MXPA97004450A - Compositions of flammable thermoplastic resin - Google Patents

Abstract

The present invention relates to: flame-resistant thermoplastic resin compositions comprising (A) a base resin consisting of (1) about 75 to 96% by weight of a halogen-free, thermoplastic polycarbonate and (2) about 4 to 25% by weight of a styrene-containing graft copolymer having a grafting index of at least 40 and a gel content of at least 60% by weight, wherein the styrene-containing graft copolymer is grafted to the graft copolymer. to 45% by weight of a styrene, 5 to 15% by weight of an acrylonitrile and 0 to 20% by weight of an acrylate monomer, (B) about 5 to 20 parts by weight per 100 parts by weight of the resin (A) base, of a phosphate composition, (C) about 0.1 to 2.0 parts by weight, per 100 parts by weight of the base resin (A), of a perfluoroalkane polymer, and (D) about 0.1 to 10 parts by weight, per 100 parts by weight of the base resin (A), of a zeolite. As for the styrene-containing graft copolymer, a core-shell type graft copolymer can be preferably used. The phosphate composition is represented by the general formula (I): wherein R1, R2, R3, R4, or R5 independently of each other are C6-C20 aryl or C6-C20 aryl substituted with alkyl and n is 0 to 5 , and where the average n of the phosphate composition is on the scale of about 0.3 to

Description

COMPOSITIONS OF FLAME-PROOF THERMOPLASTIC RESIN Field of the Invention The present invention relates to flame-proof thermoplastic resin compositions, and specifically to those for molding, comprising a base resin consisting of a halogen-free polycarbonate and a graft copolymer containing base, a phosphate composition, a polymer of pe fluoralkane and a zeolite. The thermoplastic resin compositions of the present invention may further contain additives such as inorganic fillers, thermal stabilizers, colorants and / or pigments in fractions as needed.

