
     Uncrosslinked elastomers having thermoplastic properties are known in the thermoplastics industry and readily commercially available. Any olefinic elastomer that is capable of being melt blended with a poly(vinyl halide) to form an alloy is suitable for use in the present invention. One skilled in the art without undue experimentation can select an appropriate uncrosslinked elastomer, such as chlorinated polyethylene (CPE) elastomer, metallocene-catalyzed ethylene-octene copolymer, or uncrosslinked ethylene propylene diene monomer terpolymer (EPDM). Also, without undue experimentation, one skilled in the art can determine other suitable uncrosslinked elastomers from the category of additives called impact modifiers, to the extent that such materials are olefinic, not crosslinked, elastomeric, yet processible as do thermoplastics. 
     A commercial example of an uncrosslinked chlorinated olefin elastomer is Duracryn 7160 NC from Advanced Polymer Alloys of Wilmington, Del., a division of Ferro Corporation of Cleveland, Ohio USA. 
     Optional Additives 
     The compound of the present invention can include conventional plastics additives in an amount that is sufficient to obtain a desired processing or performance property for the compound. The amount should not be wasteful of the additive nor detrimental to the processing or performance of the compound. Those skilled in the art of thermoplastics compounding, without undue experimentation but with reference to such treatises as  Plastics Additives Database  (2004) from Plastics Design Library (www.williamandrew.com), can select from many different types of additives for inclusion into the compounds of the present invention. 
     Non-limiting examples of optional additives include adhesion promoters; biocides (antibacterials, fungicides, and mildewcides), anti-fogging agents; anti-static agents; bonding, blowing and foaming agents; dispersants; fillers and extenders; fire and flame retardants and smoke suppresants; impact modifiers; initiators; lubricants; micas; pigments, colorants and dyes; plasticizers; processing aids; release agents; silanes, titanates and zirconates; slip and anti-blocking agents; stabilizers; stearates; ultraviolet light absorbers; viscosity regulators; waxes; and combinations of them. 
     Table 1 shows acceptable and preferred ingredients for the alloys of the present invention. 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 Ingredient 
                 Brand Name 
                 Maker 
                 Acceptable 
                 Preferred 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Poly(Vinyl Halide) 
                 Oxyvinyl 220F 
                 Oxyvinyls 
                  25-50% 
                 30-40% 
                   
               
               
                 Plasticizer 
                 Synplast NOTM 
                 PolyOne 
                  20-45% 
                 30-40% 
               
               
                 Uncrosslinked 
                 Duracryn 7160NC 
                 Advanced 
                   5-50% 
                 10-30% 
               
               
                 Elastomer 
                   
                 Polymer 
               
               
                   
                   
                 Alloys 
               
               
                 Mixed Metal 
                 CPS 507 
                 Amfine 
                  0.5-2.5% 
                 1-2% 
               
               
                 Stabilizer 
                   
                 Chemicals 
               
               
                 Internal Lubricant 
                 AX-71 
                 Amfine 
                 0.01-0.2% 
                 0.05-0.10% 
               
               
                   
                   
                 Chemicals 
               
               
                 Fatty Acid Ester 
                 LS-10 
                 Amfine 
                 0.01-0.2% 
                 0.05-0.10% 
               
               
                   
                   
                 Chemicals 
               
               
                 Phosphite 
                 CPL-1551 
                 Amfine 
                   0.2-2% 
                 0.5-1% 
               
               
                 Stabilizer 
                   
                 Chemicals 
               
               
                 Pigment Dispersion 
                 642H V Dk 
                 PolyOne 
                   0.1-5% 
                 0.5-2.5% 
               
               
                   
                 Pewter MB 
                 Corporation 
               
               
                 Polyvinyl Chloride 
                 Vinnolit P70 
                 Vinnolit 
                   0.5-5% 
                 2-5% 
               
               
                 resin dispersion 
               
               
                   
               
            
           
         
       
     
