JP2002249558A - Method for preparing polyester film and polyester film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preparing a polyester film, wherein a polyester film that is excellent in heat stability and color, and has few defects due to foreign materials, is prepared at a low cost, without using an antimony or germanium compound as a main catalyst for polyester, and to provide a polyester film thereby. SOLUTION: A polyester is prepared by polymerization, using one or more selected from the group consisting of aluminum and compounds thereof as a catalyst. The polyester is used as a main raw material for preparing a polyester film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film obtained by improving the quality of a conventional polyester film. Specifically, the present invention relates to a film which is polymerized using a polyester polymerization catalyst which does not use a germanium or antimony compound as a catalyst main component. The present invention relates to a method for producing a polyester film having less defects characterized by using a modified polyester and a polyester film thereof.

[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. It is used in a wide range of fields such as films and sheets for tapes, magnetic disks, cards, ribbons, capacitors, photographs, optics, and mold release for ceramic capacitors.

[0003] In particular, in the case of films for magnetic tapes, magnetic disks, photographs, optics, and mold release films such as ceramic capacitors, the defects present in the film become defects in the final product. Is desired.

Hitherto, antimony trioxide has been widely used as a polyester polymerization catalyst used in the polycondensation of polyester. Antimony trioxide is a catalyst which is inexpensive and has excellent catalytic activity.However, if this is used as a main component, that is, in an amount added so as to exhibit a practical polymerization rate, metal antimony during polycondensation is used. Has a problem that blackening or foreign matter is generated in the polyester. Under such circumstances, a polyester containing no antimony or containing no antimony as a main component of a catalyst is desired.

When a biaxially stretched film is formed using a polymer obtained by using antimony trioxide as a main component of the catalyst, even if a filter is used at the time of melt extrusion, fine metal antimony passes through the filter and the film is cast. In some cases, the crystallization of the surrounding polyester was promoted, and the problem that the film after biaxial stretching became a major drawback was not solved.

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

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

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

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

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

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

There is also known a technique in which an alkali metal compound is added to an aluminum compound to obtain a polyester polymerization catalyst having sufficient catalytic activity. When such a known catalyst is used, a polyester having excellent heat stability can be obtained. However, catalysts using this alkali metal compound in combination
In order to obtain a practical catalytic activity, a large amount of these additives is required. As a result, the amount of foreign substances caused by the alkali metal compound in the obtained polyester polymer increases,
Film properties and the like deteriorate. In addition, there is a problem that the hydrolysis resistance and thermal oxidation stability of the polyester polymer are reduced.

As a catalyst other than an antimony compound, which has excellent catalytic activity and provides a polyester having excellent thermal stability and thermal oxidation stability, a germanium compound has already been put into practical use, but this catalyst is very expensive. And the problem that it is difficult to control the polymerization because the catalyst concentration of the reaction system changes because it is easy to distill out of the reaction system during polymerization. Has a problem.

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

As described above, a film using a polymer obtained from a polymerization catalyst having excellent catalytic activity using a metal component other than antimony and germanium as a main metal component of the catalyst, and having undergone thermal degradation during melt molding. Polyester excellent in thermal stability and thermo-oxidative stability which hardly causes water-soluble is desired as a film raw material.

[0016]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an antimony compound and a germanium compound which are excellent in heat stability and color tone without using as a main catalyst of polyester.
An object of the present invention is to provide a polyester film production method and a polyester film for inexpensively producing a polyester film having few defects caused by foreign matter.

[0017]

The present invention is characterized in that a polyester polymerized using at least one selected from the group consisting of aluminum and its compounds as a catalyst is used as a main raw material in producing a film. This is a method for producing a polyester film. Further, it is a polyester film produced by the above production method.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester used as a main raw material in producing the polyester film of the present invention is a polyester polymerized using at least one selected from the group consisting of aluminum and its compounds as a catalyst. .

In the production of the polyester used for the polyester film of the present invention, as the aluminum or aluminum compound constituting the polycondensation catalyst, not only metal aluminum but also known aluminum compounds can be used without limitation.

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. Carboxylate such as aluminum lactate, aluminum citrate, aluminum salicylate, inorganic acid salt such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxy Side, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t -Aluminum alkoxide such as butoxide, aluminum acetylacetonate,
Examples thereof include aluminum chelate compounds such as aluminum acetylacetate, aluminum ethyl acetoacetate, and aluminum ethyl acetoacetate diiso-propoxide; organic aluminum compounds such as trimethylaluminum and triethylaluminum; partial hydrolysates thereof; and aluminum oxide.

Of these, carboxylate, inorganic acid salt and chelate compound are preferred, and among these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

The amount of the aluminum compound to be added is preferably 0.001 to 0.05 mol% with respect to the mol number of all the constituent units of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the obtained polyester. More preferably, it is 0.005 to 0.02 mol%. As described above, even when the addition amount of the aluminum component or the alkali metal component is small, the polymerization catalyst according to the present invention is greatly characterized in that it exhibits a sufficient catalytic activity. As a result, by using this polyester polymerization catalyst, the generation of foreign matter is suppressed,
A polyester having excellent thermal stability and thermal oxidation stability can be produced.

The catalyst used in the present invention, which contains at least one member selected from the group consisting of aluminum and its compounds,
Using this catalyst, polyethylene terephthalate (hereinafter referred to as P
When polymerizing ET) and using PET as the catalyst, it is preferable that the PET polymerized satisfies one or more of the following formulas (1) to (6) in the numerical range of the following parameters.

(1) Activity parameter (AP) <2T (wherein, the activity parameter AP is an intrinsic viscosity (IV) at 275 ° C. and a reduced pressure of 13.3 Pa (0.1 Torr) using a predetermined amount of catalyst. Time required to polymerize 0.65 dl / g of polyethylene terephthalate (min)
Is shown. T indicates AP (min) when antimony trioxide is used as a catalyst. However, antimony trioxide is added in an amount of 0.05 mol% as antimony atoms to the acid component in the produced polyethylene terephthalate. )

In measuring T, antimony trioxide having a purity of 99% or more, for example, commercially available Antimony (III) oxi
de (ALDRICH CHEMICAL, purity 99.999%) is used.

(2) Thermal stability parameter (TS) <0.
30 (In the above formula, TS is a polyethylene terephthalate (P) having a melt-polymerized intrinsic viscosity (IV) of about 0.65 dl / g.
ET) 1 g of resin chip was placed in a glass test tube,
After vacuum drying at 12 ° C. for 12 hours,
It can be obtained from the IV after maintaining the molten state at 00 ° C. for 2 hours using the following formula. TS = 0.245 × ([IV] f2 ^-1.47- [IV] i
^-1.47 ) [IV] i and [IV] f2 indicate the IV (dl / g) before and after the melting test, respectively. )

The non-circulating nitrogen atmosphere means a non-circulating nitrogen atmosphere. For example, a glass test tube containing a resin chip is connected to a vacuum line, and the pressure is reduced and nitrogen is sealed.
This is a state in which nitrogen is sealed and sealed so that the pressure becomes 100 Torr after the repetition is repeated at least 100 times.

(3) Thermal oxidation stability parameter (TOS)
<0.10 (in the above formula, TOS has a melt-polymerized IV of about 0.65
A dl / g PET resin chip was freeze-pulverized to a powder having a size of 20 mesh or less, which was vacuum-dried at 130 ° C. for 12 hours, and 0.3 g was placed in a glass test tube.
After vacuum drying for 2 hours, and heating at 230 ° C. for 15 minutes under air dried with silica gel, it can be obtained by the following formula from IV. TOS = 0.245 ｛[IV] f1 ^-1.47- [IV] i
^-1.47 ｝ [IV] i and [IV] f1 indicate the IV (dl / g) before and after the heating test, respectively. As a method of heating under air dried with silica gel, for example, a method of attaching a drying tube containing silica gel to the upper part of a glass test tube and heating under dry air can be used.

(4) Hydrolysis resistance parameter (HS) <
0.10 (HS has an intrinsic viscosity of about 0.65 obtained by melt polymerization.
dl / g PET chips were freeze-pulverized to powder having a size of 20 mesh or less. The powder was vacuum-dried at 130 ° C. for 12 hours. 1 g of the dried powder was placed in a beaker together with 100 ml of pure water. It is a numerical value calculated from the intrinsic viscosity ([IV] f2) after stirring for 6 hours under pressurized conditions by the following formula. HS = 0.245 ｛[IV] f2 ^-1.47- [IV] i
^-1.47 ｝) [IV] i and [IV] f1 indicate the IV (dl / g) before and after the heating test, respectively. )

The beaker used for measuring the HS is as follows:
Use one that does not elute acid or alkali. Specifically, it is preferable to use a stainless beaker or a quartz beaker.

