JP2001163962A - Fire retarding polyester resin composition and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a fire retarding polyester resin composition in high productivity which not only shows a high fire retarding property but has an excellent hue and good physical and mechanical properties. SOLUTION: A fire retarding polyester resin composition showing a high fire retarding property and having an excellent hue and excellent hydrolysis resistance is obtained by use of a combination of a specific phosphorous compound with a specific polymerization catalyst, each amount being also specific.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polyester resin composition and a method for producing the same. For more information,
The present invention relates to a flame-retardant polyester resin composition having high flame retardancy, good hue and hydrolysis resistance, and a method for producing the same with high productivity.

[0002]

2. Description of the Related Art Hitherto, polyesters, particularly polyethylene terephthalate, have been widely used for various molded articles such as fibers, films, bottles and the like, utilizing the excellent chemical and physical properties thereof. However, polyethylene terephthalate is insufficient in flame retardancy, and various efforts have been made to improve this point. For example, a method of adding a flame retardant during polymer production and copolymerizing or blending it, a method of kneading the flame retardant at the time of molding, a method of processing a molded article, and attaching or impregnating the flame retardant to the surface or inside of the molded article. And so on.

[0003] Among the above methods, the method of imparting flame retardancy by processing has a drawback that the method falls off and the performance is reduced. Further, in the method of kneading the flame retardant, the flame retardant exudes in the fiber production process, which causes a trouble. On the other hand, the method of copolymerizing a flame retardant during polymer production can overcome the above-mentioned disadvantages,
It has the highest industrial value. As a method of copolymerizing this flame retardant, many methods have been proposed so far. For example, Japanese Patent Publication No. 49-22958 discloses that a phosphate ester is copolymerized with a polyester as a phosphorus compound. However, if the phosphorus compound is blended to an amount that imparts the desired flame retardancy, gelation of the polyester occurs due to three-dimensionalization. In addition, Japanese Patent Publication No. 36-21
No. 050, JP-B-38-9449 uses phosphonic acid or phosphonic acid esters as the phosphorus compound, but the phosphorus compound is scattered during the production of the polymer and the desired phosphorus amount cannot be blended. .

As a method for solving such problems, there is disclosed a method of copolymerizing carboxyphosphinic acid by the methods described in JP-B-53-13479 and JP-B-55-41610. However, there were problems such as a decrease in the polymerization rate due to the phosphorus compound, darkening due to the reduction of the antimony catalyst and deterioration in the processability, and a poor hue due to the yellow tint of the monomer itself.

Therefore, Japanese Patent Application Laid-Open No. Hei 6-16796 discloses that the polymerization rate,
A method for improving the hue of a polymer is disclosed. However, in this method, although the polymerization rate can be improved, the use of a titanium catalyst deteriorates the thermal stability of the polymer, and increases the yellow coloration of the polymer, especially after molding. As a result, the hue of the polymer can be improved to some extent,
There was a problem that the whiteness itself could not be improved, and it could not be used for applications requiring a high degree of whiteness. Furthermore, because the phosphorus atom is incorporated into the polymer backbone,
There is a problem that the hydrolysis resistance of polyester is poor.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a flame retardant polyester having high flame retardancy, extremely good hue and resistance to hydrolytic decomposition. An object of the present invention is to provide a resin composition for producing a molded article, and a method for producing the resin composition with high productivity.

[0007]

Means for Solving the Problems The present inventors have conducted various studies to solve the above problems, and as a result, have finally completed the present invention. That is, the present invention provides: (1) ethylene terephthalate as a main structural unit,
A resin composition comprising a polyester obtained by copolymerizing or blending a phosphorus compound or a polyester containing the same, wherein the following formula (1) is satisfied, and the b value measured by a Hunter type dye meter is 10.00 or less. A flame-retardant polyester resin composition, comprising: % BB <0.5 (Equation 1) (However,% BB indicates the degree of ester bond breakage when immersed in a closed system of pure water at 130 ° C for 6 hours. The intrinsic viscosity before immersion is [η] _i , Is defined as [η] _f, and the intrinsic viscosity is a value measured at 30 ° C. in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio: 3/2). % BB = 0.244 × [[η] _f ^-1.471- [η] _i ^-1.471 ] (Formula 2) (2) The phosphorus compound is contained at 500 to ¹⁵⁰⁰⁰ ppm as a phosphorus atom with respect to the polyester. And 0.0001 to 1% by weight of an organic fluorescent whitening agent, and further contains an antimony compound, a germanium compound and a cobalt compound as polycondensation catalysts in amounts satisfying the following formulas (a) to (c) at the same time. (2) The flame-retardant polyester resin composition according to (2). 30 ≦ S ≦ 400 10 ≦ G ≦ 100 5 ≦ C ≦ 40 200 ≦ S + 2G + C ≦ 400 (however, S, G and C are the contents of antimony atom, germanium atom and cobalt atom, respectively, with respect to polyester.
(ppm). (3) The phosphorus compound represented by the general formula (1):

