JPH06145489A - Injection molded article of flame-retardant polyester resin - Google Patents

Abstract

PURPOSE:To provide an injection-molded article of a flame-retardant polyester resin having excellent moldability and mechanical properties, free from the emission of noxious gas and corrosive gas and the lowering of hydrolysis resistance and suitable for parts for electric and electronic equipment, automobile parts and machinery parts. CONSTITUTION:The objective article is produced by injection-molding a composition produced by compounding (A) 100 pts.wt. of a thermoplastic polyester produced by using a 8-20C aromatic dicarboxylic acid or its lower alkyl ester and a 2-20C aliphatic or alicyclic diol as starting raw materials with (B) 0.5-100 pts.wt. (especially 5-50 pts.wt.) of a polyphosphonamide having a recurring unit of formula (R<1> is aryl, alkyl, aralkyl or cycloalkyl; R<2> and R<4> are H, aryl or alkyl; R<3> is arylene, aralkylene or alkylene; the diamine group may have a cyclic structure containing directly bonded R<2> and R<4>). The component B is especially preferably a compound having a weight reduction of <=6wt.% at 280 deg.C when heated in a thermobalance at a heating rate of 10 deg.C/min in a nitrogen stream.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin injection-molded article containing a non-halogen flame retardant. More specifically, it has excellent mechanical properties and does not cause generation of harmful gas or corrosive gas and deterioration of hydrolysis resistance.
The present invention relates to a flame-retardant polyester resin injection-molded product suitable for electric / electronic device parts such as relays, switches, case members, transformer members, coil bobbins, automobile parts, and machine parts.

[0002]

2. Description of the Related Art Thermoplastic polyester resins typified by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, etc. are used as injection molding materials for mechanical mechanism parts and electrical parts by making use of their excellent characteristics. ,
It is being used in a wide range of fields such as automobile parts. On the other hand, since thermoplastic polyester resin is inherently flammable, it is required to have flame safety, that is, flame retardancy, in addition to the general balance of chemical and physical properties for use in these industrial materials. It is often done.

A common method for imparting flame retardancy to a thermoplastic resin is to compound a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant aid into the resin. However, in this method, a large amount of smoke is generated during combustion, halogen is liberated and corrosive hydrogen halide gas is generated during processing and use of molded products, which causes corrosion of molds and metal contacts. May be a source of pollution. Further, the antimony compound, which is a flame retardant aid usually used in combination to enhance the effect of the flame retardant, is a foreign substance to the resin, which causes a decrease in mechanical properties. In addition, recently, it has been pointed out that toxic brominated dibenzodioxin or brominated dibenzofuran is generated when a resin containing some brominated flame retardant is processed or burned.

Therefore, in recent years, it has been strongly desired to use a flame retardant containing no halogen in order to overcome the drawbacks of these halogen flame retardants.

Up to now, copolymerization and blending of phosphorus compounds have been widely known as methods for flame retarding resins without using halogen-based flame retardants, and various methods have been proposed mainly for fiber applications. . As a typical method, copolymerization of a phosphonic acid unit or a phosphinic acid unit into polyester (JP-A-51-54691 and JP-A-50-56).
488), copolymerization of monomers having a pendant cyclic phosphinite skeleton (JP-A-52-98089, JP-A-55-5916, JP-A-60-24).
No. 0755, etc.), polyphosphonate blends (US Pat. No. 3,719,727), and red phosphorus blends (JP-A-49-74240). Among them, JP-A-55-5916 and JP-A-49-742
Although there is an example of an injection molding composition in Japanese Patent No. 40,
The conventional flame-retardant technology using phosphorus compounds is basically intended for fibers and films, and not for injection-molded products.

In addition to this, a method of adding polyphosphonic acid amide is disclosed in Japanese Patent Laid-Open No. 159540/1975, but this is also mainly aimed at the washing resistance and flame retardancy of the fiber. Is not listed.

