JPH0124176B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyester resin composition that exhibits flame retardancy, has excellent physical properties such as mechanical strength, and has excellent heat resistance in which a flame retardant does not bleed onto the surface of the resin composition at high temperatures. Terephthalic acid polyesters, such as polyethylene terephthalate (hereinafter abbreviated as PET), polybutylene terephthalate (hereinafter abbreviated as PBT)
Due to its excellent physical properties and moldability, it is used in mechanical parts, electrical parts, and many other fields.
Recently, there has been a high demand for fire safety, especially in the field of electrical and electronic parts, and the demand for making them flame retardant is increasing. Generally speaking, the method of making polyester resin flame retardant is to add relatively low molecular weight organic halogen compounds, but if the amount added is increased solely for the purpose of imparting flame retardance, the mechanical strength of polyester resin will be reduced. In practice, polyester resins and such flame retardants must be blended in appropriate proportions. Moreover, additive flame retardants for aromatic halogen compounds such as decabrom diphenyl ether, brominated phthalic anhydride, brominated diphenyl, brominated diphenyl ether, brominated bisphenol A, or derivatives thereof are added to molded products. When kneaded, the flame retardant efficiency decreases due to bleeding or easy sublimation of the flame retardant itself, and even decabrom diphenyl ether, which is considered to be the best of these, has poor dispersibility in polyester resin. This was extremely poor and it was difficult to produce a flame retardant polymer with sufficiently excellent mechanical strength. On the other hand, various flame-retardant polyester resins using halogen-containing monomers or comonomers are known for the purpose of uniformly dispersing flame retardants, improving mechanical strength, and reducing sublimation.
Publication No. 81939, Japanese Patent Application Laid-Open No. 1973-6087, Japanese Patent Application Publication No. 1973
-78735 and JP-A-50-133253 disclose a bromine-containing polyester resin obtained from a brominated aromatic dicarboxylic acid or its lower alkyl ester and an alkylene glycol;
No. 54494 discloses halogen-containing aromatic diols,
Halogen-containing polyester copolymer resins obtained from aliphatic diols and aromatic dicarboxylic acids have been proposed. However, in the flame-retardant polyester resin obtained in this way, the reactivity of halogen-containing monomers is usually lower than that of non-halogen-containing monomers. Therefore, polymers or copolymers with sufficiently high molecular weights cannot be obtained; on the other hand, in order to increase the molecular weight, halogen-containing monomers must be reduced, and the halogen content is considerably lower than that of ordinary additive flame retardants. The paradox is that only 100% of polymers or copolymers can be obtained. The present inventors focused on the uniform dispersibility and low sublimation of the halogen-containing polyester polymer or copolymer in the flame-retardant polyester resin,
As a result of extensive research to improve the above-mentioned drawbacks with the premise of use as an additive flame retardant, we have developed a block copolymer made from a specific halogen-containing polyester copolymer and a specific halogen-containing bisphenol A-type epoxy resin. By using it as a flame retardant, it is possible to simultaneously improve the halogen content and molecular weight of the halogen-containing polyester copolymer flame retardant, and by using this together with an inorganic flame retardant aid, the amount of flame retardant added can be further reduced. The mechanical strength retention rate is significantly higher than that of
We have discovered a flame-retardant polyester composition that is non-bleeding, and have arrived at the present invention. That is, the present invention provides polyesters obtained by reacting () terephthalic acid-based polyesters, ()(a) halogenated phthalic anhydride, halogenated tetrahydrophthalic anhydride, or ester-forming derivatives thereof with diols or ester-forming derivatives thereof. linear polyester and (b) general formula (In the formula, R ₁ , R ₂ , R ₃ are H or CH ₃ groups, X is a halogen atom, l is 0 to 15, and m and n are integers of 1 to 4.) Halogen-containing bisphenol represented by A flame-retardant polyester resin composition comprising a block copolymer obtained from type A epoxy resin and () an inorganic flame-retardant aid, preferably in which the effective halogen element of the block copolymer () is terephthalic acid-based. The present invention provides a flame-retardant polyester resin composition in which the content of the inorganic flame retardant aid is 0.5-20% by weight based on the terephthalic acid polyester. The terephthalic acid polyester used in the present invention includes terephthalic acid or its ester,
For example, ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A,
2,2-bis(4-hydroxyethoxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane, 1,4-dimethyloltetrabromobenzene, etc. It is a polyester consisting of glycols such as phenol and tetrachloroethane.
