Abstract:
A vinyl halide resin stabilizer composition which essentially contains: 
     (a) a calcium, zinc or mixed calcium/zinc salt of a higher fatty acid; 
     (b) a polyhydroxy alcohol component wherein at least 50% of this component is either di-or tri-pentaerythritol; and 
     (c) a magnesium compound, particularly magnesium hydroxide or magnesium acetate 
     These compositions synergistically contribute to the heat stability of vinyl halide resin compositions and offer significant heat stabilization economies. Early color as well as long term heat stability performances of the metal salt compounds are improved in the compositions disclosed thereby permitting the reduction in amounts of such compounds needed for stabilization.

Description:
BACKGROUND OF THE INVENTION 
     Degradation by the action of heat and light is a major problem in the use of vinyl halide resins. Various additives have been proposed as stabilizers to offset the deleterious effects of heat and light in the manufacture of useful articles from such resins. The problem has been compounded in recent times by the numerous governmental regulations designed to safeguard the environment and to reduce or eliminate potential hazards to the well being of the populace. 
     The emphasis on environmental quality and the increasing awareness of toxicological requirements have led the plastics industry, and in particular the vinyl halide resin field, to seek a satisfactory replacement for the high performance stabilizers based upon the compounds of the heavy metals, such as cadmium, barium, lead, etc., currently in wide usage in the industry. 
     The use of calcium and zinc salts of higher fatty acids for the stabilization of vinyl halides is well recognized in the art. However, these salts, and similar salts of magnesium and tin, do not provide the same degree of effectiveness as the salts of barium and cadmium. It is, therefore, clearly a desirable objective to increase the effectiveness of the stabilizers based upon calcium and zinc, and thereby provide an effective replacement for the lead, barium and cadmium based stabilizers. 
     REFERENCE TO RELATED APPLICATIONS 
     In U.S. Patent Application Ser. No. 45,551 entitled &#34;LOW TOXICITY VINYL HALIDE STABILIZER COMPOSITIONS&#34; by Gerald Baum and Ramchandra Hulyalkar, filed June 4, 1979, there is disclosed an improved stabilizer composition comprising a calcium and/or zinc salt of a higher fatty acid in combination with a polyhydric alcohol from the group consisting of dipentaerythritol, tripentaerythritol, mixtures of these two polyhydric alcohols, and mixtures of these two polyhydric alcohols, either separately or in combination, with certain other polyhydric alcohols, particularly with pentaerythritol, mannitol or sorbitol. 
     SUMMARY OF THE INVENTION 
     The present invention is directed to further improvements in vinyl halide resin stabilizer systems based upon calcium and zinc compounds. This invention in one of its aspects provides for synergistic heat stabilizer compositions of such calcium and zinc compounds and certain polyhydric alcohols as stabilizers together with one or more of a magnesium compound from the group consisting of magnesium oxide, magnesium hydroxide, magnesium acetate, magnesium carbonate, magnesium benzoate, magnesium citrate, magnesium stearate and magnesium phosphate. It has been found that early color heat performances of zinc and calcium compounds and particular polyhydric alcohol stabilizer compositions are significantly improved according to the principles of this invention by their combination with particular magnesium compounds. Furthermore, improvements in long term heat stability are achievable along with early color heat improvements. In another of its significant features, stabilizer compositions are provided which are shelf-stable at ambient temperatures. Such stable compositions are easily formulated into vinyl halide resin systems and offer synergistically heat stabilized resin systems with enhanced resistance to both early discoloration and long term heat degradation of molded plastics. These and other advantages will become apparent in the following detailed description. 
     This invention is predicated in part upon the unexpected heat stabilization of vinyl halide resins containing stabilizer compositions based upon zinc and calcium salts in combination with certain polyhydric alcohols through the further presence of certain magnesium compounds. In particular, where a polyol selected from the group consisting of dipentaerythritol and tripentaerythritol and mixtures thereof, both with each other and with other previously known alcohols, such as pentaerythritol, mannitol and sorbitol, and a zinc and/or calcium containing compound are employed as stabilizer compositions unexpected and significant improvements in the early color stability and heat stability of vinyl halide resins are obtained by the inclusion of magnesium compounds selected from the group consisting of magnesium oxide, magnesium hydroxide, magnesium acetate, magnesium carbonate, magnesium benzoate, magnesium citrate, magnesium stearate and magnesium phosphate. It has been found that synergistic heat stabilizations are provided by such compositions, i.e., the sum of the stabilizing effects of an amount of each of the component alone upon the