[0007]

A polyester resin composition for injection molding has a crystallization property from the viewpoint of mechanical performance of a molded product and moldability such as a molding cycle. Hydrolysis resistance is required to maintain reliability even when used.

In this respect, it has been found that the conventional technique has the following problems.

(1) In copolymerization of a phosphonic acid unit or a phosphinic acid unit, the P—O bond of the main chain is easily hydrolyzed, and as a result, the hydrolysis resistance of the molded product is significantly deteriorated.

(2) When a phosphorus-containing monomer is copolymerized with polyester, a large amount of copolymerization rate will be obtained when trying to obtain the level of flame retardancy required for electric / electronic parts, and the melting point and crystal of the polyester resin The chemical conversion rate is greatly reduced, and it can no longer be used as a resin for injection molding.

(3) When the polyphosphonate is blended with the polyester resin, the P--O bond in the flame retardant is also easily hydrolyzed, and the hydrolysis product acts catalytically on the hydrolysis of the polyester itself, resulting in durability. Reduce performance.

(4) In the blend of red phosphorus, there are problems such as deterioration of mechanical properties of the polyester resin, concern about safety, coloring, etc., and the effect of making polybutylene terephthalate flame retardant is small.

As described above, there are many problems in applying the conventional technique mainly for fibers and films to injection molding.

In view of the above situation, the present inventors have made extensive studies and as a result have found that polyphosphonic acid amide has a particularly excellent performance balance in injection molding applications, and arrived at the present invention.

That is, according to the present invention, a non-halogen flame retardant is used to impart flame retardancy to a thermoplastic polyester, and at the same time, it has good moldability, and has good hydrolysis resistance and mechanical properties. It is an object to obtain a polyester resin injection molded product.

[0016]

That is, the present invention is as follows.
(A) An aromatic dicarboxylic acid having 8 to 20 carbon atoms, or a lower alkyl ester thereof, and 100 parts by weight of a thermoplastic polyester starting from an aliphatic or alicyclic diol having 2 to 20 carbon atoms (B ) Polyphosphonic acid amide having repeating unit of general formula (1) 0.5 to 100
It is a flame-retardant polyester resin injection-molded article obtained by injection-molding a flame-retardant polyester resin composition containing parts by weight.

[0017]

[Chemical 2] (However, in the above formula, R ¹ is an aryl group, an alkyl group,
Aralkyl group or cycloalkyl group, R ² and R ⁴ are the same or different hydrogen, or aryl group, alkyl group and R ³ are groups selected from arylene group, aralkylene group or alkylene group. Here, the diamine part is R
It may be a ring structure in which ² and R ⁴ are directly connected).

The thermoplastic polyester used in the present invention is a polymer or copolymer obtained by a polycondensation reaction containing a dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative as main components. .

Examples of the dicarboxylic acid used herein include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,2'-biphenyl. Dicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4 , 4'-diphenylisopropylidene dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,
4'-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4'-p
-Aromatic dicarboxylic acids such as terphenyldicarboxylic acid and 2,5-pyridinedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid Therefore, terephthalic acid and 2,6-naphthalenedicarboxylic acid can be preferably used. In addition, you may use these dicarboxylic acid in mixture of 2 or more types.

As the diol component, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol,
Examples thereof include aliphatic diols such as 2-methyl-1,3-propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and mixtures thereof. If the amount is small, one or more long chain diols having a molecular weight of 400 to 6000, that is, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like may be copolymerized.

Specific examples of thermoplastic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate and polyethylene-1,2-bis (phenoxy) ethane. In addition to -4,4'-dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene terephthalate /
Mention may be made of copolyesters such as isophthalate, polybutylene terephthalate / decane dicarboxylate and polycyclohexane dimethylene terephthalate / isophthalate. Of these, polybutylene terephthalate with well-balanced mechanical properties and moldability,
Polybutylene naphthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate and polyethylene terephthalate can be preferably used.

