JP2002327052A - Polyester and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester eliminating problems concerning a foreign material which gives yarn breakage, increase of filtering pressure, luminescent spots, etc., lowering productivity and quality of the product in production of a fiber, film, bottle, etc., and to provide a method for producing the same. SOLUTION: In a method for producing a polyester from polycarboxylic acids including dicarboxylic acids or their ester-forming derivatives with polyhydric alcohols including glycols or their ester-forming derivatives, this method for producing the polyester is characterized by using aluminum or its compound by a specified amount, and the molar ratio of the polyhydric alcohols including glycols or their ester-forming derivatives to the polycarboxylic acids including dicarboxylic acids or their ester-forming derivatives in this reaction system is 1.2-2.1 at the time when the aluminum or its compound is added.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyester, and more particularly, to a method for producing a polyester using a novel polyester polymerization catalyst which does not use a germanium or antimony compound as a catalyst main component. It relates to the produced polyester.

[0002]

2. Description of the Related Art Polyethylene terephthalate (PE)
T), polyesters represented by polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and the like are excellent in mechanical properties and chemical properties, and depending on the properties of each polyester, for example, for clothing and It is used in a wide range of fields such as fibers for industrial materials, films and sheets for packaging and magnetic tape, bottles that are hollow molded products, casings for electric and electronic parts, and other engineering plastic molded products.

[0003] A typical polyester which is mainly composed of aromatic dicarboxylic acid and alkylene glycol is, for example, polyethylene terephthalate (PE).
In the case of T), bis (2-hydroxyethyl) terephthalate is produced by esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylene glycol, and this is polycondensed at high temperature and under vacuum using a catalyst. It is industrially manufactured by a polycondensation method or the like.

Hitherto, antimony trioxide has been widely used as a polyester polymerization catalyst used in such polycondensation of polyester. Antimony trioxide is a catalyst that is inexpensive and has excellent catalytic activity.
When this is used as a main component, that is, in an amount added so that a practical polymerization rate is exhibited, since metallic antimony is precipitated during polycondensation, there is a problem that blackening and foreign matter are generated in polyester. I have. Under such circumstances, a polyester containing no antimony or containing no antimony as a main component of a catalyst is desired.

[0005] The above-mentioned foreign substances in the polyester cause the following problems, for example. (1) In polyester for a film, the precipitation of antimony metal becomes a foreign substance in the polyester and causes not only stains on a die at the time of melt extrusion but also surface defects on the film. In addition, when a raw material such as a hollow molded article is used, it is difficult to obtain a hollow molded article having excellent transparency. (2) Foreign matter in the polyester for fibers becomes a foreign matter that causes a decrease in strength in the fibers, and causes stains on a spinneret during yarn production. In the production of polyester fibers, a polyester polymerization catalyst free of foreign matter is required mainly from the viewpoint of operability.

[0006] As a method for solving the above-mentioned problem, an attempt has been made to use antimony trioxide as a catalyst and to suppress the occurrence of darkening or foreign matter in PET. For example, in Japanese Patent No. 2666502, generation of black foreign matter in PET is suppressed by using a compound of antimony trioxide, bismuth, and selenium as a polycondensation catalyst.
JP-A-9-291141 describes that when antimony trioxide containing sodium and iron oxides is used as a polycondensation catalyst, the precipitation of antimony metal is suppressed. However, these polycondensation catalysts cannot ultimately achieve the purpose of reducing the content of antimony in the polyester.

As a method for solving the problems of the antimony catalyst for applications requiring transparency such as PET bottles, for example, JP-A-6-279579 describes
A method is disclosed in which the transparency is improved by defining the amount ratio of the antimony compound to the phosphorus compound. However, the hollow molded article made of the polyester obtained by this method cannot be said to have sufficient transparency.

Japanese Patent Application Laid-Open No. 10-36495 discloses a continuous process for producing a polyester having excellent transparency using antimony trioxide, phosphoric acid and a sulfonic acid compound. However, the polyester obtained by such a method has a problem that heat stability is poor and the acetaldehyde content of the obtained hollow molded article is high.

Studies have been made on polycondensation catalysts which can replace antimony catalysts such as antimony trioxide. Titanium compounds and tin compounds represented by tetraalkoxy titanates have already been proposed. Polyesters are susceptible to thermal degradation during melt molding and have the problem that the polyester is significantly colored.

As an attempt to overcome such problems when using a titanium compound as a polycondensation catalyst, for example, JP-A-55-116722 discloses a method in which a tetraalkoxy titanate is used simultaneously with a cobalt salt and a calcium salt. Has been proposed. Also, Japanese Patent Application Laid-Open No. 8-735
No. 81 proposes a method in which a tetraalkoxy titanate is used simultaneously with a cobalt compound as a polycondensation catalyst and a fluorescent whitening agent is used. However, in these techniques, although the coloring of PET is reduced when tetraalkoxy titanate is used as a polycondensation catalyst, the P
Effective suppression of thermal decomposition of ET has not been achieved.

As another attempt to suppress thermal degradation during melt molding of a polyester polymerized using a titanium compound as a catalyst, for example, Japanese Patent Application Laid-Open No. Hei 10-259296 discloses a method in which a polyester is polymerized using a titanium compound as a catalyst and then phosphorus-based. Methods for adding compounds are disclosed. But,
At present, it is not only technically difficult to effectively mix the additive into the polymer after polymerization, but also to increase the cost, so that it is not practically used.

Aluminum compounds are generally known to have poor catalytic activity. Among the aluminum compounds,
It has been reported that aluminum chelate compounds have higher catalytic activity as polycondensation catalysts than other aluminum compounds, but that they have sufficient catalytic activity compared to the above-mentioned antimony compounds and titanium compounds. In addition, polyesters polymerized over a long period of time using an aluminum compound as a catalyst are not practical because of problems such as a decrease in thermal stability, coloring and generation of foreign matter.

There is also known a technique of adding an alkali metal compound to an aluminum compound to obtain a polyester polymerization catalyst having sufficient catalytic activity. Use of such a known catalyst can provide a polyester having excellent thermal stability.However, a catalyst using this alkali metal compound in combination requires a large amount of addition thereof in order to obtain practical catalytic activity.
As a result, at least one of the following problems occurs due to the alkali metal compound in the obtained polyester polymer. 1) The amount of foreign matters increases, and when used for fibers, the spinning properties and yarn properties are deteriorated, and when used for films, the film properties and the like are deteriorated. 2) The hydrolysis resistance of the polyester polymer decreases, and the transparency decreases due to the generation of foreign substances. 3) Poor color tone of the polyester polymer, that is, a phenomenon in which the polymer is colored yellow occurs, and when used for a film, a hollow bottle, or the like, there is a problem that the color tone of a molded product is deteriorated. 4) The filter pressure at the time of melting and producing a molded article increases due to clogging of foreign matter, and the productivity also decreases.

According to JP-A-11-228681, the molar ratio of the reaction system (the molar ratio of the diol or its ester-forming derivative to the aromatic dicarboxylic acid or its ester-forming derivative) when the aluminum compound is added as a catalyst is 1 If it is .25 to 2.0, the amount of foreign substances is reduced, and the increase in the filtration pressure and the breakage of the yarn are eliminated. However, in order to have catalytic activity, the amount of aluminum added must be increased. Therefore, the amount of foreign matters of the polyester still obtained is large, which causes a large increase in filtration pressure and breakage of the yarn, which is a practical problem.

[0015] Germanium compounds have already been put to practical use as catalysts which provide polyesters which have excellent catalytic activity and do not have the above-mentioned problems except for antimony compounds. However, this catalyst is very expensive. And
Since it is easy to distill out of the reaction system during polymerization, the catalyst concentration in the reaction system changes, making it difficult to control the polymerization, and there is a problem in using it as the main component of the catalyst.

Further, as a method for suppressing thermal deterioration during melt molding of polyester, there is a method of removing a catalyst from polyester. As a method for removing a catalyst from polyester, for example, JP-A-10-251394 discloses a method in which a polyester resin is contacted with an extractant which is a supercritical fluid in the presence of an acidic substance.
However, such a method using a supercritical fluid is not preferable because it is technically difficult and leads to an increase in product cost.