(5) Color delta b value parameter (Δ
b) <4.0 (in the above formula, Δb was measured using a colorimeter using a polyethylene terephthalate (PET) resin chip having an intrinsic viscosity of about 0.65 dl / g, which was melt-polymerized using a predetermined catalyst. The value obtained by subtracting the b value when antimony trioxide is used as a catalyst from the b value of the hunter is shown, where antimony trioxide is 0.05 mol% as an antimony atom with respect to the acid component in the produced polyethylene terephthalate.
Added. As antimony trioxide, antimony trioxide having a purity of 99% or more, for example, commercially available Antimony (III) oxi
de (ALDRICH CHEMICAL, purity 99.999%) is used.

(6) Solution haze value (Haze) <3.0 (In the above formula, Haze is a melt-polymerized polyethylene terephthalate (PE) having an intrinsic viscosity of about 0.65 dl / g.
T) Resin chips were p-chlorophenol / 1,1,1
The value (%) is shown by dissolving in a 3/1 mixed solvent (weight ratio) of 2,2-tetrachloroethane to make a solution of 8 g / 100 ml, and using a haze meter. The haze was measured using a cell having a cell length of 1 cm.
The solution is filled in a cell and measured.

With such a constitution, the catalyst is excellent in activity and therefore the productivity of polyester is high, and the heat deterioration during melt molding is effectively suppressed without deactivating or removing the catalyst, and the heat stability is excellent. Polyester polymerization catalysts that are excellent in thermal oxidation stability, excellent in hydrolysis resistance, excellent in color tone, and further provide polyesters with little defect generation and excellent transparency, and a film made of polyester polymerized using the catalyst. can get.

The AP is preferably 1.5T or less, more preferably 1.3T or less, more preferably 1.
It is particularly preferable that it is 0T or less. TS is more preferably 0.25 or less, particularly preferably 0.20 or less. TOS is more preferably 0.09 or less, still more preferably 0.08 or less. HS is more preferably 0.09 or less, and particularly preferably 0.08 or less. Δb value is more preferably 3.0 or less,
More preferably, it is 2.5 or less. Haze is more preferably 2.0 or less, further preferably 1.0 or less.

The method of measuring AP is specifically as follows. 1) BHET Production Process A mixture of bis (2-hydroxyethyl) terephthalate (BHET) and an oligomer having a degree of esterification of 95% using terephthalic acid and twice the amount of ethylene glycol (hereinafter referred to as a BHET mixture). To manufacture.

2) Catalyst Addition Step A predetermined amount of a catalyst is added to the above BHET mixture, and the mixture is stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure.
The temperature of the reaction system of the oligomer mixture is gradually lowered to 0.1 Torr while the temperature is raised to 275 ° C. over a period of minutes.

3) Polycondensation Step A polycondensation reaction is carried out at 275 ° C. and 13.3 Pa (0.1 Torr), and the IV of polyethylene terephthalate is 0.6.
Polymerize until reaching 5 dl / g.

4) AP (min) The polymerization time required for the polycondensation step is defined as AP (min).
The above process is performed using a batch-type reactor.

The production of the BHET mixture is performed by a known method. For example, terephthalic acid and a 2-fold molar amount of ethylene glycol are charged into a batch type autoclave equipped with a stirrer, and an esterification reaction is performed while distilling water out of the system at 245 ° C. under a pressure of 0.25 MPa. Manufactured.

The "predetermined amount of the catalyst" means the amount of the catalyst used in a variable amount according to the activity of the catalyst. The amount of the catalyst is small for a highly active catalyst and large for a low active catalyst. . The amount of the catalyst added is at most 0.1 mol% as an aluminum compound based on the number of moles of terephthalic acid. If more is added, the residual amount in the polyester is large,
It is no longer a practical catalyst.

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

It is known that a catalyst having sufficient catalytic activity can be obtained by adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound. By using such a known catalyst, a polyester having excellent heat stability can be obtained. However, known catalysts using an alkali metal compound or an alkaline earth metal compound in combination need to increase the amount of addition in order to obtain practical catalytic activity.

When an alkali metal compound is used in combination, the amount of foreign substances caused by the compound increases, and when the polyester obtained using the catalyst is used for a film, the physical properties, transparency, thermal oxidation stability, etc. of the film deteriorate. I do.

In addition, when an alkaline earth metal compound is used in combination, to obtain practical catalytic activity, the thermal stability and thermo-oxidative stability of the obtained polyester are reduced, the coloring by heating is large, The amount of generation also increases.

When an alkali metal, an alkaline earth metal or a compound thereof is added, the addition amount M (mol%) is
It is preferably from 1 × 10 ^{−6 to} less than 0.1 mol%, more preferably from 5 × 10 ^{−6 to} 0.05, based on the number of moles of all the polycarboxylic acid units constituting the polyester.
Mol%, more preferably 1 × 10 ^{−5 to} 0.03.
Mol%, particularly preferably 1 × 10 ^{−5 to} 0.01.
Mol%.

That is, since the added amount of the alkali metal and the alkaline earth metal is small, it is possible to increase the reaction rate without causing problems such as a decrease in thermal stability, generation of foreign matter, and coloring. Further, problems such as a decrease in hydrolysis resistance do not occur.

When the addition amount M of the alkali metal, alkaline earth metal, or a compound thereof is 0.1 mol% or more, a decrease in thermal stability, generation of foreign matter, and an increase in coloring may cause problems in product processing. Occurs. If M is less than 1 × 10 ⁻⁶ mol%, the effect is not clear even if added.

The alkali metal and alkaline earth metal constituting the second metal-containing component which is preferably used in addition to the aluminum or its compound include Li and N.
It is preferably at least one selected from a, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba, and more preferably an alkali metal or a compound thereof. When an alkali metal or a compound thereof is used, L
The use of i, Na, K is preferred.

Examples of the alkali metal or alkaline earth metal compounds include saturated aliphatic carboxylate such as formic acid, acetic acid, propionic acid, butyric acid and oxalic acid, and unsaturated aliphatic carboxylic acid such as acrylic acid and methacrylic acid. Carboxylates, aromatic carboxylate such as benzoic acid, halogen-containing carboxylate such as trichloroacetic acid, lactic acid, citric acid,
Hydroxycarboxylic acid salts such as salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid,
Inorganic acid salts such as chloric acid and bromic acid, organic sulfonates such as 1-propanesulfonic acid, 1-pentanesulfonic acid and naphthalenesulfonic acid, organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy and iso Alkoxides such as -propoxy, n-butoxy and tert-butoxy; chelate compounds with acetylacetonate; hydrides, oxides and hydroxides.

When strong alkalis such as hydroxides are used among these alkali metals, alkaline earth metals or compounds thereof, they tend not to be easily dissolved in organic solvents such as diols such as ethylene glycol or alcohols. Therefore, an aqueous solution must be added to the polymerization system, which may cause a problem in the polymerization step. Furthermore, when a strong alkali such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during polymerization, and the polymerized polyester tends to be colored, and the hydrolysis resistance is also reduced. Tend to.

Accordingly, the above-mentioned alkali metal or its compound, or alkaline earth metal or its compound suitable as the alkali metal or alkaline earth metal saturated aliphatic carboxylate, unsaturated aliphatic carboxylate, Aromatic carboxylate, halogen-containing carboxylate, hydroxycarboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid,
An inorganic acid salt selected from hydrobromic acid, chloric acid, and bromic acid, an organic sulfonate, an organic sulfate, a chelate compound, and an oxide.

Of these, from the viewpoints of ease of handling and availability, the use of alkali metal or alkaline earth metal saturated aliphatic carboxylate, particularly acetate, is preferred.

The above-mentioned catalyst is preferably a mixture of an aluminum compound and a phenolic compound or a phosphorus compound, particularly a phosphorus compound having a phenol moiety in the same molecule.

The phenolic compound constituting the polycondensation catalyst is not particularly limited as long as it has a phenol structure. For example, 2,6-di-tert-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-te
rt-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'-oxazamide bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-
Methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl
-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl2- {β- (3-t
ert-butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2- (3 , 5-di-tert-
Butyl-4-hydroxycinnamoyloxy)) ethoxyphenyl] propane, β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester, tetrakis- [methyl-3- (3 ′, 5 '-Di-tert-butyl-4-hydroxyphenyl) propionate] methane, octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-
Butylphenyl) butane, thiodiethylene-bis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3- (5-tert-
Butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis-[-3- (3 ′ -tert-butyl-4-hydroxy-5-methylphenyl)] propionate, 1,1,3-tris [2-methyl-4- [3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane.

These can be used in combination of two or more at the same time. Of these, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis- [methyl-3- (3 ′, 5 ′) -Di-tert-butyl
4-Hydroxyphenyl) propionate] methane and thiodiethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] are preferred.

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

The phenolic compound may be added in an amount of 5 × 10 ^{-7 to} 0.01 with respect to the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the obtained polyester. Mol is preferable, and more preferably 1 × 10 ^{−6 to} 0.005 mol.

Further, a phosphorus compound may be used in combination with the phenolic compound.

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

The above phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds are represented by the following chemical formulas (1) to (6), respectively. Refers to a compound having the structure shown below.

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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Examples of the phosphonic acid-based compound include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, and the like. Examples of the phosphinic acid compound of the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate and the like. Examples of the phosphine oxide-based compound of the present invention include diphenylphosphine oxide, methyldiphenylphosphine oxide, triphenylphosphine oxide, and the like.

Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds and phosphine compounds, the phosphorus compounds of the present invention are represented by the following formulas (7) to (12). It is preferred to use the compounds represented.

[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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

As the phosphorus compound constituting the above-mentioned polycondensation catalyst, it is preferable to use a compound represented by the following general formulas (13) to (15), since the effect of improving the catalytic activity is particularly large.

[0078]

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[0079]

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[0080]

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(In the formulas (13) to (15), R ¹ , R ⁴ ,
R ^5, R ⁶ each independently represents a hydrogen, a hydrocarbon group having 1 to 50 carbon atoms containing a hydrocarbon group, a hydroxyl group or a halogen group, an alkoxyl group, or an amino group having 1 to 50 carbon atoms. R ² and R ³ each independently represent hydrogen, carbon number 1 to 5
Represents a hydrocarbon group having 1 to 50 carbon atoms, including a 0 hydrocarbon group, 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. )

Examples of the phosphorus compound constituting the polycondensation catalyst include R ¹ , R ⁴ and R in the above formulas (13) to (15).
Compounds in which ⁵ and R ⁶ are groups having an aromatic ring structure are particularly preferred.

Examples of the phosphorus compound constituting the above-mentioned polycondensation catalyst include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, and diethyl benzylphosphonate. , Diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate, diphenylphosphine oxide, methyldiphenylphosphine oxide, triphenylphosphine oxide and the like. Of these, dimethyl phenylphosphonate and diethyl benzylphosphonate are particularly preferred.

The amount of the phosphorus compound to be added is 5 × 10 ^{−7 to} 0.01 mol per mol of all the constituent units of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the obtained polyester. And more preferably 1 × 10 ^{−6 to} 0.005 mol.

The phosphorus compound having a phenol moiety in the same molecule that constitutes the polycondensation catalyst is not particularly limited as long as it is a phosphorus compound having a phenol structure. ,
Phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds,
It is preferable to use one or more compounds selected from the group consisting of phosphine-based compounds because the effect of improving the catalytic activity is large. Among these, the use of a phosphonic acid-based compound having one or more phenol moieties in the same molecule is particularly preferred because the effect of improving the catalytic activity is particularly large.

As the phosphorus compound having a phenol moiety in the same molecule constituting the polycondensation catalyst of the present invention, when compounds represented by the following general formulas (16) to (18) are used, the catalytic activity is particularly improved. Is preferred.

[0087]

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[0088]

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[0089]

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(In the formulas (16) to (18), R ¹ contains a substituent such as a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, 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, wherein 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 represents a hydrocarbon group having 1 to 50 carbon atoms, including: R ² and R ³
Are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms,
Represents a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may include a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl. The terminals of R ² and R ⁴ may be bonded to each other. )

Examples of the phosphorus compound having a phenol moiety in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, and p-hydroxyphenylphosphonate.
Diphenyl hydroxyphenylphosphonate, bis (p-
(Hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, phenyl bis (p-hydroxyphenyl) phosphinate, p-hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, p-hydroxyphenylphenyl Phenyl phosphinate, 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 compounds represented by the following formulas (19) to (22). Among these, a compound represented by the following formula (21) and dimethyl p-hydroxyphenylphosphonate are particularly preferred.

[0092]

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[0093]

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[0094]

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[0095]

Embedded image As the compound represented by the above formula (21), SAN
KO-220 (manufactured by Sanko Corporation) is commercially available and can be used.

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

The amount of the phosphorus compound having the phenol moiety in the same molecule may be 5 × with respect to the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the obtained polyester. 10 ^{-7 to} 0.0
1 mol is preferable, and more preferably 1 × 10 ^{−6 to} 0.0
05 mol.

It is preferable to use a metal salt compound of phosphorus as the phosphorus compound. The metal salt compound of phosphorus, which is a preferred phosphorus compound constituting the polymerization catalyst, is not particularly limited as long as it is a metal salt of a phosphorus compound. . Examples of the metal salt of a phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.

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

As the phosphorus metal salt compound constituting the polymerization catalyst, it is preferable to use at least one compound selected from the compounds represented by the following general formula (23) because the effect of improving the catalytic activity is large.

[0101]

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(In the formula (23), R ¹ is hydrogen and has 1 to 1 carbon atoms.
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups, halogen groups, alkoxyl groups, or amino groups. R ² is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 5 carbon atoms.
Represents a hydrocarbon group of 0. R ³ is hydrogen, 1 to 50 carbon atoms
Represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group, a hydroxyl group, an alkoxyl group or a carbonyl. l represents an integer of 1 or more; m represents 0 or an integer of 1 or more;
+ M) is 4 or less. M represents a (l + m) -valent metal cation. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

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

Among the compounds represented by the general formula (23), it is preferable to use at least one selected from the compounds represented by the following general formula (24).

[0105]

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(In the chemical formula (24), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group or an amino group. ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl, 1 is an integer of 1 or more, and m is an integer of 0 or 1 or more. And (l +
m) is 4 or less. M represents a (l + m) -valent metal cation. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

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

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

In the above chemical formula (24), M is L
i, Na, K, Be, Mg, Sr, Ba, Mn, Ni,
It is preferable to use one selected from Cu and Zn because the effect of improving the catalytic activity is large. Of these, Li, N
a and Mg are particularly preferred.

Examples of the above phosphorus metal salt compounds include lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [(1-naphthyl) methylphosphonate], Potassium [ethyl (2-naphthyl) methyl phosphonate], magnesium bis [(2-naphthyl) methyl phosphonate], lithium [ethyl benzyl phosphonate], sodium [ethyl benzyl phosphonate], magnesium bis [ethyl benzyl phosphonate], Beryllium bis [ethyl benzylphosphonate],
Strontium bis [ethyl benzylphosphonate], manganese bis [ethyl benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonic acid], sodium [ethyl (9-anthryl) methylphosphonate], magnesium bis [(9-anthryl) ) Ethyl methyl phosphonate], sodium [ethyl 4-hydroxybenzyl phosphonate], magnesium bis [ethyl 4-hydroxybenzyl phosphonate], sodium [phenyl chlorophenyl phosphonate], magnesium bis [4-chlorobenzyl phosphonate ethyl] ], Sodium [methyl 4-aminobenzylphosphonate], magnesium bis [methyl 4-aminobenzylphosphonate], sodium phenylphosphonate, magnesium bis [phenylphosphonate] Ethyl phosphate], zinc bis [phenylphosphonic acid ethyl] and the like.

Among these, lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [ethyl (1-naphthyl) methylphosphonate], lithium [benzylphosphonic acid] Ethyl], sodium [ethyl benzylphosphonate], magnesium bis [ethyl benzylphosphonate], sodium benzylphosphonate, and magnesium bis [benzylphosphonic acid] are particularly preferred.

The phosphorus metal salt compound is another preferred phosphorus compound constituting the polymerization catalyst, and is at least one compound selected from the compounds represented by the following general formula (25).

[0113]

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(In the chemical formula (25), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
³ represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. Examples of R ⁴ O ⁻ include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion.
l represents an integer of 1 or more, m represents 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 or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among them, it is preferable to use at least one selected from compounds represented by the following general formula (26).

[0116]

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(In the chemical formula (26), M ^{n +} represents an n-valent metal cation, and n represents 1, 2, 3, or 4)

In the above formula (25) or (26),
M is Li, Na, K, Be, Mg, Sr, Ba, M
It is preferable to use one selected from n, Ni, Cu, and Zn because the effect of improving the catalytic activity is large. Of these, L
i, Na and Mg are particularly preferred.

Specific metal salt compounds of phosphorus include lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] and sodium [3,5-di-tert-butyl-4-hydroxybenzyl]. Ethyl phosphonate, sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], potassium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [3 , 5-Di-tert-butyl-4-hydroxybenzylphosphonate ethyl], 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] -Ethyl hydroxybenzylphosphonate], barium bis [3,5-di-tert-
Butyl-4-hydroxybenzylphosphonate], manganese bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], nickel bis [3,
Ethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate], copper bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], zinc bis [3,5-
Ethyl di-tert-butyl-4-hydroxybenzylphosphonate].

Among these, lithium [3,5-di-tert.
Ethyl-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzyl] Ethyl phosphonate] is particularly preferred.

Another embodiment is a polyester polymerization catalyst containing at least one selected from aluminum salts of phosphorus compounds. The aluminum salt of the phosphorus compound may be used in combination with another aluminum compound, a phosphorus compound, a phenol compound, or the like.

The aluminum salt of the above phosphorus compound is
There is no particular limitation as long as it is a phosphorus compound having an aluminum part, but the use of an aluminum salt of a phosphonic acid compound is preferred because the effect of improving the catalytic activity is large. Examples of the aluminum salt of the phosphorus compound include a monoaluminum salt, a dialluminum salt, and a trialuminum salt.

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

It is preferable to use at least one selected from the compounds represented by the following formula (27) as the aluminum salt of the phosphorus compound because the effect of improving the catalytic activity is large.

