JP2003040993A - Polyester and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester and its production method in which the problems of the foreign materials which reduce the productivity and quality such as a yarn breakage, rise in filtration pressure and blip in the production of a fiber, film, bottle or the like are solved. SOLUTION: The method for producing the polyester from a polyvalent carboxylic acid containing a dicarboxylic acid or an ester formative derivative thereof and a polyhydric alcohol containing a glycol or the derivative thereof is characterized in that a polymerization catalyst comprising aluminum or its compound and a phosphorus compound and/or a phenolic compound is used and a molar ratio of the polyhydric alcohol or the derivative to the polyvalent carboxylic acid or the derivative in a reaction system is 1.2-2.1 when 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 specifically, a method for producing a polyester using a novel polyester polymerization catalyst which does not use germanium or antimony compound as a catalyst main component, and a method for producing the same. It relates to the polyester produced.

[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 or 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.

A typical polyester having aromatic dicarboxylic acid and alkylene glycol as main constituents 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, which is polycondensed with a catalyst at high temperature and under vacuum. It is industrially produced by the polycondensation method or the like.

Conventionally, 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,
If this is used as the main component, that is, in an addition amount such that a practical polymerization rate is exhibited, since metal antimony is precipitated during polycondensation, there is a problem that darkening and foreign matter occur in the polyester. There is. Under such circumstances, polyesters containing no antimony or no antimony as a catalyst main component are desired.

The above-mentioned foreign matters in the polyester cause the following problems, for example. (1) In the polyester for a film, the deposition of metal antimony becomes a foreign substance in the polyester, which not only causes stain on the die during melt extrusion, but also causes a surface defect of the film. Further, when used as a raw material for a hollow molded article or the like, it is difficult to obtain a hollow molded article having excellent transparency. (2) The foreign matter in the polyester for the fiber becomes a foreign matter that causes a decrease in strength in the fiber, and becomes a cause of stain on the spinneret during spinning. In the production of polyester fibers, a polyester polymerization catalyst that does not generate foreign matter is required mainly from the viewpoint of workability.

As a method for solving the above problems, attempts have been made to use antimony trioxide as a catalyst and suppress the darkening of PET and the generation of foreign matter. For example, in Japanese Patent No. 2666502, by using a compound of antimony trioxide and bismuth and selenium as a polycondensation catalyst, generation of black foreign matter in PET is suppressed.
Further, JP-A-9-291141 describes that when antimony trioxide containing an oxide of sodium and iron is used as a polycondensation catalyst, precipitation of metallic antimony is suppressed. However, these polycondensation catalysts cannot eventually achieve the purpose of reducing the content of antimony in the polyester.

As a method for solving the problems of antimony catalysts in applications requiring transparency such as PET bottles, Japanese Patent Laid-Open No. 6-279579 discloses, for example,
A method is disclosed in which the transparency is improved by defining the amount ratio of the antimony compound and the phosphorus compound used. However, the hollow molded article made of polyester obtained by this method does not have sufficient transparency.

Further, Japanese Unexamined Patent Publication No. 10-36495 discloses a continuous production method of polyester having excellent transparency using antimony trioxide, phosphoric acid and sulfonic acid compounds. However, the polyester obtained by such a method has a problem that the thermal stability is poor and the obtained hollow molded article has a high acetaldehyde content.

[0009] Polycondensation catalysts replacing antimony-based catalysts such as antimony trioxide have also been studied, and titanium compounds and tin compounds represented by tetraalkoxy titanates have already been proposed. Further, polyester has a problem that it is susceptible to thermal deterioration during melt molding and that the polyester is markedly colored.

As an attempt to overcome the above problems when a titanium compound is used as a polycondensation catalyst, for example, in JP-A-55-116722, a method in which a tetraalkoxy titanate is used at the same time as a cobalt salt and a calcium salt is used. Is proposed. Also, Japanese Patent Laid-Open No. 8-735
No. 81 proposes a method in which a tetraalkoxy titanate is used as a polycondensation catalyst at the same time as a cobalt compound and an optical brightener is used. However, although these techniques reduce the coloring of PET when tetraalkoxy titanate is used as a polycondensation catalyst, P
Effective suppression of thermal decomposition of ET has not been achieved.

As another attempt to suppress thermal deterioration during melt molding of a polyester polymerized by using a titanium compound as a catalyst, for example, in JP-A-10-259296, a phosphorus compound is used after polymerizing a polyester by using a titanium compound as a catalyst. Methods of adding compounds are disclosed. But,
It is not only technically difficult to effectively mix an additive into a polymer after polymerization, but also it is not practically used because of cost increase.

Aluminum compounds are generally known to have poor catalytic activity. Among aluminum compounds,
It has been reported that an aluminum chelate compound has higher catalytic activity as a polycondensation catalyst than other aluminum compounds, but it is said that it has sufficient catalytic activity as compared with the above-mentioned antimony compound or titanium compound. Not to mention, moreover, the polyester polymerized using an aluminum compound as a catalyst for a long time has problems such as deterioration of thermal stability, coloring, and generation of foreign matter, and thus is not practical.

A technique is also known in which an alkali metal compound is added to an aluminum compound to obtain a polyester polymerization catalyst having sufficient catalytic activity. Polyester excellent in thermal stability can be obtained by using such a known catalyst, but the catalyst in which this alkali metal compound is used in combination requires a large amount of them in order to obtain practical catalytic activity,
As a result, at least one of the following problems is caused by the alkali metal compound in the obtained polyester polymer. 1) The amount of foreign matter becomes large, and when used for fibers, the yarn-forming properties and yarn properties deteriorate, and when used for films, the film properties deteriorate. 2) The hydrolysis resistance of the polyester polymer decreases, and the transparency decreases due to the generation of foreign matter. 3) Poor color tone of the polyester polymer, that is, a phenomenon in which the polymer is colored yellow, and when used in a film, a hollow bottle, or the like, the color tone of a molded product deteriorates. 4) The filter pressure at the time of melting to produce a molded product increases due to the clogging of foreign matter, and the productivity also decreases.

Further, according to JP-A-11-228681, the molar ratio of the reaction system when adding an aluminum compound as a catalyst (the molar ratio of the diol or its ester forming derivative to the aromatic dicarboxylic acid or its ester forming derivative) is 1. If it is 0.25 to 2.0, the amount of foreign matter is decreased, and the increase in filtration pressure and the breakage of yarn are eliminated. However, in order to have catalytic activity, the addition amount of aluminum must be increased. Therefore, the amount of foreign matters in the polyester still obtained is large, which causes a large increase in filtering pressure and a large number of yarn breakage, which is a problem in practical use.

