Abstract:
A fire-retardant formulation for styrene-containing polymers comprising tris(2,4,6-tribromophenoxy)-s-triazine (FR-245), antimony trioxide and polytetrafluoroethylene (PTFE), wherein the bromine concentration in said fire-retardant formulation is from about 9.0 to about 10.5 wt. %, said antimony trioxide concentration being lower than about 3.2 wt. %.

Description:
REFERENCE TO CO-PENDING APPLICATIONS 
     Priority is claimed as a divisional application of U.S. patent application Ser. No. 11/597,784 having a 371(c) filing date of Nov. 27, 2006 (currently allowed), which further claims priority from a 371 of international of PCT/IL2005/000612, filed on Jun. 9, 2005, which claims priority to Israeli patent application number 162449, filed on Jun. 10, 2004. 
    
    
     FIELD OF THE INVENTION 
     The present invention relates to improved fire-retardant formulations. More specifically, the present invention relates to improved fire-retardant formulations for styrene polymers and more particularly for High Impact Polystyrene (HIPS) and Acrylonitrile-Butadiene-Styrene terpolymer (ABS). 
     BACKGROUND 
     Styrenic resins are widely used in many applications including those where fireproof materials are necessary. Such applications include for example TV cabinets, in which there is a need for the incorporation of fire-retardants (FR) in styrene-polymeric materials. 
     Traditional FRs for these applications include, inter cilia, decabromodiphenyl oxide and more recently tris(2,4,6-tribromophenoxy)-s-triazine the latter known as FR-245. The advantages of FR-245 are good balance of properties, high level of mechanical properties, high processing heat stability, good light stability, high melt flow and no blooming. However, unlike formulations based on decabromodiphenyl oxide, the formulations based on FR-245 tend to induce long after glow time. This effect is enhanced when carbon black is added to the formulation. 
     JP 11323064 discloses the incorporation of fire-retardant formulation comprising tris(2,4,6-tribromophenoxy)-s-triazine known as FR-245, tris(3-bromo-2,2(bromomethyl)propyl)phosphate known as FR-370, antimony trioxide (Sb203) and PTFE (polytetrafluoroethylene) in rubber reinforced polystyrene also known as HIPS, wherein the bromine content, the main component responsible for fire retardation, is between 9.5 and 11 wt. % and wherein antimony trioxide, serving as a synergist, is between 3.5 and 3.7 wt. %. 
     This formulation is claimed to successfully meet the requirement of UL-94 class V-0 according to the flammability tests, where five specimens are ignited, twice each, and the fulfillment of 5 requirements is necessary to pass a UL-94 V-0 standard, namely: 
     1. Maximum after flame time≦10 seconds (for each ignition). 
     2. Total after flame time of 10 ignitions less or equal to 50 seconds. 
     3. Maximum after flame+after glow time less or equal to 30 seconds. 
     4. None of the test specimens burns or glows up to the holding clamp. 
     5. No cotton ignition by dripping. 
     UL-94V is UL (Underwriter Laboratories) Standard for Safety for Tests for Parts in Devices and Appliances. 
     A fire-retardant formulation containing FR-245 with 11.5 wt. % Br, 0.08 wt. % PTFE and 3.5 wt. % antimony trioxide is also rated UL-94 V-0, but reducing the bromine content to 10.5 wt. % Br results in derating to UL-94 V-1 because of long afterglow time. JP 11323064 overcomes this problem by introducing FR-370 to the formulation, which effectively reduces that time, while keeping relatively low levels of bromine-based fire-retardant. 
     Although JP 11323064 states that incorporation of FR-370 in the formulation allows maintaining low levels of bromine, which enhances technical properties of articles incorporating it and leads to cost-effective FR formulations, the inventors of the present invention note that FR-370 is a very expensive material and its use in fire-retardant formulations offers a high-cost non-economical solution for reducing or eliminating the afterglow phenomenon and for achieving V-0 flammability test rating. 
     SUMMARY OF THE INVENTION 