Embedded image (In the formula, R ¹ and R ² represent an organic group or a halogen atom, m and n each represent an integer of 0 to 4. When m is an integer of 2 to 4, a plurality of R ¹ are the same or different. When n is an integer of 2 to 4, a plurality of R's may be present.
² may be the same or different. A represents an organic group containing the same or different hydrogen atom as R ¹ and R ² . The flame-retardant polyester resin composition according to (1) or (2), which is represented by the following formula: (4) The content of the phosphorus compound is 3000 to 10000 ppm as a phosphorus atom with respect to the polyester (1) to (1).
The flame-retardant polyester resin composition according to (3). (5) The content of the phosphorus compound is 3000 to 5000 ppm as a phosphorus atom with respect to the polyester (1) to (4).
The flame-retardant polyester resin composition according to the above. (6) The flame-retardant polyester resin according to (1) to (5), wherein an antimony compound, a germanium compound, or a cobalt compound is used as a polycondensation catalyst in an amount that simultaneously satisfies the following formulas (a) to (c). A method for producing the composition. 30 ≦ S ≦ 400 10 ≦ G ≦ 100 5 ≦ C ≦ 40 200 ≦ S + 2G + C ≦ 400 (however, S, G and C are the contents of antimony atom, germanium atom and cobalt atom, respectively, with respect to polyester.
(ppm). )

As described above, in the production of a flame-retardant polyester containing a phosphorus compound, by using a specific phosphorus compound and a specific polycondensation catalyst in a specific amount, a high degree of flame retardancy, good color tone and resistance to water are obtained. A flame-retardant polyester resin composition having decomposability can be obtained.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The flame retardant component referred to in the present invention is not particularly limited as long as it is a compound containing phosphorus in general, and a specific example preferably used is a compound represented by the general formula (1):

Embedded image (Wherein, R ¹ and R ² represent an organic group or a halogen atom, and m and n each represent an integer of 0 to 4. When m is an integer of 2 to 4, a plurality of R ¹ are the same or different. When n is an integer of 2 to 4, a plurality of R's may be present.
² may be the same or different. A represents an organic group containing the same or different hydrogen atom as R ¹ and R ² . )).

As the organic group (A), various types can be exemplified, and among the organic groups, those having an organic group containing an ester-forming functional group such as a hydroxyl group, a carboxyl group, a carboxylic ester group, etc. Is preferably used as a polyester copolymer component. Specific examples preferably used as the organic phosphorus compound represented by the general formula (1) include the following chemical formulas (a) to (z) and (α).
Examples represented by (δ) can be given.

[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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Alkyl esters such as methyl ester, ethyl ester, propyl ester, butyl ester, propion glycol ester and ester with butanediol, cycloalkyl ester, aryl ester, or alkylene glycol ester such as ethylene glycol ester of these compounds; Or derivatives thereof such as cyclic acid anhydrides thereof, but not limited thereto. Furthermore, it is also possible to use these mixtures.

In the present invention, the phosphorus compound represented by the general formula (1) may have a phosphorus atom as a ring member,
It is extremely thermally stable as compared with the case where a commonly used phosphorus compound is used. Therefore, it has particularly good color tone and has better physical properties than conventional flame-resistant polyester.
Therefore, this polyester makes it possible to produce a flame-retardant molded article having excellent properties. However,
Since the phosphorus compound has a particularly strong reducing power as compared with other phosphorus compounds, the polymerization catalyst is easily deactivated, and thus a problem in the production process is easily caused. When the phosphorus compound represented by the general formula (1) is used, the effects of the present invention are most remarkably exhibited.