     Processing 
     The preparation of compounds of the present invention is uncomplicated. The compound of the present can be made in batch or continuous operations. 
     Mixing in a continuous process typically occurs in an extruder that is elevated to a temperature that is sufficient to melt the polymer matrix with addition either at the head of the extruder or downstream in the extruder of the solid ingredient additives of any optional additive. Extruder speeds can range from about 50 to about 500 revolutions per minute (rpm), and preferably from about 100 to about 300 rpm. Typically, the output from the extruder is pelletized for later extrusion or molding into polymeric articles. 
     In the present invention, it is desirable to dry-blend the PVC and other non-elastomeric ingredients before extruding the PVC and the uncrosslinked elastomer. 
     Mixing in a batch process typically occurs in a Banbury mixer that is also elevated to a temperature that is sufficient to melt the polymer matrix to permit addition of the solid ingredient additives of any optional additive. The mixing speeds range from 60 to 1000 rpm and temperature of mixing can be ambient. Also, the output from the mixer is chopped into smaller sizes for later extrusion or molding into polymeric articles. 
     Alternatively, mixing in a batch process typically occurs in a Henschel mixer that mixes via mechanical action rather than bringing the polymer matrix to a melting temperature. The mixing speeds range from 60 to 1000 rpm and temperature of mixing can be ambient. 
     Alloys of the present invention can be also formed into powder, cubes, or pellets for further extrusion or molding into polymeric products. 
     Subsequent extrusion or molding techniques are well known to those skilled in the art of thermoplastics polymer engineering. Without undue experimentation but with such references as “Extrusion, The Definitive Processing Guide and Handbook”; “Handbook of Molded Part Shrinkage and Warpage”; “Specialized Molding Techniques”; “Rotational Molding Technology”; and “Handbook of Mold, Tool and Die Repair Welding”, all published by Plastics Design Library (www.williamandrew.com), one can make articles of any conceivable shape and appearance using alloys of the present invention. 
     After extruding or other mixing, preferably, slush molding can be used to form useful articles from the alloys of the present invention. Slush molding utilizes an open-end mold design for forming articles (e.g., vehicle instrument panels) as a polymeric skin. One skilled in the art can understand the principles of slush molding by referring to U.S. Pat. No. 6,797,222 (Hausmann et al.) and U.S. Pat. No. 2,736,925; U.S. Pat. No. 3,039,146; European Patent Publication 0 339 222, European Patent Publication 0 476 742 and PCT Patent Publication WO 0207946. 
     Briefly, slush molding generally involves the following steps: a) an open-air tank is first filled with a suitable polymer powder in a sufficient quantity and with grain sizes typically below 500 micrometers; b) a mold, usually electroplated with nickel, is then heated to a given temperature; c) the tank and the mold are then coupled in a closed system with suitable coupling means; d) the system is moved so that the tank transfers the powder onto the mold, thus obtaining a uniform layer of partially or completely melted powder which adheres to the mold; e) the closed system is then opened after being brought to the initial conditions again; at this stage the possible excess polymer powder deposits again into the tank and can thus be regenerated; f) the mold can now be heated in order to complete the melting; g) the mold is then cooled with suitable cooling means; and h) the formed sheet is stripped off as a semi-finished product which can then be assembled with a support in order to obtain the finished product in the form of instrument panels, door panels, etc. for the upholstery of cars. 
     The alloys of the present invention are particularly suitable for use with slush molding processing techniques because the uncrosslinked elastomer allows for improved melt flow of the alloy, reducing the potential for pinholes and other processing defects during the formation of the polymeric skin. 
     Usefulness of the Invention 
     Alloys of the present invention are particularly suitable for use with slush molding techniques to make thin polymeric film products for simulated leather, simulated cloth, and other goods used in residential and vehicular upholstery. For example, a “polymeric skin” can be formed using slush molding from alloys of the present invention. This polymeric skin has a very large aspect ratio of length or width to thickness and can mimic the shape of the mold to create random or repeating patterns of the appearance of grain in leather, wood, or other naturally-occurring items. 
    