The one having an intrinsic viscosity [η] of 0.3 to 1.5 dl/g as measured at 30° C. in a mixed solvent with a ratio of 4 to 4 (weight ratio) is used. This terephthalic acid polyester contains 40 mol% or less of other dibasic acids based on the total acid components, such as isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,
4'-diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, α,β-bis(4-carboxyphenoxy)ethane, adipic acid, sebacic acid,
Azelaic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, etc.; other hydroxycarboxylic acids such as glycolic acid, hydroxybutyric acid, hydroxycaproic acid, hydroxybenzoic acid, hydroxyphenylacetic acid, naphthylglycolic acid, etc. may also be included. Also, propiolactone,
It may contain 40 mol% or less of a lactone compound such as butyrolactone, valerolactone, caprolactone, caprylolactone or a polymer thereof as a constituent component. On the other hand, the terephthalic acid polyester used in the present invention contains 40 mol% or less of the total glycol component in addition to the glycol component described above, and contains polyalkylene ether glycols such as polyethylene glycol and polytetramethylene ether glycol, and polyesters having hydroxyl groups at both ends. It may also contain an aliphatic polyester oligomer or the like as a constituent component. Further, the polyester contains a trifunctional or higher functional ester-forming component such as trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, trimellitic acid, trimesic acid, pyromellitic acid, etc. within a range that can maintain thermoplasticity. Good too. Furthermore, the terephthalic acid polyester may contain 40% by weight or less of other organic polymers. Examples of such other organic polymers include polyolefin, polystyrene, AS resin,
ABS resin, MBS resin, ASA resin, acrylic resin, vinyl acetate resin, ethylene-vinyl acetate copolymer, polyacetal, polycarbonate, polyester, polyurethane, polyamide, modified
Thermoplastic resins such as PPO resins; elastomers or rubbers such as acrylic rubber graftomers, styrene-butadiene rubbers, ethylene-propylene rubbers, and polyester ether elastomers. In addition, low molecular weight polyalkylene terephthalate having a hydroxyl group at the end ([η] = 0.1 to 0.5 dl/g)
A polyester polyurethane obtained by increasing the molecular weight with a polyfunctional isocyanate can also be used as the terephthalic acid polyester. The block copolymer used in the present invention is a polymer obtained by reacting (a) halogenated phthalic anhydride, halogenated tetrahydrophthalic anhydride, or an ester-forming derivative thereof with a diol or an ester-forming derivative thereof. polyester and (b) general formula (In the formula, R ₁ , R ₂ , R ₃ are H or CH ₃ groups, X is a halogen atom, l is 0 to 15, and m and n are integers of 1 to 4.) Halogen-containing bisphenol represented by It is obtained from A-type epoxy resin. The linear polyester used in this case has a carboxyl group or/and a hydroxyl group as a terminal group, preferably a carboxyl group. As the acid component, halogenated phthalic anhydride, halogenated tetrahydrophthalic anhydride, or ester-forming derivatives thereof are mainly used. Phthalic anhydride, dibromo phthalic anhydride, dichloro phthalic anhydride, monobromo phthalic anhydride, monochloro phthalic anhydride, tetrabrom tetrahydrophthalic anhydride, tetrachlorotetrahydrophthalic anhydride,
tribromotetrahydrophthalic anhydride, trichlortetrahydrophthalic anhydride, dibromotetrahydrophthalic anhydride, dichlorotetrahydrophthalic anhydride, monobromotetrahydrophthalic anhydride,
Examples include monochlorotetrahydrophthalic anhydride or lower alkyl esters thereof, or a mixture of two or more thereof. In addition to these acid components,
Up to 40 mol% of other polybasic acids, such as terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, α, β-bis(4
-carboxyphenoxyethane), halogen-containing terephthalic acid, adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, maleic anhydride, fumaric acid, itaconic acid, etc.; other hydroxycarboxylic acids, For example, it may contain glycolic acid, hydroxybutyric acid, hydroxycaproic acid, hydroxybenzoic acid, hydroxyphenylacetic acid, naphthylglycolic acid, and the like. Furthermore, the linear polyester may contain a lactone compound or a polymer thereof in an amount of 40 mol% or less based on the linear polyester. Examples of diols used as raw materials for linear polyester include HO(CH ₂ ) pOH (p=2 to