BACKGROUND OF THE INVENTION Polycarbonate molding compositions are widely used for automotive parts and electrical appliances. They have a good combination of transparency, high resistance - impact and thermal resistance. However, the polycarbonate molding compositions do not have good processability during the molding process, so other resins have to be used with the polycarbonate resin. For example, a molding composition comprising a polycarbonate resin and a styrenic resin has good processability as well as high notch impact strength. The polycarbonate molding compositions used for housing materials of household appliances and computers must be flame resistant to prevent fires. For this purpose, hanogen and / or antimony containing compounds have been used to make the flame retardancy to the thermoplastic molding compositions. For example, U.S. Patent Nos. 4,983,658 and 4,883,835 describe the use of a halogen-containing compound as a flame retardant. The halogen-containing compound, however, results in the co-erosion of the mold itself due to the hydrogen halide gases not released during the molding processes which are fatally damaged due to the toxic gases released in the event of fire. U.S. Patent No. 4,692,488 discloses a thermoplastic molding composition comprising a halogen-free aromatic polycarbonate, a styrene-acrylonitrile halogen-extruded thermoplastic copolymer, a halogen-free phosphorus compound, a tetrafluoroethylene polymer. wood and polys of ABS grafting. The use of a phosphorus compound and a perfluoroalkan polymer to impart flame retardancy to a polycarbonate / ABS resin composition prevents the dripping of flaming particles during combustion. Even when the resin composition results in satisfactory flame retardancy, surface cracking can occur due to the flame retardant during a molding process of "bleeding", degrading the properties in this way. fícas of the resin composition. To prevent the degree phenomenon, an oligomeric phosphate can be used in polycarbonate / ABS resin compositions, as described in U.S. Patent No. 5,204,394. U.S. Patent No. 5,204,394 discloses a polymer blend comprising an aromatic polycarbonate, a copolymer containing styrene and / or graft co-liner containing styrene and an oligomeric phosphate or a mixture of oligomeric phosphates as a flame retardant. in the above-mentioned US Patents, representative examples of the phosphorus compound are triaging oligomeric phosphates and phosphates. When a strong shear stress is applied to the surface of resin compositions containing monomeric triaryl phosphates, the laminates tend to be fused on the surface. This can result in a bleeding phenomenon during the molding processes, which causes the thermal resistance of the resin compositions to be reduced. A bleeding phenomenon may not occur with oligo-rich triaryl phosphates, however, when oligomeric phosphates are added a resin with the same content as monomeric triaryl phosphate., the flame retardance of oligomeric phosphates is lower than that of monomeric triaryl phosphate. In addition, after exposure to elevated temperatures such as 80 ° C or higher for a period of time, the phosphate has a tendency to decompose and reduce to phosphoric acid. This phenomenon causes the mechanical properties of a flame retardant resin to degrade. And the tendency of deterioration of the mechanical properties due to the decomposition of phosphate is more severe in oligomeric phosphate compared to monomeric phosphate. In case of using a base resin comprising halogen-free polycarbonate, a styrene-containing graft copolymer and a styrene-containing copolymer in the resin position, the present inventors have found that the particles of the styrene-containing copolymer are agglomerated with the particles of the graft copolymer containing styrene no. It is believed that the styrene-containing copolymer does not have good compatibility with polycarbonates. In the sine composition, the particles of the graft copolymer containing reindeer are not uniformly distributed in the whole resin, thus causing an agglomeration. This phenomenon can not provide a resin composition with volatile physical properties, in particular, the physical properties of the resin composition deteriorate during a molding process. There are two types of a graft copolymer that has styrene, i.e., a hemisphere-type copolymer and a core-shell type copolymer, depending on the shell structure of the copolymer. In this invention, the present inventors have also discovered that the resin composition containing a core-shell-type styrene-containing graft copolymer has properties superior to the resin composition containing a graft copolymer containing styrene-type non-styrene. of hemisphere in thermal resistance, sa phenomenon, capacity of rpocesamiento, appearance and agglomeration of -particles. A zeolite is preferably used to improve the long-term thermal stability of the resin composition according to this invention. It is believed that a phosphate composition such as phosphates is reduced to a phosphoric acid by degradation thereof at an elevated temperature over a period of time. Accordingly, conventional polycarbonates show low mechanical properties, i.e., tensile strength, when held at an elevated temperature for a period of time. The addition of a zeolite to a polycarbonate resin provides excellent stability of mechanical strength at elevated temperatures over a period of time. It is believed that the zeolite absorbs part of the low molecular impurities and ions that can induce the degradation of the -resin. Consequently, in order to overcome the aforementioned disadvantages, the present inventors have developed adjunctly a new resin composition comprising a base resin consisting of a halogen-free polycarbonate, and a graft copolymer containing styrene, a composition of phosphate, a polymer of perfluoro lcano and a zeolite. t OBJECTS OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin composition that is reliable with a good combination of processability, appearance, flame retardancy and that does not exhibit bleeding phenomenon. This composition comprises a base resin consisting of a halogen-free polycarbonate and a graft copolymer containing styrene, a phosphate composition, a perfluoroalkane polymer and a zeolite. Another object of the invention is to provide a flame-proof thermoplastic resin composition having excellent mechanical strength stability at elevated temperature - (i.e., long term thermal stability, which comprises a base resin consisting of an exempt polycarbonate. of halogen, a graft copolymer containing styrene, a phosphate composition, a perfluoroalkane polymer and a zeolite A further object of the invention is to provide a flame-proof thermoplastic resin composition whose particles are uniformly dispersed without causing agglomeration with the change of processing conditions, comprising a base resin consisting of a halogen-free polycarbonate and a styrene-containing graft copolymer, a phosphate composition, a perfluoroalkane polymer and a zeolite. Another aspect of the present invention is to provide a resin composition Flame-proof opiatry whose molded articles have good impact resistance regardless of the thickness of the articles.