resin is exceeded when the same amounts of components are together in the vinyl halide resin formula. Such unexpected results and other advantages are empirically demonstrated in the operating examples of this invention, and a further understanding thereof will become apparent in view of the detailed description herein. The synergistic effectiveness is especially exhibited by an enhanced resistance of the resin formula to early discoloration during heating to elevated temperatures of about 300° F. to about 400° F. Also, long term heat stability improvement can be achieved in addition to resistance to early discoloration. &#34;Early color&#34; development is a term well understood in the art and means the time within which the resin formula starts to yellow under the action of heat, either under static oven or dynamic working conditions. Whereas, &#34;long term&#34; heat stability refers to the time within which such resin formula under the action of heat severely darkens or degrades to a dark color such as dark red or black. 
     Broad ranges of components of the stabilized compositions and components of the stabilizer compositions can be employed in this invention. Particularly useful stabilized compositions of this invention are achieved with a total parts by weight range on the order of about 0.5 to about 5 parts by weight based upon 100 parts by weight (phr) of the vinyl halide resin. A most useful range of total parts by weight of stabilizer composition is on the order of about 0.5 to about 3 phr and this depends upon the desired heat stability in a particular vinyl halide resin composition consistent with other requirements and economiies. 
     There are certain generally preferred weight ratios of the calcium and zinc containing compounds relative to the particular polyhydric alcohol and the magnesium compounds. This will become apparent in view of the detailed operating examples. However, it is to be emphasized that the most desirable weight ratios of each of the essential components of the composition of this invention for a particular application and resin system can be arrived at in accordance with the teachings of this invention. Thus, in its broader aspects, this invention is not limited to weight ratios of components. It has been found that synergistic stabilization levels of particular polyhydric alcohols, particular calcium and zinc containing compounds and particular magnesium compounds will vary as exemplified herein. But, most preferably and in general, the combination of magnesium compound and polyhydric alcohol with the calcium and/or zinc containing compound is utilized at total parts on the order of about 0.1 to about 5 phr; and where the polyhydric alcohol is from about 10 to about 100 percent by weight of the zinc and/or calcium compound and the magnesium compound is from about 10 to about 100 percent based on the polyhydric component. 
     DESCRIPTION OF THE PREFERRED EMBODIMENT 
     The novel stabilizer composition of the present invention as previously disclosed in this application is comprised of three components; first, a calcium, a zinc or a mixed calcium-zinc salt of a higher fatty acid; second, a polyhydric alcohol from the group consisting of dipentaerythritol, tripentaerythritol, mixtures of these two polyhydric alcohols, and mixtures of these two polyhydric alcohols, either separately or in combination, with certain other polyhydric alcohols, particularly with pentaerythritol, mannitol or sorbitol and third, a magnesium compound from the group consisting of magnesium oxide, magnesium hydroxide, magnesium acetate, magnesium carbonate, magnesium benzoate, magnesium citrate, magnesium stearate and magnesium phosphate. 
     Dipentaerythritol or tripentaerythritol can be used individually or in any proportions in a mutual combination. In combinations with the other recited polyhydric alcohols, the di-and/or-tripentaerythritol component will be present in an amount of from about 20% to about 100%. Preferably, at least about 50% of any such combination will consist of the di-and/or-tripentaerythritol component. 
     The salt component can be a calcium or zinc salt of a carboxylic acid, advantageously of a C 8  -C 24  carbon chain length monocarboxylic acid such as lauric, oleic or stearic acid. It can also be a mixed calcium/zinc salt of such acids, such salts and their preparation being familiar to those skilled in the art to which the present invention pertains. In the preferred embodiment of the present invention, it is preferred to employ zinc stearate as the metal salt component. 
     The particular magnesium compounds employed can be used individually or in any proportions in mutual combinations. While the use of the various magnesium compounds set forth above is contemplated, it is preferred to use either magnesium hydro-oxide or magnesium acetate. 
     The stabilizer compositions of the present invention can include various additional compounds as set forth hereafter: 
     (a) Lubricants for providing the chlorine-containing polymer composition with lubricity: 
     higher aliphatic alcohols; 
     higher aliphatic amides; 
     comparatively macromolecular organic polymers such as AC polyethylene (oxidized polyethylene wax sold by Allied Chemicals under the trade name of AC Polyethylene). 
