JP2011088972A - Polyester resin composition and molded article comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin composition excellent in color tone and thermal stability, excellent in transparency of a molded article, and excellent in solid phase polymerization activity, and to provide a method for producing the polyester resin composition. <P>SOLUTION: The polyester resin composition contains an aluminum compound and a phosphorus compound, wherein the chemical shift in the P-NMR of the polyester resin composition satisfies specified conditions. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyester resin composition, a production method thereof, and a use thereof, and more specifically, a polyester resin composition having an improved solid-phase polymerization rate, excellent transparency, and reduced coloring, a production method thereof, and The present invention relates to a hollow molded article, fiber, and film produced using this polyester resin composition.

  Polyester resins represented by polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc. are excellent in mechanical properties and chemical properties. According to the properties of each polyester, For example, it is used in a wide range of fields such as fibers for clothing and industrial materials, films and sheets for packaging and magnetic tape, bottles that are hollow molded products, casings for electrical and electronic parts, and other engineering plastic molded products. Yes. In particular, bottles made of saturated polyesters such as polyethylene terephthalate are excellent in mechanical strength, heat resistance, transparency and gas barrier properties, so containers for filling beverages such as juices, carbonated drinks and soft drinks, and containers for eye drops, cosmetics, etc. As widely used.

  For example, in the case of polyethylene terephthalate (PET), a polyester mainly composed of aromatic dicarboxylic acid and alkylene glycol, which is a typical polyester, is an esterification reaction or transesterification of terephthalic acid or dimethyl terephthalate and ethylene glycol. An oligomer mixture such as bis (2-hydroxyethyl) terephthalate is produced by reaction, and this is subjected to melt polycondensation using a catalyst at high temperature and under vacuum, and after granulation, solid phase polycondensation is performed to produce pellets for molding. . The polyester pellets thus manufactured are manufactured by injection molding to produce a preform, and then the preform is blow-molded, biaxially stretched, and molded into a bottle shape.

  Conventionally, antimony or germanium compounds have been widely used as the polyester polycondensation catalyst used in such polycondensation of polyester. Antimony trioxide is an inexpensive catalyst with excellent catalytic activity. However, if it is used in an amount of such a main component, that is, a practical polymerization rate, metal antimony is used during polycondensation. As a result of precipitation, blackening and foreign matter are generated in the polyester resin, which may cause surface defects of the film. Further, when a raw material such as a hollow molded product is used, it is difficult to obtain a hollow molded product having excellent transparency. Under such circumstances, a polyester resin containing no antimony or containing antimony as a main catalyst component is desired.

  Germanium compounds have already been put to practical use as catalysts that give polyester resins that have excellent catalytic activity other than antimony compounds and that do not have the above-mentioned problems. The catalyst concentration in the reaction system changes due to the tendency of distilling out of the reaction system during the polymerization, making it difficult to control the polymerization, and the problem of poor thermal oxidation stability of the polyester resin. There is a problem with using as.

  Studies have been conducted on polycondensation catalysts to replace antimony or germanium catalysts, and titanium compounds typified by tetraalkoxy titanates have already been proposed. Polyester resins produced using these compounds are heated during melt molding. There is a problem that the polyester resin is easily deteriorated and the polyester resin is remarkably colored.

  Although it is known that an aluminum compound is generally inferior in catalytic activity (see, for example, Patent Document 1), it is known that the catalytic activity of an aluminum compound is improved by using a phosphorus compound in combination with the aluminum compound ( For example, refer to Patent Documents 2 to 11.) When the catalyst is used, a polyester resin excellent in color tone can be obtained. However, problems to be solved have been found in order to stably produce industrially.

Japanese Patent Publication No.46-40711 JP 2001-131276 A JP 2002-256068 A JP 2002-220446 A JP 2002-220451 A Japanese Patent Laid-Open No. 2002-249666 JP 2002-249568 A JP 2002-322259 A Japanese Patent Laid-Open No. 2002-249469 Japanese Patent No. 3461175 JP 2007-137914 A

  For example, when the compound described in Patent Document 11 and the benzylphosphonic acid diethyl ester described in Patent Document 2 are used alone as the phosphorus compound, the catalytic activity is slightly insufficient and the content of fine foreign matter insoluble in polyester It turns out that there is a problem that there are many. Moreover, the thermal oxidation stability of the polyester resin obtained using this catalyst also had the problem that it was lower than the time of using an Sb catalyst.

  Further, when 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester described in Patent Document 10 is used alone as a phosphorus compound, thermal oxidation of a polyester resin obtained using this catalyst Although it is excellent in stability, it has been found that foaming may occur during the manufacturing process, which is a problem.

  Moreover, when calcium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate methyl] described in Patent Document 10 is used alone as the phosphorus compound, the polyester obtained using this catalyst It was found that although the thermal oxidation stability was excellent and there was no foaming during the production process, the solid phase polymerization activity was low and the productivity was poor.

  Moreover, when the catalyst system which combined the aluminum compound and the phosphorus compound of patent documents 2-11 is used, although melt polymerization activity is equivalent to the conventional antimony catalyst, there exists a problem that solid-phase polymerization activity is inferior compared with an antimony catalyst. there were. This problem is particularly problematic in applications that require high viscosity such as tire cords. If the solid-phase polymerization activity is low, the productivity is inferior, and this is a big problem for industrially producing polyester, and is an important problem to be solved.