The polyphosphonic acid amide (B) used in the present invention has a repeating unit represented by the following formula (1).

[0023]

[Chemical 3] In the above formula, R ¹ represents a group selected from an aryl group, an alkyl group, an aralkyl group, or a cycloalkyl group. Among them, those having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms are preferable, and R ² and R ⁴ are the same. Or, it represents different hydrogen or a group selected from an aryl group and an alkyl group, and in the case of an aryl group and an alkyl group, those having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms are preferable. R ³ represents a group selected from an arylene group, an aralkylene group or an alkylene group, and among them, those having 1 to 24 carbon atoms are preferably used. The diamine portion may have a ring structure in which R ² and R ⁴ are directly connected.

The polyphosphonic acid amide (B) is generally obtained by reacting a diamine with an aryl or alkylphosphonic acid dihalide in a solvent such as chloroform or tetrahydrofuran in the presence of a hydrogen halide scavenger, or with a diamine and an aryl or alkyl. A method in which dichlorophosphine is similarly reacted and then oxidized with hydrogen peroxide or the like can be easily obtained with a high yield.

Specific examples of the phosphorus component include methylphosphonic acid dichloride, ethylphosphonic acid dichloride, sec.
-Butylphosphonic acid dichloride, cyclohexylphosphonic acid dichloride, benzylphosphonic acid dichloride, phenylphosphonic acid dichloride, dichloromethylphosphine, dichloroethylphosphine, dichlorosec-butylphosphine, dichlorobenzylphosphine, dichlorophenylphosphine, etc., and specific examples of diamine components As, piperazine, hexamethylenediamine, 1,7
-Diaminoheptane, 1,12-diaminododecane, m
-Phenylenediamine, p-phenylenediamine, m-
Xylylenediamine, p-xylylenediamine, 4,
4'-methylenedianiline, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfoxide, 4,
4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylamine, 4,4'-diaminobiphenyl (benzidine), 4,4'-diaminotriphenylamine, 3,3'-dimethylbenzidine (o-tolidine),
3,3'-dimethoxybenzidine (o-anisidine),
3,3'-diethylbenzidine, 4,4'-diaminotriphenylphosphine, 2,5-diaminotoluene,
There are 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminotoluene and the like.

Specific examples of the polyphosphonic acid amide in the present invention include the following examples, but the invention is not limited thereto.

[0027]

[Chemical 4]

[Chemical 5]

[Chemical 6] Of these, as diamine components, piperazine, hexamethylenediamine, m-phenylenediamine, m-xylylenediamine, 4,4′-methylenedianiline, 3,3 ′
-Use of dimethylbenzidine and 2,4-diaminotoluene is particularly preferable because high flame retardancy is obtained.

The number average degree of polymerization of the phosphonamide is preferably in the range of 5 to 70.

The amount of the polyphosphonic acid amide (B) used in the present invention is 0.5 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the thermoplastic polyester. Is. If the addition amount is less than 0.5 parts by weight, the flame retardant effect is not sufficient,
If the amount is more than parts by weight, the mechanical properties of the molded product deteriorate, which is not preferable.

When a monomer or the like remains in the polyphosphonic acid amide, a bad odor during compounding, contamination of the mold during injection molding, gas generation from the molded product, and marked coloring of the molded product are likely to occur. In order to prevent these, it is particularly preferable to use, as the polyphosphonic acid amide to be used, a polyphosphonic acid amide in which the weight loss at 280 ° C. is 6% by weight or less when heated at a rate of 10 ° C./min under a nitrogen stream in a thermobalance. preferable. Also,
As a method for purifying the polyphosphonic acid amide, a method of washing a powdery material obtained by polymerization with water or an organic solvent, a method of dissolving the polymer in an organic solvent and then performing reprecipitation purification by adding a poor solvent, and the like can be adopted. However, the method by reprecipitation purification is more preferable for purification to the above-mentioned level.