α,ω-alkylene glycol, propylene glycol, 1,3-butanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanedimethanol, hydroquinone, bisphenol A, bisphenol S, 2, 2-bis(4-hydroxyethoxyphenyl)propane or sulfone, tetrabromobisphenol A, tetrabromobisphenol S, 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane or Examples include sulfone, 1,4-dimethyloltetrabromobenzene, 1,4-dimethyloltetrachlorobenzene, and in addition to these, 40
up to mol%, e.g. polyethylene glycol,
It may also contain other diols such as polyalkylene ether glycols such as polytetramethylene ether glycol and aliphatic polyester oligomers having hydroxyl groups at both ends. Of course, instead of diols, their ester-forming derivatives, such as diacetates of diols, can also be used. Known methods can be used to produce these linear polyesters. For example, the above-mentioned acid and diol components are charged during the transesterification or esterification reaction, followed by a polycondensation reaction, or a small amount of halogenated phthalic anhydride or halogenated tetrahydrophthalic anhydride is reacted with the diol component in advance and the remaining It can be produced by a method in which halogenated phthalic anhydride or halogenated tetrahydrophthalic anhydride is added little by little and esterification and polycondensation reactions are carried out. The halogen content in the linear polyester thus obtained is preferably as high as possible, but is usually selected from a range of 10 to 62% by weight, preferably 25 to 62% by weight. On the other hand, the halogen-containing bisphenol A type epoxy resin, which is another component of the block copolymer, is represented by the following general formula. (In the formula, R ₁ , R ₂ , R ₃ are H or CH ₃ groups, X is a halogen atom, l is 0 to 15, and m and n are integers of 1 to 4.) This halogen-containing bisphenol A type The epoxy resin preferably has a halogen content of 20% by weight or more, and X is bromine or chlorine, and m and n are 2 to 4.
Preferably. Further, such halogen-containing bisphenol A-type epoxy resin is synthesized, for example, by condensation of halogenated bisphenol A and epichlorohydrin, but it can also be synthesized by the reaction of diglycidyl ether of halogenated bisphenol A with halogenated bisphenol A. It is easily synthesized. The halogen content can be adjusted to any desired ratio by partially cocondensing bisphenol A. The block copolymer used in the present invention is synthesized by reacting the linear polyester with the halogen-containing bisphenol A type epoxy resin in the presence of a catalyst. By appropriately selecting the type, the terminal group can have a hydroxyl group, a carboxyl group, or both. However, when reacting with a halogen-containing bisphenol A-type epoxy resin, a relatively high reaction temperature and long reaction time are required if the epoxy resin is hydroxyl-terminated. Since there is a risk of gelation due to reaction with a carboxyl group, it is preferable to use a carboxyl group-terminated one that does not require very strict control of the reaction temperature and reaction time. In addition, when the terminal group of the linear polyester is a hydroxyl group, for example, one having a terminal carboxyl group by reacting with succinic anhydride, phthalic anhydride, tetrabromophthalic anhydride, or tetrachlorophthalic anhydride It can be converted into and used. In addition, linear polyester usually has an average molecular weight of
The number used is 1,000 to 20,000, preferably 1,500 to 15,000. The molecular weight of linear polyester is determined by the hydroxyl value (OHV; the number of mg of KOH equivalent to the acid required to esterify 1 g of sample) and the acid value (AN;
The number of mg of KOH required to neutralize 1 g of sample is calculated using the following formula. Molecular weight of linear polyester=56100×2/(OHV+AN) Furthermore, this linear polyester
It is desirable that the content be 30% by weight. If the amount of linear polyester in the composition is less than 3% by weight, the compatibility with the terephthalic acid polyester, which is the main raw material, will be poor, and if it exceeds 30% by weight, it will be separated from this and the halogen-containing bisphenol A epoxy resin. Since the amount of the block copolymer used is too large, the physical properties of the terephthalic acid polyester, which is the main raw material, cannot be fully exhibited, which is not preferable. When synthesizing the block copolymer, the molar ratio of linear polyester (=A) and halogen-containing bisphenol A type epoxy resin (=B) is A:B.