  An object of the present invention is to provide a polyester resin composition that does not contain a heavy metal compound as a catalyst, is excellent in color tone and thermal stability, has little foaming during polymerization, and has excellent solid-phase polymerization activity, and a method for producing the same. . In particular, an object of the present invention is to provide a polyester resin composition excellent in solid phase polymerization activity in order to improve the productivity of the polyester resin.

  As a result of intensive studies aimed at solving the above problems, the polyester resin composition containing an aluminum compound and a phosphorus compound contains two specific phosphorus compounds as a phosphorus compound in a specific molar ratio. Surprisingly, it has been found that the solid-phase polymerization activity is superior to the case where these phosphorus compounds are contained alone, and the present invention has been achieved. The polyester resin composition of the present invention is excellent in color tone and thermal stability, excellent in transparency of the molded product, has few foreign matters, is excellent in thermal oxidation stability, and has little foaming during polymerization.

That is, the present invention
(1) A polyester resin composition comprising an aluminum compound and a phosphorus compound, wherein the phosphorus compound comprises at least a phosphorus compound represented by the following formula (formula 1) and the following formula (formula 2), When the integral value of the peak derived from the following formula (formula 1) in the P-NMR spectrum of the resin composition is (a) and the integral value of the peak derived from the formula (formula 2) is (b) (A) / (b) is 0.1-10, The polyester resin composition characterized by the above-mentioned.

[In the formula (1), R ⁰ represents an alkyl group or a hydrogen atom. R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ]

[In (Chemical Formula 2), R ³ and R ⁴ each independently represents a hydrocarbon group having 1 to 20 carbon atoms. M is a metal selected from Li, Na, K, Be, Mg, Ca, Sr, Ba, Mn, Ni, Cu, and Zn, and M ^{n +} represents an n-valent metal cation. ]
(2) 0.001 to 0.05 mol% of the aluminum compound as an aluminum atom with respect to the number of moles of all constituent units of the polycarboxylic acid component of the polyester resin composition, and the phosphorus compound as a phosphorus atom and a polyester resin The polyester resin composition according to (1), which is contained in an amount of 0.0005 to 0.1 mol% with respect to the number of moles of all constituent units of the polycarboxylic acid component of the composition.
(3) The aluminum compound is at least one selected from aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate (1) or (2) The polyester resin composition as described in 2.
(4) In the above (Formula 1), in Formula (1), R ⁰ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and R ¹ and R ² are each independently a hydrogen atom or carbon number. The polyester resin composition according to any one of (1) to (3), which is a phosphorus compound having 1 to 4 alkyl groups.
(5) The polyester resin composition according to any one of (1) to (4), wherein (Formula 2) is a phosphorus compound represented by the following formula (Formula 3).

(6) The polyester resin composition as described in (1) whose (a) / (b) is 0.5-5.
(7) A hollow molded body comprising the polyester resin composition according to any one of (1) to (6).
(8) A fiber comprising the polyester resin composition according to any one of (1) to (6).
(9) A film comprising the polyester resin composition according to any one of (1) to (6).

  According to the present invention, a polyester resin composition excellent in color tone and thermal stability is provided, and a polyester resin composition excellent in solid phase polymerization activity and a method for producing the same are provided.

The aluminum compound and phosphorus compound according to the present invention are used as a polyester polymerization catalyst and are contained in the resulting polyester resin composition.
The polyester resin composition referred to in the present invention is a composition containing the following polyester, an aluminum compound used as a polymerization catalyst, and a phosphorus compound.

  Specific examples of the aluminum compound according to the present invention include aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum terephthalate, and trimellit. Carboxylates such as aluminum acid, aluminum pyromellitic acid, aluminum trichloroacetate, aluminum lactate, aluminum citrate, aluminum tartrate, aluminum salicylate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate , Inorganic acid salts such as aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxa Aluminum, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-butoxide, etc. Aluminum alkoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate diiso-propoxide, etc. Aluminum chelate compounds, organoaluminum compounds such as trimethylaluminum and triethylaluminum and partial hydrolysates thereof, reaction products of aluminum alkoxides and aluminum chelate compounds with hydroxycarboxylic acids, aluminum oxide, ultrafine aluminum oxide, aluminum silicate , Aluminum and titanium or silicon or zirconium Etc., alkali metal or composite oxides such as alkaline earth metals. Of these, aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

Here, aluminum hydroxide chloride is a general term for what is generally called polyaluminum chloride or basic aluminum chloride, and those used for water supply can be used. These are represented by, for example, the general structural formula [Al ₂ (OH) _n Cl _6-n ] _m (where 1 ≦ n ≦ 5). Among these, those having a low chlorine content are preferable from the viewpoint of not corroding the device.

  The above-mentioned aluminum acetate is a general term for those having a structure of an aluminum salt of acetic acid represented by basic aluminum acetate, aluminum triacetate, aluminum acetate solution, etc. Among these, from the viewpoint of solubility and solution stability The use of basic aluminum acetate is preferred. Of the basic aluminum acetates, aluminum monoacetate, aluminum diacetate, or those stabilized with boric acid are preferred. When using the one stabilized with boric acid, it is preferable to use one stabilized with boric acid in an amount of equimolar or less with respect to the basic aluminum acetate, and in particular, 1/2 to 1/3 molar amount. The use of basic aluminum acetate stabilized with boric acid is preferred. Examples of basic aluminum acetate stabilizers include urea and thiourea in addition to boric acid. Any of the above basic aluminum acetates solubilized in water or alkylene glycols, particularly those solubilized in water and / or ethylene glycol are preferably used from the viewpoint of catalytic activity and the quality of the resulting polyester.