[0125]

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(In the chemical formula (27), 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. ² is hydrogen, a carbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group,
Represents up to 50 hydrocarbon groups. R ³ is hydrogen, carbon number 1 to
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups, alkoxyl groups, or carbonyl.
l represents an integer of 1 or more, m represents 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 or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

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

Examples of the aluminum salt of the phosphorus compound include an aluminum salt of ethyl (1-naphthyl) methylphosphonate, an aluminum salt of (1-naphthyl) methylphosphonic acid, an aluminum salt of ethyl (2-naphthyl) methylphosphonate, and benzylphosphonic acid. Aluminum salt of ethyl acid, aluminum salt of benzylphosphonic acid, (9-
Anthryl) aluminum salt of ethyl methylphosphonate, aluminum salt of ethyl 4-hydroxybenzylphosphonate, aluminum salt of ethyl 2-methylbenzylphosphonate, aluminum salt of phenyl 4-chlorobenzylphosphonate, methyl 4-aminobenzylphosphonate Aluminum salts, aluminum salts of ethyl 4-methoxybenzylphosphonate, aluminum salts of ethyl phenylphosphonate and the like can be mentioned.

Of these, aluminum salts of ethyl (1-naphthyl) methylphosphonate and aluminum salts of ethyl benzylphosphonate are particularly preferred.

In another embodiment, the following general formula (2)
It is a polyester polymerization catalyst comprising at least one selected from aluminum salts of phosphorus compounds represented by 8). The aluminum salt of the phosphorus compound may be used in combination with another aluminum compound, a phosphorus compound, a phenol compound, or the like.

[0131]

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(In the formula (28), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
³ represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. l is an integer of 1 or more, m
Represents an integer of 0 or 1 or more, and (l + m) is 3. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among these, it is preferable to use at least one selected from compounds represented by the following general formula (29).

[0134]

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(In the formula (29), R ³ is hydrogen, carbon number 1
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group or an alkoxyl group. R ⁴ is hydrogen,
It represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group or carbonyl. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and (l + m) is 3. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

The above R³For example, hydrogen, methyl
, Ethyl, propyl, isopropyl, n-butyl
Tyl group, sec-butyl group, tert-butyl group, long chain
Aliphatic, phenyl, naphthyl, substituted
Nyl group, naphthyl group, -CH _TwoCH_TwoGroup represented by OH
And so on. R above⁴O^-As, for example, water
Oxide ion, alcoholate ion, ethylene glycola
Ion, acetate ion and acetylacetone ion
And the like.

Examples of the aluminum salt of the phosphorus compound include aluminum salt of ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, and aluminum salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonate. Aluminum salt of methyl, aluminum salt of isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5
Aluminum salts of phenyl-di-tert-butyl-4-hydroxybenzylphosphonate, aluminum salts of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and the like.

Among them, 3,5-di-tert-butyl-4
Particularly preferred are the aluminum salts of ethyl-hydroxybenzylphosphonate and the methyl salts of methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.

In the present invention, PO is used as the phosphorus compound.
It is preferable to use a phosphorus compound having at least one H bond. Preferred P- constituting the above-mentioned polymerization catalyst
The phosphorus compound having at least one OH bond is not particularly limited as long as it is a phosphorus compound having at least one P-OH bond in a molecule. Among these phosphorus compounds, the use of a phosphonic acid-based compound having at least one P-OH bond is preferable because the effect of improving the catalytic activity is large.

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

When at least one selected from the compounds represented by the following general formula (30) is used as the phosphorus compound having at least one P-OH bond constituting the polymerization catalyst, the effect of improving the catalytic activity is improved. Large and preferred.

[0142]

Embedded image (In the formula (30), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group or an amino group. R ² represents Represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, n represents an integer of 1 or more, and the hydrocarbon group has an alicyclic structure such as cyclohexyl or the like. It may contain a branched structure or an aromatic ring structure such as phenyl or naphthyl.)

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

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

Examples of the phosphorus compound having at least one P-OH bond include ethyl (1-naphthyl) methylphosphonate, (1-naphthyl) methylphosphonic acid, and (2)
-Naphthyl) ethyl methylphosphonate, ethyl benzylphosphonate, benzylphosphonic acid, (9-anthryl)
Ethyl methyl phosphonate, ethyl 4-hydroxybenzyl phosphonate, ethyl 2-methylbenzyl phosphonate,
Examples thereof include phenyl 4-chlorobenzylphosphonate, methyl 4-aminobenzylphosphonate, and ethyl 4-methoxybenzylphosphonate. Among them, ethyl (1-naphthyl) methylphosphonate and ethyl benzylphosphonate are particularly preferred.

As the preferred phosphorus compound used in the present invention, a specific phosphorus compound having at least one P-OH bond can be mentioned. The preferred specific phosphorus compound having at least one P-OH bond that constitutes the polymerization catalyst means at least one compound selected from the compounds represented by the following general formula (31).

[0147]

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(In the formula (31), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
³ represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among these, it is preferable to use at least one selected from compounds represented by the following general formula (32).

[0150]

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(In the chemical formula (32), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group is cyclohexyl or the like. May contain an alicyclic structure, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

The above R³For example, hydrogen, methyl
, Ethyl, propyl, isopropyl, n-butyl
Tyl group, sec-butyl group, tert-butyl group, long chain
Aliphatic, phenyl, naphthyl, substituted
Nyl group, naphthyl group, -CH _TwoCH_TwoGroup represented by OH
And so on.

Examples of the specific phosphorus compound having at least one P-OH bond include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-
Methyl tert-butyl-4-hydroxybenzylphosphonate, isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, phenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,3 5-di-tert
Octadecyl-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid and the like.

Among them, 3,5-di-tert-butyl-4
-Ethyl hydroxybenzylphosphonate, 3,5-di-ter
Methyl t-butyl-4-hydroxybenzylphosphonate is particularly preferred.

A preferred phosphorus compound is represented by the following formula (3)
And the phosphorus compound represented by 3).

[0156]

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(In the chemical formula (33), R ¹ has 1 to 4 carbon atoms.
9 represents a hydrocarbon group, and R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. Further, more preferably, R ¹ in the chemical formula (33),
At least one of R ² and R ³ is a compound containing an aromatic ring structure.

Specific examples of the phosphorus compound are shown below.

[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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The phosphorus compound having a higher molecular weight is more preferable because it is difficult to be distilled off during polymerization.

Further, another phosphorus compound preferably used as a polycondensation catalyst is at least one phosphorus compound selected from compounds represented by the following general formula (40).

[0167]

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(In the chemical formula (40), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
³ and R ⁴ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, 1 to ⁴ carbon atoms including a hydroxyl group or an alkoxyl group.
Represents 50 hydrocarbon groups. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Of the above general formula (40), it is preferable to use at least one selected from the compounds represented by the following general formula (41) because the effect of improving the catalytic activity is high.

[0170]

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(In the formula (41), R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

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

Examples of the specific phosphorus compound include 3,5-
Diisopropyl di-tert-butyl-4-hydroxybenzylphosphonate, di-n-butyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert
Dioctadecyl-butyl-4-hydroxybenzylphosphonate, diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and the like.

Among them, 3,5-di-tert-butyl-4
-Dioctadecyl hydroxybenzylphosphonate, 3,5
Diphenyl di-tert-butyl-4-hydroxybenzylphosphonate is particularly preferred.

Another phosphorus compound that is preferably used as a polycondensation catalyst is at least one phosphorus compound selected from the compounds represented by chemical formulas (42) and (43).

[0176]

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[0177]

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As the compound represented by the above formula (42), Irganox 1222 (manufactured by Ciba Specialty Chemicals) is commercially available. As the compound represented by the chemical formula (43), Irganox 1425 (manufactured by Ciba Specialty Chemicals) is commercially available.

Although phosphorus compounds are generally well known as antioxidants, even when these phosphorus compounds are used in combination with a conventional metal-containing polyester polymerization catalyst,
It is not known to greatly promote melt polymerization. In fact, when a polyester compound is melt-polymerized using a typical catalyst for polyester polymerization such as an antimony compound, a titanium compound, a tin compound or a germanium compound as a polymerization catalyst, even if a phosphorus compound is added, a substantially useful level is obtained. No accelerated polymerization is observed.

That is, by using the above phosphorus compound in combination, sufficient catalytic activity can be exhibited even if the content of aluminum in the polyester polymerization catalyst is small.

The amount of the phosphorus compound to be added is preferably 0.0001 to 0.1 mol%, and more preferably 0.005 to 0.05 mol%, based on the number of moles of all the constituent units of the polycarboxylic acid component in the obtained polyester. % Is more preferable.

The amount of the phosphorus compound added is 0.0001 mol%
If it is less than the above, the effect of addition may not be exhibited.
On the other hand, if it is added in excess of 0.1 mol%, the catalytic activity as a polyester polymerization catalyst may be reduced.
The tendency of the catalyst activity to decrease varies depending on the amount of aluminum added and the like.