When the phosphorus compound represented by the general formula (1) used in the practice of the present invention has one ester-forming functional group, the phosphorus compound may act as a terminal stopper in some cases. It is preferable to use a known polyfunctional compound such as pentaerythritol and a trifunctional carboxylic acid in combination.

The above-mentioned phosphorus compound is used when producing the flame-retardant polyester of the present invention.
It is preferable to dissolve or disperse in a dihydric alcohol such as a dihydric alcohol, ethylene glycol, propylene glycol, and butylene glycol, and then add it to the reaction system.

These phosphorus compounds are added so that the amount of phosphorus element in the polymer is 500 to 15000 ppm.
Preferably it is 3000 to 10000 ppm. If the amount of the phosphorus compound is less than this range, sufficient flame retardancy is not exhibited,
Conversely, when the amount is large, not only the physical properties inherent in the polyester are impaired, but also the operability in producing the polyester resin composition is unpreferably reduced. However, particularly because the phosphorus compound represented by the general formula (1) has a ring structure, it has a high flame retarding ability,
A sufficient flame retardancy is exhibited with a phosphorus content of 00 ppm.

As a method for obtaining such a polyester,
It is not necessary to employ special polymerization conditions, and it can be synthesized by any method employed when a polycarboxylic acid and / or an ester-forming derivative thereof is reacted with a glycol to produce a polyester. it can. The phosphorus compound is added during the production of the polyester, and the phosphorus compound can be added at any stage from the early stage of the esterification process to the late stage of the initial condensation. From the viewpoint of suppressing side reactions and the problem of corrosion of the reactor bed, it is preferable to add the compound from the latter stage of the esterification process to the earlier stage of the initial condensation.

The most important feature of the present invention is that an antimony compound, a cobalt compound, and a germanium compound are used in combination at a specific ratio as a polycondensation catalyst when producing the polyester to which the phosphorus compound is added. That is, it is important to use the compound in a ratio satisfying the following expressions (a) to (d). 30 ≦ S ≦ 400 (a) 10 ≦ G ≦ 100 (b) 5 ≦ C ≦ 40 (c) 200 ≦ S + 2G + C ≦ 400 (d) (However, S, G and C are antimony atoms, germanium atoms, cobalt atoms, respectively. Content of polyester
(ppm). )

If the amount of the antimony compound is less than the above range, the polycondensation reaction will be slow, while if it exceeds the above range, the L value of the resulting polymer will be undesirably reduced. Further, in general, when a large amount of a phosphorus compound is added, the antimony compound is reduced by the phosphorus compound, so that the reduced product becomes a foreign substance, which not only deteriorates the molding operability but also deteriorates the quality of the product, which is not preferable. . One of the great effects of the present invention for reducing the amount of antimony catalyst is an improvement in productivity.

When the amount of the germanium compound is less than the above range, the rate of the polycondensation reaction is slow. On the other hand, when the amount exceeds the above range, the production cost is increased because germanium is very expensive. Without the resin composition
The b value increases, which is not preferable.

When the addition amount of the cobalt compound is less than the above range, the b value of the color tone of the obtained polymer increases, and when it exceeds the range, the b value tends to be too low and the L value tends to decrease. It is not preferable.

Further, when G, S and C do not satisfy the above formula (d) and S + 2G + C is less than the above range, the polycondensation reaction rate becomes insufficient. It is not preferable because color tone and stability deteriorate.

In the present invention, the timing of addition of the polycondensation catalyst is not particularly limited as long as it is before the start of the polycondensation reaction, and may be performed according to a conventionally known method. For example,
Examples thereof include a transesterification method, a direct polymerization method, and a continuous polymerization method.

In the method for producing a flame-retardant polyester according to the present invention, additives generally used, for example, tetraethylammonium hydroxide which is an ether bond inhibitor, an organic amine, an organic carboxylic acid amide, Add together with basic salts such as sodium acetate and lithium acetate, such as titanium dioxide as a matting agent, other flame retardant aids, pigments such as carbon black, plasticizers, stabilizers, electrostatic agents, and tinting agents. Things are also possible.