Germanium compounds have already been put into practical use as catalysts for polyesters having excellent catalytic activity other than antimony compounds and not having the above problems, but this catalyst is very expensive. Or
Since it is easy to distill out from the reaction system during the polymerization, there is a problem that the catalyst concentration in the reaction system changes and it becomes difficult to control the polymerization, and there is a problem in using it as a catalyst main component.

Further, as a method for suppressing the thermal deterioration of the polyester during melt molding, a method of removing the catalyst from the polyester can be mentioned. As a method of removing the catalyst from the polyester, for example, Japanese Patent Application Laid-Open No. 10-251394 discloses a method of bringing a polyester resin into contact with an extractant which is a supercritical fluid in the presence of an acidic substance.
However, the method using such a supercritical fluid is not preferable because it is technically difficult and leads to an increase in the cost of the product.

Due to the above-mentioned circumstances, it is a polymerization catalyst having a metal component other than antimony and germanium as a main metal component of the catalyst, has excellent catalytic activity, and has a problem caused by foreign matters such as increase in filtration pressure and yarn breakage. A polyester that does not occur is desired.

[0018]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polyester capable of solving the above-mentioned problems caused by foreign matters in the polyester, and a polyester obtained by the method. That is, the present invention does not include an antimony compound or a germanium compound as a catalyst main component, has aluminum as a main metal component, is excellent in catalytic activity, and is a method for producing a polyester capable of eliminating the generation of foreign matter due to the catalyst, and the method. The polyester obtained by the above is provided.

[0019]

The present invention provides a polycarboxylic acid containing a dicarboxylic acid or an ester-forming derivative thereof and a polyhydric alcohol containing a glycol and an ester-forming derivative thereof by an esterification reaction or transesterification reaction. In the method for producing a polyester by subjecting the obtained product to a polycondensation reaction, a polycondensation catalyst comprising an aluminum or its compound and a phosphorus compound and / or a phenol compound, particularly a phosphorus compound having a phenol moiety in the same molecule is used. The molar ratio of the polyvalent carboxylic acid containing dicarboxylic acid and the polyhydric alcohol containing glycol to the ester-forming derivative of the reaction system and the ester-forming derivative thereof in the reaction system at the time of adding aluminum or its compound is 1.2. To 2.1. The present invention relates to a method for producing a reester, and by the method, a polyester having excellent catalytic activity and capable of eliminating the generation of foreign matter due to the catalyst can be obtained.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is obtained by an esterification reaction or transesterification reaction with a polyvalent carboxylic acid containing a dicarboxylic acid or an ester-forming derivative thereof and a polyhydric alcohol containing a glycol or an ester-forming derivative thereof. Polycondensation reaction of the obtained product, in the method for producing a polyester, aluminum or a compound thereof and a phosphorus compound and / or phenolic compound,
In particular, using a polycondensation catalyst composed of a phosphorus compound having a phenol moiety in the same molecule, a polyvalent carboxylic acid containing a dicarboxylic acid in the reaction system at the time of adding aluminum or the compound and a glycol for ester-forming derivatives thereof The present invention relates to a method for producing a polyester, characterized in that the polyhydric alcohol contained therein and the ester-forming derivative thereof have a molar ratio of 1.2 to 2.1, and a polyester having a small amount of foreign matter obtained by this method.

The polyester of the present invention is not particularly limited as long as it is a polyester synthesized from a polyvalent carboxylic 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 copolymers thereof are particularly preferable.

The characteristics of the present invention are obtained by an esterification reaction or a transesterification reaction with a polyvalent carboxylic 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 polycondensation reaction of the product, aluminum or a compound thereof and a phosphorus compound and / or a phenolic compound, particularly using a polycondensation catalyst comprising a phosphorus compound having a phenol moiety in the same molecule, aluminum or When the compound is added, the molar ratio of the polyhydric carboxylic acid containing the dicarboxylic acid and the polyhydric alcohol containing glycol to the ester forming derivative of the reaction system and the ester forming derivative thereof 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, and therefore the effect of suppressing foreign matter cannot be obtained. Further, when the molar ratio exceeds 2.1, dimerization of the polyhydric alcohol is likely to occur, and more of this by-product is copolymerized in the polymer than usual, so that the physical properties of the obtained polymer such as the softening point are lowered. The problem of inducing occurs. It is more preferably 1.3 to 2.0, still more preferably 1.4 to 1.8.

The molar ratio as described above is 1.2 to 2.
As a specific method for obtaining 1, a polyvalent carboxylic acid containing a dicarboxylic acid or a polyhydric alcohol containing a glycol with respect to an ester-forming derivative thereof until or at the same time as the addition of aluminum or its compound, or It is preferable to add the ester-forming derivative, because the by-product of the dimer of the polyhydric alcohol can be suppressed. In addition to this, there is a method of synthesizing polyester by setting the molar ratio as described above in advance, but this method makes it easy to produce a dimer of a polyhydric alcohol,
It is not preferable because it reduces the physical properties such as the softening point of the obtained polyester. The amount of the polyhydric alcohol to be added needs to be 0.1 to 0.9 times by mole based on the polycarboxylic acid including the dicarboxylic acid or the ester-forming derivative thereof. The amount is preferably 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 exceeds 0.9 times the molar amount of the polycarboxylic acid containing dicarboxylic acid or the ester-forming derivative thereof, a sufficient foreign matter suppressing effect cannot be obtained. Further, if the amount of the polyhydric alcohol added is less than 0.1 times the molar amount, there is a problem that the effect of addition is not clearly shown.

The polyhydric alcohol containing the glycol or the ester-forming derivative thereof may be added at the same time as other additives, or only the polyhydric alcohol may be added. However, it is preferable to add aluminum or its compound until or at the same time.

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 and aluminum salicylate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, polyaluminum chloride,
Inorganic acid salts such as aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate, 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 ethylacetoacetate, aluminum ethylacetoacetate diiso-propoxide, trimethylaluminum, triethylaluminum and other organoaluminum compounds and their partial hydrolysates. , Aluminum alkoxide and aluminum chelate and hydrate 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. Among these, carboxylates, inorganic acid salts and chelate compounds are preferable, and among these, aluminum sulfate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferable. The basic aluminum acetate may be stabilized with an additive such as boric acid.