As described above, the polymerization catalyst is a polymerization catalyst in which a metal component other than antimony and germanium is a main metal component of the catalyst, and has excellent catalytic activity and has a problem that foreign matter such as an increase in filtration pressure and breakage of yarn is caused. A polyester that does not generate is desired.

[0018]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polyester which can solve the above-mentioned problems caused by foreign matters of the polyester, and a polyester obtained by the method. That is, the present invention provides a method for producing a polyester which does not contain an antimony compound or a germanium compound as a main component of a catalyst, uses aluminum as a main metal component, has excellent catalytic activity, and can eliminate the generation of foreign matter caused by the catalyst, and the method. A polyester obtained by the method.

[0019]

SUMMARY OF THE INVENTION The present invention provides an esterification or transesterification reaction between a polycarboxylic acid containing a dicarboxylic acid or an ester-forming derivative thereof and a polyhydric alcohol containing a glycol or an ester-forming derivative thereof. In a method of producing a polyester by subjecting the obtained product to a polycondensation reaction, an amount of aluminum or a compound thereof satisfying the following formula (1) is added to the finally obtained polymer, and at the time of the addition, Wherein the molar ratio of the polyhydric alcohol containing glycol and the ester-forming derivative thereof to the polycarboxylic acid containing dicarboxylic acid and the ester-forming derivative thereof is 1.2 to 2.1. A process for producing a polyester having excellent catalytic activity, and Occurrence of foreign matters caused by medium can be obtained polyesters such as can be eliminated. Al ≦ 70 (ppm) (1) (In the formula (1), Al indicates the content (ppm) of aluminum atoms with respect to the finally obtained polyester.)

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is obtained by an esterification reaction or a transesterification reaction with a polycarboxylic acid containing a dicarboxylic acid or an ester-forming derivative thereof and a polyhydric alcohol containing a glycol or an ester-forming derivative thereof. In the method for producing a polyester by subjecting the obtained product to a polycondensation reaction, an amount of aluminum or a compound thereof satisfying the above formula (1) is added to the finally obtained polymer, and The molar ratio of the polyhydric alcohol containing glycol and these ester-forming derivatives to the polycarboxylic acid containing dicarboxylic acids and the ester-forming derivatives thereof in the reaction system is 1.2 to 2.1. The present invention relates to a method for producing a polyester and a polyester having a small amount of foreign matter obtained by the method. It is intended.

The polyester of the present invention is not particularly limited as long as it is a polyester synthesized from a polycarboxylic acid containing a dicarboxylic acid or an ester-forming derivative thereof and a polyhydric alcohol containing a glycol or an ester-forming derivative thereof.

The polyester of the present invention includes 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 its copolymer are particularly preferred.

The feature of the present invention is obtained by an esterification reaction or a transesterification reaction with a polycarboxylic acid containing a dicarboxylic acid or an ester-forming derivative thereof and a polyhydric alcohol containing a glycol or an ester-forming derivative thereof. The product is subjected to a polycondensation reaction to produce a polyester, using a polycondensation catalyst comprising aluminum or a compound thereof and a phosphorus compound and / or a phenolic compound, particularly a phosphorus compound having a phenol moiety in the same molecule. When the compound is added, the molar ratio of the polyhydric alcohol containing glycol and these ester-forming derivatives to the polycarboxylic acid containing dicarboxylic acids and their ester-forming derivatives in the reaction system is 1.2 to 2. Must be 1. When the molar ratio is less than 1.2, the dispersibility of the catalyst in the polymerization system is low, so that the foreign matter suppressing effect cannot be obtained. On the other hand, if the molar ratio exceeds 2.1, dimerization of the polyhydric alcohol tends to occur, and the by-products are copolymerized in the polymer in an amount larger than usual. The problem of mingling occurs. It is more preferably from 1.3 to 2.0, and still more preferably from 1.4 to 1.8.

The molar ratio as described above is set to 1.2 to 2.
As a specific method for obtaining 1, polyhydric alcohol containing glycol with respect to polycarboxylic acid containing dicarboxylic acid or their ester-forming derivatives until aluminum or its compound is added, or at the same time, The addition of the ester-forming derivative is preferable because the by-product of the polyhydric alcohol dimer can be suppressed. Besides this, there is a method of synthesizing polyester by setting the molar ratio as described above in advance, but in this method, a dimer of polyhydric alcohol is easily produced as a by-product,
It is not preferable because physical properties such as a softening point of the obtained polyester are deteriorated. The amount of the polyhydric alcohol to be added must be 0.1 to 0.9 times the mol of the polycarboxylic acid containing dicarboxylic acid or the ester-forming derivative thereof. Preferably it is 0.2 to 0.7 times mol, more preferably 0.3 to 0.5 times mol.

If the amount of the polyhydric alcohol to be added is more than 0.9 times the mol of the polycarboxylic acid containing dicarboxylic acid or the ester-forming derivative thereof, a sufficient foreign matter suppressing effect cannot be obtained. Further, when the amount of the polyhydric alcohol to be added is smaller than 0.1 times the mole, there is a problem that the effect of the addition is not clearly exhibited.

The above-mentioned method of adding the glycol-containing polyhydric alcohol or an ester-forming derivative thereof may be added simultaneously with other additives, or only the polyhydric alcohol may be added. However, it is preferable to add aluminum before or at the same time as adding aluminum or its compound.

As the aluminum or aluminum compound constituting the polycondensation catalyst used in the present invention, known aluminum compounds can be used without limitation in addition to metallic aluminum.

Specific examples of the aluminum compound include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, and aluminum trichloroacetate. , Aluminum lactate,
Carboxylates such as aluminum citrate, aluminum salicylate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, poly aluminum chloride,
Inorganic acid salts such as aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate and aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-butoxide, etc. Aluminum chelate compounds such as aluminum alkoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethyl acetoacetate, aluminum ethyl acetoacetate di-iso-propoxide, organic aluminum compounds such as trimethylaluminum, triethylaluminum, and partial hydrolysates thereof , Aluminum alkoxides and aluminum chelates and hydrides Reaction products of Kishikarubon acid, aluminum oxide ultrafine particles of aluminum oxide, aluminum silicate, and composite oxides such as aluminum and titanium, silicon or zirconium and an alkali metal or an alkaline earth metal. Of these, carboxylate, inorganic acid salt and chelate compound are preferable, and among these, aluminum sulfate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferable. As the basic aluminum acetate, one stabilized with an additive such as boric acid may be used.

The amount of the aluminum or aluminum compound to be added in the present invention must be 70 ppm or less based on the polyester finally obtained as aluminum atoms. Preferably, it is 1 ppm to 60 ppm, more preferably 10 ppm to 40 ppm.
If the addition amount is less than 1 ppm, the catalytic activity may not be sufficiently exhibited. If the addition amount exceeds 70 ppm, thermal stability and thermal oxidative stability decrease, generation of foreign matter due to aluminum and increase in coloring may occur. A problem may occur.
As described above, even when the addition amount of the aluminum component is small, the polymerization catalyst of the present invention is greatly characterized in that it exhibits a sufficient catalytic activity. As a result, thermal stability and thermal oxidation stability are excellent, and foreign matter and coloring due to aluminum are reduced.