  In this invention, it is preferable that the aluminum compound contains 0.001-0.05 mol% with respect to the mole number of all the structural units of the polycarboxylic acid component of a polyester resin composition as an aluminum atom. More preferably, it is 0.005-0.02 mol%. The polycarboxylic acid component of the polyester resin composition refers to a polyvalent carboxylic acid containing a dicarboxylic acid constituting the polyester described below. If the aluminum atom content is less than 0.001 mol%, the catalytic activity during the polymerization of the polyester may not be sufficiently exhibited, which is not realistic. When the content of aluminum atoms exceeds 0.05 mol%, there are cases where thermal stability and thermal oxidation stability are lowered, and foreign matter generation due to aluminum and increase in coloration become problems. Since the aluminum compound is hardly removed out of the system even under a reduced pressure environment during polyester polymerization, the amount added as a catalyst remains in the polyester resin composition as it is. Therefore, the content of aluminum atoms in the polyester resin composition can be adjusted by considering the amount used as a catalyst.

The polyester resin composition of the present invention is derived from the integrated value of the peak derived from the above formula (Formula 1) in the P-NMR spectrum obtained by the measurement method described later (a) and from the above formula (Formula 2). When the integrated value of the peak to be performed is (b), (a) / (b) needs to be 0.1-10.
Regarding the chemical shift below, the peak with the largest integrated value among the peaks derived from phosphoric acid added during P-NMR measurement is the chemical shift of 1.66 ppm.
The peak derived from the phosphorus compound of the above formula (Formula 1) is a peak between chemical shifts of 30 to 32 ppm, and the peak derived from the phosphorus compound of the above formula (Formula 2) is from more than 32 chemical shifts to 34 ppm. Is the peak between.
Regarding the chemical shift of the phosphorus compounds of (Chemical Formula 1) and (Chemical Formula 2), the same measurement was separately performed for the phosphorous compound alone and confirmed.

(A) / (b) substantially represents the molar ratio of [phosphorus compound derived from (formula 1)] / [phosphorus compound derived from (formula 2)] contained in the polyester resin composition of the present invention. It is thought that it shows. This is confirmed from the fact that the addition ratio of the two phosphorus compounds at the time of polyester polymerization and (a) / (b) are almost the same.
In practice, (Chemical Formula 1) and (Chemical Formula 2) react with polyester to detect peaks other than the above chemical shifts, but their integrated values are usually higher than those of (a) and (b). There are few.

  Compared with the case where (a) / (b) of the obtained polyester resin composition is larger than 10, when (a) / (b) is 0.1-10, the polyester resin composition has foreign matters. Reduced and has excellent thermal oxidation stability. In particular, the polyester resin composition in which (a) / (b) is 0.1 to 10 has a surprising effect that the solid-phase polymerization activity is excellent. From the viewpoint of these effects, (a) / (b) is preferably 0.5 to 5.

  When (a) / (b) is 0.1 to 10 compared to the case where (a) / (b) of the obtained polyester resin composition is smaller than 0.1, the polyester resin composition is Solid phase polymerization rate is fast and foaming during melt polymerization is low. From the viewpoint of these effects, (a) / (b) is preferably 0.5 to 5.

  In order for (a) / (b) of the polyester resin composition to be 0.1 to 10, the compounds represented by the above (Formula 1) and the above (Formula 2) are used as the phosphorus compounds constituting the polymerization catalyst. It is obtained by adjusting the molar ratio of (Formula 1) / (Formula 2) to 0.1-10.

  Two types of phosphorus compounds of (Formula 1) and (Formula 2) when using only (Formula 1) and when the molar ratio of (Formula 1) / (Formula 2) exceeds 10. (Chemical Formula 1) / (Chemical Formula 2) = 0.1 to 10 (molar ratio), not only improves the solid-phase polymerization catalyst activity, but also has a foreign matter reducing effect and thermal oxidation stability. Can be given. In particular, when (Chemical Formula 1) / (Chemical Formula 2) = 0.1-10 (molar ratio) is used, (Chemical Formula 1) is used alone, and (Chemical Formula 2) is used alone. A surprising effect is obtained that the solid-phase polymerization activity is superior to that at times. From the viewpoint of these effects, it is preferable that (Formula 1) / (Formula 2) = 0.5 to 5 (molar ratio). It is important that the compound of Formula 1 is benzylphosphonic acid, benzylphosphonic acid having a substituent at the ortho position of the benzene ring of the benzyl group, or a phosphonic acid ester compound thereof.

  When using only (formula 2) and when the molar ratio of (formula 1) / (formula 2) is less than 0.1, two types of (formula 1) and (formula 2) are used. When a phosphorus compound is used at (Chemical Formula 1) / (Chemical Formula 2) = 0.1 to 10 (molar ratio), a polyester having a high solid-phase polymerization rate and less foaming during melt polymerization can be provided. From the viewpoint of these effects, it is preferable that (Formula 1) / (Formula 2) = 0.5 to 5 (molar ratio). A hydroxy group having a weak electron-withdrawing property and a strong electron-donating property (Formula 2) improves thermal oxidation stability because the hydroxy group becomes a radical.

By using two phosphorus compounds of (Formula 1) and (Formula 2) at (Formula 1) / (Formula 2) = 0.1-10 (molar ratio), solid-phase polymerization activity is improved. The reason for this has not been clearly clarified, but it is presumed that the interaction including the aluminum compound affects the solid-state polymerization rate.
If two types of phosphorus compounds of (Formula 1) and (Formula 2) are used at (Formula 1) / (Formula 2) = 0.1-10 (molar ratio) For example, you may use together the phosphorus compound of a 3rd component in the range which does not impair the effect of this invention.