Further, the polyphosphonic acid amide used in the present invention has an extremely slight effect of promoting the hydrolysis of the polyester as compared with other conventionally known phosphorus-based flame retardants. The compounds tend to undergo modification, which aids in the hydrolysis of the polyester. It has been found in the present invention that this tendency can be prevented by using a hindered phenol stabilizer in combination, and good hydrolysis resistance can be maintained for a long period of time. Examples of such stabilizers include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol-bis [3- (3,3. 5-di-t-butyl-4-
Hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-
4-Hydroxyphenyl) propionate], 2,2-
Thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3, 5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, bis or tris (3-t-butyl-6-
Methyl-4-hydroxyphenyl) propane, N, N '
-Hexamethylenebis (3,5-di-t-butyl-4-
Hydroxy-hydrocinnamamide), N, N′-trimethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) and the like.

The preferred addition amount of the hindered phenol stabilizer is 0.1% based on 100 parts by weight of the total composition.
The amount is 01 to 1 part by weight, more preferably 0.03 to 0.5 part by weight.

Further, with respect to the polyester composition of the present invention, phosphorus-based or sulfur-based antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, release agents, and dyes are used within the range not impairing the object of the present invention. -One or more ordinary additives such as colorants including pigments can be added.

Also, a small amount of thermoplastic resin such as polycarbonate, polyamide, polyphenylene oxide, polypropylene, polyethylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene copolymer. , Ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene / propylene-g-
It is also possible to add a maleic anhydride copolymer, a polyester polyether elastomer, a polyester polyester elastomer and the like.

Although not particularly required, by adding a fibrous and / or granular filler to the composition of the present invention, the rigidity can be significantly improved without impairing other physical properties. You can

Examples of such a filling material include glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos,
Examples thereof include potassium titanate whiskers, wollastonite, glass flakes, glass beads, talc, mica, clay, calcium carbonate, barium sulfate, titanium oxide and aluminum oxide, and among them, chopped strand type glass fibers are preferably used. The addition amount of these is 5 with respect to 100 parts by weight of the thermoplastic polyester.
To 140 parts by weight are preferred, and 5 to 100 are particularly preferred.
Parts by weight.

The injection-molded article of the present invention is usually produced by a known method. For example, a method in which thermoplastic polyester, polyphosphonic acid amide, and other necessary additives are melt-mixed in an extruder and then injection-molded, or after the particles are mechanically mixed uniformly, a direct injection molding machine is used. And a method of molding at the same time as mixing.

[0038]

EXAMPLES The effects of the present invention will be described in more detail with reference to the following examples. Here, all parts are parts by weight. The measuring method of each characteristic is as follows.

(1) Mechanical Properties ASTM dumbell test pieces obtained by injection molding
Tensile yield strength and breaking elongation were measured according to D-638.

(2) LOI (Limiting Oxygen Concentration Index) A 150 mm × 6 mm × 1 mm strip-shaped test piece was prepared from the pellet, and the LOI was measured according to ASTM D-2863. The larger the LOI, the higher the flame retardancy.

(3) Hydrolysis resistance The dumbbell test piece was treated in a thermo-hygrostat at 80 ° C. and 95% RH for a predetermined time, and the molecular weight change of the polyester before and after the treatment was measured by GPC.

(4) Crystallization characteristics The pellets were measured by DSC. Both heating and cooling are performed at a rate of 20 ° C./min.
After holding at 0 ° C. for 10 minutes, the temperature was lowered. Tm represents the melting point of polyester, and Tc represents the crystallization temperature from the molten state.

Reference Example 1 An equimolar amount of piperazine and phenylphosphonic acid dichloride and 2.1-fold amount of triethylamine were reacted in chloroform at room temperature overnight. The reaction solution obtained is acidified to pH.
The salt was removed by washing with conditioned water and the organic phase was dried. The obtained residue was dissolved in methanol and further poured into water to form a precipitate, which was separated by decantation and dried. Yield 85%. The polyphosphonic acid amide thus obtained is designated as flame retardant A. In addition, the weight reduction rate of the flame retardant A at 280 ° C. in the thermobalance was 10.5%.