The phenolic compound constituting the polycondensation catalyst used in the present invention is not particularly limited as long as it is a compound having a phenol structure.
t-butyl-4-methylphenol, 2,6-di-tert-butyl-4-
Ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol,
2,6-di-tert-amyl-4-methylphenol, 2,6-di-tert
-Octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-tert-butylphenol, 2-tert-butyl-2-ethyl
-6-tert-octylphenol, 2-isobutyl-4-ethyl-
6-tert-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,3-tris (2-methyl-4 -Hydroxy-5-tert-butylphenyl) butane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-
Hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3- (3,5 -Di-tert-butyl-4,4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5
-Di-tert-butyl-4-hydroxy-hydrocinnamide),
1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-
Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4-tert -Butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-
Octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, tetrakis [methylene (3,5-di-tert-butyl-4-hydroxy) hydrocinnamate ] Methane, bis [(3,3-bis (3-tert-butyl-4-hydroxyphenyl) butylic acid) glycol ester, N, N'-bis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionyl] hydrazine, 2,2′-oxazamide bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl -6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4 -Hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl2- ｛β-
(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2 -(3,5-di-te
rt-butyl-4-hydroxycinnamoyloxy)) ethoxyphenyl] propane, β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester, tetrakis- [methyl-3- (3 ′) , 5'-Di-tert-butyl-4-hydroxyphenyl) propionate] methane, octadecyl-3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-
Butylphenyl) butane, thiodiethylene-bis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3- (5-tert-
Butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis-[-3- (3 ′ -tert-butyl-4-hydroxy-5-methylphenyl)] propionate, 1,1,3-tris [2-methyl-4- [3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane. These can be used in combination of two or more at the same time. Of these, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis- [methyl-3- (3 ′, 5 ′) -Di-tert-butyl
4-Hydroxyphenyl) propionate] methane and thiodiethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] are preferred.

By adding these phenolic compounds during the polymerization of the polyester, the catalytic activity of the aluminum compound is improved, and the thermal stability of the polymerized polyester is also improved.

The phenolic compound used in the present invention is used in an amount of 5 × 10 ^-5 to 1 mol per mol of all the constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. %, More preferably 1 × 10 ^{−4 to} 0.5 mol%.

In the present invention, a phosphorus compound may be used together with the phenolic compound.

The phosphorus compound constituting the polycondensation catalyst used in the present invention is not particularly restricted but includes phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, It is preferable to use one or more compounds selected from the group consisting of phosphine-based compounds because the effect of improving the catalytic activity is large. Among these, the use of one or two or more phosphonic acid compounds is particularly preferable because the effect of improving the catalytic activity is particularly large.

The phosphonic acid-based compound, phosphinic acid-based compound, phosphine oxide-based compound, phosphonous acid-based compound, phosphinous acid-based compound and phosphine-based compound referred to in the present invention are represented by the following formulas (Chem. 8) to (Chem. 8), respectively. 13)
Means a compound having a structure represented by

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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The phosphonic acid compounds of the present invention include, for example, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate and the like. Can be Examples of the phosphinic acid compound of the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate,
Phenylphosphinic acid, methyl phenylphosphinate,
And phenyl phenylphosphinate. As the phosphine oxide compound of the present invention, for example,
Examples include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide.

Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds, the phosphorus compounds of the present invention are represented by the following formulas (14) to (14). It is preferable to use the compound represented by the formula:

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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Of the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

As the phosphorus compound constituting the polycondensation catalyst of the present invention, the compounds represented by the following general formulas (Formula 20) to (Formula 22) are particularly preferable because the effect of improving the catalytic activity is large.

[0052]

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[0053]

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[0054]

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(In the formulas (Formula 20) to (Formula 22), R ¹ ,
R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, having 1 to 50 carbon atoms.
Represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. R ² and R ³ each independently represent hydrogen and carbon number 1 to
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups or alkoxyl groups. However, the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the phosphorus compound constituting the polycondensation catalyst used in the present invention, R in the above formulas (Chemical Formulas 20 to 22)
Compounds in which ¹ , R ⁴ , R ⁵ and R ⁶ are groups having an aromatic ring structure are particularly preferred.

As the phosphorus compound constituting the polycondensation catalyst used in the present invention, for example, dimethyl methylphosphonate,
Diphenyl methylphosphonate, Dimethyl phenylphosphonate, Diethyl phenylphosphonate, Diphenyl phenylphosphonate, Dimethyl benzylphosphonate, Diethyl benzylphosphonate, Diphenylphosphinic acid, Methyl diphenylphosphinate, Phenyl diphenylphosphinate, Phenylphosphinic acid, Phenylphosphinic acid Examples include methyl, phenyl phenylphosphinate, diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide. Of these, dimethyl phenylphosphonate,
Diethyl benzylphosphonate is particularly preferred.

As the phosphorus compound constituting the polycondensation catalyst used in the present invention, it is preferable to use a phosphorus compound having a phenol moiety in the same molecule. The phosphorus compound having a phenol moiety in the same molecule is not particularly limited as long as it is a phosphorus compound having a phenol structure, but a phosphonic acid compound, a phosphinic acid compound, and a phosphine oxide compound having a phenol moiety in the same molecule. Compound,
It is preferable to use one or more compounds selected from the group consisting of phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds because the effect of improving the catalytic activity is large. Among these, the use of a phosphonic acid-based compound having one or more phenol moieties in the same molecule is particularly preferred because the effect of improving the catalytic activity is particularly large. Further, as the phosphorus compound having a phenol moiety in the same molecule constituting the polycondensation catalyst of the present invention, the following general formula (Chemical Formula 2)
It is preferable to use the compounds represented by 3) to (Formula 25) since the catalytic activity is particularly improved.

[0059]

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[0060]

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[0061]

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(In the formulas (Formula 23) to (Formula 25), R ¹ is a substituent such as a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, a hydroxyl group or a halogen group, an alkoxyl group or an amino group, and a phenol moiety. And R ⁴ , R ⁵ , and R ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, an amino group, or the like. Represents a hydrocarbon group having 1 to 50 carbon atoms including a substituent, wherein R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a carbon atom having 1 substituent, such as a hydroxyl group or an alkoxyl group; represents the 50 hydrocarbon group. However, end each other hydrocarbon groups branched structure or cyclohexyl alicyclic structure or a phenyl or naphthyl aromatic ring structure that may contain .R ² and R ⁴ of the coupling May be )

Examples of the phosphorus compound of the present invention having a phenol moiety in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, and p-hydroxyphenylphosphonic acid.
Diphenyl hydroxyphenylphosphonate, bis (p
-Hydroxyphenyl) phosphinic acid, bis (p-hydroxyphenyl) phosphinic acid methyl, bis (p-hydroxyphenyl) phosphinic acid phenyl, p-hydroxyphenylphenylphosphinic acid, p-hydroxyphenylphenylphosphinic acid methyl, p-hydroxyphenyl Phenyl phenylphosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, bis (p-hydroxyphenyl) phosphine oxide, tris (p-hydroxyphenyl) phosphine oxide, bis ( (p-hydroxyphenyl) methylphosphine oxide, and the following formulas (Formula 26) to (Formula 2)
And the compound represented by 9). Among these, a compound represented by the following formula (Formula 28) and dimethyl p-hydroxyphenylphosphonate are particularly preferred.

[0064]

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[0065]

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[0066]

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[0067]

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As the compound represented by the above formula (Formula 28), there is SANKO-220 (manufactured by Sanko Co., Ltd.), which can be used.

By adding a phosphorus compound having such a phenol moiety in the same molecule during the polymerization of the polyester, the catalytic activity of the aluminum compound is improved and the thermal stability of the polymerized polyester is also improved.

In the present invention, it is preferable to use a metal salt compound of phosphorus as the phosphorus compound. The metal salt compound of phosphorus is not particularly limited as long as it is a metal salt of a phosphorus compound, but the use of a metal salt of a phosphonic acid-based compound is preferred because the effect of improving the catalytic activity is large. Examples of the metal salt of a phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.

In the above-mentioned phosphorus compounds, the metal portion of the metal salt is Li, Na, K, Be, Mg, Sr,
It is preferable to use one selected from Ba, Mn, Ni, Cu, and Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, and Mg are particularly preferred.

As the metal salt compound of phosphorus constituting the polymerization catalyst used in the present invention, it is preferable to use at least one selected from compounds represented by the following general formula (Formula 30) because the effect of improving the catalytic activity is large.

[0073]

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(Wherein R ¹ is hydrogen, carbon number 1)
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group, a halogen group, an alkoxyl group or an amino group. R ² is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 1 carbon atoms.
Represents 50 hydrocarbon groups. R ³ is hydrogen, carbon number 1-5
And represents a hydrocarbon group having 1 to 50 carbon atoms including 0 hydrocarbon group, hydroxyl group, alkoxyl group or carbonyl. l
Represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m
Is 4 or less. M represents a (l + m) -valent metal cation. n
Represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the above R ¹ , for example, phenyl,
Examples include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. R above
^{As 2} , for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted Phenyl and naphthyl groups,
And a group represented by —CH ₂ CH ₂ OH. R ³
Examples of O ^- include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion.