SUMMARY OF THE INVENTION The present invention relates to flame-proof thermoplastic resin compositions comprising (A) a base resin consisting of (1) about 75 to 96% by weight of a halogen-free polycarbonate, thermoplastic and (2) about 4 to 25% by weight of a graft copolymer containing styrene having a grafting index of at least 40 and a gel content of at least 60% by weight when the ABS resin is it dissolves in acetone, where the graft copolymer containing styrene is made by grafting 25 to 45% by weight of a styrene, 5 to 15% by weight of an acrylonitrile and 0 to 20% by weight of acrylate monomer to rubber of butadiene, (B) about 5 to 20 parts by weight, per 100 parts by weight of the resin (A of base, of a phosphate composition, (C) about 0.1 to 2.0 parts by weight, per 100 parts by weight weight of the resin (A) of b_ se, of a perfluoroalkane polymer, and (D) about 0.1 to 10 parts by weight, per 100 parts by weight of the resin (A) of ba se, of a zeolite. As for the graft copolymer which has styrene, a core-shell type graft copolymer can preferably be used. The phosphate composition is a mixture of oligomeric aryl phosphate. This phosphate composition is represented as the general formula (I): II where R ,, R, R, R, and Re independent of one another are aryl of Cg-C ri ° 9ri ^ - of C6"^ 20 substituted with alkyl and n is 0 to 5, and where the average of The phosphate composition is on a scale of about 0.3 to 0.8, Zeolite A or Zeolite X is preferably used in this invention, which are metal hydroxides of a metalic alu or having approximately 2 to 10 A. pore size The thermoplastic resin compositions of the present invention may further contain additives such as inorganic fillers, thermal stabilizers, colorants, and / or fractions, as needed.

Detailed Description of the Invention Flame-proof thermoplastic resin compositions according to the invention comprise a resin (A) -based, a phosphate composition (B), a perfluor-alkane (C) poly mer and a zeolite (D) Detailed descriptions of each component follow. i (A) Base Resin The base resin used in this invention is a mixture of a halogen-free polycarbonate, a thermoplastic and a graft copolymer containing styrene. More particularly, the base resin consists of from about 75 to 96% by weight of a thermoplastic, halogen-free polycarbonate and about 25 to 4% by weight of a styrene-containing graft copolymer.

In accordance with substituted groups of polycarbonate to, aromatic polycarbonates, aliphatic polycarbonates and aromatic / aliphatic polycarbonates are found, and a polycarbonate or a mixture of the polycarbonates can be used in this invention. Aromatic polycarbonates are preferable, and aromatic polycarbonates synthesized from 2,2'-bis (4-hydroxy-1-phenyl) propane, so-called "Bisphenol A", are preferred. There are two types of graft copolymer that contain styrene, that is, a hemisphere-type copolymer and a core-shell type LAD CODE, depending on the shell structure of the copolymer. In this invention, the present inventors have also discovered that the resin composition containing a graft copolymer containing core-co bre styrene has properties superior to the resin composition containing a graft copolymer containing styrene-like-type. in thermal stability, bleeding phenomenon, processability, appearance and particle agglomeration. In a process for preparing a hemisphere type or core-shell type of graft copolymer containing styrene which includes an ABS (acrylonitrile / butadiene / styrene), a conventional polymerization process can be employed by a person with ordinary experience in the field. An emulsion polymerization process may be preferably used to prepare a graft copolymer containing core-shell styrene in this invention. The styrene-containing graft copolymer is made by grafting 25 to 45% by weight of a styrene, 5 to 15% by weight of an acrylonitrile and 0 to 20% by weight of an acrylate monomer to butadiene rubber. In this invention, it is preferable that the styrene-containing copolymer has a grafting index of at least 40, and a gel content of at least 60% by weight, when the ABS resin is dissolved in acetone. The base resin of the present invention may contain a SAN (styrene / acrylonitrile) copolymer up to 10% by weight per 100% by weight of the base resin. It is preferable that the SAN lime coke contains approximately 60 to 90% by weight of styrene. The base resin of the invention consists of 75 to 96% by weight of a halogen-free polycarbonate, thermoplastic and 25 to 4% by weight of a graft copolymer containing core-shell styrene. If the amount of the polycarbonate is less than 75% by weight, the resin composition has low delay to reliability. on the other hand, if the amount of the polycarbonate is in excess of 96% by weight, the resin composition has low impact strength notched.