The amount of the aluminum or aluminum compound used in the present invention is 0.001 to 0.05 mol based on the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the polyester obtained. % Is preferable, and 0.005-0.0 is more preferable.
It is 2 mol%. If the amount used is less than 0.001 mol%, the catalytic activity may not be sufficiently exhibited, and if the amount used is 0.05 mol% or more, the thermal stability and the thermal oxidative stability are deteriorated and aluminum is caused. Occurrence of foreign matter and increase in coloring sometimes become a problem. As described above, the polymerization catalyst of the present invention has a great feature in that it exhibits sufficient catalytic activity even if the addition amount of the aluminum component is small. As a result, the thermal stability and the thermal oxidation stability are excellent, and the foreign substances and coloring caused by 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, but for example, 2,6-di-ter.
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) butyric acid) glycol ester, N, N'-bis [3- (3,5-di-tert-butyl- 4-Hydroxyphenyl) propionyl] hydrazine, 2,2'-Ogizamide 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-dimethyl 2- {β-
(3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -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, triethyleneglycol-bis-[-3- (3 ' -tert-Butyl-4-hydroxy-5-methylphenyl)] propionate, 1,1,3-tris [2-methyl-4- [3- (3,
Examples thereof include 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane. These may 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, thiodiethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] are preferred.

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

The amount of the phenolic compound used in the present invention is 5 × 10 ^-5 to 1 mol per mol of all 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 phenol compound may be used together with a phosphorus compound.

The phosphorus compound constituting the polycondensation catalyst used in the present invention is not particularly limited, but it may be a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphonous acid compound, a phosphinic acid compound, It is preferable to use one kind or two or more kinds of compounds selected from the group consisting of phosphine compounds, because the effect of improving the catalytic activity is large. Among these, the use of one or more phosphonic acid compounds is particularly preferable because the effect of improving the catalytic activity is particularly large.

The phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds referred to in the present invention are represented by the following formulas (Formula 8) to (Formula 8) 13)
A compound having a structure represented by

[0036]

[Chemical 8]

[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040]

[Chemical 12]

[0041]

[Chemical 13]

Examples of the phosphonic acid compounds of the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate and diethyl benzylphosphonate. To be Examples of the phosphinic acid compound of the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate,
Phenylphosphinic acid, methyl phenylphosphinate,
Examples include phenyl phenylphosphinate and the like. Examples of the phosphine oxide compound of the present invention include:
Examples thereof include diphenylphosphine oxide, methyldiphenylphosphine oxide and triphenylphosphine oxide.

Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds and phosphine compounds, the phosphorus compounds of the present invention are represented by the following formulas (formula 14) to (formula 19). It is preferable to use the compound represented by the formula (1).

[0044]

[Chemical 14]

[0045]

[Chemical 15]

[0046]

[Chemical 16]

[0047]

[Chemical 17]

[0048]

[Chemical 18]

[0049]

[Chemical 19]

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

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

[0052]

[Chemical 20]

[0053]

[Chemical 21]

[0054]

[Chemical formula 22]

(In the formulas (Formula 20) to (Formula 22), R ¹ ,
R ⁴ , R ⁵ and R ⁶ are each independently hydrogen and 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 are each independently hydrogen and have 1 to 1 carbon atoms.
It represents a hydrocarbon group of 50, a hydrocarbon group of 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. 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 (Formula 20) to (Formula 22) is used.
^A compound in which ¹ , R ⁴ , R ⁵ , and R ⁶ are groups having an aromatic ring structure is particularly preferable.

The phosphorus compound constituting the polycondensation catalyst used in the present invention is, 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 thereof 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 it has a phenol moiety in the same molecule, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound. Compound,
It is preferable to use one kind or two or more kinds of compounds selected from the group consisting of phosphonous acid-based compounds, phosphinic acid-based compounds, and phosphine-based compounds, because the catalytic activity improving effect is large. Among these, it is preferable to use a phosphonic acid compound having one or more phenol moieties in the same molecule, because the effect of improving the catalytic activity is particularly large. Further, the phosphorus compound having a phenol moiety in the same molecule constituting the polycondensation catalyst of the present invention is represented by the following general formula:
It is preferable to use the compounds represented by the formulas (3) to (Chem. 25) since the catalytic activity is improved.

[0059]

[Chemical formula 23]

[0060]

[Chemical formula 24]

[0061]

[Chemical 25]

(In the formulas (Formula 23) to (Formula 25), R ¹ is a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, a substituent such as a hydroxyl group, a halogen group, an alkoxyl group or an amino group, and a phenol moiety. Represents a hydrocarbon group having 1 to 50 carbon atoms including 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 containing a substituent, R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, and a carbon number 1 containing a 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 having a phenol moiety in the same molecule of the present invention include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate and p.
-Diphenyl hydroxyphenylphosphonate, bis (p
-Hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, phenyl bis (p-hydroxyphenyl) phosphinate, p-hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, 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)
Examples thereof include compounds represented by 9). Among these, the compound represented by the following formula (Formula 28) and dimethyl p-hydroxyphenylphosphonate are particularly preferable.

[0064]

[Chemical formula 26]

[0065]

[Chemical 27]

[0066]

[Chemical 28]

[0067]

[Chemical 29]

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

By adding a phosphorus compound having these phenol moieties in the same molecule during the polymerization of 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 it is preferable to use a metal salt of a phosphonic acid compound because the catalytic activity improving effect is large. Examples of metal salts of phosphorus compounds include monometal salts, dimetal salts, trimetal salts and the like.

In addition, among the above 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 preferable.

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

[0073]

[Chemical 30]

(In the formula (Formula 30), R ¹ is hydrogen and has 1 carbon atom.
Represents a hydrocarbon group having 50 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group and having 1 to 50 carbon atoms. R ² is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and 1 to 1 carbon atoms.
It represents 50 hydrocarbon groups. R ³ is hydrogen, having 1 to 5 carbon atoms
It represents a hydrocarbon group of 0, a hydroxyl group, an alkoxyl group, or a carbonyl-containing hydrocarbon group of 1 to 50 carbon atoms. l
Is an integer of 1 or more, m is 0 or an integer of 1 or more, 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 such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

Examples of R ¹ are phenyl,
1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like can be mentioned. R above
Examples of ² include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, and substituted Phenyl and naphthyl groups,
Examples thereof include a group represented by —CH ₂ CH ₂ OH. R ³
Examples of O ⁻ include hydroxide ion, alcoholate ion, acetate ion and 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]

[Chemical 31]

(In the formula (Formula 31), R ¹ is hydrogen and has 1 carbon atom.
Represents a hydrocarbon group having 50 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group and having 1 to 50 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms containing 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. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

Examples of R ¹ are phenyl,
1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like can be mentioned. Examples of R ³ O ⁻ include hydroxide ion, alcoholate ion,
Examples thereof include acetate ion and acetylacetone ion.