Among the compounds represented by the above general formula (Formula 30), it is preferable to use at least one selected from the compounds represented by the following general formula (Formula 31).

[0077]

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(In the formula, R ¹ is hydrogen and has 1 carbon atom.
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group, a halogen group, an alkoxyl group or an amino group. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the above R ¹ , for example, phenyl,
Examples include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion,
Examples include acetate ion and acetylacetone ion.

Among the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

In the above formula (Formula 31), M is Li,
Na, K, Be, Mg, Sr, Ba, Mn, Ni, C
It is preferable to use one selected from u and Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, M
g is particularly preferred.

Examples of the phosphorus metal salt compound of the present invention include lithium [ethyl (1-naphthyl) methylphosphonate],
Sodium [ethyl (1-naphthyl) methyl phosphonate], magnesium bis [(1-naphthyl) methyl phosphonate], potassium [ethyl (2-naphthyl) methyl phosphonate], magnesium bis [(2-naphthyl) methyl phosphonate], Lithium [ethyl benzyl phosphonate], sodium [ethyl benzyl phosphonate], magnesium bis [ethyl benzyl phosphonate], beryllium bis [ethyl benzyl phosphonate],
Strontium bis [ethyl benzylphosphonate], manganese bis [ethyl benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonic acid], sodium [ethyl (9-anthryl) methylphosphonate], magnesium bis [(9-anthryl) ) Ethyl methylphosphonate], sodium [ethyl 4-hydroxybenzylphosphonate], magnesium bis [ethyl 4-hydroxybenzylphosphonate], sodium [phenyl chlorobenzylphosphonate], ethyl magnesium bis [4-chlorobenzylphosphonate] ], Sodium [methyl 4-aminobenzylphosphonate], magnesium bis [methyl 4-aminobenzylphosphonate], sodium phenylphosphonate, magnesium bis [phenylphosphonate] Ethyl phosphate], zinc bis [phenylphosphonic acid ethyl] and the like. Among these, lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [(1-naphthyl) methylphosphonate], lithium [ethyl benzylphosphonate], Sodium [ethyl benzylphosphonate],
Magnesium bis [ethyl benzylphosphonate], sodium benzylphosphonate and magnesium bis [benzylphosphonic acid] are particularly preferred.

The metal salt compound of phosphorus, which is another preferred phosphorus compound constituting the polymerization catalyst used in the present invention, is at least one selected from compounds represented by the following general formula (Formula 32).

[0084]

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(In the formula, R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. R ³
Represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. R ⁴ O ^- as, for example,
Hydroxide ion, alcoholate ion, acetate ion, acetylacetone ion and the like. l is 1
M is an integer of 0 or 1 or more, and l + m is 4
It is as follows. M represents a (l + m) -valent metal cation. n is 1
Represents the above integer. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among these, it is preferable to use at least one selected from compounds represented by the following general formula (Formula 33).

[0087]

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(In the formula (Formula 33), M ^{n +} represents an n-valent metal cation. N represents 1, 2, 3, or 4)

In the above formula (Formula 32) or (Formula 33), M is Li, Na, K, Be, Mg, Sr, Ba,
It is preferable to use one selected from Mn, Ni, Cu, and Zn since the effect of improving the catalytic activity is large. Of these,
Li, Na and Mg are particularly preferred.

The specific phosphorus metal salt compounds of the present invention include lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-t-t
ethyl ert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], potassium [3,5-di-tert-butyl]
-Butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-]
Ethyl hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate methyl], Strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], barium bis [3,5-
Phenyl di-tert-butyl-4-hydroxybenzylphosphonate], manganese bis [3,5-di-tert-butyl-4
-Ethyl ethyl hydroxybenzylphosphonate], nickel bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], copper bis [3,5-di-tert-butyl-4]
-Ethyl ethyl hydroxybenzylphosphonate] and zinc bis [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate]. Among them, lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [ Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

When a polycondensation catalyst comprising aluminum or a compound thereof and a phosphorus compound is used in the present invention, at least one selected from aluminum salts of phosphorus compounds may be used. An aluminum salt of a phosphorus compound may be used in combination with another aluminum compound, a phosphorus compound, a phenol compound or the like. The aluminum salt of the phosphorus compound of the present invention is not particularly limited as long as it is a phosphorus compound having an aluminum portion. However, the use of an aluminum salt of a phosphonic acid compound is preferred because the effect of improving the catalytic activity is large. Examples of the aluminum salt of the phosphorus compound include a monoaluminum salt, a dialluminum salt, and a trialuminum salt.

Among the above-mentioned aluminum salts of phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

The aluminum salt of a phosphorus compound constituting the polymerization catalyst used in the present invention is represented by the following general formula (Formula 34)
The use of at least one selected from the compounds represented by the following formulas is preferred because the effect of improving the catalytic activity is large.

[0094]

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((In the formula, R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group or an amino group.) R ² is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group,
Represents up to 50 hydrocarbon groups. R ³ is hydrogen, carbon number 1 to
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups, alkoxyl groups, or carbonyl.
l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m
Is 3. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the above R ¹ , for example, phenyl,
Examples include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. R above
^{As 2} , for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted Phenyl and naphthyl groups,
And a group represented by —CH ₂ CH ₂ OH. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion, an ethylene glycolate ion, an acetate ion and an acetylacetone ion.

Examples of the aluminum salt of the phosphorus compound of the present invention include an aluminum salt of ethyl (1-naphthyl) methylphosphonate, an aluminum salt of (1-naphthyl) methylphosphonic acid, an aluminum salt of ethyl (2-naphthyl) methylphosphonate, and benzyl. Aluminum salt of ethyl phosphonate, aluminum salt of benzylphosphonic acid, (9
Aluminum salt of ethyl -anthryl) methylphosphonate, aluminum salt of ethyl 4-hydroxybenzylphosphonate, aluminum salt of ethyl 2-methylbenzylphosphonate, aluminum salt of phenyl 4-chlorobenzylphosphonate, methyl 4-aminobenzylphosphonate Aluminum salt of ethyl 4-methoxybenzylphosphonate, aluminum salt of ethyl phenylphosphonate, and the like. Among them, (1-
Naphthyl) aluminum salt of ethyl methylphosphonate,
Aluminum salts of ethyl benzylphosphonate are particularly preferred.

When a polycondensation catalyst comprising aluminum or a compound thereof and a phosphorus compound is used in the present invention, at least one selected from aluminum salts of a specific phosphorus compound represented by the following general formula (Formula 35) is used. The effect of improving the catalyst activity is large and preferable. The aluminum salt of the phosphorus compound may be used in combination with another aluminum compound, a phosphorus compound, a phenol compound, or the like. The aluminum salt of a specific phosphorus compound constituting the polymerization catalyst used in the present invention means at least one selected from compounds represented by the following general formula (Formula 35).

[0099]

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((In the formula (Formula 35), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. R ³
Represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. l is an integer of 1 or more, m is 0
Or, represents an integer of 1 or more, and l + m is 3. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among these, it is preferable to use at least one selected from compounds represented by the following general formula (Formula 36).

[0102]

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(In the formula, R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, and R ⁴ represents hydrogen. Represents a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl, l is an integer of 1 or more, m is 0 or an integer of 1 or more, + m is 3. The hydrocarbon group may contain an alicyclic structure such as cycloalkylhexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

Examples of R ³ include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, Examples include a naphthyl group, a substituted phenyl group and a naphthyl group, and a group represented by —CH ₂ CH ₂ OH. Examples of R ⁴ O ⁻ include a hydroxide ion, an alcoholate ion, an ethylene glycolate ion, an acetate ion and an acetylacetone ion.