(B) Phosphate Composition The phosphate composition is an oligomeric mixture of aryl phosphate. The oleyogenic aryl phosphates are represented by the general formula (I): where R,, R2 », 4 and R? independent of each other are arc of C -C n ° ar i 1 ° of C6"C20 substituted with alkyl and n is 0 a and where the average of n of the phosphate composition is the scale of about 0.3 to 0.8. , the phosphate composition is a mixture of oligomeric phosphates represented by the formula (I), wherein n is 0, 1, 2, 3, 4 or 5. Where n is 0, the phosphate compositions are triaryl phosphates. In the case of N, where n is 1, 2, 3, 4 or 5, the phosphate compositions are oligomeric arylphosphates. The examples of triaryl phosphates are trigenylphosphate, tri (2,6-di met i lfeni 1) phosphate, tri (4), -methyl-phenyl) phosphate, tri-cre-silphosphate, diphenyl-2-eti-lcresi-phosphate, diphenyl-l-phosphate, tri-isopropyl-l-phenyl-1-phosphate, trixylenyl phosphate, xylene Idifeni-1-phanth, etc. When only monomeric phosphates with n = 0 used only in a resin composition, a bleed problem could appear during the molding process, because Monomeric triacylphosphates volatilize at approximately 230 ° C or higher. If a mixture of phosphates with an average of 0.8 or higher is used in a resin composition, a bleeding problem can be improved, but the flam delay and the physical properties of the resin deteriorate. Additionally, in the case of a mixture of phosphates having an average of 0.8 or higher, the phosphate mixture has a tendency to gradation and causes appearance problems such as black point and / or black band. Phosphates with an average n is about 0.3 to .8 can preferably be used in this invention in order to improve the physical properties as well as the flame retardation of the resin compositions. For the phosphate compositions to have an average of about 0.3 to 0.8, the phosphate compositions consist of 30 to 60% by weight of monomeric triarylphosphate 6 to 40% by weight of oligomeric aryl phosphates. Synthetic oligomeric arfosfostos can also be used in this invention, in which the average n of synthetic oligomeric aryl phosphates is 0.3 to 0.8. Synthetic oligomeric aryl phosphates are prepared by adding phenol, resorcinol and dichloromagnesium to benzene, heating the solution and leaving trichlorophosphonoxide in the solution. Synthetic oligomeric aryl phosphates with an average n of 0.3 to 0.8 are extracted from the resulting solution. The phosphate composition is used in an amount of about 5 to 20 parts by weight per 100 parts by weight of the base resin.

(C) Perfluoroalkane Polymer Flame-proof thermoplastic resin compositions in accordance with the present invention include a perfluoroalkane polymer. Examples of perfluoroalc polymers are not polytetrafluoroethane, polyvinylidene fluoride, copolymer of polytetrafluorocarbon and polyvinylidene fluoride, copolymer of tetrafluoroethane and fluoroalkyl ether, and tetrafluoroethylene copolymer and hexafluoropolymer. At least one of the perfluoroalkane polymers can be used in the flame-proof thermoplastic resin composition. The per-fluoroalkane polymer decreases the melt flow rate of the flame-retardant thermoplastic resin during combustion by forming a fibrous network in the resin and increases the shrinkage of the resin, thus preventing leakage of the resin from the resin. fusion during combustion. The perfluoroalkane polymer can preferably be used in a powder form so as to disperse and mix uniformly in a flame-proof thermoplastic resin composition. The polytetrafluoreti log with a particle size of 20 to 500 micrometers is conventionally available for this invention. 0.1 to 2.0 parts by weight of a perfluoroalkane polymer are mixed per 100 parts by weight of the base resin.