The alkyl group of R ^{0 in} the general formula (Formula 1) preferably has 1 to 15 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms. R ⁰ is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. If the number exceeds 15 carbon atoms, foaming may occur during polymerization, which is not preferable. When the number of carbon atoms is large, it is cut under polymerization conditions and causes foaming.

R ¹ and R ² in the general formula (Formula 1) each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. When the number of carbon atoms exceeds 20, it is not preferable for the same reason as described above. R ¹ and R ² are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ³ and R ⁴ in the general formula (Formula 2) each independently represent a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group for R ³ and R ⁴ is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms. When the number of carbon atoms exceeds 20, foaming may occur during polymerization, and even when the number of carbon atoms is 15 to 20, foaming may be caused by a substituent. If R ³ and R ⁴ are hydrogen atoms, the thermal oxidation stability of the obtained polyester is lowered. . The positions of R ³ and R ⁴ must be positioned on both sides of hydroxy in order to stabilize the radical of the hydroxy group and improve the thermal oxidation stability. Examples of ^R 3, ^{R 4} of the general formula (Formula 2) is preferably an alkyl group having 1 to 4 carbon atoms.

Examples of the phosphorus compound represented by the general formula (Formula 1) in the present invention include, but are not limited to, the following.
Benzylphosphonic acid, benzylphosphonic acid monomethyl ester, benzylphosphonic acid dimethyl ester, benzylphosphonic acid monoethyl ester, benzylphosphonic acid diethyl ester, 2-methylbenzylphosphonic acid, 2-methylbenzylphosphonic acid monomethyl ester, 2-methylbenzylphosphone Acid dimethyl ester, 2-methylbenzylphosphonic acid monoethyl ester, 2-methylbenzylphosphonic acid diethyl ester, 2-ethylbenzylphosphonic acid, 2-ethylbenzylphosphonic acid monomethyl ester, 2-ethylbenzylphosphonic acid dimethyl ester, 2- Ethylbenzylphosphonic acid monoethyl ester, 2-ethylbenzylphosphonic acid diethyl ester, 2-n-propylbenzylphosphonic acid monoethyl ester, 2-n-propyl Pyrbenzylphosphonic acid, 2-isopropylbenzylphosphonic acid diethyl ester, 2-isopropylbenzylphosphonic acid monoethyl ester, 2-isopropylbenzylphosphonic acid, 2-n-butylbenzylphosphonic acid diethyl ester, 2-n-butylbenzylphosphonic acid Monoethyl ester, 2-n-butylbenzylphosphonic acid, 2-sec-butylbenzylphosphonic acid diethyl ester, 2-sec-butylbenzylphosphonic acid monoethyl ester, 2-sec-butylbenzylphosphonic acid, 2-tert-butyl Examples include benzylphosphonic acid diethyl ester, 2-tert-butylbenzylphosphonic acid monoethyl ester, 2-tert-butylbenzylphosphonic acid and the like.

Examples of the general formula (Formula 2) in the present invention include the following, but are not limited thereto.
Lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], potassium [3,5-di- tert-butyl-4-hydroxybenzylphosphonate ethyl], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], beryllium bis [3,5-di-tert-butyl-4- Methyl hydroxybenzylphosphonate], calcium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate methyl], strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl] Barium bis [3,5-di-tert-butyl-4-hydroxybenzene] Ethyl diphosphonate], manganese bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], nickel bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], copper Examples include bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl] and zinc bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate]. Among these, calcium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate methyl] is particularly preferable from the viewpoint of improving solid-phase polymerization activity.

  Moreover, the phosphorus compound concerning this invention can also be used in combination with metal containing components other than an aluminum compound as a polymerization catalyst.

In the present invention, the phosphorus compound (including both of the phosphorus compounds of (Formula 1) and (Formula 2) is used as the phosphorus atom with respect to the number of moles of all constituent units of the polycarboxylic acid component of the polyester resin composition. It is preferable to contain 0.0005-0.1 mol%. More preferably, it is 0.001-0.05 mol%. If the phosphorus atom content is less than 0.0005 mol%, the catalytic activity during the polymerization of the polyester may not be sufficiently exhibited, which is not realistic. If the phosphorus atom content exceeds 0.1 mol%, the catalytic activity as a polyester polymerization catalyst may be reduced, which is not realistic.
It is necessary to determine the addition amount of the phosphorus compound in consideration of that about 10 to 40% of the addition amount is removed out of the system depending on the conditions under a reduced pressure environment at the time of polyester polymerization. Actually, it is necessary to carry out several trial experiments under different conditions to determine the addition amount. Even when the phosphorus compounds of (Chemical Formula 1) and (Chemical Formula 2) are used in combination, the ratio of (Chemical Formula 1) and (Chemical Formula 2) removed outside the system is the molar ratio at the time of addition. It is almost the same.

  The aluminum compound constituting one of the polyester polymerization catalysts according to the present invention is solubilized in a solvent such as water or alkylene glycol, in particular, after dissolving in water, alkylene glycol is added, and then water is distilled off to remove the aluminum compound. It is a preferred embodiment to make an alkylene glycol solution of This is preferable from the viewpoint of reducing the heat shock when the polymerization catalyst is added. Further, the other phosphorus compound constituting the polyester polymerization catalyst according to the present invention is preferably used by being dissolved in at least one solvent selected from the group consisting of alkylene glycols in view of catalytic activity. The alkylene glycol solution of the aluminum compound and the alkylene glycol solution of the phosphorus compound can be added and used separately. However, it is preferable to use a polymerization catalyst system in which an aluminum glycol solution and an alkylene glycol solution of a phosphorus compound are mixed from the viewpoint of improving catalyst activity and reducing foreign matter.