A range of =2:1 to 1:2 is desirable, and in order to reduce the possibility of gelation of the epoxy resin itself, the linear polyester is first synthesized in a reaction vessel, and then the halogen-containing bisphenol A type epoxy resin is synthesized. A method of adding and reacting in a pot is preferred. The amount of the block copolymer used in the present invention is such that the amount of halogen element in the block copolymer is in the range of 2 to 30% by weight based on the terephthalic acid polyester from the viewpoint of flame retardancy of the composition. amount is preferred. If the amount of halogen element in the block copolymer relative to the terephthalic acid polyester is less than 2% by weight, the flame retardance of the composition will not be sufficient, while if it exceeds 30% by weight, the amount of block copolymer will be excessive and the composition will The physical properties of the material deteriorate significantly. The composition of the present invention contains an inorganic flame retardant auxiliary agent, and by using this flame retardant auxiliary agent in combination, the amount of flame retardant used can be reduced, thereby making it possible to further reduce deterioration of the mechanical properties of the composition. Such inorganic flame retardant aids include antimony trioxide, antimony tetroxide, antimony pentoxide, antimony trisulfide, sodium antimonate, sodium pyroantimonate, stannic oxide, barium metaborate, borax, and boric acid. zinc,
Examples include aluminum hydroxide, zirconium oxide, and molybdenum oxide. The amount of inorganic flame retardant aid added is 0.5 to 20 per terephthalic acid polyester.
The amount is preferably within the range of % by weight. If the amount of the inorganic flame retardant aid is less than 0.5% by weight, the effect as a flame retardant aid will be small, and if it exceeds 20% by weight, the mechanical strength will be significantly reduced. Particularly preferably,
The amount of the inorganic flame retardant aid is 1 to 10% by weight based on the terephthalic acid polyester. In addition to the above-mentioned components, the composition of the present invention may further contain asbestos or/and ethylene/vinyl acetate copolymer, if necessary, and these compounds may be present in an amount of 1 to 10% by weight in the entire composition. %, particularly preferably 1 to 5% by weight. Incorporation of these compounds is preferred because it provides an effect of preventing dripping of the melt upon ignition of the composition or after removal of the fire source. The ethylene-vinyl acetate copolymer preferably has a vinyl acetate content of 50% by weight or more. In the block copolymer of the present invention, the linear polyester as a constituent component not only has the effect of improving compatibility with the terephthalic acid polyester, but also has the effect of improving compatibility with the terephthalic acid polyester during production and molding of the composition. Partial transesterification produces effects such as improving the physical properties of the resulting composition and preventing bleeding of the flame retardant in the composition. On the other hand, halogen-containing bisphenol A type epoxy resin, which is the same component, is effective in improving the surface adhesion of the composition due to the hydroxyl groups it possesses, and when epoxy groups remain in the block copolymer, it is effective to improve the surface adhesion of the composition. It helps prevent deterioration by trapping some of the hydrogen halide generated during thermal decomposition, and also causes interfacial bonding between the reinforcing agent and the polymer, especially when reinforcing agents such as glass fiber, glass beads, mica, and talc are blended. This has a significant effect on improving the mechanical strength of the composition. The composition of the present invention may further contain an inorganic compound such as glass fiber, glass beads, mica, or talc as a reinforcing agent. Those treated with a titanium-based coupling agent or a titanium-based coupling agent are preferable, and can be supplied in the form of rovings, chopped strands, beads, flakes, powder, etc.
The amount of such reinforcing agent used is preferably 5 to 60% by weight in the composition, but the amount used is 5% by weight.