(D) Zeolite A zeolite is preferably used to improve the physical properties of the resin composition according to this invention. It is believed that a phosphate composition such as phosphates is reduced to a phosphoric acid by degradation thereof at an elevated temperature over a period of time. Accordingly, conventional polycarbonates show low mechanical properties, i.e., tensile strength, when held at an elevated temperature for a period of time. According to the present invention, the higher the average of n in formula (I), the lower the mechanical strength of polycarbonates after aging for a long time. Also, the mechanical strength of conventional polycarbonates decreases when they are maintained at 80 ° C or higher for many hours. The addition of zeol ta to a polycarbonate resin provides excellent stability of mechanical strength at elevated temperatures over a period of time, the zeolite absorbs some low molecular weight impurities and ions that could degrade the physical properties of the resin. In other words, the impurities and ions that are produced at an elevated temperature can be blocked in the pore of the zeolite. Zeolite A or zeolite X i is preferably used in this invention, which are metal hydroxides of an inosyl or alu having 2 to 10 A of pore size. Approximately 0.1 to 10 parts by weight of a zeolitc are mixed 100 parts by weight of the base resin. Flame-proof thermoplastic resin compositions may further include additives such as inorganic fillers, thermal stabilizers, oxidation inhibitors, light stabilizers, pigments and / or dyes depending on specific aolications. The examples of Iso inorganic fillers are as besto, fiberglass, talc or ceramic. Other additives are conventionally available to a person experienced in this technical field. The additives can be mixed in a resin composition with an amount of up to about -30 parts by weight Dor 100 parts by weight of the base resin. Flame-proof thermoplastic resin compositions are prepared by mixing a base resin, a phosphate composition, a perfluoroalkane polymer and a zeolite with a conventional mixer. An additive may be included in the mixture. Flame-proof thermoplastic resin compositions are prepared in a granular form by extruding the mixture with a conventional extruder. Flame-proof thermoplastic resin compositions have the effect that the compositions prevent the emission of toxic gases during combustion, and have a good combination of thermal resistance, procesabi 1, appearance, flame retardancy and stability of mechanical resistance at elevated temperatures (prolonged term thermal stability), and exhibit no bleeding phenomenon The invention can be better understood by reference to the following examples which are intended for the purpose of illustration, and are not to be construed in any way as limiting the scope of the present invention, which is defined in the claims appended hereto.

EXAMPLES The components for preparing the flame-proof thermoplastic resin compositions in Examples 1-4 and Comparison Examples 14 are as follows: (A) Base Resin (A, |) Polycarbonate: L-1225L Degree of teijin, Inc. from Japan was used. (A2) Graft copolymer containing n-core co-styrene 50 parts by weight of butadiene latex powder, 12 parts by weight of styrene, 4 parts by weight of acrylonitrile, and 150 parts by weight of deionized water were mixed, and 1.0 part by weight of turpentine soap, 0.2 parts by weight of tetrasodium pyrophosphate, 0.4 parts by weight of glucose, 0.006 parts by weight of ferrous sulfate, 0.25 parts by weight of cumene and droperoxide and 0.2 parts by weight of tertiary tertiary mercaptan were added to the mixed solution. The resulting solution was maintained at 75 ° C for 1 hour. 26 parts by weight of styrene, 8 parts by weight of acrylonitrile, 0.25 parts by weight of peroxide and 0.2 parts by weight of tertiary mercacaptane were added to the mixed solution for 3 hours to provide ABS graft polymer of core-shell type. . In the core-shell type ABS graft polymer latex, 1% FLSO was added to provide powder-coated core-shell type ABS resin. (Ag) Graft copolymer containing hemisphere styrene. 50 parts by weight of butadiene latex powder, 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, and 150 parts by weight of deionized water were mixed, and 1.0 parts by weight of potassium oleate, 0.4 parts by weight of copper peroxide and 0.3 parts by weight of a grafting reagent were added to the mixed solution. The resulting solution was maintained at 75ec for 5 hours to prepare graft cooolymer containing styrene. The styrene-containing graft copolymer - 0.3 parts by weight of H ?S0 was added. oara pro-oxidize hemisphere powder-type ABS resin.