In the present invention, an organic fluorescent whitening agent can be used for the purpose of improving the color tone of the polymer.
Specifically, a benzoxazole-based compound is preferable,
HostaluxKS (manufactured by Clariant) is particularly preferred. The amount of addition is 0.0001 to 1% by weight, and if it is less than 0.0001% by weight, a sufficient improvement effect cannot be obtained, which is not preferable. Further, even if it is added in an amount of 1% by weight or more, the effect is not improved. More preferably, it is 0.0001 to 0.05% by weight. The organic fluorescent whitening agent may contain a bluish dye for the purpose of improving hue.

The polyester in which the main structural unit is ethylene terephthalate in the present invention is ethylene terephthalate in which at least 70 mol% of the repeating structural units is ethylene terephthalic acid or dimethyl terephthalate and ethylene glycol or ethylene oxide as raw material components.
As the copolymerization component, the phosphorus compound represented by the above-mentioned general formula 1 is used. However, other than the above, as long as the effects of the present invention are not impaired, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalene Dicarboxylic acid, 5-sodium sulfoisophthalic acid, 4,4'-diphenyldicarboxylic acid, bis
(4-carboxyphenyl) ether, bis (4-carboxyphenyl) sulfone, 1,2-bis (4-carboxyphenoxy) ethane, 2,5-dibromoterephthalic acid, aromatic dicarboxylic acids such as tetrabromoterephthalic acid and It is also possible to use derivatives thereof, aliphatic and alicyclic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, hexahydroterephthalic acid and derivatives thereof, and mixtures thereof. On the other hand, glycols such as trimethylene glycol, tetramethylene glycol, neopentyl glycol, 1,4-cyclohexynediol, 1,4-cyclohexynedimethanol, diethylene glycol and polyethylene glycol, p-hydroxybenzoic acid, p-hydroxyethoxybenzoic acid It is also possible to use oxycarboxylic acids such as oxypivalic acid and derivatives thereof, or mixtures thereof.

The flame-retardant polyester resin composition of the present invention must have a hydrolysis resistance in the range represented by the above formula (1). If the hydrolysis resistance is larger than the range of the formula 1, the influence of water during the production and use of the molded article is large, and the production conditions of the product, the intended use, and the like are not preferred.

It is also possible to further improve the flame retardancy by combining with known flame retardants. The combination referred to here means, for example, a method of adding a flame retardant during polymer production and copolymerizing or blending, a method of kneading the flame retardant at the time of molding, and a post-processing of a polyester molded product, and a flame retardant to the surface or inside. And a method of adhering or infiltrating. Examples of the blend type flame retardant include tetrabromobisphenol (TBA), decabromodiphenyl oxide (DBDPO), hexabromocyclododecane (HBCD), octabromodiphenyl oxide, bistribromophenoxyethane (BTBPE), and tribromophenol (TBPPE). ), Ethylene bistetrabromophthalimide, TBA polycarbonate oligomer, brominated polystyrene, TBA epoxy oligomer / polymer, decabromodiphenylethane, polydibromophenyl oxide, bromine compounds such as hexabromobenzene, chlorinated paraffin, perchlorocyclopentadecane, etc. Halogen flame retardants such as chlorine compounds are exemplified. Or phosphate-based, halogen-containing phosphate-based, polyphosphate, phosphorus-based flame retardants such as red phosphorus, silicone-based flame retardants such as silicone polymer powder, triazine compounds,
Organic flame retardants such as melanin cyanurate and guanidine compounds are exemplified. Further, inorganic difficulties such as antimony trioxide, aluminum hydroxide, guanidine nitride, antimony pentoxide, magnesium hydroxide, zinc borate, zirconium compounds, calcium aluminate, ammonium phosphate, ammonium carbonate, molybdenum compounds, zinc stannate, etc. And the like. The above-mentioned flame retardants are not limited to those described, and include derivatives and analogs thereof. These flame retardants may be used alone or in combination.

[0034]

A method of copolymerizing a bifunctional ester-forming phosphorus compound with polyethylene terephthalate has heretofore been proposed for simultaneously satisfying high flame retardancy and mechanical properties. However, the phosphorus compound used here reduces, deactivates, and blackens the catalyst antimony, and the polycondensation reaction time is long with the antimony polycondensation catalyst used alone when polycondensing polyethylene terephthalate. In order to obtain a polyester having a sufficiently high degree of polymerization, there is a problem that the color tone of the polymer deteriorates (the L value measured by a Hunter color difference meter decreases).