If the amount is less, the reinforcing effect will be small, and if it exceeds 60% by weight, the moldability of the composition will be poor, which is not preferable. Any method can be used to produce the composition of the present invention. For example, a block copolymer is added and mixed during or after the polycondensation reaction of terephthalic acid polyester, and then an inorganic flame retardant aid is added as necessary. A method of adding and mixing reinforcing agents and anti-dripping agents. After homogeneously melt-mixing molten terephthalic acid polyester and block copolymer, cooling and solidifying the resulting granules, inorganic flame retardant aids are added as necessary. Examples include a method of mixing a reinforcing agent and an anti-dripping agent, and a method of mixing a terephthalic acid polyester pellet, a granulated block copolymer, an inorganic flame retardant aid, and, if necessary, a reinforcing agent and an anti-dripping agent. The composition of the present invention is preferably kneaded using an extruder, and the conditions are: heating temperature 180-300°C;
Preferably, the temperature is 180 to 285°C and the mixing time is 0.2 to 30 minutes. If the temperature is too high or the mixing time is too long, the block copolymer is likely to decompose, so care must be taken. Furthermore, the mechanical properties of the composition of the present invention can be improved by using a compound containing two or more epoxy groups depending on the purpose, and by using a carboxylic acid metal salt or waxes in combination. Heat resistance, light resistance, moldability, etc. can be improved. In addition, the composition of the present invention contains a crystal nucleating agent, a reinforcing filler,
Plasticizers, mold release agents, lubricants, matting agents, heat stabilizers, antioxidants, ultraviolet absorbers, foaming agents, coupling agents, and the like may be added. The flame-retardant polyester resin composition obtained in this way not only has excellent flame retardancy, but also has excellent properties such as mechanical strength, and has industrial value because the flame retardant does not bleed from the surface of the composition. It is extremely large and is used not only for molding mechanical parts, electrical and electronic parts, automobile parts, building material parts, etc., but also for textiles,
It can also be used for films, adhesives, etc. EXAMPLES Hereinafter, examples will be given to explain the present invention more specifically, but the present invention is not limited to the examples unless the gist thereof is exceeded. Note that parts and % in the examples indicate parts by weight and % by weight, respectively. Reference Example (A) Synthesis of brominated bisphenol A type epoxy resin: 1110 parts of tetrabromobisphenol A diglycidyl ether [epoxy equivalent (molecular weight per epoxy group): 370], 544 parts of tetrabromobisphenol A, and tetrabromobisphenol A diglycidyl ether [epoxy equivalent (molecular weight per epoxy group): 370] Charge 1.6 parts of a 10% aqueous solution of methylammonium chloride into a flask (tetrabromobisphenol A diglycidyl ether/tetrabromobisphenol A = 3/2 molar ratio), heat and melt at 150°C,
Gradually raise the temperature to 190℃ after 4 hours, then further to 190℃.
It was kept at ℃ for 2 hours. After the reaction was completed, the cooled and solidified product was crushed to obtain yellow granules. The product had a softening point of 130°C, an epoxy equivalent of 1654, and a bromine content of 51.3%, and was confirmed to have the structure of the following formula by IR spectrum and NMR spectrum. (B) Linear polyester and brominated bisphenol A
Synthesis of block copolymer with type epoxy resin: 0.5 mol of tetrabromophthalic anhydride and 1.3 mol of ethylene glycol were charged into a reactor equipped with a rectification column, a distillation condenser, a distillate receiver, and a stirrer, and heated. After the contents were melted, zinc acetate was added as a catalyst in an amount of 0.2% based on the total acid components, and the temperature was raised to 200°C. After reaching 200°C, 0.5 mol of tetrabromophthalic anhydride was added in two portions, and the reaction was further carried out at 200°C for 2 hours. next
Maintained at 200℃ for 2 hours under reduced pressure of 100mmHg, acid value 40, hydroxyl value 10, number average molecular weight (calculated value)
2244 linear polyester was obtained. 100 parts of this linear polyester, brominated bisphenol A type epoxy resin synthesized in Reference Example (A)
125 parts and as a catalyst in pure proportion to the total amount charged
A 10% aqueous solution of tetramethylammonium chloride in an amount of 100 ppm was gradually added to the reactor and uniformly melted and mixed at 185-190°C. Thereafter, the reaction was carried out for 3 hours at 185-190°C/normal pressure. After the reaction was completed, the contents were taken out, and the solidified product was crushed. The product has an acid value
3.2, a block polymer (B-1) having epoxy groups with a bromine content of 55.0%. Furthermore, various block copolymers B-2 were prepared in the same manner based on the raw materials and their composition ratios shown in Table-1.
~6 was synthesized. The contents of B-1 to B-6 are summarized in Table-1.

[Table] Example 1 Before taking out 53 parts of PBT of [η] = 0.8 dl/g obtained by transesterification and polycondensation of dimethyl terephthalate and 1,4-butanediol by a known method from the polycondensation vessel, Add 14 parts of the block copolymer (B-1) synthesized in the example, and
After mixing at ℃ for 20 minutes, the mixture was taken out from the pot, cooled, solidified, and granulated. To this mixture, 3 parts of antimony trioxide and 30 parts of chopped strand type glass fiber treated with an aminosilane coupling agent were premixed uniformly. The premix was supplied to a full-flight vented 65 mm extruder heated to 250° C., and after plasticization and kneading, the mixture was cooled to obtain pellets. A test piece was made from this pellet using an injection molding machine and its physical properties were measured, and the physical properties were as shown in Table 2. All measurements of mechanical properties and heat distortion temperature were conducted in accordance with ASTM.