(B) Composition of phosphate (B.,) Triphenyl phosphate (n = 0): A triphenylphosphate was used from Daihachi Co., of Jaon. (B2) Oligomeric phosphate (n = 1.3): CR-733S from Daihachi Co. of Japan was used. (B3) synthetic oligomeric phosphate: 114.7 g of phenol, 200 g of resorcinol, and 0.2 g. of agnesium dichlor were added to 100 ml of benzene. The solution was heated to 70 ° C. they dripped -82.8 g. of trichlorophosphine oxide in the solution for 2 hours at a temperature of 70 ° C. The resulting solution was stirred at 120 ° C for 3 hours to no longer release hydrogen chloride gas. The solvent and the impurities were extracted from the solution in order to prepare synthetic oligomeric phosphate in liquid at room temperature having n of 0.6 in the general formula (I).

(C) Percluoroalkane polymer Teflon (registered trademark) 7AJ from Mitsui Dupont, Inc. of Japan was used.

(D) Zeolite 13X Zeolite from Union Carbide Corp. of E.U.A.

Examples 1-4 and Comparative Examples 1-4 The compositions of each component used in Examples 1-4 and Comparative Examples 1-4 and the physical properties are shown in Table 1. In the Examples and Comparison Examples, the components were mixed and extruded in a ring shape with a twin screw extruder at 250 ° C. And the resin beads were molded into test specimens.

Table 1 Examples Examples of comparison speakers 2 3 1 2 3 5) (A ^) ool icarbonate 90 90 90 90 90 90 90 90 (A2) core-shell type 10 10 (Ag) hemisphere type 10 10 10 10 10 10) (B.,) TPP (n = 0) 8 8 (B2) CR-733S (n = 13) 8 8 B3) ( n = 0.6) 8 8 8 8) Teflon (R) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5) Zeolite 13X 0.6 0.6 0.6 0.6 Melting rate 240 270 240 270 240 270 240 270 adro 1 (continued) Examples Comparison Examples 2 3 1 2 3 4 Physical properties 94 VB (1.59 mm) * VO VO VO VO VO VI VI Impact resistance (3.18 m) ** 58.60 62 59 65 60 60 55 Impact resistance (6.35 mm) ** 32 29 33 15 35 18 26 12 Thermal resistance (VST) *** 106 106 106 106 04 104 108 108 ngrado **** XXXX 0 0 XX prolonged thermal thermal stability * **** 22885500 22778800 22554400 22555500 1980 1990 1410 1380 two component numbers are in grams) * UL 94 VB (1.59 mm) was tested in accordance with UL 94 VB. ** Resistance to impact (kgf * cm / cm) was tested in accordance with ASTM D256 *** Thermal resistance was tested in accordance with ASTM D306, **** Bleeding was observed with an optical microscope, after the specimens were stored at 80 ° C for 24 hours. (X: No bleeding was observed, 0: bleeding was observed) ***** time (hours) reaching the tensile strength at half the initial tensile strength when the sample specimens were kept in an oven 100 s C As shown in Table I, Examples 1-4 in accordance with the present invention show good physical properties in flame retardancy, impact resistance, heat resistance, bleeding and prolonged term thermal stability. Comparison Examples 1 and 2 show bleeding phenomenon. Examples 3 and 4 of Comparison are low in retardation ds flame and long term thermal stability. Particularly, Example 1 is superior to Comparative Example 3 in prolonged term thermal stability. In example 1, the resistance the 6.35 mm Izod device retains its property regardless of the molding temperature. It is evident from the foregoing that many modifications and changes are possible without abandoning the spirit and scope of the present invention. fifteen