Examples of the aluminum salt of the specific phosphorus compound of the present invention include aluminum salt of ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-t-t
Aluminum salt of methyl ert-butyl-4-hydroxybenzylphosphonate, aluminum salt of isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzyl Aluminum salt of phenyl phosphonate, 3,5-di-tert-
Aluminum salt of butyl-4-hydroxybenzylphosphonic acid; Of these, 3,5-di-ter
Aluminum salts of ethyl t-butyl-4-hydroxybenzylphosphonate and aluminum salts of methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

In the present invention, it is preferable to use a phosphorus compound having at least one P-OH bond as the phosphorus compound. A phosphorus compound having at least one P-OH bond,
There is no particular limitation as long as it is a phosphorus compound having at least one P-OH in the molecule. Among these phosphorus compounds,
Use of a phosphonic acid-based compound having at least one P-OH bond is preferred because the effect of improving the catalytic activity is large.

Among the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

As the phosphorus compound having at least one P-OH bond constituting the polymerization catalyst of the present invention, when at least one selected from compounds represented by the following general formula (Formula 37) is used, the catalytic activity is improved. The effect is large and preferable.

[0109]

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(In the formula (Formula 37), R ¹ is hydrogen, and has 1 carbon atom.)
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group, a halogen group, an alkoxyl group or an amino group. R ² is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 1 carbon atoms.
Represents 50 hydrocarbon groups. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the above R ¹ , for example, phenyl,
Examples include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. R above
^{As 2} , for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted Phenyl and naphthyl groups,
And a group represented by —CH ₂ CH ₂ OH.

Of the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

Examples of the phosphorus compound having at least one P-OH bond according to the present invention include ethyl (1-naphthyl) methylphosphonate, (1-naphthyl) methylphosphonic acid,
Ethyl (2-naphthyl) methylphosphonate, ethyl benzylphosphonate, benzylphosphonic acid, ethyl (9-anthryl) methylphosphonate, ethyl 4-hydroxybenzylphosphonate, ethyl 2-methylbenzylphosphonate, phenyl 4-chlorobenzylphosphonate , Methyl 4-aminobenzylphosphonate, ethyl 4-methoxybenzylphosphonate, and the like. Of these, (1
-Naphthyl) ethyl methylphosphonate and ethyl benzylphosphonate are particularly preferred.

As the preferred phosphorus compound used in the present invention, a specific phosphorus compound having at least one P-OH bond can be mentioned. The specific phosphorus compound having at least one P-OH bond refers to at least one compound selected from compounds represented by the following general formula (Formula 38).

[0115]

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(Wherein R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms; R ³
Represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among them, it is preferable to use at least one selected from compounds represented by the following general formula (Formula 39).

[0118]

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(In the formula, R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group is cycloalkylhexyl) And the like, and may contain an alicyclic structure or branched structure such as phenyl or naphthyl.)

Examples of R ³ include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, Examples include a naphthyl group, a substituted phenyl group and a naphthyl group, and a group represented by —CH ₂ CH ₂ OH.

Specific phosphorus compounds having at least one P-OH bond according to the present invention include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-tert-butyl- Methyl 4-hydroxybenzylphosphonate, isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-
Phenyl hydroxybenzylphosphonate, 3,5-di-ter
Octadecyl t-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid and the like can be mentioned. Of these, ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

As a preferable phosphorus compound, a phosphorus compound represented by a chemical formula (Formula 40) can be mentioned.

[0123]

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(In the formula, R ¹ represents a hydrocarbon group having ¹ to 49 carbon atoms, or a hydrocarbon group having ¹ to 49 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group or an amino group; ² and R ³ are each independently hydrogen and carbon number 1
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group or an alkoxyl group. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. )

More preferably, the chemical formula (Formula 40)
At least one of R ¹ , R ² and R ^{3 in} the compound is a compound containing an aromatic ring structure.

Specific examples of the phosphorus compound used in the present invention are shown below.

[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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The phosphorus compound used as a polycondensation catalyst in the present invention has a higher molecular weight and is more effective because it is less likely to be distilled off during polymerization.

Another phosphorus compound desirably used in the present invention is at least one phosphorus compound selected from the compounds represented by the following general formula (Formula 47).

[0135]

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(In the formula (Formula 47), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
³ and R ⁴ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, 1 to 5 carbon atoms including a hydroxyl group or an alkoxyl group.
Represents a hydrocarbon group of 0. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Of the above general formulas (Chemical formula 47), it is preferable to use at least one compound selected from the compounds represented by the following general formula (Chemical formula 48) because the effect of improving the catalytic activity is high.

[0138]

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(In the above formula, R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may include an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

The above R ³ and R ⁴ are, for example, short-chain aliphatic groups such as hydrogen, methyl group and butyl group, long-chain aliphatic groups such as octadecyl, phenyl group, naphthyl group and substituted phenyl group. aromatic groups such as groups or naphthyl group, -CH ₂ CH ₂
And a group represented by OH.

The specific phosphorus compound of the present invention includes 3,5
-Di-tert-butyl-4-hydroxybenzylphosphonate diisopropyl, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate di-n-butyl, 3,5-di-ter
dioctadecyl t-butyl-4-hydroxybenzylphosphonate, diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and the like. Among these, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-
Diphenyl hydroxybenzylphosphonate is particularly preferred.

Another phosphorus compound desirably used in the present invention is at least one phosphorus compound selected from the compounds represented by the chemical formulas (Formula 49) and (Formula 50).

[0143]

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[0144]

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As the compound represented by the above chemical formula (Chemical Formula 49), Irganox1222 (manufactured by Ciba Specialty Chemicals) is commercially available, and as the compound represented by the chemical formula (Chemical Formula 50), Irgano
x1425 (manufactured by Ciba Specialty Chemicals)
Is commercially available and can be used.

When the phosphorus compound of the present invention is used in combination, a catalyst exhibiting a sufficient catalytic effect can be obtained even if the amount of aluminum added in the polyester polymerization catalyst is small. As a result, the amount of foreign matter is reduced, and the increase in filtration pressure and breakage of yarn are reduced.

The amount of the phosphorus compound of the present invention to be used is preferably 0.0001 to 0.1 mol% with respect to the total number of moles of all constituent units of the polycarboxylic acid component of the obtained polyester.
More preferably, it is 0.005 to 0.05 mol%. When the addition amount of the phosphorus compound is less than 0.0001 mol%, the effect of addition may not be exhibited. When the addition amount exceeds 0.1 mol%, on the contrary, the catalytic activity as a polyester polymerization catalyst may decrease. The tendency changes depending on the amount of aluminum used and the like. The above catalyst is an alkali metal,
Preferably, they do not contain an alkaline earth metal or a compound thereof.

On the other hand, in the present invention, it is preferable that a small amount of at least one selected from alkali metals, alkaline earth metals and compounds thereof be coexisted as the second metal-containing component in addition to aluminum or its compound. is there. The coexistence of such a second metal-containing component in the catalyst system increases the catalytic activity in addition to the effect of suppressing the production of diethylene glycol, and therefore, a catalyst component having a higher reaction rate is obtained, which is effective for improving the productivity. .

It is known that a catalyst having sufficient catalytic activity can be obtained by adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound. The use of such a known catalyst can provide a polyester having excellent thermal stability. However, the known catalyst using an alkali metal compound or an alkaline earth metal compound in combination is not suitable for obtaining a practical catalytic activity. When an alkali metal compound is used, the amount of foreign matter caused by the alkali metal compound increases, and when used for fibers, the spinning properties and yarn properties, and when used for films, the film properties, transparency, and heat stability Properties, thermal oxidation stability, hydrolysis resistance, etc. are deteriorated. Further, the color tone of a melt-formed product such as a fiber or a film deteriorates.
In addition, when an alkaline earth metal compound is used in combination, the thermal stability and thermal oxidative stability of the obtained polyester are reduced in order to obtain practical activity, the coloring due to heating is large, and the amount of foreign matter generated is also small. More.

