Document DvwK2DwDr9aM5qkQ07000gZoB

United States Patent ti9] Mizuno et al. nu 4,222,926 [45] Sep. 16, 1980 [54] FLAME-RETARDANT THERMOPLASTIC POLYESTER RESIN COMPOSITIONS [75] Inventors: Shioji Mizuno, Osaka; Norio Enokimoto, Izumi, both of Japan [73] Assignee: Dainippon Ink & Chemicals, Inc., Tokyo, Japan [21] Appl. No.: 893,349 [22] Filed: Apr. 4,1978 [30] Foreign Application Priority Data Apr. 15. 1977 [JP] Japan.................................... 52/43347 [51] Int CL2.........................C08K 3/10; C08K 5/02; C08K 5/03; C08K 67/02 [52] U.S. CL .......................... 260/40 R; 260/45.7 R; 260/45.7 S; 260/45.75 R; 260/45.75 V; 260/45.75 B; 525/56; 525/57; 525/58; 525/60; 525/165; 525/169; 525/171; 525/176; 525/439; 525/440; 525/441 [58] Field of Search.......... 260/873, 45.75 R, 45.7 R, 260/45.7 S, 45.7 V, 40 R, 45.75 V, 45.75 B; 525/56, 57, 58, 60 [56] References Cited U.S. PATENT DOCUMENTS 3,887,649 3,904,707 3,975,354 3,988,388 6/1975 9/1975 8/1976 10/1976 Takida et al............................. 260/873 Gebhart et al........................... 260/873 Buxbaum et al..................... 260/40 R Alberts et al............................ 260/862 OTHER PUBLICATIONS Lyons, The Chem. and Uses ofFire Retardants, (Wiley, 1970), pp. 21, 23. Primary Examiner--J. Ziegler Attorney, Agent, or Firm--Sherman & Shalloway [57] ABSTRACT A flame-retarding thermoplastic polyester resin compo sition comprising (1) a polyester obtained from a terephthalic acid or an alkyl ester thereof and a glycol having 2 to 4 carbon atoms, (2) an organohalogen compound, (3) an inorganic flame-retarding supplementary agent, and (4) at least one polymer selected from a saponified polyvinyl acetate having a saponification degree of greater than 50%, an ethylene/vinyl acetate copolymer and a saponified ethylene/vinyl acetate copolymer, and optionally (5) a reinforcing agent; and a process for production thereof. 18 Claims, No Drawings 4,222,926 12 drip, as well as to provide a process for producing the FLAME-RETARDANT THERMOPLASTIC same. POLYESTER RESIN COMPOSITIONS Another object of the present invention is to provide polyester resin molded articles having excellent physi The present invention is concerned with flame- 5 cal properties and appearance and which, even when retardant thermoplastic polyester resin compositions. exposed to flame, do not allow the melt to drip. More specifically, the present invention deals with im Other objects of the present invention will become proved flame-retardant thermoplastic polyester resin obvious from the below-mentioned description. compositions which even when exposed to flame do not The inventors of the present invention have found allow the melt to drip. 10 that the abovementioned objects of the present inven Thermoplastic polyesters obtained by the reaction of tion can be fulfilled by the compositions which are a terephthalic acid or an alkyl ester thereof with a gly obtained by adding to the polyesters at least one poly col having 2 to 4 carbon atoms, have been extensively mer (hereinafter often referred to as a drip-preventing used as materials for producing fibers and molded arti agent) selected from a saponified polyvinyl acetate hav cles. Such polyesters, in general, have melting points 15 ing a saponification degree of greater than 50%, an higher than 200" C. and have increased resistance ethylene/vinyl acetate copolymer and a saponified against heat. Further, because of their high crystallinity, ethylene/vinyl acetate copolymer, in addition to a the thermoplastic polyesters exhibit small water absorp flame-retarding agent (organohalogen compound), an tion properties. Furthermore, their excellent properties inorganic flame-retarding supplementary agent (metal such as mechanical properties, electric properties and 20 oxides, etc.) and optionally a reinforcing agent (glass resistance against chemicals, make the polyesters very useful materials. Moreover, the compositions obtained fiber, etc.) and heating and kneading the mixture. Thus, according to the present invention, there are by blending a reinforcing agent such as a glass fiber into the polyesters, are used as materials for injection mold ing owing to their excellent mechanical properties and resistance against heat. However, these polyesters and reinforcing agentcontaining polyesters catch fire if they are brought into contact with a flame and continue to bum even after the 25 30 provided flame-retarding