  In the present invention, in addition to aluminum or a compound thereof, a small amount of alkali metal, alkaline earth metal and at least one selected from the compound are preferably present as the second metal-containing component. The coexistence of such a second metal-containing component in the catalyst system is effective in improving productivity by obtaining a catalyst component having an increased reaction rate in addition to an effect of suppressing the formation of diethylene glycol, and thus a higher reaction rate. .

  A technique of adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound to obtain a catalyst having sufficient catalytic activity is known. When such a known catalyst is used, a polyester having excellent thermal stability can be obtained. However, a known catalyst used in combination with an alkali metal compound or an alkaline earth metal compound is added in an amount to obtain practical catalytic activity. However, when an alkali metal compound is used, the hydrolysis resistance of the resulting polyester is reduced and the amount of foreign matter resulting from the alkali metal compound is increased. Moreover, when used for a film, the film properties and the like deteriorate. In addition, when an alkaline earth metal compound is used in combination, the thermal stability of the obtained polyester is lowered when it is attempted to obtain practical activity, coloring due to heating is large, the amount of foreign matter generated is increased, and water resistance is increased. Degradability also decreases.

  The polycondensation catalyst according to the present invention is different from other polycondensation catalysts such as antimony compounds, germanium compounds, and titanium compounds, and the addition of these components causes problems in products such as polyester characteristics, processability and color tone as described above. Coexistence within the range of a small amount added is effective in improving productivity by shortening the polymerization time.

  In that case, the antimony compound is preferably added in an amount of 50 ppm or less as antimony atoms to the polyester obtained by polymerization. A more preferable addition amount is 30 ppm or less. When the amount of antimony added is 50 ppm or more, metal antimony is precipitated, and darkening and foreign matter are generated in the polyester.

  In that case, the germanium compound is preferably added in an amount of 20 ppm or less as germanium atoms to the polyester obtained by polymerization. A more preferable addition amount is 10 ppm or less. If the amount of germanium added is 20 ppm or more, it is not preferable because it is disadvantageous in terms of cost.

  In that case, the titanium compound is preferably added in an amount of 5 ppm or less as a titanium atom to the polyester obtained by polymerization. A more preferable addition amount is 3 ppm or less, and further preferably 1 ppm or less. If the amount of titanium added is 5 ppm or more, the resulting polyester is markedly colored, and the thermal stability is significantly reduced, which is not preferable.

  In the polyester resin composition of the present invention, it is preferable to add a cobalt compound as a cobalt atom in an amount of less than 10 ppm with respect to the polyester for the purpose of improving the color tone. More preferably, it is 5 ppm or less, More preferably, it is 3 ppm or less. The cobalt compound is not particularly limited, and specific examples include cobalt acetate, cobalt nitrate, cobalt chloride, cobalt acetylacetonate, cobalt naphthenate, and hydrates thereof. Of these, cobalt acetate tetrahydrate is particularly preferred.

  Manufacture of the polyester resin composition by this invention can be performed by the method provided with the conventionally well-known process except the point which uses the polyester polymerization catalyst concerning this invention as a catalyst. For example, when producing PET, a direct esterification method in which terephthalic acid is directly reacted with ethylene glycol and, if necessary, other copolymerization components to distill off water and esterify, followed by polycondensation under reduced pressure. Alternatively, it is produced by a transesterification method in which dimethyl terephthalate is reacted with ethylene glycol and other copolymerization components as required to distill off methyl alcohol and transesterify, followed by polycondensation under reduced pressure. The Further, solid phase polymerization may be performed as necessary to increase the intrinsic viscosity. In order to promote crystallization before solid phase polymerization, the melt-polymerized polyester may be subjected to heat crystallization after moisture absorption, or may be heated and crystallized by spraying water vapor directly onto a polyester chip.

  The melt polycondensation reaction may be performed in a batch reactor or may be performed in a continuous reactor. In any of these methods, the esterification reaction or the transesterification reaction may be performed in one stage, or may be performed in multiple stages. The melt polycondensation reaction may be performed in one stage or may be performed in multiple stages. The solid phase polymerization reaction can be carried out by a batch type apparatus or a continuous type apparatus, similarly to the melt polycondensation reaction. Melt polycondensation and solid phase polymerization may be carried out continuously or separately.

  When terephthalic acid is used as a raw material, the esterification reaction can be carried out without a catalyst by the catalytic action of terephthalic acid as an acid, but may be carried out in the presence of a polycondensation catalyst.

  Also, tertiary amines such as triethylamine, tri-n-butylamine, benzyldimethylamine, quaternary ammonium hydroxides such as tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide, and lithium carbonate When a small amount of a basic compound such as sodium carbonate, potassium carbonate or sodium acetate is added, the proportion of dioxyethylene terephthalate component units in the main chain of polyethylene terephthalate is relatively low (total 5 mol% or less) with respect to the diol component.

  In cases where low acetaldehyde content or low cyclic trimer content is required, such as low-flavor beverages and heat-resistant hollow molded products for mineral water, the melt polycondensed polyester thus obtained is not solid. Phase polymerized. The polyester is solid-phase polymerized by a conventionally known method. First, the polyester subjected to solid phase polymerization is pre-crystallized by heating at a temperature of 100 to 210 ° C. for 1 to 5 hours in an inert gas, under reduced pressure, or in an atmosphere of water vapor or water vapor-containing inert gas. The Subsequently, solid state polymerization is performed at a temperature of 190 to 230 ° C. for 1 to 30 hours in an inert gas atmosphere or under reduced pressure.