Among the above-mentioned phosphorus compounds, it is preferable to use a compound having an aromatic ring structure 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 [(1-naphthyl) methylphosphonate ethyl],
Sodium [(1-naphthyl) methylphosphonate], magnesium bis [(1-naphthyl) methylphosphonate], potassium [(2-naphthyl) methylphosphonate], magnesium bis [(2-naphthyl) methylphosphonate], Lithium [ethyl benzyl phosphonate], sodium [ethyl benzyl phosphonate], magnesium bis [ethyl benzyl phosphonate], beryllium bis [ethyl benzyl phosphonate],
Strontium bis [ethyl benzyl phosphonate], manganese bis [ethyl phosphonate], sodium benzyl phosphonate, magnesium bis [benzyl phosphonate], sodium [(9-anthryl) methyl phosphonate], magnesium bis [(9-anthryl) ) Ethyl methylphosphonate], sodium [ethyl 4-hydroxybenzylphosphonate], magnesium bis [ethyl 4-hydroxybenzylphosphonate], sodium [phenyl chlorobenzylphosphonate], magnesium bis [ethyl 4-chlorobenzylphosphonate] ], Sodium [methyl 4-aminobenzylphosphonate], magnesium bis [methyl 4-aminobenzylphosphonate], sodium phenylphosphonate, magnesium bis [phenylphosphine] Ethyl phosphate], zinc bis [phenylphosphonic acid ethyl] and the like. Among these, lithium [(1-naphthyl) methylphosphonate ethyl], sodium [(1-naphthyl) methylphosphonate ethyl], magnesium bis [(1-naphthyl) methylphosphonate ethyl], lithium [benzylphosphonate ethyl], Sodium [ethyl benzylphosphonate],
Particularly preferred are magnesium bis [ethyl benzylphosphonate], sodium benzylphosphonate and magnesium bis [benzylphosphonate].

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

[0084]

[Chemical 32]

(In the formula (Formula 32), 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 hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group or an alkoxyl group or carbonyl. As R ⁴ O ⁻ , for example,
Examples thereof include hydroxide ion, alcoholate ion, acetate ion and acetylacetone ion. l is 1
An integer greater than or equal to m, 0 is an integer greater than or equal to 1, and l + m is 4
It is the following. M represents a (l + m) -valent metal cation. n is 1
Represents the above integers. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

Of these, at least one selected from the compounds represented by the following general formula (Formula 33) is preferably used.

[0087]

[Chemical 33]

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

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

Specific phosphorus metal salt compounds of the present invention include lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-t].
ert-Butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], potassium [3,5-di-tert.
-Butyl-4-hydroxybenzylphosphonate ethyl], 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], Strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], barium bis [3,5-
Di-tert-butyl-4-hydroxybenzylphosphonate phenyl], manganese bis [3,5-di-tert-butyl-4]
-Hydroxybenzylphosphonate], nickel bis [3,5-di-tert-butyl-4-ethyl ethyl hydroxybenzylphosphonate], copper bis [3,5-di-tert-butyl-4]
-Ethyl hydroxybenzylphosphonate], zinc bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate] and the like. Among these, lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], magnesium bis [ethyl Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

When a polycondensation catalyst comprising aluminum or its compound and a phosphorus compound is used in the present invention, at least one selected from aluminum salts of phosphorus compounds may be used. The 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, but it is preferable to use the aluminum salt of a phosphonic acid compound because the effect of improving the catalytic activity is large. Examples of aluminum salts of phosphorus compounds include monoaluminum salts, dialuminum salts, and trialuminum salts.

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

The aluminum salt of a phosphorus compound which constitutes the polymerization catalyst used in the present invention is represented by the following general formula (Formula 34)
It is preferable to use at least one selected from the compounds represented by since the effect of improving the catalytic activity is large.

[0094]

[Chemical 34]

(In the formula (Formula 34), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms including an amino group. R ² is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and 1 carbon atoms.
Represents a hydrocarbon group of 50. R ³ is hydrogen, having 1 to 1 carbon atoms
It represents a hydrocarbon group having 50, a hydroxyl group, an alkoxyl group, or a carbonyl-containing hydrocarbon group having 1 to 50 carbon atoms.
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 contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

Examples of R ¹ are phenyl,
1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like can be mentioned. R above
Examples of ² include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, and substituted Phenyl and naphthyl groups,
Examples thereof include a group represented by —CH ₂ CH ₂ OH. Examples of R ³ O ⁻ include hydroxide ion, alcoholate ion, ethylene glycolate ion, acetate ion and acetylacetone ion.

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

When a polycondensation catalyst comprising aluminum or its compound and a phosphorus compound is used in the present invention, at least one selected from the aluminum salts of specific phosphorus compounds represented by the following general formula (Formula 35) is used. It is preferable because it has a large catalytic activity improving effect. The aluminum salt of a phosphorus compound may be used in combination with another aluminum compound, a phosphorus compound, a phenolic compound or the like. The aluminum salt of a specific phosphorus compound that constitutes the polymerization catalyst used in the present invention refers to at least one selected from the compounds represented by the following general formula (Formula 35).

[0099]

[Chemical 35]

(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 hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group or an alkoxyl group or carbonyl. l is an integer of 1 or more, m is 0
Alternatively, it 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 such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

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

[0102]

[Chemical 36]

In the formula (Formula 36), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group, and R ⁴ represents hydrogen. Represents a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl, l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, l + m is 3. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

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

The aluminum salt of the specific phosphorus compound of the present invention includes an aluminum salt of ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-t.
ert-Butyl-4-hydroxybenzylphosphonic acid methyl aluminum salt, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid isopropyl aluminum salt, 3,5-di-tert-butyl-4-hydroxybenzyl Aluminum salt of phenyl phosphonate, 3,5-di-tert-
Examples thereof include an aluminum salt of butyl-4-hydroxybenzylphosphonic acid. Among these, 3,5-di-ter
The aluminum salt of ethyl t-butyl-4-hydroxybenzylphosphonate and the aluminum salt 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. The 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,
It is preferable to use a phosphonic acid compound having at least one P-OH bond because the effect of improving the catalytic activity is large.

Among the above-mentioned phosphorus compounds, it is preferable to use a compound having an aromatic ring structure 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, at least one selected from the compounds represented by the following general formula (Formula 37) is used to improve the catalytic activity. Great effect and preferable.

[0109]

[Chemical 37]

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

Examples of R ¹ are phenyl,
1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like can be mentioned. R above
Examples of ² include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, and substituted Phenyl and naphthyl groups,
Examples thereof include a group represented by —CH ₂ CH ₂ OH.

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

Examples of the phosphorus compound having at least one P—OH bond of 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. Among these, (1
Ethyl-naphthyl) methylphosphonate, ethyl benzylphosphonate are particularly preferred.

The preferred phosphorus compound used in the present invention is a specific phosphorus compound having at least one P-OH bond. The specific phosphorus compound having at least one P-OH bond means at least one compound selected from the compounds represented by the following general formula (Formula 38).