thermoplastic polyester resin compositions comprising; (1) a polyester obtained from a terephthalic acid or an ester thereof, and a glycol having 2 to 4 carbon atoms; (2) an organohalogen compound; (3) an inorganic flame-retarding supplementary agent; and source of the flame is removed. (4) at least one polymer selected from a saponified A variety of methods have been proposed to give polyvinyl acetate having a saponification degree of flame-retardant property to the polyesters. For exam greater than 50%, an ethylene/vinyl acetate co ple, a method by which an organohalogen compound is polymer and a saponified ethylene/vinyl acetate blended into a polyester (Japanese Patent Publication 35 copolymer; and optionally No. 15,555/69), a method by which a flame-retarding (5) a reinforcing agent, agent such as phosphorus compound is blended into a as well as a process for producing said compositions by polyester (Japanese Patent Publication No. 22,958/74), heating and kneading the aforementioned components. a method by which a flame-retarding agent is included The aforementioned polyester (1) of the present in in the polymer skeltal structure of a polyester by a 40 vention obtained from a terephthalic acid or an alkyl chemical reaction (U.S. Pat. No. 3,883,611), and a ester thereof and a glycol having 2 to 4 carbon atoms method by which an inorganic flame-retarding assistant may concretely be a polyethylene terephthalate, poly such as antimony compound is blended into a flame- propylene terephthalate or a polybutylene terephthal retarding agent-containing polyester in order to in ate. The polyester, usually, has an intrinsic viscosity [tj] crease the flame-retarding property (U.S. Pat. No. 45 of 0.5 to 1.5 deciliters/gram (as measured in a mixture 3,873,491). Although the flame-retardant polyesters solvent of phenol and ethane tetrachloride at a weight obtained by the aforementioned methods are provided ratio of 6 to 4, at 30" C.). Such polyester (1) is usually with satisfactory flame-retarding properties, they still synthesized by the polycondensation of a terephthalic have a probability of presenting secondary fire, because acid as an acid component or an alkyl ester thereof with when they are formed into thin sheets (of a thickness of, 50 a glycol having 2 to 4 carbon atoms as an alcohol com for example, less than 1.6 mm), the melt of the polyester ponent, i.e., with an ethylene glycol, a propylene glycol exposed to the flame easily undergoes dripping. To or a butylene glycol. Here, less than 40 mole% of the prevent the dripping of the melt, it was attempted to acid component or the alcohol component may be sub incorporate an elongated whiskered substance (i.e., stituted by other acid or alcohol, respectively. Exam asbestos) into the flame-retarding polyesters (U.S. Pat. 55 ples of such other acid components are aliphatic dicar- No. 3,751,396), to add a tetrafluoroethylene (U.S. Ser. boxylic acids such as adipic acid, sebacic acid, and No. 140,596), and to add a fumed colloidal silica (U.S. lower alkyl esters thereof; alicyclic dicarboxylic acids Ser. No. 176,316). The polyesters obtained according to such as cyclohexane dicarboxylic acid, and lower alkyl these methods, however, contain the aforesaid various esters thereof; and aromatic dicarboxylic acids such as substances that are not compatible with the polymer. 60 isophthalic acid and alkyl esters thereof. Examples of Therefore, when formed into molded articles, the re such other alcohol components are aliphatic glycols sulting products exhibit poor appearance, poor physical such as 1,3-butane diol, 1,6-hexane diol; alicyclic gly properties and poor stretchability. cols such as 1,4-cyclohexane dimethanol; and aromatic Therefore, it is a primary object of the present inven glycols such as 4,4'-hydroxyethyl-oxyphenyl propane. tion to provide flame-retarding thermoplastic polyester 65 Further, less than 40% by weight of the polyester (1) compositions which give good molded articles having may be substituted by a thermoplastic resin such as excellent physical properties and appearance and polyolefin, polystyrene, ABS, acrylic resin, vinyl ace which, when exposed to flame, do not allow the melt to tate resin, polyacetal, polycarbonate, polyurethane or 4,ZZZ,!9Z0 34 the like. Further, a high-molecular weight polyester tary agent (3) are antimony trioxide, antimony pentox- polyurethane composed of a low-molecular weight ide, antimony trisulfide, antimony trichloride, antimony polybutylene terephthalate having hydroxyl groups at pentachloride, antimony tribromide, antimony penta- the terminals (an intrinsic viscosity [tj]=0. 