When an alkali metal, an alkaline earth metal or a compound thereof is added, the amount of use M (mol%) is
It is preferably from 1 × 10 ^{−6 to} less than 0.1 mol%, more preferably from 5 × 10 ^{−6 to} 0.05, based on the number of moles of all the polycarboxylic acid units constituting the polyester.
Mol%, more preferably 1 × 10 ^{−5 to} 0.03.
Mol%, particularly preferably 1 × 10 ^{−5 to} 0.01.
Mol%. Since the added amount of the alkali metal and the alkaline earth metal is small, the reaction rate can be increased without causing problems such as a decrease in thermal stability, generation of foreign matter, and coloring. Further, the reaction rate can be increased without causing a problem such as a decrease in hydrolysis resistance. When the amount M of the alkali metal, alkaline earth metal or compound thereof is 0.1 mol% or more, there is a problem in product processing such as a decrease in thermal stability, an increase in generation of foreign matter and coloring, and a decrease in hydrolysis resistance. Cases occur. If M is less than 1 × 10 ⁻⁶ mol%, the effect is not clear even if added.

The alkali metal and alkaline earth metal constituting the second metal-containing component which is preferably used in addition to aluminum or its compound in the present invention include Li, Na, K, Rb, Cs, Be, Mg, Ca,
It is preferably at least one selected from Sr and Ba, and more preferably an alkali metal or a compound thereof. When an alkali metal or a compound thereof is used, it is particularly preferable to use Li, Na, and K. Examples of the alkali metal or alkaline earth metal compounds include, for example, saturated aliphatic carboxylate such as formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid, and unsaturated aliphatic carboxylate such as acrylic acid and methacrylic acid. Aromatic carboxylate such as benzoic acid, halogen-containing carboxylate such as trichloroacetic acid, hydroxycarboxylate such as lactic acid, citric acid, salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphorus Inorganic acid salts such as oxyhydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, and bromic acid, and organic sulfonic acid salts such as 1-propanesulfonic acid, 1-pentanesulfonic acid, and naphthalenesulfonic acid , Organic sulfates such as lauryl sulfate, methoxy, ethoxy, n
-Propoxy, iso-propoxy, n-butoxy, t
alkoxides such as tert-butoxy, chelate compounds with acetylacetonate and the like, hydrides, oxides,
Hydroxide and the like.

When strong alkalis such as hydroxides are used among these alkali metals, alkaline earth metals or compounds thereof, they tend not to be easily dissolved in diols such as ethylene glycol or organic solvents such as alcohols. Therefore, an aqueous solution must be added to the polymerization system, which may cause a problem in the polymerization step. Further, when a strong alkali such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during polymerization, and the polymerized polyester tends to be easily colored, and the hydrolysis resistance is also reduced. Tend to. Accordingly, the alkali metal or a compound thereof or an alkaline earth metal or a compound thereof suitable for the present invention is preferably a saturated aliphatic carboxylate, an unsaturated aliphatic carboxylate, or an aromatic salt of an alkali metal or an alkaline earth metal. Group carboxylate, halogen-containing carboxylate, hydroxycarboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid,
It is an inorganic acid salt selected from chloric acid and bromic acid, an organic sulfonate, an organic sulfate, a chelate compound, and an oxide. Among these, from the viewpoints of ease of handling and availability, it is preferable to use an alkali metal or alkaline earth metal saturated aliphatic carboxylate, particularly an acetate.

In a preferred embodiment, the polyester polymerization catalyst used in the present invention is further added with a cobalt compound as a cobalt atom in an amount of less than 10 ppm based on the polyester. More preferably, it is less than 5 ppm, and still more preferably 3 ppm or less.

It is known that the cobalt compound itself has a certain degree of polymerization activity. However, if the cobalt compound is added to such an extent that a sufficient catalytic effect is exhibited, the resulting polyester polymer may have a reduced brightness and a lower thermal stability. Decrease occurs. The polyester obtained according to the present invention has good color tone and thermal stability, but can be obtained by adding a cobalt compound in an amount such that the catalytic effect of the addition by a small amount as described above is not clear. The coloring can be more effectively eliminated without lowering the brightness of the polyester. The purpose of the cobalt compound in the present invention is to eliminate coloration, and it may be added at any stage of the polymerization or after the completion of the polymerization reaction.

The cobalt compound is not particularly limited, but specific examples thereof include cobalt acetate, cobalt nitrate,
Cobalt chloride, cobalt acetylacetonate, cobalt naphthenate, and hydrates thereof are exemplified. Among them, cobalt acetate tetrahydrate is particularly preferred.

The amount of the cobalt compound to be added is such that the total of aluminum atoms and cobalt atoms is 50 ppm or less and 10 pp of cobalt atoms with respect to the polymer finally obtained.
It is preferably less than m. More preferably, the total of aluminum atoms and cobalt atoms is 40 ppm or less,
The cobalt atom is 8 ppm or less, more preferably the total of the aluminum atom and the cobalt atom is 25 ppm or less, and the cobalt atom is 5 ppm or less. From the viewpoint of the thermal stability of the polyester, the total of aluminum atoms and cobalt atoms is less than 50 ppm,
It is preferably 0 ppm or less. In order to have sufficient catalytic activity, the total amount of aluminum atoms and cobalt atoms is preferably more than 0.01 ppm.

The production of the polyester according to the present invention can be carried out by a method having conventionally known steps except that the polyester polymerization catalyst of the present invention is used as a catalyst. For example, when producing PET, after esterification of terephthalic acid and ethylene glycol, a method of polycondensation, or after performing an ester exchange reaction between an alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, Any of the polycondensation methods can be used. Also, the polymerization apparatus is a batch type,
It may be a continuous type.

The interpretation of claim 1 when the present invention is carried out by using a continuous apparatus is that polycarboxylic acids including dicarboxylic acids and ester formation thereof in the polymerization reactor at the time of adding the catalyst. It means that the molar ratio of the glycol-containing polyhydric alcohol and the ester-forming derivative thereof to the acidic derivative is 1.2 to 2.1. The interpretation of claim 2 is that the molar ratio of the polyhydric alcohol containing glycol and these ester-forming derivatives to the polycarboxylic acid containing dicarboxylic acids and their ester-forming derivatives becomes low in the first kettle of the continuous system. The polyhydric alcohol containing glycol was added in such a manner that the polycondensation catalyst used in the present invention was added continuously or in a kettle in which the polycondensation catalyst used in the present invention was added, or in a kettle before the polycondensate was added in a molar amount of 0.1 to 0.9 times. Means to fall within the scope of claim 1.

The catalyst used in the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization and solution polymerization, and polyester can be produced by any method.

The aluminum or the compound thereof of the present invention may be added at a molar ratio after completion of the esterification and in the system (polyhydric carboxylic acid containing dicarboxylic acid and polyhydric alcohol containing glycol with respect to the ester-forming derivative thereof and glycol). After the above (molar ratio of the ester-forming derivative) falls within the range as described above.

The timing of adding the phenolic compound or phosphorus compound used in the present invention is not particularly limited.

The method for adding the polymerization catalyst of the present invention is not particularly limited as long as it falls within the scope of the claims of the present invention. The method for adding the polycondensation catalyst of the present invention may be a powder or neat addition, or may be a slurry or solution addition of a solvent such as ethylene glycol,
There is no particular limitation. Further, a mixture of aluminum metal or a compound thereof and another component, preferably a phenolic compound or a phosphorus compound of the present invention, may be added in advance, or they may be added separately. Also,
Aluminum metal or its compound and another component, preferably a phenolic compound or a phosphorus compound, may be added to the polymerization system at the same time, or they may be added at different times.

When the polymerization catalyst used in the present invention is added in the form of a slurry or a solution using a glycol-containing polyhydric alcohol or an ester-forming derivative thereof, the molar ratio in the system after the addition (dicarboxylic acid Is added so that the molar ratio of the polyhydric alcohol containing glycol and the ester-forming derivative thereof to the polyhydric carboxylic acid containing these and the ester-forming derivative thereof is in the range described above.

The catalytic activity of the polymerization catalyst used in the present invention preferably satisfies the following parameter ranges. By satisfying this range, the polymerization time is shortened, so that the polyester production time is preferably shortened. (2) AP (min) <2T (min) where AP is 275 ° C., 0.1
Time required to polymerize polyethylene terephthalate having an intrinsic viscosity of 0.65 dl / g at a reduced pressure of Torr (m
where T is 0.05 mol% as antimony atom (317 ppm based on the finally obtained polymer) with respect to the acid component in polyethylene terephthalate produced using antimony trioxide as a catalyst. AP. In the present invention, antimony trioxide used for comparison is antimony trioxide having a purity of 99% or more, for example, commercially available antimony (III) oxide (ALDR
(ICH CHEMICAL, purity 99.999%) is used.