Further, the flame retardant A was dissolved in chloroform and added dropwise to diethyl ether for reprecipitation purification. This purified product is designated as flame retardant B. The heat loss rate of the flame retardant B in the thermobalance was 3.6%.

Reference Example 2 Equimolar amounts of hexamethylenediamine and phenylphosphonic acid dichloride and 2.1 volumes of triethylamine were reacted in chloroform under reflux conditions for 5 hours. The precipitate was filtered off from the obtained reaction solution, and the solution side was washed with water whose pH was adjusted to be acidic to remove salts. Water was added to this organic phase for liquid separation, and an oily substance suspended on the aqueous phase side was separated and dried. The polyphosphonic acid amide thus obtained is used as a flame retardant C. Yield 89%. The heat loss of the flame retardant C was 9.4%.

Reference Example 3 Equimolar amounts of m-phenylenediamine and phenylphosphonic acid dichloride and 2.0 volumes of triethylamine were reacted in chloroform for 5 hours under reflux conditions. The insoluble matter was removed by filtration from the obtained reaction mixture, and water was added to the filtrate to precipitate a precipitate. The precipitate was filtered, washed further with water and dried. The polyphosphonic acid amide thus obtained is designated as flame retardant D. Yield 87%. The heat loss of the flame retardant D was 5.5%.

Reference Example 4 A polyphosphonic acid amide was synthesized in the same manner as in Example 2 except that m-xylylenediamine was used instead of hexamethylenediamine. Yield 81%, in thermobalance 280
The loss on heat at 0 ° C was 0.5%. Let this polyphosphonic acid amide be the flame retardant E.

Reference Example 5 A polyphosphonic acid amide was synthesized in the same manner as in Example 2 except that p-xylylenediamine was used instead of hexamethylenediamine. Yield 78%, in thermobalance 280
The thermal loss at 0 ° C was 0.6%. This polyphosphonamide is used as the flame retardant F.

Reference Example 6 A polyphosphonic acid amide was synthesized in the same manner as in Example 2 except that 2,4-diaminotoluene was used instead of hexamethylenediamine. Yield 97%, in thermobalance, 28
The loss on heat at 0 ° C. was 2.4%. Let this polyphosphonic acid amide be the flame retardant G.

Reference Example 7 A polyphosphonic acid amide was synthesized in the same manner as in Example 2 except that 3,3-dimethylbenzidine (o-tolidine) was used instead of hexamethylenediamine. Yield 99
%, The thermal loss at 280 ° C. in the thermobalance was 3.1%. This polyphosphonamide is used as the flame retardant H.

Reference Example 8 A polyphosphonic acid amide was synthesized in the same manner as in Example 2 except that 4,4'-methylenedianiline was used instead of hexamethylenediamine. Yield 99%, in thermobalance,
The loss on heat at 280 ° C was 3.9%. This polyphosphonamide is designated as flame retardant I.

Reference Example 9 Bisphenol S with reference to JP-A-47-39300
Polyphosphonates were synthesized from and phenylphosphonyl dichloride. Yield 95%. This is designated as flame retardant J.

Examples 1 to 1, Comparative Examples 1 to Polybutylene terephthalate having an intrinsic viscosity of 0.85 (25 ° C., o-chlorophenol solution), various phosphorus compounds shown in Tables 1 and 2 and other additives. And the resin temperature of 260 using a 30 mmφ twin-screw extruder.
Melt extruded at ° C. After the obtained pellets were dried, a tensile test piece specified in ASTM D-638 was prepared by injection molding (mold temperature: 80 ° C). In addition, press molding was performed to prepare a sample for LOI measurement.

Tables 1 and 2 collectively show the measurement results of LOI, mechanical properties, color tone of molded products, and hydrolysis resistance of each sample.