Claims (8)

CLAIMS:

1. - A flame-proof thermoplastic resin composition comprising: (A) a base resin consisting of (1) approximately 75 to 96% by weight of a halogen-free, thermoplastic polycarbonate and (2) about 4 to 25% by weight of a graft copolymer containing styrene, having a grafting index of at least 40 and a gel content of at least 60% by weight; (B) about 5 to 20 parts by weight, per 100 parts by weight of the base resin (A), of a phosphate composition of the general formula: 0 0 II II wherein R., R2, Rg, R * and p- independently of one another are aryl of C5_C 0 ° ari ^ ° of ^ d ~ C20 substituted with alkyl and n is 0 to 5, and wherein the average n of the composition of phosphate is on the scale of approximately 0.3 to 0.8. i (C) about 0.1 to 2.0 parts by weight, per 100 parts by weight of the base resin (A), of a perfluorinated alkane polymer; and (D) about 0.1 to 10 parts by weight, per 100 parts by weight of the base resin (A), of a zeolite.

2. The thermoplastic resin composition of claim 1, wherein the graft copolymer it contains is styrene is a graft copolymer containing core-shell type styrene.

3. The thermoplastic resin composition of claim 1, wherein the graft copolymer it contains is tyrosine by grafting 25 to 45% by weight of a styrene, 5 to 15% by weight of an acrylonitrile and 0 to 20% by weight of an acrylate monomer to butadiene rubber.

4. The thermoplastic resin composition of claim 1, wherein the graft copolymer it contains is tireno, an ABS resin.

5. The thermoplastic resin composition of claim 1, wherein the perfluoroalkane polymer is selected from the group consisting of polytetrafluorocarbon. polyvinylidene fluoride, copolymer of tetraf luoreti wood and vinylidene fluoride, copolymer of tetrafluoreti wood and fluoroalkyl vinyl ether, and copolymer of tetrafluoreti wood and hexafluoropropylene.

6. The thermoplastic resin composition of claim 1, wherein the zeolite is zeolite A or X having 2 or 10 A pore size.

7. The thermoplastic resin composition of claim 1, wherein the resin composition also includes inorganic fillers, thermal stabilizers, oxidation inhibitors, light stabilizers, pigments and / or dyes. SUMMARY OF THE INVENTION: The present invention relates to flame-proof thermoplastic resin compositions comprising (A) a base resin consisting of (1) about 75 to 96% by weight of a halogen-free, thermoplastic polycarbonate and (2) about 4 to 25% by weight of a graft copolymer containing styrene having a graft index of at least 40 and a gel content of at least 60% by weight, wherein the styrene-containing graft copolymer it is made by grafting 25 to 45 by weight of a styrene, 5 to 15% by weight of an acrylonitrile and 0 20% by weight of an acrylate monomer, (B) about 5 to 20 parts by weight per 100 parts by weight of the base resin (A), of a phosphate composition, (C) about 0.1 to 2.0 parts by weight, per 100 parts by weight of the base resin (A), of a perfluoroalkane polymer, and (D) ) about 0.1 to 10 parts by weight, per 100 parts by weight of the base resin (A), of a zeolite. As for the graft copolymer containing styrene no, a graft-shell-type graft copolymer can be used preferably. The phosphate composition is a mixture of oligomeric aryl phosphates. The phosphate composition is represented by the general formula (I): wherein R., R2 > Rg, R * u Rr independently of one another are Cg-C20 aryl or CC-C2Q aryl substituted with alkyl and n is 0 to 5, and where the average n of the phosphate composition is on the scale of about 0.3 to 08.