The method for measuring AP is specifically as follows. 1) (BHET production process) Terephthalic acid and a 2-fold molar amount of ethylene glycol are used, and the esterification ratio is 95
% Bis (2-hydroxyethyl) terephthalate (B
HET) and a mixture of oligomers (hereinafter, referred to as a BHET mixture). 2) (Catalyst addition step) A predetermined amount of a catalyst is added to the above BHET mixture, and the mixture is stirred at 245 ° C. for 10 minutes under a normal pressure under a nitrogen atmosphere, and then heated to 275 ° C. in 50 minutes. Is gradually reduced to 0.1 Torr. 3) (Polycondensation step) A polycondensation reaction is performed at 275 ° C. and 0.1 Torr, and polymerization is performed until the intrinsic viscosity (IV) of polyethylene terephthalate reaches 0.65 dl / g. 4) The polymerization time required for the polycondensation step is defined as AP (min). These are performed using a batch-type reactor. The production of the BHET mixture in 1) (BHET production step) is performed by a known method. For example, terephthalic acid and a 2-fold molar amount of ethylene glycol are charged into a batch type autoclave equipped with a stirrer, and an esterification reaction is performed while distilling water out of the system at 245 ° C. under a pressure of 0.25 MPa. It is manufactured by The AP is more preferably 1.5 T or less, further preferably 1.3 T or less, and particularly preferably 1.0 T or less. 2) "Predetermined amount of catalyst" in (catalyst addition step)
The amount of the catalyst used is varied depending on the activity of the catalyst. The amount of the catalyst used is small for a highly active catalyst, and is large for a less active catalyst.

The polymerization catalyst used in the present invention includes other polymerization catalysts such as an antimony compound, a titanium compound, a germanium compound, a tin compound, and the like. Coexistence within the range of the addition amount that does not cause a problem,
This is advantageous and preferable in improving productivity by shortening the polymerization time.

However, as the antimony compound, as an antimony atom, a polyester obtained by polymerization is used.
It can be added in an amount of 50 ppm or less. More preferably 30 ppm
It is to be added in the following amount. The amount of antimony added
If it exceeds 50 ppm, precipitation of metallic antimony occurs, and blackening or foreign matter is generated in the polyester, which is not preferable.

The titanium compound can be added in a range of 10 ppm or less based on the polymer obtained by polymerization. More preferably 5ppm or less, more preferably 2ppm
It is to be added in the following amount. Add 10ppt titanium
If it is larger than m, the thermal stability of the obtained resin is significantly reduced.

The germanium compound can be added to the polyester obtained by polymerization in an amount of 20 ppm or less as a germanium atom. More preferably 10
It is to be added in the amount of ppm or less. If the amount of germanium added is more than 20 ppm, it is not preferable because it is disadvantageous in terms of cost.

When polymerizing a polyester using the polymerization catalyst of the present invention, one or more of an antimony compound, a titanium compound, a germanium compound, and a tin compound can be used.

The antimony compound, titanium compound, germanium compound and tin compound used in the present invention are not particularly limited.

Specifically, antimony compounds include:
Examples include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycooxide, and the like. Of these, antimony trioxide is preferable.

Further, as the titanium compound, tetra-n-
Propyl titanate, tetraisopropyl titanate,
Tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, titanium oxalate and the like.
-Butoxytitanate is preferred.

Examples of the germanium compound include germanium dioxide and germanium tetrachloride. Of these, germanium dioxide is preferable.

Examples of the tin compound include dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate, monobutyltin trilaurate. Examples thereof include chloride, dibutyltin sulfide, dibutylhydroxytin oxide, methylstannoic acid, and ethylstannoic acid, and the use of monobutylhydroxytin oxide is particularly preferable.

The dicarboxylic acids used in the present invention include:
Oxalic 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,
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 or their ester-forming derivatives exemplified, fumaric acid, maleic acid, unsaturated aliphatic dicarboxylic acids or their ester-forming derivatives exemplified by itaconic acid, etc., orthophthalic acid, isophthalic acid, Terephthalic acid, 5
-(Alkali metal) sulfoisophthalic acid, dipheninic acid, 1,3 naphthalenedicarboxylic acid, 1,4 naphthalenedicarboxylic acid, 1,5 naphthalenedicarboxylic acid, 2,
6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,
4'-biphenylsulfone dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p 'dicarboxylic acid, pamoic acid,
Aromatic dicarboxylic acids exemplified by anthracene dicarboxylic acid and the like and ester-forming derivatives thereof are exemplified.

Of these dicarboxylic acids, terephthalic acid and naphthalenedicarboxylic acid, particularly 2,6-naphthalenedicarboxylic acid, are preferred in view of the physical properties of the resulting polyester, and other dicarboxylic acids may be used as a component if necessary.

Examples of polycarboxylic acids other than these dicarboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid. Examples include carboxylic acids and their ester-forming derivatives.

Glycols used in the present invention include 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-cyclohexanedimethanol, 1.3
-Cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc. Aliphatic 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 And aromatic glycols such as bis- (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5 naphthalene diol, and 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.

As polyhydric alcohols other than these glycols, trimethylolmethane, trimethylolethane,
Trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like.

The polyester of the present invention may contain a known phosphorus compound as a copolymer component. As the phosphorus compound, a bifunctional phosphorus compound is preferable.
-Carboxyethyl) methylphosphinic acid, (2-carboxyethyl) phenylphosphinic acid, 9,10-dihydro-10-oxa- (2,3-carboxypropyl) -10-phosphaphenanthrene-10-oxide and the like. No. By including these phosphorus compounds as copolymer components, it is possible to improve the flame retardancy and the like of the obtained polyester.

As the constituent components of the polyester of the present invention,
In a preferred embodiment, a polycarboxylic acid having a sulfonate alkali metal base is used as a copolymer component in order to improve dyeability when polyester is used as a fiber.

The metal sulfonate group-containing compound to be used as the copolymerizable monomer is not particularly limited, but may be 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, or 2-lithium sulfoisophthalic acid. Examples thereof include terephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid, and lower alkyl ester derivatives thereof. In the present invention, use of 5-sodium sulfoisophthalic acid or an ester-forming derivative thereof is particularly preferred.

The amount of the metal sulfonate group-containing compound to be copolymerized is 0.3 to 10.0 with respect to the acidic component constituting the polyester.
Mol% is preferred, and more preferably 0.80 to 5.0 mol%. If the copolymerization amount is too small, the dyeability of the basic dye is inferior. If the copolymerization amount is too large, not only the spinning properties are poor, but also the fiber does not have sufficient strength due to the thickening phenomenon. The metal sulfonate-containing compound was 2.0 mol%
By copolymerizing as described above, it is also possible to impart normal pressure dyeability to the obtained modified polyester fiber. It is possible to appropriately reduce the amount of the metal sulfonate group-containing compound by selecting an appropriate dye for facilitating dyeing. Examples of the easily dyeable monomer include, but are not particularly limited to, long-chain glycol compounds represented by polyethylene glycol and polytetramethylene glycol, and aliphatic dicarboxylic acids represented by adipic acid, sebacic acid, and azelaic acid.

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

The polyester of the present invention may contain an organic, inorganic, or organometallic toner, a fluorescent whitening agent, and the like. Coloring such as yellowing can be suppressed to a more excellent level. Also, any other polymer, antistatic agent, defoamer, dyeability improver, dye,
Pigments, matting agents, optical brighteners, stabilizers, antioxidants and other additives may be included. As the antioxidant, an aromatic amine type, a phenol type or the like antioxidant can be used, and as the stabilizer, a phosphorus type such as phosphoric acid or a phosphoric ester type, a sulfur type, an amine type or the like can be used. Can be used.