15 to 0.5 bromide, barium metaborate, lead borate, aluminum diciliter/gram) of which molecular weight is increased 5 hydroxide, zirconium oxide, molybdenum oxide and the by a polyfunctional isocyanate, such as aromatic, ali like. phatic or alicyclic diisocyanate (Japanese Patent Laid- It is usually suitable that the contents of the inorganic Open No. 99741/74) may also be used as the polyester flame-retarding supplementary agent (3) contained in (D- the composition of the present invention range from 0.5 Preferred examples of the alkyl esters of the tereph- 10 to 20 parts by weight, preferably from 3 to 10 parts by thalic acid used as a starting material of the polyester (1) weight per 100 parts by weight of the polyester (1). If may be lower alkyl esters, particularly methyl esters the amount is less than 0.5 part by weight, the flame- and ethyl esters. retarding property of the polyester is not sufficiently The organohalogen compound (2) of the present exhibited. If the amount exceeds 20 parts by weight, on invention imparts flame-retarding property to the poly 15 the other hand, the properties of the polyester are dete ester, and possesses two or more chlorine and/or bro riorated. mine atoms in one molecule. Concrete examples are As mentioned earlier, the polymer (4) which is used aliphatic halogen compounds such as tetrabromoe- as a drip-preventing agent in the present invention is thane, l,2-dibromo-l,l,2,2-tetrachloroethane, 1,2- selected from (i) a saponified polyvinyl acetate having a dibromo-3-chloropropane, 1,2,3-tribromopropane, 20 saponification degree of greater than 50%, (ii) an 1,2,3,4-tetrabromobutane, and chlorinated paraffin; aro ethylene/vinyl acetate copolymer, and (iii) a saponified matic halogen compounds such as hexabromobenzene, ethylene/vinyl acetate copolymer. pentabromotoluene, pentabromophenol, tetrabromoph- The saponified polyvinyl acetate (i) having a poly thalic anhydride, tetrachlorophthalic anhydride, merization degree of from 300 to 3,000, and a saponifi 3,3',5,5'-tetrabromobiphenyl ether, 3,3',5,5'-tetra- 25 cation degree of greater than 50% is_usually suitable. chlorobiphenyl ether, 3,3',5,5'-tetrabromobiphenyl sul Examples are GOHSENOL NL-05 (P=500, saponifi fide, 3,3',5,5'-tetrachlorobiphenyl sulfide, 3,5-dichloro- cation degree of greater than 98.5%, produced by The 3',5'-dibromobiphenyl sulfide, 2,4-dichloro-3',4',5'-tri- Nippon Synthetic Chemical Industry Co., Ltd.), GOH bromobiphenyl methane, decabromobiphenyl ether, SENOL NM-14 (P=1400, saponification degree of 2,2',4,4',6,6'-hexachlorobiphenyl, 2,2',4,4',6,6'-hexa- 30 greater than 99%, produced by The Nippon Synthetic bromobiphenyl, tetrabromobisphenol A, tetrachlorobis- Chemical Industry Co., Ldt.), GOHSENOL NH-20 phenol A, or the reaction products of tetrabromobis (P=2000, saponification degree of greater than 99%, phenol A with epichlorohydrin, or brominated naph produced by The Nippon Synthetic Chemical Industry thalene or tetrabromophthalimide; or perchlorocyclo- Co., Ltd.), GOHSENOL GL-08 (P=1100, saponifica decane, tris-(2,3-dibromopropyl) isocyanulate, tris-(2- 35 tion degree of greater than 85%, produced by The bromoethyl) phosphate, tris-(2,3-dichloro)phosphate, Nippon Synthetic Chemical Industry Co., Ltd.), and tris-(2,3-dibromo) phosphate, tris-(2,4,6-tribromophe- GOHSENOL GH-17 (P=2100, saponification degree nyl) phosphate, and the like. Among these compounds, of greater than 85%, produced by The Nippon Syn aromatic halogen compounds are most preferred. The thetic Chemical Industry Co., Ldt.). aforementioned organohalogen compound (2) may be 40 The ethylene/vinyl acetate copolymer (ii) should used in combination with a phosphorus compound such preferably have a vinyl acetate content of greater than as trimethyl phosphite, dimethyl phosphonate, diamyl 50% by weight and a Mooney viscosity of 10 to 80, and phosphonate, tributyl phosphonate, 2-ethylhexyl di more preferably a vinyl acetate content of 60 to 90% by phenyl phosphonate, triphenyl phosphate, tricresyl weight and a Mooney viscosity of 20 to 70. The phosphate, or the like. 45 ethylene/vinyl acetate copolymer (ii) can be prepared It is usually suitable that the contents of the or by a known polymerization method, or preferably by