[0115]

[Chemical 38]

(In the formula (Formula 38), 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 such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

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

[0118]

[Chemical Formula 39]

In the formula (Formula 39), 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 the hydrocarbon group is cyclohexyl. May contain an alicyclic structure or branched structure such as or an aromatic ring structure such as phenyl or naphthyl.)

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

Specific phosphorus compounds having at least one P-OH bond of the present invention include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-tert-butyl- Methyl 4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-isopropyl 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. Among these, ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferable.

Examples of preferable phosphorus compounds include phosphorus compounds represented by the chemical formula (Formula 40).

[0123]

[Chemical 40]

In the formula (Formula 40), R ¹ represents a hydrocarbon group having ¹ to 49 carbon atoms, or a hydroxyl group, a halogen group, an alkoxyl group, or an amino group-containing hydrocarbon group having 1 to 49 carbon atoms; ² and R ³ are independently hydrogen and carbon number 1
It represents a hydrocarbon group of ˜50, a hydrocarbon group of 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain an alicyclic structure, a branched structure or an aromatic ring structure. )

Further, more preferably, the chemical formula (Formula 40)
At least one of R ¹ , R ² and R ³ therein is a compound containing an aromatic ring structure.

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

[0127]

[Chemical 41]

[0128]

[Chemical 42]

[0129]

[Chemical 43]

[0130]

[Chemical 44]

[0131]

[Chemical formula 45]

[0132]

[Chemical formula 46]

Further, the phosphorus compound used as the polycondensation catalyst in the present invention is preferably one having a large molecular weight because the effect is large because it is less likely to be distilled off during the polymerization.

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

[0135]

[Chemical 47]

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

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

[0138]

[Chemical 48]

In the above formula (Formula 48), R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

Examples of R ³ and R ⁴ include hydrogen, methyl group, butyl group and other short chain aliphatic groups, octadecyl and other long chain aliphatic groups, phenyl group, naphthyl group and substituted phenyl. aromatic groups such as groups or naphthyl group, -CH ₂ CH ₂
Examples thereof include a group represented by OH.

Specific phosphorus compounds of the present invention include 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 can be mentioned. Among these, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-
Diphenyl hydroxybenzylphosphonate is particularly preferred.

Another phosphorus compound preferably 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]

[Chemical 49]

[0144]

[Chemical 50]

As the compound represented by the chemical formula (Formula 49), Irganox 1222 (manufactured by Ciba Specialty Chemicals) is commercially available, and as the compound represented by the chemical formula (Formula 50), Irgano.
x1425 (Ciba Specialty Chemicals)
Is commercially available and can be used.

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

The phosphorus compound of the present invention is preferably used in an amount of 0.0001 to 0.1 mol% based on the number of moles of all constituent units of the polycarboxylic acid component of the polyester obtained.
It is more preferably 0.005 to 0.05 mol%. If the addition amount of the phosphorus compound is less than 0.0001 mol%, the addition effect may not be exhibited, and if it is added in excess of 0.1 mol%, the catalytic activity as a polyester polymerization catalyst may decrease, and The tendency changes depending on the amount of aluminum used and the like.

It is preferable that the above-mentioned catalyst does not contain an alkali metal, an alkaline earth metal, or a compound thereof.

On the other hand, in a preferred embodiment of the present invention, in addition to aluminum or its compound, a small amount of at least one selected from alkali metal, alkaline earth metal and its compound is allowed to coexist as the second metal-containing component. is there. The coexistence of such a second metal-containing component in the catalyst system is effective in improving the productivity as well as the effect of suppressing the production of diethylene glycol and enhancing the catalytic activity, and thus the catalyst component having a higher reaction rate is obtained. . A technique for adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound to obtain a catalyst having sufficient catalytic activity is known. When such a known catalyst is used, a polyester having excellent thermal stability can be obtained, but a known catalyst in which an alkali metal compound or an alkaline earth metal compound is used in combination is added in an amount such that a practical catalytic activity is required. When an alkali metal compound is used, the amount of foreign matter resulting from it is large, and when it is used as a fiber, it has good spinnability and thread physical properties, and when it is used as a film, it has film physical properties, transparency, and heat stability. Properties, thermal oxidation stability, hydrolysis resistance, etc. deteriorate. Furthermore, the color tone of melt-formed products such as fibers and films deteriorates. When an alkaline earth metal compound is used in combination, the thermal stability and thermal oxidative stability of the polyester obtained when attempting to obtain practical activity are reduced, the coloring due to heating is large, and the amount of foreign matter generated is also large. Will increase.

When an alkali metal, an alkaline earth metal or a compound thereof is added, the amount M (mol%) used is
It is preferably 1 × 10 ⁻⁶ or more and less than 0.1 mol%, more preferably 5 × 10 ^{−6 to} 0.05 with respect to the total number of 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 amount of alkali metal or alkaline earth metal added is small, the reaction rate can be increased without causing problems such as deterioration of thermal stability, generation of foreign matter, and coloring. In addition, the reaction rate can be increased without causing a problem such as deterioration in hydrolysis resistance. When the amount M of the alkali metal, alkaline earth metal and its compound used is 0.1 mol% or more, the thermal stability is lowered, the generation of foreign substances and the increase of coloration, the deterioration of hydrolysis resistance and the like become problems in the processing of the product. There are cases. If M is less than 1 × 10 ⁻⁶ mol%, the effect is not clear even if added.

In the present invention, as the alkali metal or alkaline earth metal constituting the second metal-containing component which is preferably used in addition to aluminum or its compound, Li, Na, K, Rb, Cs, Be, Mg, Ca,
At least one selected from Sr and Ba is preferable, and use of an alkali metal or a compound thereof is more preferable. When using an alkali metal or a compound thereof, use of Li, Na and K is particularly preferable. Examples of the alkali metal or alkaline earth metal compound include, for example, saturated aliphatic carboxylic acid salts such as formic acid, acetic acid, propionic acid, butyric acid and oxalic acid, and unsaturated aliphatic carboxylic acid salts such as acrylic acid and methacrylic acid. , Aromatic carboxylic acid salts such as benzoic acid, halogen-containing carboxylic acid salts such as trichloroacetic acid, hydroxycarboxylic acid salts such as lactic acid, citric acid and 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, 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 ert-butoxy, chelate compounds with acetylacetonate, hydrides, oxides,
A hydroxide etc. are mentioned.