     The applicants have surprisingly found that by lowering the concentration levels of antimony trioxide to certain ranges while maintaining low levels of bromine, a fire-retardant formulation that essentially meets the requirement UL-94 class V-0 standards is achieved without evoking the need for high-cost or other materials. In particular, it has also been found that even when incorporating additives to the formulation as carbon black pigment those concentration ranges of the respective components still allow to successfully pass the standard flammability tests. 
     It is therefore an object of the present invention to provide a fire-retardant formulation that essentially meets the requirement standard according to the flammability tests. 
     It is yet another object of the present invention to provide a pigmented fire-retardant formulation that essentially meets the requirement standard according to the flammability tests. 
     Still another object of the present invention is to provide a fire-retardant formulation with improved technical and mechanical properties. 
     Still another object of the present invention is to provide a fire-retardant formulation that is cost-effective. 
     Still another object of the present invention is to provide a fire-retarded styrene-containing polymer for injection molding or extrusion essentially comprising said fire-retardant formulation. 
     Still another object of the present invention is to provide fire-retarded styrene-containing polymer that may be HIPS or ABS. 
     This and other objects of the invention will become apparent as the description proceeds. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The present invention provides a fire-retardant formulation that meets the requirement UL-94 V-0 standard according to the flammability tests and which is also cost-effective. 
     According to the present invention the formulation comprises FR-245, antimony trioxide, PTFE and optionally carbon black pigment, in which the acceptable concentrations of bromine range between about 9.0 and about 10.5 wt. % and those of antimony trioxide range between about 1.8 and about 3.2 wt. %. 
     Styrene rubber reinforced polymers containing fire-retardant formulations (FR-HIPS) are often required to possess a black or gray color. This is achieved by the incorporation of carbon black, a preferred pigment, to these formulations. However, a side-effect of carbon black when introduced in a fire-retardant formulation is long period of time afterglow effect, where the formulation comprises essentially the same components having the same concentrations as disclosed in JP 11323064, excluding the presence of FR-370. 
     In addition to the polystyrenic polymer, halogen based fire retardant, antimony oxide, PTFE and the carbon black, there can be present in the formulation conventional additives in their conventional amounts. Examples of such additives are: fillers, pigments, dyes, impact modifiers, UV stabilizers, antioxidants, processing aids, nucleating agents, lubricants and the like. 
     The flame retarded formulations may be shaped into the final object by processes that are well known to the person skilled in the art; non limiting examples of such processes are: injection molding, extrusion, press molding, vacuum forming, etc. 
     EXAMPLES 
     The present invention will now be described in more detail with Examples and Reference Examples. 
     Tables 1-3 below summarize the materials used for the preparation of the test samples as well as the methods and conditions for their preparation. Flammability was tested according to UL-94V. 
                                   TABLE 1                   Materials                TRADE NAME   GENERAL INFO                       HIPS   Styron 472 ex Dow Chemical           ABS   Magnum 3404 ex Dow Chemical           Antimony trioxide   ACC-BS ex Antraco           FR-245 ex DSBG   Tris(2,4,6-tribromophenoxy)-s-               triazine           F-3020 ex DSBG   Endcapped brominated epoxy               oligomer (MW 2,000)           FR-1210 ex DSBG   Decabromodiphenyl oxide           Carbon Black   PSB 183 ex Hubron               manufacturing division limited           PTFE   Hostaflon 2071 ex Dynon-fine               powder (500μ)                       Antimony trioxide is added as 80% concentrate in polystyrene carrier.           Carbon black is added as 35% concentrate in polystyrene carrier.            
Compounding
 