an ganohalogen compound (2) contained in the composi emulsion polymerization method. Concrete examples of tion of the present invention range from 2 to 30 parts by the ethylene/vinyl acetate copolymer (ii) are EVATH- weight, preferably from 5 to 20 parts by weight calcu LENE 310 (vinyl acetate content of 70% by weight, lated as halogen, per 100 parts by weight of the polyes 50 Mooney viscosity of 55, a product of Dainippon Ink ter (1). If this amount is less than 2 parts by weight, the And Chemicals, Inc.), EVATHLENE 420 (vinyl ace flame-retarding property of the polyester is not suffi tate content of 60% by weight, Mooney viscosity of 35, ciently exhibited. On the other hand, if the amount a product of Dainippon Ink And Chemicals, Inc.), and exceeds 30 parts by weight, the properties of the polyes the like. ter are remarkably deteriorated. 55 Preferred examples of the saponified ethylene/vinyl Examples of the inorganic flame-retarding supple acetate copolymer (iii) are those which are obtained by mentary agent (3) are oxides, sulfides, halides, borates, saponifying the aforesaid ethylene/vinyl acetate co metaborates, sulphates, carbonates and hydroxides of polymer. The saponification degree may lie over a metals. These compounds work to further enhance the given range; however, the copolymer should preferably flame-retarding effects of the organohalogen compound 60 be saponified to an increased degree because it exhibits (2) which is used as a flame-retarding agent. Preferred improved compatibility with the polyester. A concrete examples of metals constituting the inorganic flame- example of the saponified ethylene/vinyl acetate co retarding supplementary agent (3) are antimony, bis polymer may be a GL Resin (a product of The Nippon muth, arsenic, zirconium, barium, lead and aluminum. Synthetic Chemical Industry Co., Ltd.). Among these metals, antimony, bismuth and arsenic 65 The polymer (4) having higher molecular weight (metals of the Group Vb) are preferred examples, and exhibits increased drip-preventing effect (effect for pre antimony is a particularly preferred example. Concrete venting the melt from dripping when the polyester is examples of the inorganic flame-retarding supplemem- exposed to flame). However, if the molecular weight is 4,222,926 56 too great, the copolymer may often exhibit decreased ther contain a nucleating agent, pigments, dyes, plasti compatibility with respect to the polyester. It is usually cizers, parting agent, lubricant, heat stabilizer, anti-oxi- suitable that the contents of the polymer (4) in the com dizing agent, ultraviolet ray absorbing agent, foaming position of the present invention range from 0.5 to 30 agent, coupling agent and the like. parts by weight, preferably from 1 to 20 parts by weight 5 The compositions of the present invention will find per 100 parts by weight of the polyester (1). If the extensive applications, and are particularly useful for amount is smaller than 0.5 part by weight, the drip-pre molding applications. Examples of the articles formed venting effect becomes poor, and if the amount is from the compositions of the present application will be greater than 30 parts by weight, the compatibility is injection-molded products such as sheets, tubes, coil deteriorated with respect to the polyester. Among the 10 bobbins, connectors, switches, cases and the like. The polymers (4), the ethylene/vinyl acetate copolymer (ii) compositions of the present invention are particularly exhibits the most excellent drip-preventing effects. suited for the applications where flame-retarding prop However, the increase of the amount in the composition erty is required. The compositions can usually be pro tends to deteriorate the compatibility with respect to cessed by the injection molding method. the polyester (1). The saponified product (i) and the 15 The present invention is concretely illustrated below saponified product (iii), on the other hand, exhibit some with reference to non-limitative Examples. In all Exam what smaller drip-preventing effects, but provide excel lent compatibility with respect to the polyester (1). ples, parts are all by weight. The flame-retarding properties of each of the Exam Therefore, it is preferable to use the ethylene/vinyl ples are measured and evaluated in accordance with the acetate copolymer (ii) in combination with the saponi 20 Subject 94 of Underwriters' Laboratories Standards fied polyvinyl acetate (i) or the saponified ethylene/vi (UL 94). Sheets of length of 5 inches, width of \ inch, nyl acetate copolymer (iii), because they help obtain excellent drip-preventing effect even if used in rela tively small amounts and, eventually, giving improved compatibility with the polyester. Owing to the use of 25 the polymer (4) which exhibits excellent compatibility with respect to the polyester (1), the present invention makes it possible to obtain molded articles having good and thickness of 1/16 inch or 1/32 inch formed by the injection molding are used as test specimens. A blue flame of a height of J inch without yellow tip is used as a source of flame, which is obtained by burning a gas of 1000 BTU composed principally of a methane gas using a burner having an inner diameter of inch and a length appearance with good processability, without deterio of 4 inches. A first test is performed by so holding the rating the mechanical properties of the polyester and 30 test piece that its longer side is in a vertical direction, often complementing the brittleness of the polyester exposing the test piece to the flame for 10 seconds such that is caused by the blended flame-retarding agent. that the distance between the lower end of the test piece The composition of the present invention may often and the upper end of the flame is 1 inch, and then re contain the reinforcing agent (5). Examples of the rein moving the source of flame to record the flame-sustain forcing agent (5) may be a glass fiber, cellulose fiber, 35 ing (flaming) time. Immediately after the flame has cotton fabric, paper, synthetic fiber, metal powder, extinguished, a second test is performed by exposing glass beads, asbestos, calcium silicate, magnesium sili again the test specimen to the flame for 10 seconds in cate, talc, and calcium carbonate. The glass fiber is the same manner as above, and removing the source of particularly preferred because it serves to strikingly flame to record the flame-sustaining time. If the drips of increase the mechanical strength of the composition in 40 metal fall from the test piece during these two testing proportion to the incorporated amount of the glass steps, the specimen is evaluated as "melt dripped". If no fiber, and further contributes to increase the resistance drip falls, the specimen is evaluated as "melt did not against the heat. Furthermore, the composition of the drip". Further, if the flame is extinguished within 10 present invention containing large amounts of the glass seconds in the first and second tests accompanied by the fiber exhibits good drip-preventing effect even if the 45 non-dripping of melt, the specimen is evaluated as V-0, contents of the polymer (4) is small. Preferably, the if the flame is extinguished within 30 seconds accompa glass fiber should be treated with a vinyl silane, amino nied by the non-dripping of melt, the specimen is evalu silane or a coupling agent of the epoxy type. The glass ated as V-l, and if the flame is extinguished -within 30 fiber may be in the form of either a roving glass or a seconds accompanied by the dripping of melt, the speci chopped strand glass. It is desired that the glass fiber 50 men is evaluated as V-2. present in the molded articles has a length over the range of from 0.01 to 30 mm, preferably from 0.1 to 1 EXAMPLE 1 mm. 51.6 Parts of a polybutylene terephthalate having an The reinforcing agent (5) when used in the composi intrinsic viscosity [tj]=0.8 dl/g obtained from a di tion is usually contained in an amount of 7 to 200 parts 55 methyl terephthalate and a 1,4-butane diol by a conven by weight, preferably from 20 to 150 parts by weight tional polymerization method, 10 parts of a deca- per 100 parts by weight of the polyester (1). If the bromobiphenyl ether as a flame-retarding agent, 2.4 amount of the reinforcing agent (5) exceeds 200 parts by parts of antimony trioxide as an inorganic flame-retard weight, the processability of the composition becomes ing supplementary agent, 30 parts of a chopped strand poor. 60 glass fiber of a length of 3 mm treated with an aminosi- The components for preparing the composition of the lane-type coupling agent as a reinforcing agent, 4 parts present invention can be mixed by a customary manner, of an ethylene/vinyl acetate copolymer (EVATH- but should preferably be mixed using an extruder. When LENE@ 310P, a product of Dainippon Ink And using the extruder, the heating temperature