     These lubricants may be added up to about 15 parts by weight per 100 parts by weight of the chlorine-containing polymer. 
     (b) Plasticizers: 
     phthalic esters such as dioctyl phthalate (DOP); 
     fatty acid esters such as stearic esters; 
     straight-chain dibasic acid esters such as dioctyl adipate; 
     epoxy compounds such as epoxidized soybean oil; 
     phosphate compounds such as tricresyl phosphate, chlorinated olefin, chlorinated paraffin, or chlorinated rubber. 
     These plasticizers may be employed by combining one or more of them with the chlorine-containing polymer at the rate of from about 2 to about 100 parts by weight of the former per 100 parts by weight of the latter. 
     (c) Other additives: 
     epoxy compounds--may be added at the rate of 0.1-20 parts by weight per 100 parts by weight of the chlorine-containing polymer. 
     auxiliary stabilizers such as esters of organic phosphite compounds--may be added at the rate of 0.1-5 parts by weight per 100 parts by weight of the chlorine-containing polymer. 
     antioxidant such as sulphur-containing organic compounds or hindered phenols--may be added at the rate of 0.01-2 parts by weight per 100 parts by weight of the chlorine-containing polymer. 
     light stabilizer--may be added at the rate of 0.01-2 parts by weight per 100 parts by weight of the chloride-containing polymer. 
     Further, flame retardants, chemical blowing agents, antistatic agents, pigments, dyes, extenders or fillers may also be employed in combination with the stabilizer of the present invention. 
     The vinyl halide resin employed is most commonly a a homopolymer of vinyl chloride, i.e., polyvinyl chloride. It is to be understood, however, that this invention is not limited to a particular vinyl halide resin such as polyvinyl chloride. Other halogen-containing resins which are employed and illustrate the principles of this invention include chlorinated polyethylene, chlorinated polyvinyl chloride and the vinyl halide resin type. Vinyl halide resin, as understood herein, and as appreciated in the art, is a common term and is adopted to define those resins or polymers usually derived by polymerization or copolymerization of vinyl monomers including vinyl chloride with or without other comonomers such as ethylene, propylene, vinyl acetate, vinyl ethers, vinylidene chloride, methacrylate, styrene, etc. A simple case is the conversion of vinly chloride H 2  C═CHCl to polyvinyl chloride (CH 2  --CHCl--) n  wherein the halogen is bonded to the carbon atoms of the carbon chain of the polymer. Other examples of such vinyl halide resins would include vinylidene chloride polymers, vinyl chloride-vinyl ester copolymers, vinyl chloride-vinyl ether copolymer, vinyl chloride-vinylidene copolymers vinyl chloride-propylene copolymers, chlorinated polyethylene; and the like. Of course, the vinyl halide commonly used in the industry is the vinyl chloride, although others such as vinyl bromide and vinyl fluoride may be used. Examples of the latter polymers include polyvinyl bromide polyvinyl fluroride, and copolymers thereof. 
     The stabilizing composition of the present invention can be incorporated by standard incorporation techniques. Thus, it can be added to the solid resin and mixed therein by means of hot rolls or other mixing machines adapted to mix solid resins. It can also be dissolved in a suitable solvent and then mixed with the resin, or the solution of the stabilizer can be mixed with a solution of the resin. The most important consideration is that the stabilizer and resin be thoroughly admixed and the dispersion of the stabilizer in the resin be as complete and as rapid as possible. 
     In general, chlorine containing vinyl resins, such as polyvinyl chloride, copolymers of vinyl chloride, etc. have very poor resistance to the effects of heat and/or light. It is well known to those skilled in the art that severe exposure, of the chlorine containing vinyl resins, to heat and/or light brings about discoloration, brittleness and loss of strength. This degradation is especially pronounced during the various fabrication processes such as injection molding, calendering, etc.; operations which require heating of plastic compositions. 
     It is also known that certain of the hitherto employed stabilizers, i.e. calcium and zinc stearates, have certain undesirable properties, especially as applied in rigid polyvinyl chloride (PVC) processing. Rigid PVC bottles stabilized with such salts exhibit reduced thermal stability and, in the presence of aqueous or alcoholic aqueous products, such as food products, exhibit complete loss of transparency, sometimes called water blush. This is demonstrated by the slow development of a milky opacity. 
     It is also recognized in the art to which the present invention pertains that processing stability, as measured by dynamic mill or Brabender torque, is a highly desirable characteristic in a vinyl halide resin-stabilizer system. 
     It is apparent, therefore, that the provision of a satisfactory stabilizer composition requires consideration of the many diverse requirements which must be met. The effectiveness of the stabilizer compositions of the present invention in meeting such criteria is demonstrated in the following examples, which are provided by way of illustration only and are not to be construed as limiting the scope thereof. 
    
