JP2002322259A - Polyester, blow molded product and sheetlike material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester produced by using a new polyester polymerization catalyst other than an antimony compound. SOLUTION: This polyester is characterized in that the polyester contains ethylene terephthalate as a repeating unit and is synthesized by using a catalyst comprising at least either one of aluminum or an aluminum compound and a phenolic compound and has <=0.5 wt.% cyclic trimer content.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester polymerized by using a polyester polymerization catalyst, and a hollow molded article and a sheet-like substance produced by using the polyester. The present invention relates to a polyester polymerized using a novel polyester polymerization catalyst not using as a catalyst main component, and a hollow molded article and a sheet-like substance produced using the polyester.

[0002]

2. Description of the Related Art Polyethylene terephthalate (PE)
T), polyesters represented by polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc. are excellent in mechanical properties and chemical properties, and depending on the properties of each polyester, hollow polyester such as bottles It is used in a wide range of fields such as molded articles, films for packaging and magnetic tapes, sheets for packaging, and molding materials for electric and electronic parts.

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

Polyethylene terephthalate has been used as a material for containers such as carbonated beverages, juices and mineral water because of its excellent transparency, mechanical strength, heat resistance, gas barrier properties and the like, and its use has been remarkable. .

[0005] In these applications, polyester bottles are hot-filled with beverages sterilized at a high temperature, and beverages are sterilized at a high temperature after filling the bottles. Shrinkage and deformation occur, which causes problems. As a method for improving the heat resistance of the polyester bottle, a method has been proposed in which the crystallinity is increased by heat-treating the bottle cap portion, or the stretched bottle is heat-fixed. In particular, if the plug portion is insufficiently crystallized or has a large variation in crystallinity, the sealing performance with the cap is deteriorated, and the contents may leak.

In the case of beverages that require hot filling, such as fruit juice beverages, oolong tea, and mineral water, a method of crystallizing a preform or a molded bottle by heat-treating the plug portion (Japanese Patent Application Laid-Open No. H10-163191). Methods described in JP-A-55-79237, JP-A-58-110221, etc.) are generally used. Such a method, that is, a method of improving the heat resistance by heat treatment of the plug portion and the shoulder portion, the time and temperature for the crystallization treatment greatly affect the productivity, and the crystal can be processed at a low temperature and in a short time. It is preferable that the PET is a PET having a high conversion rate. On the other hand, the body is required to be transparent even when subjected to a heat treatment at the time of molding so as not to deteriorate the color tone of the contents of the bottle, and the plug and the body need to have contradictory characteristics.

Further, in order to improve the heat resistance of the body of the bottle, for example, as described in Japanese Patent Publication No. 59-6216, a method of performing heat treatment by setting the temperature of a stretch blow mold to a high temperature is adopted. However, when a large number of bottles are continuously formed using the same mold by such a method, the bottle obtained with a long operation is whitened, the transparency is reduced, and only a bottle having no commercial value can be obtained. . It was found that this was due to the attachment of the PET-derived material to the mold surface, resulting in mold stains, and the mold stains being transferred to the bottle surface. In particular, in recent years, the molding speed has been increased along with the miniaturization of bottles, and from the viewpoint of productivity, the shortening of the heating time for crystallization of the plug and the contamination of the mold have become more serious problems. .

Further, when a large number of bottles are continuously formed using the same mold by such a heat treatment method, the bottle obtained with a long-time operation is whitened and the transparency is reduced.
Only bottles without commercial value can be obtained. It has been found that this is because deposits due to the PET resin are attached to the mold surface, resulting in mold stains, and the mold stains are transferred to the surface of the bottle. In particular, in recent years, the molding speed has been increased along with the miniaturization of bottles, and mold contamination has become a bigger problem from the viewpoint of productivity.