There is a technique for reducing the amount of the aluminum compound to be added and further preventing the coloring due to a decrease in thermal stability when the aluminum compound is used as a catalyst by adding a cobalt compound. When added to such an extent as to have, the thermal stability also decreases. Therefore,
It is difficult to balance both.

The use of the above phosphorus compound makes it possible to obtain heat stability,
It is possible to obtain a polyester polymerization catalyst which does not cause problems such as a decrease in thermal oxidation stability and the generation of foreign matter, and which has a sufficient catalytic effect even when the addition amount of the first metal-containing component as aluminum is small. Thermal stability during melt molding of polyester film,
The heat aging resistance and the generation of foreign matter are improved.

Further, even if a phosphoric acid ester such as phosphoric acid or trimethylphosphoric acid is added in place of the phosphorus compound, the effect of addition is not seen and it is not practical. Furthermore, even when the phosphorus compound is used in combination with a conventional metal-containing polyester polymerization catalyst such as an antimony compound, a titanium compound, a tin compound, and a germanium compound, in the range of the preferable addition amount, the effect of promoting the melt polymerization is obtained. It is not allowed. In addition, even if the above-mentioned phosphorus compound is used alone in the above-mentioned range, no catalytic activity is observed.

The polyester used for producing the polyester film of the present invention further comprises a cobalt compound having a cobalt atom of 10 pp with respect to the polyester.
In a preferred embodiment, it is added in an amount less than m. More preferably less than 5 ppm, even more preferably 3p
pm or less.

It is known that the cobalt compound itself has a certain degree of polymerization activity, but when added to such an extent that a sufficient catalytic effect is exhibited, the thermal stability is reduced. According to the present invention, the obtained polyester has good thermal stability, but the coloring of the obtained polyester is performed by adding the cobalt compound in such a small amount that the catalytic effect of the addition is not clear as described above. Can be more effectively erased. The purpose of the cobalt compound in the present invention is to eliminate coloration, and it may be added at any stage of the polymerization or after the completion of the polymerization reaction.

The production of the polyester used for the polyester film of the present invention comprises a conventionally known process except that the polyester polymerization catalyst used for producing the polyester used for the polyester film of the present invention is used as a catalyst. Can be done in any way. For example, PE
In the polymerization method of T, a method of esterifying terephthalic acid and ethylene glycol followed by polycondensation, or
After the transesterification reaction between an alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, polycondensation can be performed. The polymerization apparatus may be of a batch type or a continuous type.

The catalyst used for producing the polyester used for the polyester film of the present invention has catalytic activity not only in polycondensation reaction but also in esterification reaction and transesterification reaction. For example, polymerization by transesterification of an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate with a glycol such as ethylene glycol is usually carried out in the presence of a transesterification catalyst such as a titanium compound or a zinc compound. Alternatively, or in combination with these catalysts, the catalyst of the present invention can be used. Further, the catalyst used in producing the polyester used in the polyester film of the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization and solution polymerization, and the polyester is produced by any method. It is possible.

The polycondensation catalyst used in producing the polyester used in the polyester film of the present invention can be added to the reaction system at any stage of the polymerization reaction.
For example, it can be added to the reaction system before the start of the esterification reaction or the transesterification reaction and at any stage during the reaction, or immediately before the start of the polycondensation reaction or during the reaction. In particular, it is preferable to add aluminum or its compound immediately before the start of the polycondensation reaction.

The method of adding the polycondensation catalyst used in producing the polyester used in the polyester film of the present invention may be a powdery or neat addition, or a slurry addition of a solvent such as ethylene glycol. Alternatively, the addition may be in the form of a solution, and is not particularly limited. Further, aluminum metal or a compound thereof and another component, preferably the phosphorus compound of the present invention, may be added as a premixed mixture or complex, or they may be added separately. The aluminum metal or its compound and another component, preferably a phosphorus compound, may be added to the polymerization system at the same time, or each component may be added at a different time.

The polycondensation catalyst used for producing the polyester used in the polyester film of the present invention is other polycondensation catalysts such as antimony compounds, germanium compounds and titanium compounds. It is effective to improve the productivity by shortening the polymerization time, and it is preferable to use coexistence within the range of the addition amount which does not cause a problem in the product such as the characteristics, processability, and color tone of the polyester.

However, the antimony compound can be added in an amount of 50 ppm or less as the remaining amount of antimony atoms remaining in the polyester obtained by polymerization. A more preferable residual amount is 30 ppm or less. When the residual amount of antimony is 50 ppm or more, precipitation of metallic antimony occurs, and blackening or foreign matter is generated in polyester, which is not preferable.

The germanium compound can be added in an amount of 30 ppm or less as a residual germanium atom in the polyester obtained by polymerization. A more preferable addition amount is 20 ppm or less. It is not preferable to set the remaining amount of germanium to 30 ppm or more, because it is disadvantageous in terms of cost.

Suitable antimony compounds include, as suitable compounds, antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoside, and the like, with the use of antimony trioxide being particularly preferred. Examples of the germanium compound include germanium dioxide and germanium tetrachloride, with germanium dioxide being particularly preferred.

Examples of other polymerization catalysts such as titanium compounds and tin compounds include tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate,
Examples thereof include tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, and tetrabenzyl titanate, and the use of tetrabutyl titanate is particularly preferred. Further, as the tin compound, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin sulfide, Examples thereof include dibutylhydroxytin oxide, methylstannoic acid and ethylstannoic acid, and the use of monobutylhydroxytin oxide is particularly preferable.

The polyester as referred to in the present invention is one or two or more selected from polyhydric carboxylic acids including dicarboxylic acids and one or more selected from ester-forming derivatives thereof and polyhydric alcohols including glycols. A compound consisting of the above, a compound consisting of hydroxycarboxylic acid and an ester-forming derivative thereof, or a compound consisting of cyclic ester.

The dicarboxylic acids include oxalic acid, malonic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic Acid, 1,
Saturated aliphatic dicarboxylic acids exemplified by 2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid and the like, and ester-forming derivatives thereof, Unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid and the like and ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic 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'-biphenylsulfonedicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 1,2-bis (phenoxy) ethane-
Aromatic dicarboxylic acids exemplified by p, p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like, and ester-forming derivatives thereof are exemplified.

Among the above dicarboxylic acids, the use of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid is particularly preferred in view of the physical properties of the obtained polyester, and other dicarboxylic acids may be used as a component if necessary. I do.

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

As glycol, 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,
Aliphatic glycols exemplified by polytetramethylene glycol, hydroquinone, 4,4'-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) ) Sulfone, bis (p-hydroxyphenyl)
Ether, bis (p-hydroxyphenyl) sulfone,
Bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5-naphthalenediol,
Aromatic glycols exemplified by glycols obtained by adding ethylene oxide to these glycols, and the like can be given.

Of the above-mentioned glycols, ethylene glycol, 1,3-propylene glycol, 1,
It is preferable to use 4-butylene glycol and 1,4-cyclohexanedimethanol as main components.

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

Examples of the hydroxycarboxylic acid include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, and 4-hydroxycyclohexanecarboxylic acid. Or an ester-forming derivative thereof.

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

Examples of the ester-forming derivatives of polycarboxylic acids and hydroxycarboxylic acids include their alkyl esters, acid chlorides and acid anhydrides.

The polyester used in the present invention is preferably a polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalenedicarboxylic acid or its ester-forming derivative, and whose main glycol component is an alkylene glycol.

The polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof may be a polyester containing terephthalic acid or an ester-forming derivative thereof in a total amount of 70 mol% or more based on all the acid components. It is preferably a polyester containing more than 80 mol%, more preferably a polyester containing more than 90 mol%. Similarly, the polyester in which the main acid component is naphthalenedicarboxylic acid or an ester-forming derivative thereof is preferably a polyester containing a total of 70 mol% or more of naphthalenedicarboxylic acid or an ester-forming derivative thereof, and more preferably 80% or more. It is a polyester containing at least 90 mol%, more preferably a polyester containing at least 90 mol%.

The polyester in which the main glycol component is an alkylene glycol is preferably a polyester containing 70 mol% or more of alkylene glycol in total with respect to all glycol components, more preferably a polyester containing 80 mol% or more. And more preferably a polyester containing 90 mol% or more. The alkylene glycol referred to herein may have a substituent or an alicyclic structure in the molecular chain.

Examples of the naphthalenedicarboxylic acid or its ester-forming derivative used in the present invention include 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid exemplified as the above-mentioned dicarboxylic acids. , 2,6-naphthalenedicarboxylic acid,
2,7-Naphthalenedicarboxylic acid or their ester-forming derivatives are preferred.

Examples of the alkylene glycol used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol and the above-mentioned glycols.
1,3-butylene glycol, 2,3-butylene glycol, 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,
The use of 1,10-decamethylene glycol, 1,12-dodecanediol or the like is preferred. Two or more of these may be used simultaneously.