    
     In the examples which follow, certain materials are commonly or frequently employed and are identified by trade designations. Geon 103 EP is a polyvinyl chloride available from B. F. Goodrich and is characterized as a white powder which passes through a 42 mesh screen, a specific gravity of 1.40 and has a molecular weight of about 200,000. Admex 710 is an epoxidized soybean oil marketed by Ashland Chemical Co. Sancticizer 711 is a phthalate plasticizer marketed by Monsanto Co. and BhT is butylated hydroxytoluene. 
     EXAMPLES 1-10 
     In Examples 1-10, the highly effective performance of a combination of magnesium hydroxide with dipentaerythritol and zinc stearate is demonstrated. All of the formulations employed in Examples 1-10 contained the standard vinyl halide resin composition set forth below together with the additives set forth in Table I. 
     The standard vinyl halide resin composition is prepared by thoroughly admixing the following ingredients in the recited amounts in a clean glass vessel: 
     
         ______________________________________Geon 103 EP             100Santicizer 711          35Admex 710               5Stearic Acid            0.25BHT                     0.5Decyl diphenyl phosphite                   0.5Glycerol monostearate   0.8Zinc stearate           0.66______________________________________ 
    
     In each of the separate examples 1-10, the standard composition described above is thoroughly admixed with the remaining ingredients in the amounts set forth under each example in Table I and the remaining mixture milled on an electrically heated two-roll mill at a temperature of 340° F. and for a period of five (5) minutes after the mixture was banded on the mill. 
     In carrying out the tests whose results are reported in Table I, aging was carried out using a circulating air oven at 375° F.±1° F. One inch×one inch samples were placed on a metal sheet covered with aluminum foil, kept in the oven and the samples taken out at 10 minute intervals. The early color stability (EC) was determined as the number of minutes at which the first color change (slight yellow) was observed. The long term stability (LTHS) was indicated in minutes at which samples became dark brown or black. 
     
                       TABLE I______________________________________Example 1     2      3    4    5    6    7   8   9   10______________________________________Mg(OH).sub.2   0.0   0.1    0.2  0.3  0.4  0.5  0.6 0.7 0.8 0.9Dipenta-erythritol   0.9   0.8    0.7  0.6  0.5  0.4  0.3 0.2 0.1 0.0EarlyColorStability(min)   45     60     60   60   60   45  45  40  30  15Long TermHeat    85    120    150  155  150  105  95  60  45  30Stability______________________________________ 
    
     EXAMPLES 11-13 
     Replacing dipentaerythritol with tripentaerythritol gave results demonstrating similar improvements in early color stability and in long term heat stability. The same method of preparation is employed as in Examples 1-10 using the standard composition set forth below and the additives in the amounts specified in Table II wherein the results of the tests carried out are reported. 
     