[0009] PET generally used for such applications
Is produced mainly using terephthalic acid and ethylene glycol as raw materials, and using an antimony compound, a titanium compound, a germanium compound and a mixture thereof as a polycondensation catalyst.

[0010] Among the catalysts, antimony catalysts are inexpensive,
It is a catalyst with excellent catalytic activity.However, if this is used as the main component, that is, in an amount that is sufficient to exhibit a practical polymerization rate, metal antimony precipitates during polycondensation, so that the polyester becomes darkened. And a foreign substance are generated, and a crystallization rate of the obtained PET is faster than that in a case where a germanium compound or a titanium compound is used as a catalyst, and a hollow molded body having excellent transparency, particularly a large hollow molded body, is obtained. Is very difficult.

Under such circumstances, polyesters containing no antimony or containing no antimony as a main component of the catalyst are desired.

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, Japanese Patent Application Laid-Open No. 6-279579 specifies the ratio of the amount of the antimony compound to the phosphorus compound used. Thus, a method for improving transparency is disclosed. 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 to 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 a titanium compound is used as a polycondensation catalyst, for example, in Japanese Patent Application Laid-Open No. 55-116722, a tetraalkoxy titanate is used simultaneously with a cobalt salt and a calcium salt. A method has been proposed. Also, JP-A-8-7
No. 3,581, 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 technologies, although the coloring of PET is reduced when tetraalkoxy titanate is used as a polycondensation catalyst, it has not been achieved to effectively suppress the thermal decomposition of PET.

As another attempt to suppress thermal degradation during melt molding of a polyester polymerized using a titanium compound as a catalyst, for example, JP-A-10-259296 discloses a method in which a polyester is polymerized using a titanium compound as a catalyst and then phosphorus is added. A method for adding a system compound is disclosed. However, it is not only technically difficult to effectively mix the additive into the polymer after polymerization, but also increases the cost and is not practically used.

It is known that aluminum compounds generally have poor catalytic activity. Among the aluminum compounds,
It has been reported that aluminum chelate compounds have higher catalytic activity as polycondensation catalysts than other aluminum compounds, but that they have sufficient catalytic activity compared to the above-mentioned antimony compounds and titanium compounds. In addition, there is a problem that the polyester which is polymerized for a long time using an aluminum compound as a catalyst has poor thermal stability.

A technique is also known in which an alkali metal compound is added to an aluminum compound to obtain a polyester polymerization catalyst having sufficient catalytic activity. Use of such a known catalyst can provide a polyester having excellent thermal stability.However, a catalyst using this alkali metal compound in combination requires a large amount of addition thereof in order to obtain practical catalytic activity.
As a result, at least one of the following problems occurs due to the alkali metal compound in the obtained polyester polymer. 1) The amount of foreign substances increases, and when used in a molded article, the generation of foreign substances becomes severe, and the transparency of the molded article decreases. 2) The hydrolysis resistance of the polyester polymer decreases, and the transparency decreases due to the generation of foreign substances. 3) Poor color tone of the polyester polymer, that is, a phenomenon in which the polymer is colored yellow occurs, and the color tone of the molded product deteriorates when used in a molded product. 4) The filter pressure at the time of melting and producing a molded article increases due to clogging of foreign matter, and the productivity also decreases.

Germanium compounds have already been put into practical use as catalysts which provide polyesters having excellent catalytic activity and not having the above-mentioned problems except for antimony compounds, but this catalyst is very expensive. And
Since it easily flows out of the reaction system during the polymerization, the catalyst concentration in the reaction system changes, which makes it difficult to control the polymerization, and there is a problem in using it as the main component of the catalyst.

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

As described above, a polymerization catalyst using a metal component other than antimony and germanium as a main metal component of the catalyst is used, has excellent catalytic activity, and hardly causes thermal deterioration during melt molding. Stability, (b)
There is a need for a polyester which is excellent in at least one of thermal oxidation stability and (c) hydrolysis resistance, and has a small amount of foreign matter and excellent transparency.