The polyester film of the present invention can contain a known phosphorus compound as a copolymer component. As the phosphorus compound, a bifunctional phosphorus compound is preferable. For example, (2-carboxylethyl) methylphosphinic acid, (2-carboxylethyl) phenylphosphinic acid, 9,10-dihydro-10-oxa- (2,3-
(Carboxypropyl) -10-phosphaphenanthrene-10-oxide and the like. By including these phosphorus compounds as copolymer components, it is possible to improve the flame retardancy and the like of the obtained polyester film.

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

The polyester film of the present invention may contain an organic, inorganic, or organometallic toner, a fluorescent whitening agent, and the like.
By containing more than one kind, the coloring such as yellowing of the polyester can be suppressed to a more excellent level.
It also contains other optional polymers, antistatic agents, defoamers, dye improvers, dyes, pigments, matting agents, optical brighteners, stabilizers, antioxidants, and other additives. Is also good. As the antioxidant, an aromatic amine-based, phenol-based, etc. antioxidant can be used, and as the stabilizer, a phosphoric acid-based or phosphoric acid ester-based stabilizer, a sulfur-based, amine-based stabilizer, etc. Can be used.

Further, the polyester film of the present invention comprises:
Inert particles such as inorganic particles, organic salt particles, and cross-linked polymer particles are included in the film to improve handling properties such as slipperiness, winding properties, and blocking resistance, as well as abrasion resistance and scratch resistance. Can be done.

Examples of the inorganic particles include calcium carbonate, kaolin, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, and fluorine oxide. Lithium oxide, sodium calcium aluminum silicate, zeolite, alumina-silica composite oxide and the like.

Examples of the organic salt particles include terephthalates such as calcium oxalate, calcium, barium, zinc, manganese, and magnesium.

Examples of the crosslinked polymer particles include homo- or copolymers of divinylbenzene, styrene, acrylic acid, methacrylic acid, vinyl monomers of acrylic acid or methacrylic acid. In addition, polytetrafluoroethylene, benzoguanamine resin, thermosetting epoxy resin,
Heat-resistant organic particles such as an unsaturated polyester resin, a thermosetting urea resin, and a thermosetting phenol resin may be used.

The method for incorporating the inert particles into the polyester serving as the base film is not particularly limited.
(A) a method in which inert particles are dispersed in a slurry state in a diol that is a polyester component, and the inert particle slurry is added to a polyester polymerization reaction system; (b) a vent method in a melt extrusion process of a polyester film. Examples thereof include a method of adding a water slurry of inert particles dispersed in a molten polyester resin using a twin-screw extruder, and a method (c) of kneading the polyester resin and the inert particles in a molten state.

In the case of adding to a polymerization reaction system, it is preferable to add a diol slurry of inert particles to a reaction system having a low melt viscosity before the esterification reaction or transesterification reaction and before the start of the polycondensation reaction. When preparing a diol slurry of inert particles, it is preferable to perform a physical dispersion treatment such as a high-pressure disperser, a bead mill, or ultrasonic dispersion. Further, in order to stabilize the slurry subjected to the dispersion treatment, it is preferable to use an appropriate chemical dispersion stabilization treatment in accordance with the type of particles used.

In the dispersion stabilization treatment, for example, in the case of inorganic oxide particles or crosslinked polymer particles having a carboxyl group on the particle surface, an alkali compound such as sodium hydroxide, potassium hydroxide, lithium hydroxide or the like is used as a slurry. And re-aggregation between particles can be suppressed by electric repulsion. In the case of calcium carbonate particles or hydroxyapatite particles, it is preferable to add sodium tripolyphosphate or potassium tripolyphosphate to the slurry.

In addition, when the diol slurry of inert particles is added to the polyester polymerization reaction system, the slurry may be heated to near the boiling point of the diol, or may be subjected to heat shock (slurry and polymerization reaction) when added to the polymerization reaction system. (Temperature difference from the system) can be reduced, which is preferable in terms of particle dispersibility.

These additives can be added during or after the polymerization of the polyester or at any stage after the formation of the polyester film. The suitable stage depends on the properties of the compound and the requirements of the polyester film. They differ depending on the performance.

The polyester film of the present invention can be formed by a known film forming method. As a film forming method, a biaxial stretching method such as a uniaxial stretching method for stretching an unstretched film in a longitudinal direction or a transverse direction, an inflation method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, and then a heat fixing treatment Can be used. For example, as the sequential biaxial stretching method, in addition to the method of sequentially performing longitudinal stretching and transverse stretching or transverse stretching and longitudinal stretching, a horizontal-longitudinal-longitudinal stretching method, a vertical-horizontal-longitudinal stretching method,
A stretching method such as a longitudinal-longitudinal-lateral stretching method can be employed. As the simultaneous biaxial stretching method, a conventional simultaneous biaxial stretching method may be used, but a novel simultaneous biaxial stretching method driven by a linear motor system is preferred. Note that simultaneous biaxial stretching may be performed in multiple stages. Further, in order to further reduce the heat shrinkage, a vertical relaxation process, a horizontal relaxation process, or the like may be performed as necessary.

In order to reduce the heat shrinkage, it is preferable not only to optimize the temperature and time during the heat setting treatment, but also to perform the longitudinal relaxation treatment at a temperature lower than the maximum temperature of the heat setting treatment.

[0226]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The construction and effects of the present invention will be described below based on embodiments, but the present invention is not limited to these embodiments.

[Evaluation Method] 1) Intrinsic Viscosity (IV) Polyester was dissolved in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane in a 6/4 (weight ratio) solvent and heated at a temperature of 30 ° C. It was measured.

2) Thermal stability parameter (TS) The melt-polymerized IV was about 0.65 dl / g (before the melt test;
[IV] 1 g of PET resin chip of i)
m, placed in a glass test tube, vacuum-dried at 130 ° C. for 12 hours, set in a vacuum line, and repeatedly vacuumed and filled with nitrogen five times or more, sealed with 100 mmHg of nitrogen, and sealed.
After being immersed in a salt bath at 300 ° C. and maintained in a molten state for 2 hours or more, a sample is taken out, freeze-pulverized and vacuum-dried, and IV (after the melting test; IV) f2) is measured. I asked. The formula was quoted from a previous report (Kamiyama et al .: The Society of Rubber Industry, Japan, Vol. 63, No. 8, p. 497, 1990). TS = 0.245 × ([IV] f2 ^-1.47- [IV] i
^-1.47 )

3) Thermal Oxidation Stability Parameter (TOS) A melt-polymerized PET resin chip having an IV of about 0.65 dl / g was freeze-pulverized to a powder of 20 mesh or less, which was vacuum-dried at 130 ° C. for 12 hours. 300 mg was placed in a glass test tube having an inner diameter of about 8 mm and a length of about 140 mm.
After vacuum drying at 0 ° C. for 12 hours, a drying tube containing silica gel was placed on the upper portion of the test tube, and dried under air at 230 ° C.
IV after being immersed in a salt bath and heated for 15 minutes, was determined using the same formula as that for TS described above. Here, [IV] i and [IV] f1 indicate the IV (dl / g) before and after the heating test, respectively. For freezing and pulverization, use a freezer mill (Type 6750 manufactured by Spex, USA)
This was performed using After putting about 2 g of resin chip and dedicated impactor in the dedicated cell, set the cell in the device, fill the device with liquid nitrogen and hold for about 10 minutes, then
Milling was performed for 5 minutes with ATE10 (impacter moves around 20 times per second). TOS = 0.245 × ([IV] f1 ^-1.47- [IV] i
^-1.47 )

4) Hydrolysis resistance parameter (HS) The intrinsic viscosity obtained by melt polymerization is about 0.65 dl / g.
(Before the test; the PET resin chip of [IV] i) was frozen and pulverized in the same manner as in 3) to obtain a powder having a size of 20 mesh or less, which was vacuum-dried at 130 ° C. for 12 hours. The hydrolysis test was performed using a mini color device (TypeMC12.EL manufactured by Texam Giken Co., Ltd.).
B). 1 g of the above-mentioned powder was put into a special stainless beaker together with 100 ml of pure water, a special stirring blade was further put therein, and a closed system was set.
The mixture was stirred for 6 hours while heating and pressurizing to 30 ° C. The PET after the test was collected by filtration with a glass filter, dried under vacuum, and then measured for IV ([IV] f2), and the hydrolysis resistance parameter (HS) was determined by the following equation. HS = 0.245 × ([IV] f2 ^-1.47- [IV] i
^-1.47 )

5) Color delta b value parameter (Δ
b) When a predetermined stirring torque was reached in the melt polymerization, nitrogen was introduced into the autoclave to return to normal pressure, and the polycondensation reaction was stopped. Thereafter, the polymer was discharged into cold water in the form of strands under slight pressure and rapidly cooled. After that, the polymer was held in cold water for about 20 seconds and then cut to obtain a cylindrical resin tip having a length of about 3 mm and a diameter of about 2 mm. The resin chip thus obtained was air-dried on a filter paper at room temperature for about 24 hours, and then used for color measurement. The color measurement was performed using a PET resin chip having an IV of about 0.65 dl / g obtained by melt polymerization using a color difference meter (MODEL TC-150 manufactured by Tokyo Denshoku Co., Ltd.).
0MC-88) was used to measure the b value of the Hunter, and b of PET polymerized using 0.05 mol% of antimony trioxide as an antimony atom with respect to the acid component of PET.
It was obtained by subtracting the value.