                       TABLE II______________________________________Standard Composition  Geon 103EP     100  Santicizer 711 35  Admex 710      5  Stearic Acid   0.25______________________________________Example        11        12        13______________________________________Zinc stearate  0.66      0.66      0.66GMS            0.8       0.8       0.8Decyl diphenyl 0.5       0.5       0.5phosphiteTripentaerythritol          0.6       0.6       0.6Mg(OH).sub.2   0.3       0.4       0.25BHT            0.5       0.5       0.5E.C. (Min)     60        60        60LTHS (Min)     150       150       150______________________________________ 
    
     EXAMPLES 14-23 
     Replacing dipentaerythritol with tripentaerythritol and magnesium hydroxide with magnesium oxide gave results demonstrating similar improvement in early color stability and in long term heat stability. The same method of preparation is employed as in Examples 1-10 using the standard composition set forth below and the additives in the amounts specified in Table III wherein the results of the tests carried out are reported. 
     
                       TABLE III______________________________________Geon 103EP          100Santicizer 711      35Admex 710           5Stearic Acid        0.25BHT                 0.5Glycerol monostearate               0.8Decyl diphenyl phosphite               0.5Zinc stearate       0.66______________________________________Example 11    12    13  14   15   16   17   18   19  20______________________________________Tripenta-erythritol   --    0.1   0.2 0.3  0.4  0.5  0.5  0.7  0.8 0.9MgO     0.9   0.8   0.7 0.6  0.5  0.4  0.3  0.2  0.1 --E.C. (min)   15    30    45   55   60   60   60   60  60  60LTHS    45    60    75  105  120  135  150  150  90  90(min)______________________________________ 
    
     EXAMPLES 24-29 
     In Examples 24-29, the effectiveness of varying mixtures of magnesium hydroxide and magnesium oxide in realizing the objectives of the present invention was demonstrated. All of the formulations employed in Examples 24-29 contained the standard vinyl halide composition set forth below together with the additives set forth in Table IV. 
     
                       TABLE IV______________________________________Standard Composition  Geon 103 EP           100  Santicizer 711           35  Admex 710           5  Stearic Acid           0.25______________________________________Example    24     25     26    27    28    29______________________________________Zinc stearate       0.66   0.66   0.66  0.66  0.66  0.66BHT        0.5    0.5    0.5   0.5   0.5   0.5Glycerolmonostearate      0.8    0.8    0.8   0.8   0.8   0.8Decyl diphenylphosphite  0.5    0.5    0.5   0.5   0.5   0.5Dipentaerythritol      0.6    0.6    0.6   0.6   --    --Tripentaerythritol      --     --     --    --    0.6   0.6MgO         0.15  0.1     0.15 0.1   0.1   0.1Mg (OH).sub.2      --     0.3    0.2    0.15 0.1   0.2E. C. (Min.)       60     60     60    60    60    60LTHS (Min.)      150    150    150   150   135   150______________________________________ 
    
     EXAMPLES 30-40 
     The use of various magnesium compounds other than magnesium oxide and magnesium hydroxide is illustrated in Examples 30-40. All of the formulations employed in Examples 30-40 contained the standard vinyl halide composition set forth below together with the additives set forth in Table V wherein the results of the tests carried out are reported. 
     