[0023]

SUMMARY OF THE INVENTION The present invention provides a polyester produced using a novel polyester polymerization catalyst other than an antimony compound, and a hollow molded article and a sheet-like material using the polyester. .

Further, the present invention provides a method for preparing a melt-forming material which does not contain an antimony compound or a germanium compound as a main component of a catalyst, uses aluminum as a main metal component, has excellent catalytic activity, and does not deactivate or remove the catalyst. The present invention provides a polyester which is effectively suppressed in thermal deterioration, has excellent thermal stability, has little foreign matter generation, has excellent transparency, and further has excellent color tone.

The present invention also has improved thermal stability, generation of foreign matter, and productivity when melt-molding a hollow molded article and a sheet-like material using the catalyst, and uses a virgin resin. Another object of the present invention is to provide a polyester capable of obtaining a product having excellent quality even if waste generated during molding is reused.

Another object of the present invention is to provide a catalyst which does not contain an antimony compound or a germanium compound as a main component, contains aluminum as a main metal component, has excellent catalytic activity, has a small decrease in intrinsic viscosity at the time of melt molding, and has no foreign matter. Provide polyester with low transparency. Further, the present invention provides a polyester which is less contaminated by oligomers of a molding die or a molding roll at the time of molding, and which has less off-flavor and odor when the molded product is used as a food or beverage container.

[0027] The present invention is also directed to a virgin resin using a virgin resin, in which the intrinsic viscosity of the hollow molded article and the sheet-like substance using the catalyst is not significantly reduced during melt molding, the generation of foreign substances and the productivity are improved. Another object of the present invention is to provide a polyester which can obtain a product having excellent quality even if waste generated during molding is reused.

[0028]

The polyester according to the present invention is a polyester containing ethylene terephthalate as a repeating unit, as defined in claim 1, wherein at least one of aluminum or an aluminum compound and phenol And a cyclic compound having a cyclic trimer content of 0.5% by mass or less.

The polyester according to the present invention is a polyester containing ethylene terephthalate as a repeating unit, wherein at least one of aluminum or an aluminum compound and a phosphorus compound are contained. It is a polyester characterized by containing and having a cyclic trimer content of 0.5% by mass or less.

Further, as described in claim 3, the polyester according to the present invention is a polyester in which, in the invention according to claim 1, a phosphorus compound is further used as the catalyst.

In the polyester according to the present invention, the phosphorus compound may be a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, or the like. Phosphonous acid compound, phosphinous acid compound, or
A polyester containing at least one of phosphine-based compounds.

The polyester according to the present invention is, as described in claim 5, in the invention according to any one of claims 2 to 4, wherein the phosphorus compound is represented by the following formulas (1) to (3):
It is a polyester characterized by including at least any one of the compounds represented by these.

[0033]

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[0034]

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[0035]

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(In the formulas (1) to (3), R ¹ , R ⁴ , R ⁵ ,
R ⁶ each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms including an amino group.
R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, 1 to 1 carbon atoms including a hydroxyl group or an alkoxyl group.
Represents 50 hydrocarbon groups. However, the hydrocarbon group may include an alicyclic structure or an aromatic ring structure. Further, the polyester according to the present invention, as described in claim 6, in the invention according to any one of claims 2 to 5,
The polyester, wherein the phosphorus compound contains at least one of a phosphorus acid and a metal salt compound.

Further, in the polyester according to the present invention, as described in claim 7, in the invention according to any one of claims 2 to 6, the phosphorus compound contains at least a portion represented by the following chemical formula (4). It is a polyester characterized by the following.

[0038]

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The polyester according to the present invention, when melted at a temperature of 290 ° C. for 30 minutes in the invention according to any one of claims 1 to 7, as described in claim 8,
A polyester characterized in that the amount of cyclic trimer increased is 0.50% by mass or less.