6) Solution Haze Value (Haze) A melt-polymerized PET resin chip having an IV of about 0.65 dl / g was mixed with a 3/1 mixed solvent of p-chlorophenol / 1,1,2,2-tetrachloroethane (weight Ratio) to give a solution of 8 g / 100 ml, and measured at room temperature using a turbidity meter NDH2000 of Nippon Denshoku Industries Co., Ltd. The measuring method is based on JIS standard JIS-K7105, and the cell length is 1 cm.
The diffused transmitted light (DF) and the total light transmitted light (TT) of the solution were measured using the cell No. 2, and the solution haze value (Haze) was obtained from the following formula. Haze (%) = (DF / TT) × 100

7) Thermal Stability of Film (a) Film Formation The PET resin chips obtained by melt polymerization in each of the following Examples and Comparative Examples were vacuum dried at 135 ° C. for 6 hours. Thereafter, the mixture is fed to an extruder, melted at a set temperature of 280 ° C., and continuously filtered using a fiber type filter capable of removing 95% of 10 μm particles and a sintered type filter capable of removing 95% of 4 μm particles. Then, the mixture was melt-extruded into a sheet and quenched and solidified on a metal roll maintained at a surface temperature of 20 ° C. to obtain a cast film having a thickness of 2700 μm. In addition, the residence time in extrusion was 15 minutes.

Next, the temperature of the cast film was increased to 75 ° C. by a heated roll group, further increased to 95 ° C. by an infrared heater having a surface temperature of 750 ° C. from the vertical direction, and thereafter, a roll group having a peripheral speed difference was obtained. Was stretched 3.5 times in the longitudinal direction to obtain a uniaxially oriented PET film. Subsequently, the film was stretched 4.0 times in the width direction while increasing the temperature from 100 ° C. to 130 ° C. with a tenter, and the film width was fixed.
Heated at 30 ° C. for 30 seconds. 200 to 150 ° C
3% relaxation treatment in the width direction while cooling to
A 00 μm biaxially oriented PET film was obtained. 2 consecutive
The properties were evaluated using the film after the film was formed for 0 hours.

(B) Film Formation from Collected Pellets The PET film obtained by the method described in the above (a) is cut into strips, dried in a vacuum, put into an extruder, and melted at a temperature set at 280 ° C. After extruding the resin from a nozzle having a diameter of 5 mm, the resin was cooled and cut with water to obtain a recovered pellet.

The PET resin chips obtained by melt polymerization and the above-mentioned recovered pellets were mixed at a weight ratio of 50:50,
Vacuum dried at 35 ° C. for 6 hours. Thereafter, the mixture is fed to an extruder and melted at a set temperature of 280 ° C.
% And a sintered type filter capable of removing 95% of 4 μm particles are filtered, melt-extruded into a sheet, and placed on a metal roll maintained at a surface temperature of 20 ° C. It was quenched and solidified to obtain a cast film having a thickness of 2700 μm. In addition, the residence time in extrusion was 15 minutes.

Next, the temperature of the cast film was raised to 75 ° C. by a heated roll group, further raised to 95 ° C. by an infrared heater having a surface temperature of 750 ° C. from above and below, and then a roll group having a peripheral speed difference was obtained. Was stretched 3.5 times in the longitudinal direction to obtain a uniaxially oriented PET film. Subsequently, the film was stretched 4.0 times in the width direction while increasing the temperature from 100 ° C. to 130 ° C. with a tenter, and the film width was fixed.
Heated at 30 ° C. for 30 seconds. 200 to 150 ° C
3% relaxation treatment in the width direction while cooling to
A 00 μm biaxially oriented PET film was obtained. 2 consecutive
The properties were evaluated using the film after the film was formed for 0 hours.

(C) Evaluation of Thermal Stability of Film The appearance of the obtained film was visually observed, and depending on the degree of coloring of the film, the higher the intrinsic viscosity retention ratio and the less the coloring, the better the evaluation.

8) Heat aging resistance of the film The film obtained by the method (a) of the above 7) was treated with a length of 1
Cut out into test pieces of 0 cm and 5 cm in width, put the test pieces in a gear-type hot-air dryer, and treat them at 200 ° C for 100 hours. The better.

9) Film Water Resistance The film obtained by the above-mentioned method (7) (a) was cut into a test piece having a length of 8 cm and a width of 4 cm, and the test piece was boiled in boiling water for 5 days. The boiled film test piece was pulled in the length direction and evaluated for its easiness to cut.

10) Evaluation of Film Coloring The appearance of the film obtained by the method described in 7) (a) was visually observed to evaluate the degree of coloring. The evaluation results indicated that those with little coloring were good.

11) Presence or absence of Sb particles in the film 40 g of the polyester film obtained by the method described in (a) of 7) above was mixed with a mixed solvent of parachlorophenol and tetrachloroethane (weight ratio of 75/25). Dissolve,
The solution was filtered through a polytetrafluoroethylene membrane filter having an average pore diameter of 0.1 μm. After vacuum drying the residue on the membrane filter, particles trapped on the filter were observed with a scanning electron microscope, and the presence or absence of the Sb element was confirmed with an energy dispersive X-ray microanalyzer (EMAX2770, manufactured by Horiba, Ltd.). .

12) Foreign matter on the film surface The surface of the film obtained by the method described in 7) (a) above was magnified with a microscope and visually observed. The smaller the amount of foreign matter, the better the evaluation.

13) Film Defects The film obtained by the method described in 7) (a) above was sandwiched between two orthogonal polarizing plates, and light from a fluorescent lamp was passed from below to visually observe the area of 1 m ^2. , Marked a small shining defect. The marked defects were magnified by a stereoscopic microscope, and the number of defects having a maximum defect diameter of 50 μm or more was determined. The smaller the number of defects, the better. In Table 1, ○ indicates that the results were good, and △ indicates
Slightly bad, x means bad.

[Examples of Polyester Synthesis] (Example 1) A mixture of bis (2-hydroxyethyl) terephthalate and an oligomer produced from high-purity terephthalic acid and ethylene glycol according to a conventional method was used.
As a polycondensation catalyst, a solution of aluminum acetylacetonate in 2.5 g / l ethylene glycol was added to the acid component in the polyester in an amount of 0.015 as an aluminum atom.
mol% and Irganox 1425 (manufactured by Ciba Specialty Chemicals) in a 10 g / l ethylene glycol solution were added to the acid component at 0.01 mol% as Irganox 1425, and the mixture was added under nitrogen atmosphere at normal pressure.
Stirred at 45 ° C. for 10 minutes. Then take 50 minutes to get 2
While raising the temperature to 75 ° C, gradually lower the pressure of the reaction system to 1
Further at 275 ° C. at 3.3 Pa (0.1 Torr),
The polycondensation reaction was performed at 13.3 Pa.

When the IV of polyethylene terephthalate is 0.
Polymerization time required to reach 65 dl / g (AP)
Was 86 minutes, and the polycondensation catalyst had a practical polymerization activity.

Further, polyethylene terephthalate having an IV of 0.65 dl / g obtained by the above polycondensation was formed into chips according to a conventional method. A melting test was performed using this PET resin chip to determine a thermal stability parameter (TS). TS was 0.18, and the thermal stability was good.

The chipped PET resin was pulverized according to a conventional method, and a heating test was performed using the powder to determine a thermal oxidation stability parameter (TOS). The TOS is 0.01 or less, and the PE obtained by using the polycondensation catalyst of the present invention.
T was also excellent in thermal oxidation stability.

The chipped PET resin was pulverized according to a conventional method, and a hydrolysis test was performed using the powder to determine a hydrolysis resistance parameter (HS). HS was 0.05, and PET obtained by using the polycondensation catalyst of the present invention was also excellent in hydrolysis resistance.

The color b value was determined using the PET resin chipped. The color b value is 4.4,
As described in Comparative Example 1, the b value of the PET resin chip polymerized with antimony trioxide as a catalyst was 1.1, and thus Δb was 3.3. A solution haze value (Haze) was determined using the PET resin chipped. Ha
ze was 0.1%.

Using PET resin chips obtained by melt polymerization, the method described in 7) (a) and (b) above was used.
A film was formed, a recovered pellet was formed, and a film was formed from the recovered pellet. Table 1 shows the results of the evaluation of the defects and thermal stability of the film. The film formed using PET obtained by using the polycondensation catalyst of the present invention was excellent without any problem in film defects and thermal stability. Further, the darkening of the film was also improved as compared with the case where a polyester produced using conventional antimony trioxide as a polycondensation catalyst was used as a film raw material.