                                           TABLE V__________________________________________________________________________Standard Composition   Dipentaerythritol                0.6   BHT          0.5   Glycerol monostearate                0.8   Decyl diphenyl phosphite                0.5   Zinc stearate                0.66   Geon 103EP   100   Santicizer 711                35   Admex 710    5   Stearic acid 0.25__________________________________________________________________________Example  30 31 32 33 34 35 36 37 38 39 40__________________________________________________________________________Magnesiumcarbonate  0.2     0.2        0.3           -- -- -- -- -- -- -- --Magnesiumbenzoate  -- -- -- 0.3              0.2                 -- -- -- -- -- --Calciumstearate  -- -- -- -- 0.2                 -- -- 0.2                          -- -- 0.2MagnesiumCitrate  -- -- -- -- -- 0.2                    0.4                       0.1                          -- -- --MagnesiumPhosphate  -- -- -- -- -- -- -- -- 0.2                             0.3                                0.1E.C. (min.)   60      60         75           60  60                 45 45  75                          60 60  75LTHS (min.)  105     105        120           75 105                 75 75 105                          90 90 105__________________________________________________________________________ 
    
     EXAMPLES 41-43 
     The use of magnesium stearate is illustrated in Examples 41, 42 and 43. All of the formulations employed in Examples 41, 42 and 43 contained the standard vinyl halide composition set forth below together with the additives set forth in Table VI. 
     
                       TABLE VI______________________________________Standard Composition  Geon 103 EP           100  Stearic Acid           0.25  Santicizer 711           35.0  Admex 710           5.0______________________________________Example         41        42        43______________________________________Calcium stearate           --        0.11      0.11Zinc stearate   0.66      0.66      0.66Magnesium stearate           0.33      0.22      0.11Tripentaerythritol           0.6       0.6       1.0BHT             0.2       0.2       0.2Glycerol monostearate           0.81      0.81      0.81Decyl diphenyl phosphite           0.4       0.4       0.4E.C. (min.)     60        60        60LTHS (min.)     120       120       125______________________________________ 
    
     EXAMPLES 44 and 45 
     In order to demonstrate the effectiveness of the compositions of the present invention in providing satisfactory dynamic mill stability and Brabender stability, Examples 44 and 45 were carried out with the results reported in Table VII. 
     A standard composition is provided by mixing the following ingredients in the recited amounts in a clean glass vessel for each of Examples 44 and 45. Equal parts of the standard composition are then further admixed with Stabilizer compositions A and B set forth below. The mixtures compounded on an electrically heated two-roll mill at a temperature of 360° F. and tested with the results shown in Table VII. 
     The dynamic mill stability (DMS) is determined in the following manner. Every 5 minutes a sample (1&#34;×1&#34;) was cut out directly from the mill, using the same area of the mill each time. The time in minutes, at which the sample discolored badly or was stuck to the mill severely, was indicated as its DMS. 
     The Brabender runs were carred out at 190° C. and samples were taken out at every 5 minute intervals and pressed into discs (1/4&#34;×1/16&#34;) and then mounted on a heat chart. The torque was continuously recorded, which was constant throughout the testing period. The machine was stopped when the torque began to increase indicating crosslinking and excessive degradation of the material. In Table VII, the results are reported. 
     
                       TABLE VII______________________________________Standard Composition  Geon 103 EP           100  Santicizer 711           35  Admex 710           5  Stearic Acid           0.25______________________________________STABILIZER COMPOSITIONSComponent           A     Wt. %______________________________________Glycerol monostearate     28.5Zinc stearate             23.5Tripentaerythritol        21.3BHT                       17.8Mg (OH).sub.2              8.9                     100.0               BZinc stearate             29.2Glycerol monostearate     26.2Tripentaerythritol        19.4BHT                       15.5Mg acetate                 9.7                     100.0______________________________________     Static     OVen     Dynamic    Brabender                                  Static     Aging    Mill Stab. Stability                                  Oven     (Min)    (Min)      (Min)    (Min)     375° F.              360° F.                         375° F.                                  375° F.     (3 Phr)  (3 Phr)    (3 Phr)  (1 Phr)______________________________________Example 44Formulation AE.C.       60      --         --       --LTHS      150      90+        90+      80+Example 45Formulation BE.C.       60      --         --       --LTHS      150      65         62       80+______________________________________ N.B. &#34;+&#34; indicates test was discontinued at this point; samples had not yet failed.