should pref Chemicals, Inc.), and 2 parts of a saponified ethylene/- erably from 180 to 300 C., and the mixing time should 65 vinyl acetate copolymer (GL Resin, a product of the preferably be from 0.2 to 30 minutes. Nippon Synthetic Chemical Industry Co., Ltd.) as drip In addition to the aforementioned components (1) to preventing agents, were uniformly mixed together. The (5), the composition of the present invention may fur thus obtained mixture was supplied to a 65-mm full- 4,222,926 78 flighted extruder with vent heated at 250" C., plasti The thus obtained composition was tested in the same cized, kneaded, extruded and cooled to obtain pellets. manner as in Example 1, to obtain the following results. Test pieces were prepared from the pellets using an TS was 1200 kg/cm2, TE was 2.0%, FS was 1600 injection molding machine, and measured for their kg/cm2, and II was 6 kg.cm/cm. The flame-retarding physical properties in accordance with ASTM. The 5 property was evaluated as UL 94 V-0 (using a test piece results were as follows: a tensile strength (hereinafter having a thickness of 1/32 inch). abbreviated as TS) of 1100 kg/cm2; a tensile elongation The procedure was conducted in the same manner as (hereinafter abbreviated as TE) of 2.5%; a flexural in Example 2 but using 42.5 parts of a polyester polyure strength (hereinafter abbreviated as FS) of 1500 thane obtained by the reaction of 100 parts of a low kg/cm2; and a notched Izod impact strength (hereinaf- 10 molecular polybutylene terephthalate having OHV = 15 ter abbreviated as II) of 8 kg.cm/cm. and AN=0 with 5 parts of a diphenylmethane-4,4'- In the case of a test piece of a thickness 1/32 inch, the diisocyanate in place of 42.5 parts of the polyethylene flame-retarding property was evaluated as UL 94 V-0, terephthalate that was used in Example 2. The results and the dripping of the melt was not at all recongized. were as follows: TS of 1350 kg/cm2, TE of 2.5%, FS of Further, even when the flame of the flame source was 15 1700 kg/cm2, II of 8 kg.cm/cm, and the flame-retarding brought into contact with the test piece having a thick property was evaluated as UL 94 V-0 (using a test piece ness of 1/32 inch and maintained under this condition having a thickness of 1/32 inch). for 60 seconds, the dripping of the melt was not at all exhibited. EXAMPLE 4 Comparative Example 1 20 70 Parts of a polybutylene terephthalate having an intrinsic viscosity of [t)] = 1.0 dl/g, 15 parts of a deca- The procedure was repeated in the same manner as in bromobiphenyl ether, 5 parts of antimony trioxide, and Example 1 but without using the dip-preventing agent, 10 parts of a saponified polyvinyl acetate (GOH and changing the amount of the glass fiber to 27.4 parts, SENOL G-17) having a polymerization degree of 2100 to obtain the following results. 25 and a saponification degree of higher than 86%, were TS was i i 50 kg/cm2, TE was 1.5%, FS was 1600 uniformly heated and kneaded at 230 C. kg/cm2 and II was 5 kg.cm/cm. The thus obtained composition was tested in the same In the case of a test piece having a thickness of 1/32 manner as in Example 1 to obtain the following results. inch, the flame-retarding property was evaluated as UL TS was 600 kg/cm2, TE was greater than 100%, FS 94 V-2,and the dripping of melt was recognized. Fur- 30 was 850 kg/cm2, II was 4 kg.cm/cm, and the flame- ther, when the test piece having a thickness of 1/32 inch retarding property was evaluated as UL 94 V-0 (using a was brought into contact with with flame in the same test piece having a thickness of 1/16 inch). manner as in Example, the melt started to drip after 15 seconds have passed. EXAMPLE 5 EXAMPLE 2 35 70 Parts of a polybutylene terephthalate having an intrinsic viscosity of [17]= 1.0 dl/g, 15 parts of a hexa- 42.5 Parts of a polyethylene terephthalate having an bromobenzene, 5 parts of antimony trioxide and 10 parts intrinsic viscosity [tj] = 0.8 dl/g, 14 parts of an epoxy of an ethylene/vinyl acetate copolymer (EVATH resin (epoxy equivalent of 1654) obtained by the reac LENE 310P), were uniformly heated and kneaded at tion of a tetrabromobisphenol A with an epichlorohy- 40 225 C. drin, 3.5 parts of an antimony oxide, 30 parts of a glass The thus obtained composition was tested in the same fiber, and 4 parts of an ethylene/vinyl acetate copoly manner as in Example 1 to obtain the following results. mer (EVATHLENE 310P, a product of Dainippon TS was 550 kg/cm2, TE was