     All formulations were prepared under the same conditions. 
     The components are weighed on Sartorius semi-analytical scales with consequent manual mixing in plastic bags, All the components are introduced into an extruder via K-SFS 24 gravimetric feeding system ex. K-Tron. 
     Compounding is performed in a co-rotating twin-screw extruder ZE25 ex Berstorff with L/D=32. The compounding conditions are presented in Table 2. The extruded strands are pelletized in pelletizer 750/3 ex Accrapak Systems Limited. 
     The obtained pellets are dried in a circulating air oven ex Heraeus Instruments at 75° C. for 4 hours. 
                                       TABLE 2                   Compounding conditions                PARAMETER   UNITS   Set values                       Feeding zone temperature (T 1 )   ° C.   no heating           T 2     ° C.   160           T 3     ° C.   230           T 4     ° C.   230           T 5     ° C.   230           T 6     ° C.   230           T 7     ° C.   200           T 8     ° C.   230           T 9     ° C.   230           Temperature of melt   ° C.   230           Screw speed   RPM   300                        
Injection Molding
 
     Test specimens were prepared by injection molding in an Allrounder 500 150 ex. Arburg. All test specimens were prepared under the same conditions. The injection molding conditions are presented in Table 3. 
                                                         TABLE 3                   Injection molding conditions                PARAMETER   UNITS   Set values                            T 1  (Feeding zone)   ° C.   180           T 2     ° C.   200           T 3     ° C.   230           T 4     ° C.   230           T 5  (nozzle)   ° C.   230           Mold temperature   ° C.   40           Injection pressure   bar   500           Holding pressure   bar   250           Back pressure   bar   20           Injection time   sec   0.1           Holding time   sec   10.0           Cooling time   sec   5.0           Mold closing force   kN   500           Filling volume (portion)   ccm   21           Injection speed   ccm/sec   10                        
Conditioning
 
     Prior to UL-94 testing test specimens are conditioned at 70° C. for 168 hours and at 23° C. for 168 hours. 
     Compositions and flammability test results are presented in Table 4 for HIPS compositions and in Table 5 for ABS compositions. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 4 
               
               
                   
               
             
             
               
                 HIPS compositions and flammability test results 
               
             
          
           
               
                   
                   
                 Reference 
                 Reference 
                 Reference 
                 Reference 
                 Reference 
                 Reference 
                 Reference 
                 Reference 
                 Reference 
               
               
                 Components 
                 Units 
                 Example 1 
                 example 2 
                 example 3 
                 example 4 
                 example 5 
                 example 6 
                 example 7 
                 example 8 
                 example 9 
               
               
                   
               
               
                 HIPS Styron 472 
                 % 
                 82.5 
                 81.5 
                 84.4 
                 84.5 
                 83.4 
                 79.2 
                 78.2 
                 81.5 
                 81.6 
               
               
                 FR-245 
                 % 
                   
                   
                   
                   
                   
                 17.2 
                 17.2 
                 14.9 
                 14.9 
               
               
                 FR-1210 
                 % 
                 13.9 
                 13.9 
                 12.0 
                 12.0 
                 12.0 
               
               
                 F-3020 
                 % 
               
               
                 Antimony trioxide 
                 % 
                 3.5 
                 3.5 
                 3.5 
                 3.5 
                 3.5 
                 3.5 
                 3.5 
                 3.5 
                 3.5 
               
               
                 PTFE Hostaflon 2071 
                 % 
                 0.1 
                 0.1 
                 0.1 
                   
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 Carbon Black 
                 % 
                   
                 1.0 
                   
                   
                 1 
                   
                 1.0 
               
               
                 Bromine calculated 
                 % 
                 11.5 
                 11.5 
                 10 
                 10 
                 10 
                 11.5 
                 11.5 
                 10 
                 10 
               
             
          
           
               
                 Flammability UL-94V at 1.6 mm 
               
             
          
           
               
                 Max flaming time 
                 sec 
                 2 
                 1 
                 2 
                 4 
                 1 
                 2 
                 1 
                 2 
                 3 
               
               
                 Total flaming time 
                 sec 
                 10 
                 9 
                 10 
                 17 
                 10 
                 11 
                 7 
                 12 
                 11 
               
               
                 Max after glow time 
                 sec 
                 12 
                 0 
                 0 
                 0 
                 11 
                 20 
                 36 
                 31 
                 0 
               
               
                 Max after glow + 
                 sec 
                 13 
                 1 
                 1 
                 1 
                 12 
                 22 
                 36 
                 31 
                 1 
               
               
                 after flame time 
               
               
                 Specimens dripped 
                 num 
                 0 
                 0 
                 0 
                 3 
                 0 
                 0 
                 0 
                 0 
                 5 
               
               
                 Cotton ignition 
                 num 
                 0 
                 0 
                 0 
                 2 
                 0 
                 0 
                 0 
                 0 
                 5 
               
               
                 Sample burned up to 
                 num 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 the holding clamps 
               
               
                 Rating 
                   
                 V-0 
                 V-0 
                 V-0 
                 V-2 
                 V-0 
                 V-0 
                 V-1 
                 V-1 
                 V-2 
               