Of these alkali metals, alkaline earth metals or their compounds, if one having a strong alkalinity such as hydroxide is used, these tend not to be dissolved in an organic solvent such as diol such as ethylene glycol or alcohol. Therefore, it must be added to the polymerization system as an aqueous solution, which may cause a problem in the polymerization process. Furthermore, when a highly alkaline substance such as a hydroxide is used, the polyester is likely to undergo a side reaction such as hydrolysis during polymerization, and the polymerized polyester tends to be colored, and the hydrolysis resistance is also lowered. Tend to do. Therefore, as the alkali metal or the compound thereof or the alkaline earth metal or the compound thereof of the present invention, a saturated aliphatic carboxylic acid salt, an unsaturated aliphatic carboxylic acid salt or an aromatic metal salt of an alkaline metal or an alkaline earth metal is preferable. Group carboxylic acid salts, halogen-containing carboxylic acid salts, hydroxycarboxylic acid salts, 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, it is more preferable to use a saturated aliphatic carboxylic acid salt of an alkali metal or an alkaline earth metal, particularly an acetic acid salt, from the viewpoints of easy handling and availability.

In the polyester polymerization catalyst used in the present invention, it is a preferred embodiment that a cobalt compound is added as a cobalt atom in an amount of less than 10 ppm with respect to the polyester. It is more preferably less than 5 ppm, still more preferably 3 ppm or less.

It is known that the cobalt compound itself has a certain degree of polymerization activity, but when it is added to the extent that it exerts a sufficient catalytic effect, the brightness and heat stability of the polyester polymer obtained can be reduced. Lowering occurs. The polyester obtained according to the present invention has good color tone and thermal stability, but is obtained by adding a cobalt compound in such a small amount as described above that the catalyst effect by addition is not clear. Coloring can be more effectively erased without causing a decrease in the brightness of polyester. The cobalt compound in the present invention has the purpose of eliminating coloring, and 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 specifically, for example, cobalt acetate, cobalt nitrate,
Examples thereof include cobalt chloride, cobalt acetylacetonate, cobalt naphthenate and their hydrates. Among them, cobalt acetate tetrahydrate is particularly preferable.

From the viewpoint of the thermal stability of the polyester, the amount of the cobalt compound added is preferably such that the total amount of aluminum atoms and cobalt atoms is 50 ppm or less and the cobalt atoms are less than 10 ppm with respect to the polymer finally obtained. More preferably, the total of aluminum atoms and cobalt atoms is 40 ppm or less, and the cobalt atoms are 8 pp.
m or less, more preferably the total of aluminum and cobalt atoms is 25 ppm or less and the cobalt atom is 5 p
It is pm or less. Further, in order to have sufficient catalytic activity, the total amount of aluminum atoms and cobalt atoms is 0.0
More than 1 ppm is preferred.

On the other hand, the cobalt compound has a cobalt atom content of 4 ppm or less and a ratio of aluminum atom to cobalt atom (Al / Co) of 0 in the finally obtained polymer in view of thermal stability and color tone of the polyester. ．
It is preferable to add it so as to be contained in 5 to 45. More preferably, the cobalt atom content is 3 ppm or less, and
The ratio of aluminum atom to cobalt atom (Al / Co) is 2.0 to 25, and more preferably 2 as cobalt atom.
It is not more than ppm and the ratio of aluminum atoms to cobalt atoms (Al / Co) is 3.0 to 15.

On the other hand, the cobalt compound is Co / (Al + Co) ≦ 0.05 (A) with respect to the polymer finally obtained from the viewpoint of thermal stability and color tone of the polyester.
l and Co represent the content (ppm) of aluminum atoms and cobalt atoms contained in the polymer finally obtained. ) And 400p as an aluminum atom
It is preferable to add it so as to contain less than pm. More preferably, the left side of the above formula is 0.005 to 0.04 and less than 200 ppm as aluminum atoms, and even more preferably the left side of the above formula is 0.01 to 0.03 and less than 100 ppm as aluminum atoms.

The polyester according to the present invention can be produced by a method including conventionally known steps except that the polyester polymerization catalyst of the present invention is used as a catalyst. For example, in the case of producing PET, after the esterification of terephthalic acid and ethylene glycol, polycondensation, or after performing the transesterification reaction between an alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, Any method of polycondensation can be used. Further, the polymerization apparatus is a batch type,
It may be a continuous type.

When the present invention is carried out using a continuous apparatus, the interpretation of claim 1 is that the polycarboxylic acid containing dicarboxylic acid and the ester formation thereof in the polymerization reactor at the time of adding the catalyst are formed. It means that the molar ratio of the glycol-containing polyhydric alcohol and the ester-forming derivative thereof to the sex derivative is 1.2 to 2.1. Further, according to the interpretation of claim 2, the molar ratio of the polyhydric carboxylic acid containing dicarboxylic acid and the polyhydric alcohol containing glycol and the ester forming derivative thereof to the polycarboxylic acid containing dicarboxylic acid and the ester forming derivative thereof becomes low in the first kettle of the continuous system. In such a manner that the polycondensation catalyst used in the present invention is added continuously, or a polyhydric alcohol containing glycol is added so that the polycondensation catalyst used in the present invention is added in an amount of 0.1 to 0.9 times by mole in the previous pot. It means to make it 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 its compound of the present invention is added at a molar ratio in the system after completion of the esterification (polyhydric carboxylic acid containing dicarboxylic acid and polyhydric alcohol containing glycol with respect to ester-forming derivative thereof and these It is preferable that the molar ratio of the ester-forming derivative (1) is within the above range.

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

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

When the polymerization catalyst used in the present invention is added in the form of a slurry or solution using a polyhydric alcohol containing glycol and an ester-forming derivative thereof, the molar ratio in the system after addition (dicarboxylic acid And the polyhydric alcohol containing glycol and the molar ratio of the polyhydric alcohol containing glycol and the ester-forming derivative thereof to 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, which is preferable because the polyester production time is shortened. (2) AP (min) <2T (min) However, AP is 0.1 at 275 ° C. using a predetermined amount of catalyst.
Time required to polymerize polyethylene terephthalate having an intrinsic viscosity of 0.65 dl / g at a reduced pressure of Torr (m
in), and T is AP when it is added to the acid component in the produced polyethylene terephthalate using antimony trioxide as a catalyst so as to be 0.05 mol% as an antimony atom. The antimony trioxide used for comparison in the present invention is antimony trioxide having a purity of 99% or more, for example, commercially available Antimony (III) oxide (AL
DRICH CHEMICAL Co., purity 99.999%) is used.