According to the present invention, there is provided a method for producing a polyester capable of obtaining a polyester free of an antimony compound as a main component of a catalyst and having a small amount of foreign matter, and a polyester obtained by the method. The polyester of the present invention includes, for example, fibers for interior materials and bedding represented by clothing fibers, curtains, carpets, futon, etc., fibers for industrial materials represented by tire cords, ropes, etc., various fabrics, various knits, and short fibers. Fibers such as fibrous nonwoven fabrics and long-fiber nonwoven fabrics, packaging films, industrial films, optical films, magnetic tape films, photographic films, can laminating films, contensor films, heat shrink films, gas barrier films, white films, Films such as easy-cut films, non-heat-resistant stretched bottles, heat-resistant stretched bottles, direct blow bottles, gas barrier bottles, pressure-resistant bottles, hollow molded products such as heat-resistant pressure bottles, sheets such as A-PET and C-PET, glass fiber reinforced polyester ,
It can be applied to various molded products such as engineering plastics represented by elastomers and the like, and paints and adhesives.

[0188]

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.

(Measurement of Intrinsic Viscosity (IV)) Phenol /
The measurement was performed at 30 ° C. using a mixed solvent of tetrachloroethane (60:40, weight ratio).

(Foreign substance evaluation) 100 g of polyester resin
To p-chlorophenol / tetrachloroethane (75: 2
(5, weight ratio) Using a mixed solvent, the mixture was dissolved at 100 ° C., filtered under pressure, and the foreign matter on the filter was observed with a scanning electron microscope (SEM). The amount of the observed foreign matter was evaluated by the following index. ：: almost none, △: slightly recognized, ×: many

Example 1 Terephthalic acid and ethylene glycol were charged at a molar ratio of 1.1, and BHET was prepared according to a conventional method.
A mixture was synthesized, and ethylene glycol and an ethylene glycol solution of a catalyst component were added so that the molar ratio to the BHET mixture was 1.6. The catalyst component aluminum hydroxide chloride was 20 ppm as an aluminum atom with respect to the polymer finally obtained, and the phosphorus compound was Irganox 1425, and 0.015 as Irganox 1425 was used for the acid component in the polyester.
mol% was added. Irganox 1425 manufactured by Ciba Specialty Chemicals was used. Thereafter, the mixture was stirred at 245 ° C. for 15 minutes at normal pressure in a nitrogen atmosphere. Then, the temperature of the reaction system was gradually lowered while the temperature was raised to 275 ° C. over 60 minutes, and the polycondensation reaction was further performed at 275 ° C. and 0.1 Torr by reducing the pressure to 0.1 Torr. Table 1 shows the results.

(Examples 2, 3, and 4 and Comparative Examples 1 and 2)
Polymerization was carried out in the same manner as in Example 1 except that the amount of the catalyst to be added, the type of the catalyst and / or the molar ratio were changed.
Table 1 shows the results.

(Reference Example 1) Antimony trioxide was added as a catalyst in an amount of 0.05 mol% as antimony atom (317 ppm with respect to the finally obtained polymer) based on an acid component in PET. The same operation as in Example 1 was performed except that it was used. As antimony trioxide, commercially available Antimony (III) oxide (ALDRICH CHEMICAL
(Purity: 99.999%). As antimony trioxide, a solution was used which was dissolved in ethylene glycol by stirring at 150 ° C. for about 1 hour so that the concentration became about 10 g / l. Table 1 shows the results.

[0194]

[Table 1]

As is clear from the results of Examples 1 to 4, the generation of foreign matters is smaller than that of Comparative Example 1.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4J029 AA01 AA03 AB04 AD01 AE01 AE02 AE03 BA03 BA04 BC05 BD03 CB06 JB191 JC451 JC461 JC471 JC541 JC561 JC571 JF011 JF111 JF221 JF321 JF361 JF371 JF471

Claims (17)

[Claims] (1) It comprises one or more selected from polycarboxylic acids containing dicarboxylic acids or ester-forming derivatives thereof and one or more selected from polyhydric alcohols containing glycols or ester-forming derivatives. In a method for producing a polyester by subjecting a product obtained by an esterification reaction or a transesterification reaction to a product to a polyester, aluminum or a compound thereof satisfies the following formula (1) with respect to a polymer finally obtained. And the molar ratio of the polyhydric alcohol containing glycol or these ester-forming derivatives to the polycarboxylic acid containing dicarboxylic acids or these ester-forming derivatives in the reaction system at the time of the addition is 1.
The method for producing a polyester according to claim 1, wherein the ratio is 2 to 2.1. Al ≦ 70 (ppm) (1) (In the formula (1), Al indicates the content (ppm) of aluminum atoms with respect to the finally obtained polyester.) 2. The method for producing a polyester according to claim 1, wherein a phenolic compound is added. 3. The method according to claim 1, wherein a phosphorus compound is added. 4. A diol in an amount of 0.1 to 0.9 times the amount of a polycarboxylic acid containing a dicarboxylic acid and an ester-forming derivative thereof at the same time as or before the addition of aluminum or its compound. The method for producing a polyester according to any one of claims 1 to 3, wherein the polycondensation reaction is performed by adding the polyester. 5. The phosphorous compound is one or more selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds. The method for producing a polyester according to claim 3, which is a compound of the formula: 6. The method for producing a polyester according to claim 5, wherein the phosphorus compound is one or more phosphonic acid compounds. 7. The method according to claim 3, wherein the phosphorus compound is a compound having an aromatic ring structure. 8. The method according to claim 3, wherein the phosphorus compound is one or more selected from the group consisting of compounds represented by the following general formulas (1) to (3). Polyester manufacturing method. Embedded image Embedded image Embedded image (Wherein R ¹ , R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. And R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. Wherein the hydrocarbon group may contain an alicyclic structure or an aromatic ring structure.) 9. A compound according to claim ¹ , wherein R ¹ , R ⁴ ,
Method for producing a polyester according to claim 8 R ^5, R ⁶ is a group having an aromatic ring structure. 10. The method for producing a polyester according to claim 3, wherein the phosphorus compound has a phenol moiety in the same molecule. 11. The phosphorus compound having a phenol moiety in the same molecule is one or more selected from the group consisting of compounds represented by the following general formulas (4) to (6). The method for producing a polyester according to the above. Embedded image Embedded image Embedded image (In the formulas (Chem. 4) to (Chem. 6), R ¹ is a C ¹ to C 50 hydrocarbon group containing a phenol moiety, a hydroxyl group or a halogen group or an alkoxyl group or an amino group and a C ¹ to C 50 carbon atom containing a phenol moiety. R ⁴ , R ⁵ , and R ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, or a carbon group having 1 to 50 carbon atoms including an alkoxyl group or an amino group. Represents a hydrogen group, R ² , R ³
Are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms,
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may have a branched structure, an alicyclic structure or an aromatic ring structure. The terminals of R ² and R ⁴ may be bonded to each other. ) 12. The method according to claim 3, wherein the polycondensation catalyst comprising aluminum or a compound thereof and a phosphorus compound is at least one selected from aluminum salts of phosphorus compounds. Method. 13. A polycondensation catalyst comprising aluminum or a compound thereof and a phosphorus compound is at least one selected from compounds represented by the following general formula (7).
Or the method for producing a polyester according to any of 4. Embedded image (In the formula, R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. Represents a hydrocarbon group having 1 to 50 carbon atoms including a group, R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. L is an integer of 1 or more, m is 0 or an integer of 1 or more, l + m is 3. n represents an integer of 1 or more.
The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. ) 14. A polyester polymerization catalyst characterized by coexistence of one or more metals and / or metal compounds selected from the group consisting of alkali metals and their compounds and alkaline earth metals and their compounds. A method for producing the polyester according to claim 1. 15. When producing a polyester, an antimony compound is converted to an antimony atom with respect to the polyester.
The compound is added in an amount of 50 ppm or less.
15. The method for producing a polyester according to any one of 14. 16. The method for producing a polyester according to claim 1, wherein a germanium compound is added as a germanium atom in an amount of 20 ppm or less to the polyester when producing the polyester. 17. A polyester obtained by the production method according to claim 1.