Regarding flammability, the US UL (=
Underwriters' Laboratories) standard 1/16
The test was carried out using inch-thick specimens. Heat resistance was evaluated qualitatively by thermal coloring after keeping the molded specimen in a dryer at 200℃ for 2 hours, and flame retardant bleedability was evaluated by keeping the molded specimen in a dryer at 150℃ for 3 hours. Evaluation was made based on the surface condition of the specimen afterward. Example 2 [η] = 0.84 dl/g PBT granulated52
Block copolymer (B-
After uniformly premixing 15 parts of granulated 2), 3 parts of antimony trioxide and 30 parts of chopped strand glass fiber treated with an epoxy silane coupling agent were mixed. This mixture was plasticized and kneaded at 245° C. in a full-flight 65 mm extruder to produce pellets. A test piece was prepared from the resulting pellets and its physical properties were measured, and the physical properties were as shown in Table 2. Examples 3 and 4 In Example 2, block copolymers (B-3) and (B-4) were used instead of the block copolymer (B-2) synthesized in the reference example, and the rest were as follows. Example 2
A test piece was prepared in the same manner as above, and its physical properties were measured. The results are shown in Table-2. Comparative Example 1 In Example 2, block copolymer (B-
A test piece was prepared in the same manner as in Example 2 except that 9 parts of decabrom diphenyl ether was used instead of 2), and its physical properties were measured. The results are shown in Table-2. Comparative Example 2 Instead of using the block copolymer (B-2) in Example 2, 7.3 parts of linear polyester, which is a component of (B-2), and 7.7 parts of the brominated bisphenol A type epoxy resin synthesized in Reference Example were used. A test piece was prepared in the same manner as in Example 2, using
Its physical properties were measured. The results are shown in Table-2.

[Table] As is clear from the results in Table 2, the composition of the present invention had excellent performance in all physical properties, and had little coloring in a high-temperature atmosphere and no bleeding was observed. On the other hand, when decabrom diphenyl ether was used as in Comparative Example 1, mechanical properties deteriorated and bleeding was severe, which caused practical problems. Furthermore, in Comparative Example 2, the constituent components before block copolymerization were used together, but the mechanical properties were generally slightly lower, and some coloring and bleeding were observed in a high-temperature atmosphere. Examples 5 to 10 and Comparative Example 3 Polyester polyurethane obtained by reaction of PBT and diisocyanate as polyester, ordinary PBT and PET, antimony trioxide, sodium pyroantimonate, stannic oxide and The same procedure as in Example 2 was carried out using barium metaborate, chopped strand glass fibers and glass beads as reinforcing agents, and asbestos or ethylene/vinyl acetate copolymer as required in the proportions shown in Table 3. Pellets were made. A test piece was prepared from the resulting pellets and its physical properties were measured, and the physical properties were as shown in Table 3.

[Table] R○
** Dainippon Ink & Chemicals, EVASLEN 310P (
Vinyl acetate content 70%)
As is clear from the results in Table 3, the molded products of Examples 5 to 9 of the present invention all have excellent mechanical properties and flame retardancy, and have little discoloration and bleed under high temperature atmosphere. was also not recognized. Moreover, the molded article of Example 10 had excellent flame retardancy, and moreover, there was little discoloration in a high-temperature atmosphere, and no bleeding was observed.

Claims (1)

[Scope of Claims] 1 () Terephthalic acid polyester () (a) Obtained from halogenated phthalic anhydride, halogenated tetrahydrophthalic anhydride, or an ester-forming derivative thereof, and a diol or an ester-forming derivative thereof Linear polyester and (b) general formula (In the formula, R ₁ , R ₂ , R ₃ are H or CH ₃ groups, X is a halogen atom, l is 0 to 15, m and n are 1 to
Indicates an integer of 4. ) A block copolymer obtained from a halogen-containing bisphenol A type epoxy resin represented by ( ) A flame-retardant polyester resin composition comprising an inorganic flame-retardant aid.