In the table, the amount of flame retardant added is the weight percentage of P content, and the antioxidant is pentaerythrutyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl). Propionate] (Ciba Geigy "I"
R-1010 ").

[0056]

[Table 1]

[0057]

[Table 2]

From the LOI values of Examples 1 to 6, 9 to 10 and 13 to 16 and Comparative Examples 1, 3 and 5, it is understood that excellent flame retardancy can be imparted by blending the polyphosphonamide of the present invention. . Further, when the polyphosphonic acid amide of the present invention is used, mechanical properties, crystallization characteristics, color tone and hydrolysis resistance of polyester are not significantly lowered unlike red phosphorus and polyphosphonic acid ester. Glass fiber reinforced Examples 7-8, 11-12 and Comparative Examples 2, 4, 6
The same can be said when comparing

The addition of the polyphosphonic acid amide of the present invention does not cause a significant decrease in hydrolysis resistance, but it does decrease a little when compared with the polyester containing no flame retardant (for example, Example 2). 5, 9 and Comparative Example 1). However, it is understood that the addition of the hindered phenolic stabilizer improves the hydrolysis resistance and shows the hydrolysis resistance close to the level of the polyester containing no flame retardant (Examples 2 and 5, Example 1). Examples 5 and 6, Examples 9 and 10). Similar tendencies are seen with glass fiber reinforced systems (Examples 7 and 8 and Examples 11 and 1).
2).

In Examples 1 and 3, the effect of the presence or absence of purification of polyphosphonic acid amide derived from piperazine on various physical properties of polyester was investigated. It can be seen that Example 3 using the purified polyphosphonamide has slightly improved mechanical properties, color tone, and hydrolysis resistance as compared with Example 1 using the unpurified polyphosphonic acid amide. You can see that there is no big difference.

[0061]

【The invention's effect】

(1) The polyphosphonic acid amide used in the present invention exhibits a higher flame retarding effect than other conventionally known phosphorus-based flame retardants. Further, since it is a polymer, no volatile matter is generated during processing of the resin, and since it does not have a P—O bond, it is an excellent flame retardant that has good hydrolysis resistance and does not adversely affect the polyester resin.

(2) The injection-molded article obtained by the present invention has not only good flame retardancy but also excellent mechanical properties, melt flowability and surface appearance, and there is no deterioration in hydrolysis resistance. It is useful as parts, electric parts and automobile parts.

(3) The injection-molded product of the present invention uses a non-halogen flame retardant, and there is a concern that harmful gas such as hydrogen halide may be generated during molding, use, or incineration after disposal. Absent.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideo Matsuoka 1-9-9 Oe-cho, Minato-ku, Nagoya-shi, Aichi Toray Industries, Inc. Nagoya Plant

Claims (2)

[Claims] 1. (A) an aromatic dicarboxylic acid having 8 to 20 carbon atoms or a lower alkyl ester thereof, and 2 to 2 carbon atoms
0.5 to 100 parts by weight of (B) a polyphosphonamide having a repeating unit of the general formula (1) is blended with 100 parts by weight of a thermoplastic polyester starting from an aliphatic or alicyclic diol of 0. Flame-retardant polyester resin injection-molded article obtained by injection-molding the flame-retardant polyester resin composition. [Chemical 1] (However, in the above formula, R ¹ is an aryl group, an alkyl group,
Aralkyl group or cycloalkyl group, R ² and R ⁴ are the same or different hydrogen, or aryl group, alkyl group and R ³ are groups selected from arylene group, aralkylene group or alkylene group. Here, the diamine part is R
It may be a ring structure in which ² and R ⁴ are directly connected). 2. The structure has the structure of the general formula (1), and the thermal loss at the time of heating by a thermobalance is 6% by weight at 280 ° C.
The flame-retardant polyester resin injection-molded article according to claim 1, wherein the following polyphosphonic acid amide is used.