Example 2 As a catalyst, a 2.5 g / l solution of aluminum acetylacetonate in ethylene glycol was added in an amount of 0.015 mol% as an aluminum atom with respect to the acid component in the polyester and cobalt acetate (I).
I) 20 g / l ethylene glycol solution of tetrahydrate is 0.005 mol% as a cobalt atom with respect to an acid component.
Except for the addition, the same operation as in Example 1 was performed. Similar to Example 1, the darkening of the obtained film was improved as compared with the case where a polyester produced using conventional antimony trioxide as a polymerization catalyst was used as a film raw material.
Other results are shown in Table 1.

Example 3 As a catalyst, a solution of 2.5 g / l of aluminum acetylacetonate in ethylene glycol was added at 0.01 mol% as aluminum atoms with respect to the acid component in the polyester and 50 g / l of lithium acetate dihydrate. The same operation as in Example 1 was performed except that 1 mol of an ethylene glycol solution was added as a lithium atom to the acid component at 0.1 mol%. Similar to Example 1, the darkening of the obtained film was improved as compared with the case where a polyester produced using conventional antimony trioxide as a polymerization catalyst was used as a film raw material. Other results are shown in Table 1.

(Comparative Example 1) The same operation as in Example 1 was carried out except that antimony trioxide was used as a catalyst such that the addition amount was 0.05 mol% as antimony atoms with respect to the acid component in PET. went. As antimony trioxide, commercially available Antimony (III) oxide (ALDRICH CHEMICAL
(Purity: 99.999%). As antimony trioxide, a solution was used which was dissolved in ethylene glycol by stirring at 150 ° C. for about 1 hour so that the concentration became about 10 g / l. Particles containing Sb as a main component were detected in the obtained film, and compared with the film of the above example,
Darkening was observed in the film.

[0255]

[Table 1]

[0256]

According to the present invention, a polyester which is excellent in heat stability and color tone and free from foreign matter caused by metal antimony particles without using an antimony compound or a germanium compound as a main component of a polyester polycondensation catalyst. Films can be manufactured at low cost. For this reason, various films such as packaging films, industrial films, optical films, magnetic tape films, photographic films, can laminate films, contensor films, heat shrink films, gas barrier films, white films, easy-cut films, etc. Ideal for film applications.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Takahiro Nakajima 2-1-1 Katada, Otsu-shi, Shiga F-term in Toyobo Co., Ltd. Research Laboratory 4F071 AA44 AA46 AF30 AF45 AH04 AH12 AH14 BA01 BB06 BB07 BB08 BB09 BC01 4J029 AA03 AB07 AC01 AC02 AD01 AD10 AE03 BA03 BA04 BA05 CB06A CC05A JA061 JA091 JA121 JA261 JB131 JB151 JB171 JC551 JC561 JC571 JC751 JF011 JF021 JF031 JF041 JF111 JF171 JF221 JF361 KB

Claims (18)

[Claims] 1. A method for producing a polyester film, comprising using a polyester polymerized by using at least one selected from the group consisting of aluminum and its compounds as a catalyst as a main raw material in producing the film. 2. The thermal stability parameter (T.sub.T) of polyethylene terephthalate polymerized using at least one selected from the group consisting of aluminum and its compounds as a catalyst.
The method for producing a polyester film according to claim 1, wherein S) satisfies the following formula (1). (1) TS <0.30 (In the above formula, TS is a melt-polymerized polyethylene terephthalate (P) having an intrinsic viscosity (IV) of about 0.65 dl / g.
ET) 1 g of resin chip was placed in a glass test tube,
After vacuum drying at 12 ° C. for 12 hours,
It can be obtained from the IV after maintaining the molten state at 00 ° C. for 2 hours using the following formula. TS = 0.245 × ([IV] f2 ^-1.47- [IV] i
^-1.47 ) [IV] i and [IV] f2 indicate the IV (dl / g) before and after the melting test, respectively. ) 3. An activity parameter (A) for polymerizing polyethylene terephthalate using at least one selected from the group consisting of aluminum and its compounds as a catalyst.
3. The method for producing a polyester film according to claim 1, wherein P) satisfies the following formula (2). (2) AP (min) <2T (min) (In the above formula, the activity parameter AP is such that the intrinsic viscosity (IV) is 275 ° C. under a reduced pressure of 13.3 Pa (0.1 Torr) using a predetermined amount of catalyst. Time required to polymerize 0.65 dl / g of polyethylene terephthalate (min)
Is shown. T indicates AP when antimony trioxide is used as a catalyst. However, antimony trioxide is added in an amount of 0.05 mol% as antimony atoms to the acid component in the produced polyethylene terephthalate. ) 4. A thermal oxidative stability parameter (TOS) of polyethylene terephthalate polymerized using at least one selected from the group consisting of aluminum and its compounds as a catalyst, satisfies the following formula (3). The method for producing a polyester film according to claim 1. (3) TOS <0.10 (wherein TOS has a melt-polymerized IV of about 0.65
A dl / g PET resin chip was freeze-pulverized to a powder having a size of 20 mesh or less, which was vacuum-dried at 130 ° C. for 12 hours, and 0.3 g was placed in a glass test tube.
After vacuum drying for 2 hours, and heating at 230 ° C. for 15 minutes under air dried with silica gel, it can be obtained by the following formula from IV. TOS = 0.245 × ([IV] f1 ^-1.47- [IV] i
^-1.47 ) [IV] i and [IV] f1 respectively indicate the IV (dl / g) before and after the heating test. ) 5. A hydrolysis resistance parameter (HS) of polyethylene terephthalate polymerized using at least one selected from the group consisting of aluminum and its compounds as a catalyst, satisfies the following formula (4). The method for producing a polyester film according to claim 1. (4) HS <0.10 (HS has an intrinsic viscosity of about 0.65 obtained by melt polymerization.
dl / g PET chips were freeze-pulverized to powder having a size of 20 mesh or less. The powder was vacuum-dried at 130 ° C. for 12 hours. 1 g of the dried powder was placed in a beaker together with 100 ml of pure water. It is a numerical value calculated from the intrinsic viscosity ([IV] f2) after stirring for 6 hours under pressurized conditions by the following formula. HS = 0.245 × ([IV] f2 ^-1.47- [IV] i
^-1.47 ) [IV] i indicates the IV (dl / g) before the heating test. ) 6. The color delta b value parameter (Δb) of polyethylene terephthalate polymerized by using at least one selected from the group consisting of aluminum and its compounds as a catalyst, satisfies the following formula (5). The method for producing a polyester film according to claim 1. (5) Δb <4.0 (In the above formula, Δb is a value obtained by using a color difference meter by using a polyethylene terephthalate (PET) resin chip having an intrinsic viscosity of about 0.65 dl / g melt-polymerized using a predetermined catalyst. The value obtained by subtracting the b value when antimony trioxide is used as a catalyst from the b value of the hunter measured by the above method is shown.
Antimony trioxide is 0.05 mol as antimony atom based on the acid component in the formed polyethylene terephthalate.
%Added. ) 7. A solution haze value (Haze) of polyethylene terephthalate polymerized using at least one selected from the group consisting of aluminum and its compounds as a catalyst.
Satisfies the following expression (6).
7. The method for producing a polyester film according to any one of items 6 to 6. (6) Haze <3.0 (%) (In the above formula, Haze is a melt-polymerized polyethylene terephthalate (PE) having an intrinsic viscosity of about 0.65 dl / g.
T) Resin chips were p-chlorophenol / 1,1,1
The value obtained by dissolving in a 3/1 mixed solvent (weight ratio) of 2,2-tetrachloroethane to obtain a solution of 8 g / 100 ml and using a haze meter is shown. ) 8. The method for producing a polyester film according to claim 1, wherein the catalyst does not contain an alkali metal, an alkaline earth metal, or a compound thereof. 9. The catalyst according to claim 1, wherein the catalyst includes at least one kind of a second metal-containing component selected from the group consisting of an alkali metal, an alkaline earth metal, and a compound thereof. 8. The method for producing a polyester film according to any one of 7. 10. The method according to claim 9, wherein the second metal-containing component is an alkali metal or a compound thereof. 11. The method according to claim 11, wherein the alkali metal is Li, Na, K.
The method for producing a polyester film according to claim 10, wherein the polyester film is at least one selected from the group consisting of: 12. An amount M (mol%) of the second metal-containing component relative to all carboxylic acid components constituting the polyester satisfies the formula (7).
12. The method for producing a polyester film according to any one of items 11 to 11. (7) M ≦ 0.05 13. The method for producing a polyester film according to claim 1, wherein the catalyst coexists with a cobalt compound. 14. The method for producing a polyester film according to claim 1, wherein the catalyst coexists with at least one selected from phosphorus compounds. 15. The method for producing a polyester film according to claim 1, wherein the catalyst coexists with at least one of an antimony compound and a germanium compound. 16. The residual amount of the antimony compound remaining in the polyester is 50 pp as an antimony atom.
The method for producing a polyester film according to claim 15, wherein the amount is not more than m. 17. The polyester film according to claim 15, wherein the remaining amount of the germanium compound remaining in the polyester is 30 ppm or less of germanium atoms relative to the polyester. Production method. 18. A polyester film produced by the production method according to claim 1. Description: