Abstract:
There is disclosed thermoplastic polymeric compositions of polycarbonates, polyamides, polyacetals, and poly(2,6-dimethyl-1,4-phenylene oxides) and which contain in a minor amount sufficient to make the thermoplastic polymeric material easily releasable from a processing mold of fatty acid ester.

Description:
FIELD OF THE INVENTION 
     This invention relates to a thermoplastic polymer composition which is easily releasable from processing molds especially during injection molding. The composition comprises thermoplastic high molecular weight polymer material and fatty acid esters as mold release agents. 
     BACKGROUND OF THE INVENTION 
     Thermoplastic polymer compositions containing polycarbonate as a main component are known. In this connection, there are also known additives which decrease adhesion of thermoplastic polymers to metals. For such purposes, additives such as products of complete or partial esterification of monocarboxylic or dicarboxylic aliphatic acids having long carbon chain with monohydric or polyhydric alcohols or phenols are employed. 
     According to European Patent No. 122,759 polyesters having g a degree of polymerization from 3 to 12 are used as additives that decrease adhesion of polycarbonates to processing mold. Those polyesters are obtained from aliphatic dicarboxylic acids containing from 2 to 6 carbon atoms and pentaerythritol, partially esterified by aliphatic monocarboxylic acids containing 2 to 6 carbon atoms. 
     According to Japanese Patent Application No. 86/261349, esters of aliphatic monocarboxylic acids containing from 12 to 30 carbon atoms reacted with C≦0 aliphatic alcohols or polyols are used as additives to decrease the adhesion of the polymer compositions to the processing mold. 
     Additives of this type are introduced by physical modification, applying 0.01 to 2.0 parts by weight of the additive per 100 parts by weight of high molecular weight of thermoplastic polymer, especially polycarbonate, which are mixed with dissolved, molten, or powdered polymer. 
     Processing molds, especially injections molds, are sometimes blocked during the processing of known thermoplastic polymer compositions. This makes the operation troublesome. 
     It is an aim of this invention to provide thermoplastic polymer compositions which exhibit decreased adhesion to metals and thus easily released from processing molds, thus avoiding blocking of the processing apparatus or devices. 
     BRIEF STATEMENT OF THE INVENTION 
     It has now been found that thermoplastic polymer compositions, containing high molecular weight thermoplastic polymer and fatty acid esters which up to now have not been used for this purpose, and optionally stabilizers, flame retardants, fillers, and dyes, achieve this aim. 
     These compositions are characterized by the fact that they comprise per 100 parts by weight of high molecular weight thermoplastic polymer, especially such as polycarbonate, polyamide, and polyacetal or blends thereof with other polymers, and 0.05-5.0 parts by weight of fatty acid esters of general formulae: ##STR1## 
     In general formula 1, R is selected from alkyl, alkenyl or alkadienyl groups containing 15-23 carbon atoms; A is a radical of general formula 4: ##STR2## and m has a value in the range of from about 0.05 to 4.0. In general formula 1, has a value in the range of from about 1 to about 4, X and Y are either the same or different and denote --OH; a radical of the general formula RCOO--, wherein R is as above defined; or a radical of general formula --OOC--E--COOH, wherein E is a radical selected from (CH 2 ) 2 , --CH═CH--or a radical of formula ##STR3## 
     In general formula 1, X is a radical having general formula ##STR4## wherein Z is (CH 2 ) 6  or a radical of formula ##STR5## or X is a radical of general formula ##STR6## wherein E is as above defined and A is a group of general formula 4, wherein E is as above defined, and A is a group of general formula 4, wherein A and m are as above defined, and X is --OH. When X in general formula 1 is a group of general formula 12 or 16, then Y is --OH or a covalent bond. In general formula 2, R and A are as above defined, a has a value from about 1.4 to about 1.96 and b has a value from about 0.04 to about 0.6, and a+b equals 2. 
     In general formula 3, R is as above defined, X is --OH or a radical of general formula RCOO--, wherein R is as above defined, or a radical of general formula HOOC--E--COO--, wherein E is as above defined. ##STR7## wherein Q is a hydrogen atom or CH 3 , and p has a value from about 0.1 to about 4.0, or a radical of general formula ##STR8## wherein p is as above defined. 
     In formula 3, r equals 2 if A is a radical of general formula 17, or r equals 4 if A is a radical of general formula 18. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Fatty acid esters coming within the above formulae and which may be employed in the compositions of this invention are prepared by known processes and preferably by the addition of saturated and unsaturated fatty acids such as, for example, palmitic acid, stearic acid, erucic acid, oleic acid and linolenic acid, or technical grade fatty acids mixtures to (a) low molecular weight or medium molecular weight epoxy resins based on epichlorohydrin and 2,2-bis(4-hydroxyphenyl) propane (Bisphenol A, BPA), bis(4-hydroxyphenyl)methane, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,6-hexanediol, phthalic anhydride, hexahydrophthalic anhydride, and (b) epoxy novolac resins based on the condensation products used in thermoplastic compositions of the present invention, of phenol, o-cresol or Bisphenol A with formaldehyde. All of these products of addition of fatty acids to epoxy resins contain hydroxyl groups. 
     The above-described addition products are then converted into the esters by condensation of fatty acids with the hydroxyl groups of the addition products and such esters thus obtained are then used in thermoplastic polymer compositions of the present invention. 
     According to the present invention, addition products of fatty acids with epoxy resins and epoxy novolac resins, obtained by known processes at a ratio of fatty acids to epoxy groups which is lower than stoichiometric amounts are also used in molding compositions. These products have ester groups, hydroxyl groups, and unreacted epoxy groups. 
     Furthermore, the compositions described in this invention contain derivatives of addition products of fatty acids with epoxy resins and epoxy novolacs, obtained by known processes. In order to obtain such derivatives, reactions with the hydroxyl groups are accomplished in accordance with know processes. 
     Particularly suitable are addition products of cyclic anhydrides of dicarboxylic acids, preferably succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride with hydroxyl groups present in addition products of the fatty acids with epoxy resins and epoxy novolacs. 
     Additionally, compositions in accordance with the present invention include reaction products of aliphatic, cycloaliphatic and aromatic diisocyanates, preferably hexamethylene diisocyanate, isophorone diisocyanate, 4,4-diphenylmethane diisocyanate, as well as 2,4- and 2,6-toluene diisocyanate, and mixtures of the last two diisocyanates, with hydroxyl groups of the addition products of the fatty acids with epoxy resins. 
     The last group of compounds according to the present invention comprises addition products of the above-mentioned epoxy resins to carboxyl groups resulting from the above-described addition of cyclic anhydrides of dicarboxylic acids to reaction products of fatty acids and epoxy resins. 
     Examples of fatty acid esters used in compositions according to the invention are listed in Table 1. 
     
                                           TABLE 1__________________________________________________________________________EXAMPLES OF FATTY ACIDS ESTERS__________________________________________________________________________General   Fatty Acid EsterExampleFormula     R     A                  X1    2    3     4                  5__________________________________________________________________________I    1    C H   Formula 4; A.sub.2 = Formula 6                              OH     17 35 X = OH; m = 0.15II   1    C H (50%)           Formula 4; A.sub.2 = Formula 5                              OH     15 33 X = OH; m = 4.0     C H (50%)     17 35III  1    C H   Formula 4; A.sub.2 = Formula 7                              OH     17 33 X = OH; m = 2.0IV   1    C H   Formula 4; A.sub.2 = Formula 8                              --OOC--E--COOH     17 31 X = OOC--E--COOH; m = 0.08                              E = (--CH.sub.2 --).sub.2           E = (--CH.sub.2).sub.2V    1    C H   Formula 4; A.sub.2 = (--CH.sub.2).sub.2                              --OOC--E--COOH     17 35 X = --OOC--E-- COOH; m = 0.15                              E = --CH═CH--           E = --CH═CH--VI   1    C H   Formula 4; A.sub.2 = (--CH.sub.2).sub.4                              --OOC--E--COOH     17 36 X = --OOC--E--COOH; m = 0.15                              E = Formula 9           E = Formula 9VII  1    C H   Formula 4; A.sub.2 = (--CH.sub.2-).sub.5                              --OOC--E--COOH     15 33 X = --OOC--E--COOH; m = 0.15                              E = Formula 10           E = Formula 10VIII 1    C H   Formula 4;         --OOC--E--COOH     17 35 A.sub.2 = (--CH.sub.2 --).sub.2 --O--(--CH.sub.2-).sub.2                              E = Formula 11           E = Formula 11; m = 0.15           X = --OOC--E--COOHIX   1    C H   Formula 4;         Formula 12;     17 35 A.sub.2 = (CH.sub.2)--O--(CH.sub.2 --)--O--(CH.sub.2)                              Z = (--CH.sub.2 --).sub.6           X =  OH; m = 0.15X    1    C H   Formula 4; A.sub.2 = Formula 6                              Formula 12;     17 35 X = OH; m = 0.15   Z = Formula 13XI   1    C H   Formula 4; A.sub.2 = Formula 6                              Formula 12;     17 35 X = OH; m = 0.15   Z = Formula 5XII  1    C H   Formula 4; A.sub.2 = Formula 6                              Formula 12;     17 35 X = OH; m = 0.15   Z = Formula 14 (65%)                              and Formula 15 (35%)XIII 1    C H   Formula 4; A.sub.2 = Formula 6                              Formula 16;     17 35 X = OH; m = 0.15   A.sub.2 = Formula 6;                              m = 0.15; X = OH;                              E = Formula 9XIV  1    C H   Formula 4; A.sub.2 = Formula 6                              Formula 16;     17 35 X = OH; m = 0.15   A.sub.2 = Formula 5                              m = 0.08; X = OH;                              E = (--CH.sub.2 --).sub.2XV   1    C H   Formula 4; A.sub.2 = Formula 6                              Formula 16;     17 35 X = OH; m = 0.15   A.sub.2 = Formula 8                              m = 4.0; X = OH;                              E = --CH═CH--XVI  1    C H   Formula 4; A.sub.2 = Formula 6                              Formula 16;     17 35 X = OH; m = 0.15   A.sub.2 = Formula 7                              X = OH; E = Formula 10                              m = 0.15XVII 1    C H   Formula 4; A.sub.2 = Formula 6                              Formula 16; A.sub.2 = (--CH.sub.2                              --).sub.2     17 35 X = OH; m = 0.15   X = OH; E = Formula 11                              m = 0.25XVIII1    C H   Formula 4; A.sub.2 = Formula 6                              Formula 16; A.sub.2 = (--CH.sub.2                              --).sub.2     17 35 X = OH; m = 0.15   X = OH; E = Formula 9                              m = 0.42XIX  1    C H   Formula 4; A.sub.2 = Formula 6                              Formula 16; A.sub.2 = (--CH.sub.2                              --).sub.2     17 35 X = OH; m = 0.15   X = OH; E = Formula 9                              m = 0.16XX   1    C H   Formula 4; A.sub.2 = Formula 6                              Formula 16; A.sub.2 = (--CH.sub.2                              --).sub.2     17 35 X = OH; m = 0.15   X = OH; E = Formula 9                              m = 0.43XXI  1    C H   Formula 4;         Formula 16;     17 35 A.sub.2 = Formula 6                              X = OH; E = Formula 9;           X = OH; m = 0.15   m = 0.71                              A.sub.2 = (--CH.sub.2 --).sub.2                              --O--(--CH.sub.2).sub.2 --O--(--CH.sub.                              2).sub.2XXII 1    C H   Formula 4;         C H COO--     17 35 A.sub.2 = Formula 6                              17 35           X = OH; m = 0.15XXIII1    C H   Formula 4;         --     17 35 A.sub.2 = Formula 6           X = OH; m = 0.15XXIV 1    C H   Formula 4;         --     15 33 A.sub.2 = Formula 6           X = OH; m = 0.15XXV  1    C H   Formula 4;         --     15 33 A.sub.2 = Formula 6 X = OH;           m = 0.15XXVI 1    C H   --                 C H COO--     17 35                    17 35XXVII1    C H   --                 OH     17 35XXVIII3    C H   --                 --OOC--E--COOH;     17 35                    E = --CH═CHXXIX 3    C H   --                 OH     17 35__________________________________________________________________________                         Fatty Acid Ester                    Example                         Y          n a  b A                    p                              r                    1    6          7 8  9 10    11                                                   12__________________________________________________________________________                    I    OH         1 -- --                                           --    --                                                   --                    II   OH         1 -- --                                           --    --                                                   --                    III  OH         1 -- --                                           --    --                                                   --                    IV   --OOC--E--COOH                                    1 -- --                                           --    --                                                   --                         E = (--CH.sub.2 --).sub.2                    V    --OOC--E--COOH                                    1 -- --                                           --    --                                                   --                         E = --CH═CH--                    VI   --OOC--E--COOH                                    1 -- --                                           --    --                                                   --                         E = Formula 9                    VII  OH         1 -- --                                           --    --                                                   --                    VIII OH         1 -- --                                           --    --                                                   --                    IX   OH         2 -- --                                           --    --                                                   --                    X    covalent   3 -- --                                           --    --                                                   --                         bond                         (50%);                         OH (50%)                    XI   covalent   4 -- --                                           --    --                                                   --                         bond                         (60%);                         OH (40%)                    XII  OH         2 -- --                                           --    --                                                   --                    XIII OH         2 -- --                                           --    --                                                   --                    XIV  OH         2 -- --                                           --    --                                                   --                    XV   OH         2 -- --                                           --    --                                                   --                    XVI  OH         2 -- --                                           --    --                                                   --                    XVII covalent   4 -- --                                           --    --                                                   --                         bond                         (60%);                         OH (40%)                    XVIII                         covalent   3 -- --                                           --    --                                                   --                         bond                         (50%);                         OH (50%)                    XIX  OH         2 -- --                                           --    --                                                   --                    XX   OH         2 -- --                                           --    --                                                   --                    XXI  OH         2 -- --                                           --    --                                                   --                    XXII C H COO--  --                                      -- --                                           --    --                                                   --                         17 35                    XXIII                         --         --                                      0.2                                         1.8                                           --    --                                                   --                    XXIV            --                                       1.96                                         0.4                                           --    --                                                   --                    XXV             --                                      1.4                                         0.6                                           --    --                                                   --                    XXVI OH         --                                      -- --                                           Formula                                                 4.0                                                   2                                           Q = H                    XXVII                         OH         --                                      -- --                                           Formula                                                 3.2                                                   2                                           Q = CH.sub.3                    XXVIII                         --         --                                      -- --                                           Formula                                                 3.2                                                   2                                           O = CH.sub.3                    XXIX --         --                                      -- --                                           Formula                                                 0.1                                                   4__________________________________________________________________________ 
    
     Examples of thermoplastic polymer compositions in accordance with the invention are given in Table 2. 
     
                                           TABLE 2__________________________________________________________________________EXAMPLES OF POLYMER COMPOSITIONS                                          Composition properties                                                    MouldingsNumber of Components, Weight Parts             Butt      Released            Fatty Acid                    joint     from            Ester                         strength                                               Butt Injection            Example                       (conical                                               joint                                                    Mould            Number                        test strength                                                    without Thermoplastic            (cf.                          bars)                                               GOST DamageExample Polymer    Table 1)                  Other Additives                           Composition preparation                                          mPa  mPa  %1     2          3     4        5              6    7    8__________________________________________________________________________XXX   Bisphenel A            I; 0.5                  Ultranox Introduction of ester (during                                          28   62   99 polycarbonate    626/1 0.1                           production of polycarbonate (BPA polycarbonate)       as dissolved in CH.sub.2 CL.sub.2) 99.5                      Evaporation of the solventXXXI  BPA polycarbonate            II; 0.3                  Ultranox 626;                           Mixing of powdered poly-                                          29   66   99 99.7             0.2 TiO (rutile)                           carbonate with powdered                  2        esterXXXII BPA polycarbonate            III; 0.2                  Ultranox 626 0.1                           Mixing of powdered poly-                                          31   67   100 99.8                      carbonate with powdered esterXXXIII BPA polycarbonate            IV; 1.0                  Ultranox 626 0.1                           Mixing of powdered                                          24   58   98 79.0 Copolymer            thermoplastics with (Acrylnitrile-            powdered ester Butadiene-Styrene) 20.0XXXIV BPA polycarobnate            V; 0.5                  Ultranox 626 0.3                           Dissolution of ester in                                          29etone;                                               60   99 99.95            Glass fibre 20.0                           Mixing with powdered poly-                           carbonate; DryingXXXV  BPA polycarbonate            VI; 0.4                  Ultranox 626 0.1                           Mixing of powdered poly-                                          26   60   100 99.6             Tinuvin 326                           carbonate with powdered                  2 0.2    esterXXXVI BPA polycarbonate            VII; 0.6                  Ultranox 626 0.1                           Dissolution of ester in                                          27lene;                                               61   100 99.4                      Mixing with powdered poly-                           carbonate; DryingXXXVII BPA polycarbonate            VIII; 0.1                  Ultranox 626 0.2                           Mixing of molten                                          28   62   100 99.9             Carbon black 0.2                           ester with molten poly-                           carbonate during granulation                           processXXXVIII BPA polycarbonate            IX; 1.1                  Ultranox 626 0.2                           Introduction of ester (during                                          29   56   100 98.9             Glass fibre 40.0                           production of polycarobnate as                           dissovled in CH.sub.2 Cl.sub.2).                           Evaporation of solventXXXIX BPA polycarbonate            X; 5.0                  Ultranox 626                           Mixing of granular                                          28   62   99 95.0             0.3      polycarbonate with granular                           20% ester masterbatch in poly-                           esterXL    BPA polycarbonate            XI; 1.8                  Ultranox 626                           Mixing of powdered poly-                                          27   58   100 98.2             0.1 Tinuvin P                           carbonate with powdered ester                  0.2 0.3XLI   BPA polycarbonate            XII; 1.6                  Ultranox 626            28   56   99 98.4             0.2XLII  BPA polycarbonate            XII; 0.7                  Ultranox 626                           Mixing of powdered thermo-                                          23   52   99 79.3 Poly(ethylene                  0.1      plastics with powdered terephthalate)            ester 20.0XLIII BPA polycarbonate            XIV; 1.5                  Ultranox 626 0.2                           Dissolution of ester in                                          29etone,                                               60   100 98.5             Glass fibre 20.0                           Mixing with powdered                  Carbon black 0.3                           polycarbonate; DryingXLIV  BPA polycarbonate            XV; 0.8                  Ultranox 626                           Dissolution of ester in                                          28etone,                                               62   100 99.2             0.3      Mixing with powdered                           polycarbonate; DryingXLV   BPA polycarbonate            XXI; 0.3                  Ultranox 626                           Dissolution of ester in                                          24etone,                                               55   98 79.7 Poly(butylene                  0.3      Mixing with powdered terephthalate)            thermoplastics; Drying 20.0XLVI  BPA polycarbonate            XXII; 0.1                  Ultranox 626 0.3                           Mixing of granular                                          28   62   100 99.9             Glas fibre 30.0                           polycarbonate with granular                  TiO.sub.2 0.3                           10% ester masterbatch in poly-                           esterXLVII BPA polycarbonate            XVIII;                  Ultranox 626 0.3                           Mixing of granular                                          28   58   99 99.1       0.9            polycarbonate with granular                           20% ester masterbatch in poly-                           carbonateXLVIII BPA polycarbonate            XIX; 1.7                  Ultranox 626 0.2                           Mixing of powdered poly-                                          27   52   99 98.3             Tituvin 234 0.3                           carbonate with powdered                           esterXLIX  BPA polycarbonate            XX; 0.3                  Ultranox 626 0.1                           Dissolution of ester in                                          29etone,                                               59   100 99.7                      Mixing with powdered poly-                           carbonate; DryingL     BPA polycarbonate            XXI; 1.4                  Ultranox 626 0.3                           Mixing of Molten                                          26   54   100 98.6             Glass fibre 30.0                           ester with molten poly-                           carbonate during granulation                           process.LI    BPA polycarbonate            XXII; 0.2                  Ultranox 626 0.2                           Mixing of powdered poly-                                          28   59   100 99.8                      carbonate with powdered                           esterLII   BPA polycarbonate            XXIII;                  Ultranox 626 0.1                           Mixing of granular                                          26   58   100 99.7       0.3            polycarbonate with granular                           10% ester masterbatch in poly-                           carbonateLIII  Polyamide 6 99.5            XXIX; 0.5                  Glass fibre 25.0                           Mixing of Molten         74                           ester with molten poly-                           amide during granulation                           processLIV   Polyamide 6 99.7            XXV; 0.3                  --       Mixing of granular       76                           polyamide with granular                           10% ester masterbatch in poly-                           amideLV    BPA polycarbonate            XXVI; 0.1                  Ultranox 626 0.1                           Mixing of granular                                          25   60   99 99.9             Tinuvin P 0.3                           polycarbonate with granular                           ester masterbatch in poly-                           carbonateLVI   BPA polycarbonate            XXVII;                  Ultranox 626 0.3                           Mixing of powdered poly-                                          28   53   100 99.3       0.2            carbonate with powdered                           esterLVII  Polyoxymethylene            XXVIII;                  Irganox 259 0.6                           Mixing of powdered polyoxy-            0.5   Dicyandiamide                           methylene with powdered                  0.4      esterLVIII BPA polycarbonate            XXIX; 1.0                  Ultranox 626 0.3                           Dissolution of ester in                                                    100 one, 99.9                      mixing with powdered                           polycarbonate; DryingLIX   BPA polycarbonate            --    Ultranox 626 0.3                           --             46   88   80 100.0LX    BPA polycarbonate            --    Ultranox 626 0.3                           --             48   89   76 100.0LXI   Poyamide 6 --    Glass fibre 25.0                           --                        0LXII  Polyamide 6            --    --       --                        0LXIII Polyoxymethylene            --    Irganox 259 0.6                           -- 100.0            Dicyandiamide                  0.4__________________________________________________________________________ 1/ Manufacturer: Borg Warner 2/ Manufacturer: CIBA GEIGY 3/ Polycarbonate  injection moulding cf. FIG. 1 Polyamide  injection moulding cf. FIG. 2 Polyoxymethylene  injection moulding cf. FIG. 2 
    
     Thermoplastic polymer compositions according to the invention are prepared by adding from about 0.05 to 5.0 parts by weight to 100 parts by weight of dissolved, powdered, or granular high molecular weight thermoplastic polymer, preferably polycarbonate, polyamide, polyacetal, or poly(2,6-dimethyl-1,4-phenylene oxide) and mixing the constituents until a substantial homogeneous mixture is obtained. If desired, other components such as stabilizers, flame retardants, powdered and fibrous fillers, preferably staple glass fiber, and colorants and the like may be added to the mixture. The above-mentioned additives--that is, fatty acid esters of general formula 1, 2, or 3 are added as melts, powders, solutions, or as a master batch in the corresponding thermoplastic polymer. 
     Thermoplastic polymer compositions thus obtained are processed preferably by injection molding, extrusion molding, compression molding, and other processes used in processing of thermoplastics. In the course of tests, neither complete nor even partial sticking to processing molds or extruder dies nor blocking of the processing molds was observed. 
     Moreover, fatty acid esters of general formulae 1, 2, and 3 do not exert negative effects on the properties of moldings obtained from the thermoplastic polymer compositions in accordance with the present invention. 
     Various modifications of the present invention may be made without departing from the spirit and scope of the invention. It is to be understood, therefore, that the invention is not to be limited to the described embodiments, except as defined in the appended claims.