greater than 100%, FS Ink And Chemicals, Inc.) and 6 parts of a 99% saponi was 750 kg/cm2. II was 4 kg.cm/cm, and the flame- fied polyvinyl acetate (GOHSENOL NH-20, polymeri- 45 retarding property was evaluated as UL 94 V-0 (using a zation degree of 2000, a product of The Nippon Syn test piece of a thickness of 1/16 inch). thetic Chemical Industry Co., Ltd.) as drip-preventing The blending ratios of the compositions of the above agents, were heated and kneaded together in the same manner as in Example 1. Examples, and the test results are tabulated below. Blend Polyester Organohalogen compound Drippreventing agent Inorganic flame-retarding"1 supplementary agent Reinforcing agent1'1 Test Results PBT1) {[tj] = 0.8) PBT ([7,1 = 1.0) PBT21 ([tj] - 0.8) Polyester polyurethane-51 dbb4) Flame-retarding epoxy51 resin HBB EVA7' Saponified FA'A51 Saponified polyvinyl1*1 acetate - l Saponified po!yvmy!!0) acetate -2 Example l 5\.6i>arls 10 4 2 2.4 30 V-0 Comparative Example 1 , 0/torrr 10 Example 2 42.5ft,ra Example 3 42.5Pttm Example 4 15 Exampli 70ftim 14 14 44 15 10 60 10 :4 3.5 3 5 5 5 2? 4 :o 30 0 0 V-2 v-o v-0 V-0 V-0 4,222,926 9 10 -continued Flame-retarding property Melted and dripped TS (kg/cm2) TE (%) FS (kg/cm2) II (kg.cm/cm) UL 94 Example l (1/32 in.) thick) No (after 60 sec.) 1100 2.5 1500 8 Comparative Example l (1/32 in. thick) Yes (after 15 sec.) 1150 1.5 1600 5 Example 2 (1/32 in. thick) No (after 60 sec.) 1200 2.0 1600 6 Example 3 (1/16 in. thick) No (after 60 sec.) 1350 2.5 1700 8 Example 4 (1/16 in. thick) No (after 60 sec.) 600 100 or more 850 4 Example 5 (1/16 in. thick) No (after 60 sec.) 550 100 or more 740 4 "PBT: Polybutylene lerephlhalate *'PET: Polyethylene terephthalate "Polyester polyurethane: A reaction product ofa polybutylene terephthalate having a OHvalue of IS and an AN value of 0 with adiphenylmethane-4,4'-diisocyanate 4,DBB: Decabromobiphenyl ether 5>Flame-retarding epoxy resin: A reaction productfepoxy equivalent of I6S4) of a tetrabromobiphenolA with an epichlorohydrin `'HBB. Hexabromobenxene 7>EVA. An cthylene/vinyl acetate copolymer(EVATHLENE3IOP) '"Saponified EVA' A saponified ethylene/vinylacetate copolymer (GL Resin, a product ofThe Nippon Synthetic Chemical IndustryCo., Ltd.) "Saponified polyvinyl acetate -1 GOHSENOL NH-20(polymerization degree of 2000, saponificationdegree of 99%, a product of TheNippon Synthetic Chemical Industry Co..Ltd.) !0'Saponified polyvinyl acetate --2: GOHSENOL G-l7(polymenzation degree of 2100, saponificationdegree of 86%, a product of TheNippon Synthetic Chemical Industry Co..Ltd.) "'Inorganic flame-retarding supplementary agent:Amimony trioxide "'Reinforcing agent: Glass fiber What is claimed is: agent (3) is 0.5 to 20 parts by weight per 100 parts by 1. A flame-retarding thermoplastic polyester resin 25 weight of the polyester (1). composition comprising (1) a thermoplastic polyester 8. A composition according to claim 1, wherein the obtained from a terephthalic acid or an alkyl ester content of the reinforcing agent (5) is 7 to 200 parts by thereof and a glycol having 2 to 4 carbon atoms selected weight per 100 parts by weight of the polyester (1). from the group consisting of ethylene glycol, propylene 9. The composition according to claim 1 wherein the glycol and butylene glycol, (2) 2 to 30 parts by weight, 30 organohalogen compound (2) is an aromatic halogen as halogen, per 100 parts by weight of (1) of an or- compound containing 2 or more halogen atoms selected ganohalogen compound, (3) an inorganic flame-retard from the group consisting of chlorine, bromine atoms ing supplementary agent, and (4) 0.5 to 30 parts by and mixtures thereof in the molecule; the inorganic weight per 100 parts by weight of (1) of at least one flame-retarding supplememtary agent (3) is selected polymer selected from the group consisting of a saponi- 35 from the group consisting of antimony trioxide, anti fied polyvinyl acetate having a saponification degree of mony pentoxide, antimony trisulfide, antimony trichlo greater than 50%, an ethylene/vinyl acetate copolymer ride, antimony pentachloride, antimony tribromide, having a vinyl acetate content of greater than 50% by antimony pentabromide, barium metaborate, lead bo weight and a Monney viscosity of 10 to 80 and a saponi rate, aluminum hydroxide, zirconium oxide and molyb fied ethylene/vinyl acetate copolymer, and optionally 40 denum oxide; and the polymer (4) is an ethylene/vinyl (5) a reinforcing agent. acetate copolymer having a vinyl acetate content of 2. A composition according to claim 1, wherein the greater than 50% by weight and a Mooney viscosity of polyester (1) has an intrinsic viscosity [t|] (as measured 10 to 80 or a mixture of the ethylene/vinyl acetate co in a mixture solvent of phenol and ethane tetrachloride polymer with saponified polyvinyl acetate having a at a weight ratio of 6 to 4, and at 30" C.) of 0.5 to 1.5 45 saponification degree of greater than 50% of a saponi deciliters per gram. fied ethylene/vinyl acetate copolymer. 