    
     EXAMPLES 
     A formulation of an alloy of the present invention as identified in Table 2 was made via slush molding using the processing parameters shown in Table 3, to yield a polymeric skin having the performance properties shown in Table 4. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
               
                 Ingredient 
                 Brand Name 
                 Maker 
                 Weight Percent 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 Poly(Vinyl Halide) 
                 Oxyvinyl 220F 
                 Oxyvinyls 
                 37.0 
               
               
                 Plasticizer 
                 Synplast NOTM 
                 Synergistics 
                 35.1 
               
               
                 Uncrosslinked 
                 Duracryn 
                 Advanced 
                 20 
               
               
                 Elastomer 
                 7160NC 
                 Polymer 
               
               
                   
                   
                 Alloys 
               
               
                 Mixed Metal 
                 CPS 507 
                 Amfine 
                 1.5 
               
               
                 Stabilizer 
                   
                 Chemicals 
               
               
                 Internal Lubricant 
                 AX-71 
                 Amfine 
                 0.1 
               
               
                   
                   
                 Chemicals 
               
               
                 Fatty Acid Ester 
                 LS-10 
                 Amfine 
                 0.1 
               
               
                   
                   
                 Chemicals 
               
               
                 Phosphite Stabilizer 
                 CPL-1551 
                 Amfine 
                 0.7 
               
               
                   
                   
                 Chemicals 
               
               
                 Pigment Dispersion 
                 642H V Dk 
                 PolyOne 
                 1.8 
               
               
                   
                 Pewter MB 
                 Corporation 
               
               
                 Polyvinyl Chloride 
                 Vinnolit P70 
                 Vinnolit 
                 3.7 
               
               
                 resin dispersion 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 3 
               
               
                   
               
               
                 Processing Conditions 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 Equipment 
                 Henschel Mixer to 
                 Extruder 
                 Mold Machine 
               
               
                   
                 Make PVC Dry Blend 
               
               
                 Speed 
                 800 rpm, 550 rpm 
                 350 rpm 
                 N/A 
               
               
                 Order of 
                 Step 1. Add 
                 Uncrosslinked 
                 N/A 
               
               
                 Addition 
                 Poly(vinyl halide), 
                 Elastomer 
               
               
                   
                 Mixed Metal 
                 and PVC Dry 
               
               
                   
                 Stabilizer, Internal 
                 Blend added at 
               
               
                   
                 Lubricant, Fatty Acid 
                 Throat 
               
               
                   
                 Ester, Phosphite 
               
               
                   
                 stabilizer, Pigment 
               
               
                   
                 dispersion 
               
               
                   
                 Step 2. Add Plasticizer 
               
               
                   
                 Step 3. Add PVC 
               
               
                   
                 Resin Dispersion 
               
               
                 Pre-Heat 
                 N/A 
                 Zone 1: 275° C. 
                 N/A 
               
               
                 Temperature 
                   
                 Zone 2: 275° C. 
               
               
                   
                   
                 Zone 3: 300° C. 
               
               
                   
                   
                 Zone 4: 300° C. 
               
               
                   
                   
                 Zone 5: 325 C. 
               
               
                   
                   
                 Zone 6: 325° C. 
               
               
                   
                   
                 Zone 7: 325° C. 
               
               
                   
                   
                 Zone 8: 325° C. 
               
               
                   
                   
                 Zone 9: 330° C. 
               
               
                   
                   
                 Zone 10: 330° C. 
               
               
                 Final Melt 
                 N/A 
                 200° C. 
                 230° C. 
               
               
                 Temperature 
               
               
                 Dwell Time 
                 N/A 
                 N/A 
                 20 seconds 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Performance Properties 
               
            
           
           
               
               
            
               
                 Test 
                 Result 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 Elongation, 
                 456% 
                   
                   
               
               
                 ASTM D638, 
               
               
                 500 mm/min 
               
               
                 Tensile, 
                 11.9 MPa 
               
               
                 ASTM D638, 
               
               
                 500 mm/min 
               
               
                 Specific 
                 1.188 
               
               
                 Gravity, 
               
               
                 ASTM D792 
               
               
                 Hardness, 
                 68 Shore A 
               
               
                 Shore A, 
               
               
                 15 Sec Delay, 
               
               
                 ASTM D1004 
               
               
                 Glass Transition 
                 −37.6° C. 
               
               
                 Temperature, 
               
               
                 E″Based, 
               
               
                 DMA Analysis 
               
               
                 Xenon Arc 
                 601.6 kJ/m 2  − 
                 1240.8 kJ/m 2  − 
                 504 kJ/m 2  − 
               
               
                 Weatherometer, 
                 DE* = 0.3 
                 DE* = 0.2 
                 DE* = 0.3 
               
               
                 SAEJ1885 
               
               
                   
               
            
           
         
       
     
     The invention is not limited to the above embodiments. The claims follow.