               
                   
               
             
          
           
               
                 HIPS compositions and test flammability results 
               
             
          
           
               
                   
                   
                 Reference 
                 Reference 
                 Reference 
                 Reference 
                 Reference 
                 Reference 
                   
                   
                   
               
               
                   
                   
                 example 
                 example 
                 example 
                 example 
                 example 
                 example 
               
               
                 Components 
                 Units 
                 10 
                 11 
                 12 
                 13 
                 14 
                 15 
                 Example 1 
                 Example 2 
                 Example 3 
               
               
                   
               
               
                 HIPS Styron 472 
                 % 
                 80.5 
                 80.8 
                 83.0 
                 81.6 
                 81.2 
                 79.6 
                 81.0 
                 81.5 
                 80.6 
               
               
                 FR-245 
                 % 
                 14.9 
                 14.9 
                 14.9 
                 14.9 
                 14-9 
                 10.4 
                 14.9 
                 14.9 
                 10.4 
               
               
                 FR-1210 
                 % 
               
               
                 F-3020 
                 % 
                   
                   
                   
                   
                   
                 5.4 
                   
                   
                 5.4 
               
               
                 Antimony trioxide 
                 % 
                 3.5 
                 3.2 
                 1.0 
                 2.5 
                 2.5 
                 3.5 
                 3.0 
                 2.5 
                 2.5 
               
               
                 PTFE Hostaflon 2071 
                 % 
                 0.1 
                 0.1 
                 0.1 
                 0.02 
                 0.4 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 Carbon Black 
                 % 
                 1 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
               
               
                 Bromine calculated 
                 % 
                 10 
                 10 
                 10 
                 10 
                 10 
                 10 
                 10 
                 10 
                 10 
               
             
          
           
               
                 Flammability UL-94V at 1.6 mm 
               
             
          
           
               
                 Max flaming time 
                 sec 
                 1 
                 3 
                 78 
                 6 
                 1 
                 3 
                 2 
                 7 
                 4 
               
               
                 Total flaming time 
                 sec 
                 9 
                 13 
                 338 
                 26 
                 7 
                 12 
                 12 
                 16 
                 18 
               
               
                 Max after glow time 
                 sec 
                 54 
                 35 
                 0 
                 31 
                 45 
                 35 
                 21 
                 2 
                 22 
               
               
                 Max after glow + 
                 sec 
                 55 
                 37 
                 78 
                 33 
                 46 
                 38 
                 22 
                 2 
                 24 
               
               
                 after flame time 
               
               
                 Specimens dripped 
                 num 
                 0 
                 0 
                   
                 3 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 Cotton ignition 
                 num 
                 0 
                 0 
                   
                 3 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 Sample burned up to 
                 num 
                 0 
                 0 
                 4 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 the holding clamps 
               
               
                 Rating 
                   
                 V-1 
                 V-1 
                 HB 
                 V-2 
                 V-1 
                 V-1 
                 V-0 
                 V-0 
                 V-0 
               
               
                   
               
             
          
         
       
     