  The catalyst according to the present invention has catalytic activity not only in the polycondensation reaction but also in the esterification reaction and transesterification reaction. For example, the catalyst of the present invention can be used in the transesterification reaction between an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate and a glycol such as ethylene glycol. Further, the catalyst of the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization or solution polymerization, and polyester can be produced by any method.

  The polymerization catalyst according to the present invention can be added to the reaction system at any stage of the polymerization reaction. For example, it can be added to the reaction system at any stage before and during the esterification reaction or transesterification reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction. In particular, in the case of a polymerization catalyst comprising an ethylene glycol solution mixed system of an aluminum compound and a phosphorus compound, it is preferable to add it immediately before the start of the polycondensation reaction from the viewpoints of polymerization activity and foreign matter reduction.

  In the method for adding a polymerization catalyst according to the present invention, addition of a solvent such as alkylene glycol in the form of a solution is effective in reducing foreign matters, and a mixture of aluminum or a phosphorus compound and other components are added in advance as a mixture. These may be added separately. Moreover, the mixture of an aluminum compound or phosphorus compound and other components may be added to the polymerization system at the same addition time, and each component may be added at different addition times. Further, the entire amount of the catalyst may be added at once, or may be added in a plurality of times.

  The polyester referred to in the present invention is composed of one or more selected from polycarboxylic acids containing dicarboxylic acids and ester-forming derivatives thereof, and one or more selected from polyhydric alcohols containing glycol. Or consisting of a hydroxycarboxylic acid and an ester-forming derivative thereof, or consisting of a cyclic ester.

  Dicarboxylic acids include succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1,3 -Cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, etc. Saturated aliphatic dicarboxylic acids exemplified, or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid, etc., or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid Acid, 5- (alkali metal) Rufoisophthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4, 4 ′ -Biphenyl dicarboxylic acid, 4,4'-biphenylsulfone dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid, etc. And aromatic dicarboxylic acids exemplified in (1) or ester-forming derivatives thereof.

  Of these dicarboxylic acids, terephthalic acid and naphthalenedicarboxylic acid, particularly 2,6-naphthalenedicarboxylic acid, are preferable from the viewpoint of the physical properties of the resulting polyester, and other dicarboxylic acids are used as constituents as necessary.

  As polyvalent carboxylic acids other than these dicarboxylic acids, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3, 4, 3 ', 4'-biphenyltetracarboxylic acid, And ester-forming derivatives thereof.

  As glycols, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4 -Butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedi Methanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetra Michile Aliphatic glycols such as glycol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) sulfone, bis ( p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5-naphthalenediol And aromatic glycols exemplified by glycols obtained by adding ethylene oxide to these glycols.

  Of these glycols, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol are preferred.

  Examples of polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like.

  Examples of the hydroxycarboxylic acid include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or these And ester-forming derivatives thereof.

  Examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, and lactide.

  Examples of ester-forming derivatives of polyvalent carboxylic acids or hydroxycarboxylic acids include these alkyl esters, acid chlorides, acid anhydrides, and the like.

  The polyester of the present invention is preferably polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly (1,4-cyclohexanedimethylene terephthalate), polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate and copolymers thereof. Of these, polyethylene terephthalate and this copolymer are particularly preferred.

  After polyester polymerization according to the method of the present invention, the thermal stability of the polyester can be further enhanced by removing the catalyst from the polyester or by deactivating the catalyst by adding a phosphorus compound or the like.

  The polyester resin composition of the present invention can contain organic, inorganic, and organometallic toners, and a fluorescent brightening agent. By containing one or more of these, the polyester resin composition can be used. Coloring such as yellowing can be suppressed to a more excellent level. It also contains other optional polymers, antistatic agents, antifoaming agents, dyeability improvers, dyes, pigments, matting agents, fluorescent brighteners, stabilizers, antioxidants, and other additives. Also good. As antioxidants, aromatic amine-based and phenol-based antioxidants can be used, and as stabilizers, phosphoric acid and phosphate ester-based phosphorus-based, sulfur-based, amine-based stabilizers, etc. Can be used.

  These additives can be added at any stage during or after polymerization of the polyester or at the time of molding the polyester. Which stage is suitable depends on the characteristics of the compound and the required performance of the polyester molded body. Are different.

  The polyester resin composition polymerized using the polyester polymerization catalyst according to the present invention can produce fibers by a conventional melt spinning method. A method of spinning and drawing in two steps and a method of carrying out in one step include: Can be adopted. Furthermore, all known fiber manufacturing methods such as staple manufacturing methods and monofilaments with crimping, heat setting and cutting steps can be applied.

The polyester resin composition of the present invention is suitably used as a hollow molded body.
Examples of the hollow molded body include beverage containers such as mineral water, juice, wine and whiskey, baby bottles, bottled food containers, containers such as hairdressing products and cosmetics, residential and dishwashing detergent containers.

  Among these, polyester is particularly suitable for various beverages as a pressure-resistant container, a heat-resistant pressure-resistant container, and an alcohol-resistant container utilizing the hygiene and strength and solvent resistance of polyester. The hollow molded body is manufactured by a method in which a polyester chip obtained by melt polymerization or solid phase polymerization is dried by a vacuum drying method or the like, and then molded by a molding machine such as an extrusion molding machine or an injection molding machine, or melted after melt polymerization. A preform with a bottom is obtained by a direct molding method in which the body is introduced into a molding machine in a molten state and molded. Further, a final hollow molded body can be obtained by blow molding such as stretch blow molding, direct blow molding, and extrusion blow molding. Of course, a molded product obtained by a molding machine such as the above-described extrusion molding machine or injection molding machine can be used as a final hollow container.