On the other hand, in the production method of the present invention, by using a compound of germanium, antimony and cobalt in a specific ratio, the polycondensation reaction rate is improved and the polycondensation reaction time can be shortened. Together, the color tone and production operability of the resulting polymer are significantly improved. In addition, by using a specific phosphorus compound, sufficient flame retardancy can be obtained with a small phosphorus content while maintaining the physical properties of the polymer.

Therefore, from the flame-retardant polyester according to the present invention, a polyester resin composition having excellent mechanical properties and physical properties such as hydrolysis resistance, a good hue, and a high degree of flame retardancy can be easily prepared. And its industrial value is extremely large.

[0037]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In Examples, “parts” means “parts by weight” and “%” means “percent by weight”. Various characteristics were evaluated by the following methods.

(1) Intrinsic viscosity [IV] It was measured in a phenol / 1,1,2,2-tetrachloroethane mixed solvent (weight ratio 3: 2) at 30 ° C., and was determined from the relative viscosity by a conventional method.

(2) Color tone (L value, b value) The L value and b value representing the color tone of the polymer are values measured using a Hunter-type color difference meter, and the higher the L value, the better. The larger the b value, the stronger the yellow tint. That is, the larger the L value and the smaller the b value, the better the color tone.

(3) Phosphorus content Fluorescent X-rays derived from phosphorus atoms of the obtained polymer were measured and calculated from the luminescence intensity.

(4) Flame retardancy The limiting oxygen index (LOI value) was measured and evaluated according to a conventional method.

(5) Hydrolysis resistance The drawn yarn was formed and treated under a pressure of 130 ° C. in a closed system of pure water for 60 minutes under pressure. The sample is prepared by drawing and setting a low-oriented undrawn yarn melt-spun in a conventional manner at a maximum draw ratio of 0.7 and a draw ratio of multifilament of 50 denier and 24 filaments. The intrinsic viscosity is determined from (1).

(Example 1) Terephthalic acid was placed in a stainless steel autoclave equipped with a stirrer, a distillation column and a pressure regulator.
42 parts, 117 parts of phosphorus compound (x) (as a 50% ethylene glycol solution) and 850 parts of ethylene glycol were charged, and 24.1 parts of antimony trioxide (as a 14 g / L ethylene glycol solution), and 15 parts of germanium dioxide (As an 8 g / L ethylene glycol solution), 5.2 parts of triethylamine,
22 parts of titanium dioxide (as a 23.5% ethylene glycol solution) was added, and the esterification reaction was carried out for 2 hours at 230 ° C. at a gauge pressure of 2.5 kg / cm 2 while sequentially removing water generated in the esterification. Subsequently, 9.6 parts of cobalt acetate tetrahydrate (as a 20 g / L ethylene glycol solution) was added, and the temperature of the system was raised to 275 ° C. in one hour, during which time the pressure of the system was gradually reduced. At 0.1 mmHg, a polycondensation reaction was carried out under these conditions for 1 hour. The intrinsic viscosity of the obtained polymer was 0.65 and the phosphorus content was 3500 ppm. This polymer was spun and drawn by a conventional method to prepare a knitted sample of 50 denier 24 filaments. The spinning operation product was good.
% BB and hue, which are scales representing flame retardancy and hydrolysis resistance, were measured. Table 1 shows the results.

Example 2 In Example 1, the catalyst addition amount was changed as shown in Table 1, and a fluorescent whitening agent (Hostalux K) was used.
The same operation as in Example 1 was performed except that 16.5 parts (as a 2% by weight ethylene glycol solution) of S (manufactured by Clariant) was added after the esterification. Table 1 shows the results. In addition, the product made by spinning operation was good.

Example 3 In Example 1, the content of phosphorus was changed to 6000 ppm as a phosphorus atom, and 16.5 parts (2% by weight) of a fluorescent brightener (HostaluxKS: manufactured by Clariant) was used.
The same operation as in Example 1 was performed, except that (as an ethylene glycol solution) was added after the esterification. Table 1 shows the results. In addition, the product made by spinning operation was good.