     Table 4 above summarizes several composition and flammability test results of prior art related fire-retardant formulations as well as of formulations relating to the present invention. From this table it is clearly seen that:
     (a) Formulations (Reference Example-6) based on JP 11323064 pass successfully the V-0 flammability test, but introducing 1 wt. % carbon black pigment (Reference Example-7), results in derating to V-1 due to long afterglow time.   (b) In fire-retardant FR-1210 (decabromodiphenyl oxide) based formulations—Reference Examples 1-5—the first two formulations substantially having the same bromine, antimony trioxide and PTFE concentrations as in Reference Examples 6 and 7 pass V-0 tests, even when containing carbon black pigment (Reference Example 2). Reducing bromine content to 10 wt. % and then further elimination of PTFE from this formulation result in V-0 and V-2 rating, respectively (Reference Example 3 and Reference Example 4), the latter is due to burning drops ignited cotton effect. Addition of carbon black to Reference Example 3 does not derate the formulation and it passes V-0 tests (Reference Example 5). It should be noted that the antimony trioxide remains essentially unchanged in all those formulation variations.   (c) Reference Example 8, Reference Example 9, Reference Example 10 and Example 2 to Example 3 relate to FR-245 containing formulations having varying concentrations of the components Further reduction of FR-245 to 10 wt. % bromine while keeping the antimony trioxide concentration relatively high (Reference Example 8) results in derating to V-1. Omission of PTFE from this formulation (Reference Example 9) results in dripping with cotton ignition and V-2 rating. Further addition of carbon black to Reference Example 8 (Reference Example 10) results in long afterglow effect and a rating of V-1. However, reduction of antimony trioxide to 2.5 wt. % (Example 2) surprisingly improves flammability retardation and is rated V-0. Further reduction of antimony trioxide to 1 wt. % (Reference Example 12) results in total burning of the specimen up to the clamps and in a HB rating. The upper concentration limit of antimony trioxide is tested in Reference Example 11 vs. Example 1; at antimony trioxide concentration of 3.2 wt. % the formulation is rated V-1 because of long after glow time (Reference Example 11); at antimony trioxide concentration of 3.0 wt. % the formulation is rated V-0 (Example 1). The concentration limits of PTFE are tested in formulations Reference Example 13, 0.02 wt. %, and Reference Example 14, 0.4 wt. %. In the first an effect of burning drops ignited cotton leads to V-2 rating. The second is rated V-1 due to long afterglow time.   (d) The employment of both FR-245 and F-3020 (MBEO endcapped brominated epoxy resin) as the bromine fire-retardants, the first contributing about 7 wt. % and the second about 3 wt. % of the bromine content, leads to long afterglow time (Reference Example 15) when incorporating 3.5 wt. % antimony trioxide, i.e. V-1 rating, and to successful results (Example 3) when lowering antimony trioxide concentration to 2.5 wt. %, i.e. V-0. These two results are similar to the ones achieved for formulations containing only FR-245, i.e. Reference Example 10 and Example 2, and further stress the optimal relation between bromine fire-retardant and antimony trioxide synergist contents.   

     
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 ABS compositions and results of flammability results 
               
             
          
           
               
                   
                   
                   
                 Reference 
                   
               
               
                   
                 Components 
                 Units 
                 example 16 
                 Example 4 
               
               
                   
                   
               
             
          
           
               
                   
                 ABS Magnum 3404 
                 % 
                 80.0 
                 81.0 
               
               
                   
                 FR-245 
                 % 
                 14.9 
                 14.9 
               
               
                   
                 Antimony trioxide 
                 % 
                 4.0 
                 3.0 
               
               
                   
                 PTFE Hostaflon 2071 
                 % 
                 0.1 
                 0.1 
               
               
                   
                 Carbon Black 
                 % 
                 1.0 
                 1.0 
               
               
                   
                 Bromine calculated 
                 % 
                 10 
                 10 
               
             
          
           
               
                 Flammability UL-94V at 1.6 mm 
               
             
          
           
               
                   
                 Max flaming time 
                 Sec 
                 5 
                 7 
               
               
                   
                 Total flaming time 
                 Sec 
                 16 
                 29 
               
               
                   
                 Max after glow time 
                 Sec 
                 36 
                 21 
               
               
                   
                 Max after glow + after 
                 Sec 
                 38 
                 23 
               
               
                   
                 flame time 
               
               
                   
                 Specimens dripped 
                 Num 
                 0 
                 0 
               
               
                   
                 Cotton ignition 
                 Num 
                 0 
                 0 
               
               
                   
                 Sample burned up to the 
                 Num 
                 0 
                 0 
               
               
                   
                 holding clamps 
               
               
                   
                 Rating 
                   
                 V-1 
                 V-0 
               
               
                   
                   
               
             
          
         
       
     
     Table 5 demonstrates that the same effects, which are observed in HIPS formulations, are also applied in ABS based formulations. 
     HIPS and ABS containing fire-retardant formulations containing FR-245 or a combination of FR-245 and BEO&#39;s at low bromine content and with the incorporation of carbon black do not pass UL-94 V-0 because of long after glow time. It is surprisingly found that at low antimony trioxide concentrations it is possible to pass UL-94 V-0 and get economic cost-effective formulations with good mechanical, thermal and processing properties. 
     While examples of the invention have been described for purposes of illustration, it will be apparent that many modifications, variations and adaptations can be carried out by persons skilled in the art, without exceeding the scope of the claims.