3. A composition according to claim 1, wherein the 10. The composition of claim 1 wherein the polyester organohalogen compound (2) contains two or more (1) consists essentially of polyethylene terephthalate, halogen atoms selected from the group consisting of polypropylene terephthalate or polybutylene tere chlorine, bromine atoms and mixtures thereof in one 50 phthalate. molecule. 11. The composition of claim 1 wherein the polyester 4. A composition according to claim 1, wherein the (1) is a polyalkylene terephthalate selected from the inorganic flame-retarding supplementary agent (3) is an group consisting of polyethylene terephthalate, poly oxide, sulfide, halide, borate, metaborate, sulfate, car propylene terephthalate and polybutylene terephthate bonate or hydroxide of a metal. 55 or a mixture of said polyalkylene terephthalate with less 5. A composition according to claim 1, wherein the than 40% by weight of a thermoplastic resin selected polymer (4) is said ethylene/vinyl acetate copolymer from the group consisting of polyolefin, polystyrene, having a vinyl acetate content of greater than 50% by acrylonitrile-butadiene-styrene polymer, acrylic resin, weight and a Mooney viscosity of 10 to 80, or said vinyl acetate resin, polyacetai, polycarbonate and poly saponified product of the ethylene/vinyl acetate co- 60 urethane. polymer. 12. The composition according to claim 9 wherein 6. A composition according to claim 1, wherein the the content of the inorganic flame-retarding supplemen reinforcing agent (5) is present and is a glass fiber, cellu tary agent (III) is 0.5 to 20 parts by weight per 100 parts lose fiber, cotton fabric, paper, synthetic fiber, metal by weight of the polyester (1). powder, glass beads, asbestos, calcium silicate, magne- 65 13. The composition according to claim 12 wherein sium silicate, talc or calcium carbonate. the reinforcing agent (5) is selected from the group 7. A composition according to claim 1, wherein the consisting of glass fiber, cellulose fiber, cotton fabric, content of the inorganic flame-retarding supplementary paper, synthetic fiber, metal powder, glass beads, asbes- 4,222,y2b 11 12 tos, calcium silicate, magnesium silicate, talc or calcium group consisting of ethylene glycol, propylene glycol carbonate and is present in an amount of from 7 to 200 and butylene glycol, (2) 20 to 30 parts by weight, as parts by weight per 100 parts by weight of the polyester halogen, per 100 parts by weight of (1) of an or- (1). ganohalogen compound, (3) an inorganic flame-retard 14. A shaped article obtained by molding a flame- 5 ing supplementary agent, and (4) 0.5 to 30 parts by retarding thermoplastic polyester resin composition of weight per 100 parts by weight of (1) of at least one claim 1. polymer selected from the group consisting of a saponi 15. The composition according to claim 7 wherein fied polyvinyl acetate having a saponification degree of the content of the reinforcing agent (5) is 7 to 200 parts greater than 50%, an ethylene/vinyl acetate copolymer by weight per 100 parts by weight of the polyester (1). 10 having a vinyl acetate content of greater than 50% by 16. A shaped article obtained by molding a flame- weight and a Mooney viscosity of 10 to 80 and a saponi retarding thermoplastic polyester resin composition of fied ethylene/vinyl acetate copolymer, and optionally claim 15. (5) a reinforcing agent. 17. A process for producing a flame-retarding ther 18. A process according to claim 17, wherein the moplastic polyester resin composition comprising heat 15 heating and kneading is performed using an extruder at ing and kneading (1) a thermoplastic polyester obtained a temperature of 180" to 300 C. and for a period of 0.2 from a terephthalic acid or an alkyl ester thereof and a glycol having 2 to 4 carbon atoms selected from the to 30 minutes. ***** 20 25 30 35 40 45 50 55 60 65