Example 4 In Example 1, the type of phosphorus, the content of phosphorus, and the amount of catalyst were changed as shown in Table 1, and 16.5 parts (2% by weight of ethylene) of a fluorescent whitening agent (HostaluxKS, manufactured by Clariant) was used. (As a glycol solution) was added after the esterification, and the same operation as in Example 1 was performed. Table 1 shows the results. In addition, the product made by spinning operation was good.

(Comparative Examples 1-2) In Example 1, the type of the phosphorus compound, the phosphorus content, the catalyst addition amount, and the fluorescent whitening agent addition amount were changed as shown in Table 1, and the polymer was polymerized.
Table 1 shows the results. Comparative Example 1 is a germanium homopolymerization catalyst, and although the L value rises remarkably, the b value is abnormally high and cannot be used for high purposes. In addition, the product made by spinning operation was good. In Comparative Example 2, since the phosphate ester site was introduced into the polymer main chain, the hydrolysis resistance was poor.

[0048]

【table 1】

[0049]

Embedded image From the results shown in Table 1, it is recognized that the present invention can produce a flame-retardant polyester resin composition having high flame retardancy and extremely good hue, and having excellent hydrolysis resistance with high productivity.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Munekazu Okuhara 2-1-1 Katata, Otsu-shi, Shiga F-term in Toyobo Co., Ltd. Research Laboratory (reference) 4J029 AA03 AB04 AC02 AD01 AE02 AE03 BA03 CB06A JC562 JF361 JF461 JF571

Claims (6)

[Claims] 1. A resin composition comprising a polyester obtained by copolymerizing or blending a phosphorus compound with ethylene terephthalate as a main constituent unit or a polyester containing the same, wherein the following formula (1) is satisfied, and a Hunter type dye is provided. A flame-retardant polyester resin composition, wherein the b value measured by a total is 10.00 or less. % BB <0.5 (Equation 1) (However,% BB indicates the degree of ester bond breakage when immersed in a closed system of pure water at 130 ° C for 6 hours. The intrinsic viscosity before immersion is [η] _i , Is defined as [η] _f, and the intrinsic viscosity is a value measured at 30 ° C. in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio: 3/2). % BB = 0.244 × [[η] _f ^-1.471- [η] _i ^-1.471 ] (Equation 2) 2. The phosphorous compound contains 500 to 15000 ppm of a phosphorus atom based on the polyester relative to the polyester, 0.0001 to 1% by weight of an organic fluorescent whitening agent, and further comprises an antimony compound, a germanium compound, and a cobalt compound as a polycondensation catalyst. The flame-retardant polyester resin composition according to claim 1, wherein the compound contains the compound in an amount satisfying the following formulas (a) to (c) at the same time. 30 ≦ S ≦ 400 10 ≦ G ≦ 100 5 ≦ C ≦ 40 200 ≦ S + 2G + C ≦ 400 (however, S, G and C are the contents of antimony atom, germanium atom and cobalt atom, respectively, with respect to polyester.
(ppm). ) 3. The method according to claim 1, wherein the phosphorus compound has the general formula (1): (Wherein, R ¹ and R ² represent an organic group or a halogen atom, and m and n each represent an integer of 0 to 4. When m is an integer of 2 to 4, a plurality of R ¹ are the same or different. When n is an integer of 2 to 4, a plurality of R's may be present.
² may be the same or different. A represents an organic group containing the same or different hydrogen atom as R ¹ and R ² . 3) The flame-retardant polyester resin composition according to claim 1 or 2, wherein 4. The method according to claim 1, wherein the content of the phosphorus compound is 3000 to 10000 ppm as a phosphorus atom with respect to the polyester.
4. The flame-retardant polyester resin composition according to any one of claims 1 to 3. 5. The method according to claim 1, wherein the content of the phosphorus compound is 3,000 to 5,000 ppm as a phosphorus atom with respect to the polyester.
5. The flame-retardant polyester resin composition according to any one of items 1 to 4. 6. An antimony compound, a germanium compound or a cobalt compound is used as a polycondensation catalyst in an amount which simultaneously satisfies the following formulas (a) to (c).
A method for producing the flame-retardant polyester resin composition as described above. 30 ≦ S ≦ 400 10 ≦ G ≦ 100 5 ≦ C ≦ 40 200 ≦ S + 2G + C ≦ 400 (however, S, G and C are the contents of antimony atom, germanium atom and cobalt atom, respectively, with respect to polyester.
(ppm). )