The AP measuring method is specifically as follows. 1) (BHET manufacturing process) Using terephthalic acid and twice its molar amount of ethylene glycol, the esterification rate is 95%.
% Bis (2-hydroxyethyl) terephthalate (B
A mixture of HET) and oligomer (hereinafter referred to as BHET mixture) is produced. 2) (Catalyst addition step) A predetermined amount of a catalyst was added to the above BHET mixture, and the mixture was stirred at 245 ° C for 10 minutes under a nitrogen atmosphere at atmospheric pressure, and then the oligomer was heated for 50 minutes to 275 ° C. The pressure of the reaction system of the mixture is gradually reduced to 0.1 Torr. 3) (Polycondensation step) Polycondensation reaction is carried out at 275 ° C. and 0.1 Torr, and polymerization is carried out until the intrinsic viscosity (IV) of polyethylene terephthalate reaches 0.65 dl / g. 4) Let AP (min) be the polymerization time required for the polycondensation step. These are carried out 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 twice its molar amount of ethylene glycol are charged into a batch type autoclave equipped with a stirrer, and the esterification reaction is carried out while distilling water out of the system at 245 ° C under a pressure of 0.25 MPa. Manufactured by. 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) means
It means the amount of the catalyst that is used in a variable amount according to the activity of the catalyst. The amount of the catalyst having a high activity is small, and the amount of the catalyst having a low activity is large.

The polymerization catalyst used in the present invention is another polymerization catalyst such as an antimony compound, a titanium compound, a germanium compound or a tin compound, and the addition of these components is a product such as the characteristics, processability and color tone of the polyester as described above. To coexist within the range of the addition amount that does not cause a problem in
It is advantageous and preferable in improving productivity by shortening the polymerization time.

However, as the antimony compound, an antimony atom is added to the polyester obtained by polymerization.
It can be added in an amount of 50 ppm or less. More preferably 30 ppm
It is to be added in the following amounts. The amount of antimony added
When it is more than 50 ppm, metal antimony is precipitated, and darkening and foreign matter are generated in the polyester, which is not preferable.

The titanium compound can be added within a range of 10 ppm or less with respect to the polymer obtained by polymerization. More preferably 5 ppm or less, even more preferably 2 ppm
It is to be added in the following amounts. Addition amount of titanium is 10pp
When it is more than m, the thermal stability of the obtained resin is remarkably reduced.

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

When the polyester is polymerized using the polymerization catalyst of the present invention, one or more antimony compounds, titanium compounds, germanium compounds and tin compounds can be used.

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

Specifically, as the antimony compound,
Examples thereof include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoxide, etc. Of these, antimony trioxide is preferable.

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, among them, tetra-n
-Butoxy titanate 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, hexaethylditinoxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin adiate, diphenyltin dilaurate and monobutyltin trioxide. Examples thereof include chloride, dibutyltin sulfide, dibutylhydroxytin oxide, methylstannonic acid, ethylstannonic acid, and the like, and use of monobutylhydroxytin oxide is particularly preferable.

The dicarboxylic acid used in the present invention includes
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, 1,
3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, etc. Saturated aliphatic dicarboxylic acid or an ester-forming derivative thereof, fumaric acid, maleic acid, itaconic acid or the like unsaturated aliphatic dicarboxylic acid or an ester-forming derivative thereof, orthophthalic acid, isophthalic acid, Terephthalic acid, 5
-(Alkali metal) sulfoisophthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,
6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,
4'-biphenylsulfone dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, pamoic acid,
Examples thereof include aromatic dicarboxylic acids exemplified by anthracene dicarboxylic acid and the like, and ester-forming derivatives thereof.

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

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

The glycol used in the present invention is 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 glycols, hydroquinones, 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 Examples include aromatic glycols such as bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5 naphthalenediol, 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 preferable.

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

The polyester of the present invention may contain a known phosphorus compound as a copolymerization component. As the phosphorus compound, a bifunctional phosphorus compound is preferable, for example, (2
-Carboxylethyl) methylphosphinic acid, (2-carboxyethyl) phenylphosphinic acid, 9,10-dihydro-10-oxa- (2,3-carboxypropyl) -10-phosphaphenanthrene-10-oxide, etc. Can be mentioned. By including these phosphorus compounds as a copolymerization component, it is possible to improve the flame retardancy and the like of the obtained polyester.

As the constituent component of the polyester of the present invention,
In order to improve the dyeability when polyester is used as the fiber, it is a preferred embodiment to use a polycarboxylic acid having an alkali metal sulfonate as a copolymerization component.

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

The copolymerization amount of the metal sulfonate group-containing compound is 0.3 to 10.0 with respect to the acidic component constituting the polyester.
Mol% is preferable, and more preferably 0.80 to 5.0 mol%. If the copolymerization amount is too small, the dyeability of the basic dye will be poor, and if it is too large, when it is made into fibers, not only the spinnability will be poor, but also sufficient strength as fibers cannot be obtained due to the thickening phenomenon. In addition, 2.0 mol% metal sulfonate-containing compound
It is also possible to impart atmospheric pressure dyeability to the obtained modified polyester fiber by the above copolymerization. In addition, it is possible to appropriately reduce the amount of the metal sulfonate group-containing compound used by selecting an appropriate dyeing monomer. The easily dyeable monomer is not particularly limited, and examples thereof include long-chain glycol compounds typified by polyethylene glycol and polytetramethylene glycol, and aliphatic dicarboxylic acids typified by adipic acid, sebacic acid, and azelaic acid.

After the polyester is polymerized according to the method of the present invention, the catalyst is removed from the polyester or the catalyst is deactivated by adding a phosphorus compound or the like, whereby the thermal stability of the polyester can be further enhanced. .

The polyester of the present invention may contain organic, inorganic, and organometallic toners, optical brighteners, and the like. By containing one or more of these, the polyester It is possible to suppress coloring such as yellowishness to an even more excellent level. In addition, any other polymer, antistatic agent, defoaming agent, dyeability improving agent, dye,
Pigments, matting agents, optical brighteners, stabilizers, antioxidants and other additives may be included. As the antioxidant, aromatic amine-based or phenol-based antioxidants can be used, and as the stabilizer, phosphoric acid or phosphate ester-based phosphorus-based, sulfur-based, amine-based, etc. stabilizers can be used. Can be used.

Industrial Applicability According to the present invention, there is provided a method for producing a polyester which does not contain an antimony compound as a main component of the catalyst, and a polyester having a small amount of foreign matter, and a polyester obtained by the method. The polyester of the present invention includes, for example, textiles for clothing, curtains, carpets, textiles for interior and bedding typified by futon cotton, fibers for industrial materials typified by tire cords, ropes, various woven fabrics, various knitted fabrics, short fabrics, etc. Fibers such as fiber non-woven fabric, long fiber non-woven fabric, packaging film, industrial film, optical film, magnetic tape film, photographic film, can laminating film, content film, heat shrink film, gas barrier film, white film, Films such as easy-cut films, non-heat-resistant stretched bottles, heat-resistant stretched bottles, direct blow bottles, gas barrier bottles, pressure-resistant bottles, pressure-resistant bottles, and other hollow molded bodies, sheets such as A-PET and C-PET, and glass fiber reinforced polyester. ,
It can be applied to various molded products such as engineering plastics typified by elastomers, and paints and adhesives.

[0190]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

(Measurement of Intrinsic Viscosity (IV)) Phenol /
It measured at 30 degreeC using the tetrachloroethane (60:40, weight ratio) mixed solvent.

(Evaluation of foreign matter) 100 g of polyester resin
To p-chlorophenol / tetrachloroethane (75: 2
(5, weight ratio) The mixed solvent was dissolved at 100 ° C., pressure filtration was performed, and foreign matter on the filter was observed with a scanning electron microscope (SEM). The amount of foreign matter observed was evaluated by the following index. ○: Almost no, △: 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 to the BHET mixture in a molar ratio of 1.6. Aluminum hydroxide chloride, which is a catalyst component, was 0.017 mol% as an aluminum atom with respect to the acid component in the polyester, and Irganox 1425 was used as the phosphorus compound, and Irganox 1425 was used as an iodine component with respect to the acid component in the polyester.
015 mol% was added. Irganox 1425 manufactured by Ciba Specialty Chemicals was used.
Then, the mixture was stirred at 245 ° C. for 15 minutes under normal pressure in a nitrogen atmosphere. Next, the temperature of the reaction system was gradually lowered while raising the temperature to 275 ° C. over 60 minutes to 0.1 Torr, and the polycondensation reaction was further carried out at 275 ° C. and 0.1 Torr. The results are shown in Table 1.

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

Reference Example 1 The same operation as in Example 1 except that antimony trioxide was used as a catalyst so that the added amount was 0.05 mol% as antimony atom with respect to the acid component in PET. I went. As antimony trioxide, commercially available Antimony (III) oxide (ALDRICH CHEMICAL
(Manufactured by the company, purity 99.999%) was used. 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 was about 10 g / l. The results are shown in Table 1.

[0196]

【table 1】

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

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J029 AA03 AB04 AC02 AE02 AE03                       BA03 BA04 BA05 BD07A                       CB06A CC05A CC06A HA01                       HA02 HB01 HB02 JA061                       JA091 JA121 JA161 JA201                       JA261 JA281 JB131 JB151                       JB171 JB191 JB271 JC341                       JC451 JC461 JC501 JC551                       JC561 JC601 JC621 JC641                       JC751 JF011 JF111 JF221                       KB02 KB13 KE02 KE03

Claims (17)

[Claims] 1. A polyvalent carboxylic acid containing a dicarboxylic acid or one or more selected from ester-forming derivatives thereof, and a polyhydric alcohol containing a glycol or one or more selected from an ester-forming derivative. In a method for producing a polyester by subjecting a product obtained by an esterification reaction or a transesterification reaction with a substance to a polyester, at least one selected from aluminum and its compounds is contained as a metal-containing component, and Using a polycondensation catalyst containing at least one selected, a polyvalent carboxylic acid containing a dicarboxylic acid in a reaction system at the time of adding aluminum or a compound thereof, or a polyhydric alcohol containing a glycol for an ester-forming derivative thereof, or these Of ester-forming derivatives of Process for producing a polyester of Le ratio is equal to or is from 1.2 to 2.1. 2. A polyvalent carboxylic acid containing a dicarboxylic acid or one or more selected from ester-forming derivatives thereof and one or more selected from a polyhydric alcohol containing glycol or an ester-forming derivative. In a method for producing a polyester by subjecting a product obtained by an esterification reaction or a transesterification reaction with a product to a polyester to contain at least one selected from aluminum and its compounds as a metal-containing component, and selecting from a phosphorus compound. Using a polycondensation catalyst containing at least one of the following, a polyhydric carboxylic acid containing a dicarboxylic acid of the reaction system at the time of adding aluminum or a compound thereof, or a polyhydric alcohol containing a glycol for an ester-forming derivative thereof or a polyhydric alcohol containing these The molar ratio of the ester-forming derivative is Process for producing a polyester which is a .2～2.1. 3. The method for producing a polyester according to claim 1, wherein a phosphorus compound is used. 4. A 0.1 to 0.9-fold molar amount with respect to a polyvalent carboxylic acid containing a dicarboxylic acid and an ester-forming derivative thereof at the same time as or before the addition of aluminum or a compound thereof to a reaction system. The method for producing a polyester according to any one of claims 1 to 3, wherein the polycondensation reaction is performed by adding the diol. 5. The phosphorus compound is one or more selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. The method for producing a polyester according to any one of claims 2 to 4, wherein the polyester is a compound. 6. The method for producing a polyester according to claim 5, wherein the phosphorus compound is one kind or two or more kinds of phosphonic acid compounds. 7. The method for producing a polyester according to claim 2, wherein the phosphorus compound is a compound having an aromatic ring structure. 8. The phosphorous compound according to claim 2, which is one kind or two or more kinds selected from the group consisting of compounds represented by the following general formulas (formula 1) to (formula 3). Method for producing polyester. [Chemical 1] [Chemical 2] [Chemical 3] (In Formulas (Chemical Formula 1) to (Chemical Formula 3), 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. Represents a hydrocarbon group having 1 to 50 carbon atoms, wherein R ² and R ³ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may include an alicyclic structure or an aromatic ring structure.) 9. R ¹ , R ⁴ in the above formulas (Formula 1) to (Formula 3),
The method for producing a polyester according to claim 8, wherein R ⁵ and R ⁶ are groups having an aromatic ring structure. 10. The method for producing a polyester according to claim 2, wherein the phosphorus compound has a phenol portion 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 (Formula 4) to (Formula 6). The method for producing a polyester according to 1. [Chemical 4] [Chemical 5] [Chemical 6] (In Formulas (Chemical Formula 4) to (Chemical Formula 6), R ¹ is a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, a hydroxyl group, a halogen group, an alkoxyl group, an amino group, or a C ^{1 to} 50 carbon atom including 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, a halogen group, an alkoxyl group or an amino group, and 1 to 50 carbon atoms. Represents a hydrogen group R ² , R ³
Are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms,
It represents a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may include a branched structure, an alicyclic structure, or an aromatic ring structure. The ends of R ² and R ⁴ may be bonded to each other. ) 12. The polyester according to claim 2, wherein the polycondensation catalyst comprising aluminum or its compound 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 the compounds represented by the following general formula (Formula 7).
5. The method for producing a polyester according to any one of 4 to 4. [Chemical 7] (In the formula (Formula 7), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. R ³ is 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, 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 is an integer of 1 or more.
The hydrocarbon group may contain an alicyclic structure, a branched structure or an aromatic ring structure. ) 14. 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 are coexistent as a polyester polymerization catalyst. The method for producing the polyester according to claim 1. 15. When producing a polyester, an antimony compound is used as an antimony atom with respect to the polyester.
It 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 the 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 method according to any one of claims 1 to 16.