  When manufacturing such a hollow molded body, waste resin generated in the manufacturing process or polyester resin recovered from the market can be mixed. Even with such a recycled resin, the polyester resin of the present invention is less deteriorated and a high-quality hollow molded product can be obtained.

  Further, the polyester resin composition of the present invention can be extruded into a sheet-like material from an extruder to form a sheet. Such sheets are processed by vacuum forming, pressure forming, stamping, etc., and used as trays and containers for food and sundries, cups, blister packs, carrier tapes for electronic components, and electronic component delivery trays. The sheet can also be used as various cards.

  The polyester polymerized using the polyester polymerization catalyst according to the present invention can be used for a film. In this method, polyester is melt-extruded and formed into a sheet shape from a T-die on a cooling rotary roll to create an unstretched sheet.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not restrict | limited to these Examples. In addition, the evaluation method was implemented with the following method.

(1) P-NMR spectrum It measured on condition of the following.
Apparatus: Fourier transform type nuclear magnetic resonance apparatus (AVANCE500 manufactured by BRUKER)
Measurement solution: 415 mg of a sample was dissolved in 2.7 ml of a mixed solvent having a volume ratio of 1: 1 of hexafluoroisopropanol and deuterated benzene, 10 μl of 25% heavy acetone solution of phosphoric acid was added, centrifuged, and the supernatant To this was added 108 mg of trifluoroacetic acid, and P-NMR measurement was immediately performed.
31P resonance frequency: 202.5 MHz
Detection pulse flip angle: 65 °
Data acquisition time: 1.5 seconds Delay time: 0.5 seconds Proton decoupling: Proton complete decoupling Integration count: 8000-20000 times Measurement temperature: Room temperature

(2) Intrinsic viscosity (IV: dl / g)
Each polyester pellet obtained by melt polycondensation and solid phase polycondensation (length: about 3 mm, diameter: about 2 mm, cylindrical shape) is made into 6/4 (weight ratio) of phenol / 1,1,2,2-tetrachloroethane. ) It melt | dissolved in the mixed solvent at 80-100 degreeC over several hours, and measured it at the temperature of 30 degreeC using the Ubbelohde viscometer. Concentration was measured at several points centered on 4 g / l, and IV was determined according to a conventional method.

(3) Measuring method of carboxy terminal amount Preparation of sample The polyester is pulverized, vacuum dried at 70 ° C. for 24 hours, and then weighed in a range of 0.20 ± 0.0005 g using a balance. The weight at that time is defined as W (g). A sample weighed with 10 ml of benzyl alcohol is added to a test tube, the test tube is immersed in a benzyl alcohol bath heated to 205 ° C., and the sample is dissolved while stirring with a glass rod. Samples with dissolution times of 3 minutes, 5 minutes, and 7 minutes are designated as A, B, and C, respectively. Next, a new test tube is prepared, and only benzyl alcohol is added and processed in the same procedure, and samples when the dissolution time is 3 minutes, 5 minutes, and 7 minutes are designated as a, b, and c, respectively.
B. Titration Titration is performed using a 0.04 mol / l potassium hydroxide solution (ethanol solution) whose factor is known in advance. Phenol red is used as the indicator, and the titration (ml) of the potassium hydroxide solution is determined with the end point being changed from yellowish green to light red. Samples A, B, and C are titrated as XA, XB, and XC (ml). The titration amounts of samples a, b, and c are Xa, Xb, and Xc (ml).
C. Calculation of the amount of carboxy terminus Using the titration amounts XA, XB, and XC for each dissolution time, the titration amount V (ml) at a dissolution time of 0 minutes is determined by the least square method. Similarly, titration volume V0 (ml) is obtained using Xa, Xb, and Xc. Subsequently, the amount of carboxy terminal was calculated | required according to following Formula.
Carboxy terminal amount (eq / ton) = [(V−V0) × 0.04 × NF × 1000] / W
NF: factor of 0.04 mol / l potassium hydroxide solution W: sample weight (g)

(4) Content of aluminum atom and phosphorus atom in polymer The content of aluminum atom and phosphorus atom was measured by a fluorescent X-ray method. The polyester resin composition as a measurement sample is put into a stainless steel ring having a height of 5 mm and a diameter of 40 mm placed on a ferrotype plate for photography, and heated in an oven at 300 ° C. for 10 minutes to melt. After taking out from the oven and cooling, a molded sample was taken out from the stainless steel ring, and a smooth surface was measured. Separately, several points of polyester resin compositions whose contents were confirmed by chemical analysis were molded by the above-mentioned method, and the values of fluorescent X-ray intensity and values obtained by chemical analysis were measured by measuring fluorescent X-ray intensity. A calibration curve was created.
Based on the calibration curve from the fluorescent X-ray intensity data of the polyester resin composition as the measurement sample, the contents of aluminum atoms and phosphorus atoms in each measurement sample were calculated.

(Preparation example 1 of aluminum compound)
After adding an equivalent amount (volume ratio) of ethylene glycol to a 20 g / l aqueous solution of basic aluminum acetate (hydroxyaluminum diacetate; manufactured by Aldrich) and stirring at room temperature for 6 hours, several times at 80 to 110 ° C. Water was distilled from the system while stirring for a time to prepare an ethylene glycol solution of 20 g / l aluminum compound.

(Preparation Example 1 of phosphorus compound)
As a phosphorus compound, benzylphosphonic acid diethyl ester was charged into a flask together with ethylene glycol, and refluxed at a liquid temperature of 180 ° C. for 25 hours while stirring under nitrogen substitution to prepare 50 g / l of an ethylene glycol solution a of the phosphorus compound. Separately, as a phosphorus compound, calcium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate methyl] was stirred in ethylene glycol at room temperature for 10 hours to obtain 50 g / l of an ethylene glycol solution of the phosphorus compound. b was prepared. The two types adjusted were adjusted so that the molar ratio a / b = 2/1.

(Preparation Example 2 of Phosphorus Compound)
As a phosphorus compound, calcium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate methyl] was stirred in ethylene glycol at room temperature for 10 hours to prepare a 50 g / l ethylene glycol solution of the phosphorus compound. did.

(Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound)
The ethylene glycol solutions obtained in Preparation Example 1 of the above aluminum compound and Preparation Example 1 of the above phosphorus compound were mixed at room temperature so that the molar ratio of aluminum atom and phosphorus atom was 1: 1.6, and the mixture was stirred for 1 day. A catalyst solution was prepared by stirring.

(Preparation example 2 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound)
A catalyst solution was prepared in the same manner as in Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound, except that the ethylene glycol solution obtained in Preparation Example 2 of the phosphorus compound was used.

Example 1
High-purity terephthalic acid and ethylene glycol were charged into a 2-liter stainless steel autoclave equipped with a stirrer, and an esterification reaction was performed according to a conventional method to obtain an oligomer mixture. As the polycondensation catalyst for this oligomer mixture, the polymerization catalyst of the above (Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound) is used, and an aluminum atom and a phosphorus atom with respect to the acid component in the polyester As 0.014 mol% and 0.0225 mol%, respectively, and then stirred at 250 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Thereafter, the pressure of the reaction system is gradually lowered to 13.3 Pa (0.1 Torr) while raising the temperature to 280 ° C. over 60 minutes, and the IV becomes about 0.60 dl / g at 280 ° C. and 13.3 Pa. The polycondensation reaction was carried out. After releasing the pressure, the resin under slight pressure is discharged into cold water in a strand form and rapidly cooled. After that, it is held in cold water for 20 seconds, and then cut to obtain a cylindrical pellet having a length of about 3 mm and a diameter of about 2 mm. It was. Table 1 shows the time (polymerization time) required for the polycondensation reaction and IV of the obtained polyester. The melt-polymerized resin thus obtained was allowed to stand at 180 ° C. for 1 hour in a vacuum state to crystallize the resin. Thereafter, vacuum drying was performed at 80 ° C. for 8 hours, the temperature was raised from 80 ° C. to 220 ° C. over 2 hours, and solid-state polymerization was performed under the condition of 0.5 Torr until IV became about 0.73 dl / g. Table 1 shows the time required for solid phase polymerization.
(Comparative Example 1)
Example 1 was carried out in the same manner as in Example 1, except that (Preparation Example 1 of Preparation of Mixture of Aluminum Compound in Ethylene Glycol Solution / Phosphorus Compound in Ethylene Glycol) was used instead of (Preparation Example 2).

  According to the present invention, it is possible to provide a polyester resin composition excellent in color tone and thermal stability and excellent in transparency of a molded product, and a method for producing the polyester resin composition. In particular, the productivity of polyester can be improved by being excellent in solid phase polymerization activity.

Claims (9)

A polyester resin composition comprising an aluminum compound and a phosphorus compound, wherein the phosphorus compound comprises at least a phosphorus compound represented by the following formula (Formula 1) and the following formula (Formula 2): In the P-NMR spectrum, when the integrated value of the peak derived from the following formula (formula 1) is (a) and the integrated value of the peak derived from the formula (formula 2) is (b), (a) ) / (B) is 0.1-10, The polyester resin composition characterized by the above-mentioned.

[In the formula (1), R ⁰ represents an alkyl group or a hydrogen atom. R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ]

[In (Chemical Formula 2), R ³ and R ⁴ each independently represents a hydrocarbon group having 1 to 20 carbon atoms. M is a metal selected from Li, Na, K, Be, Mg, Ca, Sr, Ba, Mn, Ni, Cu, and Zn, and M ^{n +} represents an n-valent metal cation. ]   0.001 to 0.05 mol% of the aluminum compound as an aluminum atom with respect to the number of moles of all constituent units of the polycarboxylic acid component of the polyester resin composition, and the phosphorus compound as the phosphorus atom of the polyester resin composition The polyester resin composition according to claim 1, which is contained in an amount of 0.0005 to 0.1 mol% with respect to the number of moles of all constituent units of the polycarboxylic acid component.   The polyester resin composition according to claim 1 or 2, wherein the aluminum compound is at least one selected from aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetonate. In the above (Formula 1), in Formula (1), R ⁰ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and R ¹ and R ² are each independently a hydrogen atom or 1 to 4 carbon atoms. The polyester resin composition according to claim 1, which is a phosphorus compound that is an alkyl group. The said (Formula 2) is a phosphorus compound represented by a following formula (Formula 3), The polyester resin composition in any one of Claims 1-4 characterized by the above-mentioned.

  The polyester resin composition according to claim 1, wherein (a) / (b) is 0.5 to 5.   The hollow molded object which consists of a polyester resin composition in any one of Claims 1-6.   The fiber which consists of a polyester resin composition in any one of Claims 1-6.   The film which consists of a polyester resin composition in any one of Claims 1-6.