Further, the polyester according to the present invention is characterized in that, in the invention according to any one of claims 1 to 8, the acetaldehyde content in the polyester is 10 ppm or less. Polyester.

Further, the polyester according to the present invention, as described in claim 10, is the invention according to any one of claims 1 to 9, wherein the intrinsic viscosity of the polyester is 0.55.
It is a polyester characterized in that it is で あ 1.50 deciliter / gram.

Further, the polyester according to the present invention, as described in claim 11, is the invention according to any one of claims 1 to 10, wherein the polyester contains 95 mol% or more of ethylene terephthalate as a repeating unit. It is a polyester characterized by being a linear polyester.

Further, a hollow molded article according to the present invention is a hollow molded article obtained by molding the polyester according to any one of claims 1 to 11 as described in claim 12.

Further, the sheet-like substance according to the present invention is a sheet-like substance obtained by molding the polyester according to any one of claims 1 to 11 as described in claim 13.

[0045]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention provides a polyester produced using a novel polycondensation catalyst other than an antimony compound. The polycondensation catalyst used for producing the polyester according to the present invention is a polyester polymerization catalyst comprising an aluminum compound and a phosphorus compound or a phenolic compound, particularly a phosphorus compound having a phenol moiety in the same molecule. Here, a phosphorus compound having a phenol moiety in the same molecule means a phenol compound which is also a phosphorus compound.

The aluminum or aluminum compound constituting the polycondensation catalyst used for producing the polyester according to the present invention includes, in addition to metallic aluminum,
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. , Aluminum lactate,
Carboxylates such as aluminum citrate and aluminum salicylate; inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate and aluminum phosphonate; aluminum methoxide, aluminum ethoxide, and aluminum n -Aluminum chelates such as propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-butoxide, aluminum alkoxide, aluminum acetylacetonate, aluminum acetyl acetate, aluminum ethyl acetoacetate, aluminum ethyl acetoacetate diiso-propoxide and the like. Organic alcohols such as aluminum, trimethyl aluminum, and triethyl aluminum Onium compounds and these partial hydrolysates, such as aluminum oxide. Among these, carboxylate, inorganic acid salt and chelate compound are preferable, and among them, aluminum acetate,
Aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

The amount of the aluminum or aluminum compound to be used is preferably 0.001 to 0.05 mol% with respect to the total number of moles of all the constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. , More preferably 0.005 to 0.02 mol%
It is. If the amount is less than 0.001 mol%, the catalytic activity may not be sufficiently exhibited, and the amount may be 0.05%.
If it is at least mol%, thermal stability and thermal oxidation stability will decrease,
There is a case where the generation of foreign matters and the increase in coloring caused by aluminum become problems. As described above, the polymerization catalyst used in the present invention has a great feature in that it exhibits sufficient catalytic activity even when the addition amount of the aluminum component is small. As a result, thermal stability and thermal oxidation stability are excellent, and foreign matter and coloring due to aluminum are reduced.

The phenolic compound constituting the polycondensation catalyst used in the present invention is not particularly limited as long as it is a compound having a phenol structure.
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
-Tert-butylphenol, 2-tert-butyl-2-ethyl-6-tert-octylphenol, 2
-Isobutyl-4-ethyl-6-tert-hexylphenol, 2-cyclohexyl-4-n-butyl-6-
Isopropylphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,3-tris (2-
Methyl-4-hydroxy-5-tert-butylphenyl) butane, triethylene glycol-bis [3- (3
-Tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-
Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3- (3,5-di-tert-butyl-
4,4-hydroxyphenyl) propionate], N,
N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3,3
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-t
tert-butyl-4-methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-tert-butyl-4-
Hydroxybenzyl) benzene, 3,9-bis [1,1
-Dimethyl 2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy}
Ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2-
(3,5-di-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 and the like can be mentioned. 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-t)
tert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene-bis [3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate] is preferred.

The addition of these phenolic compounds during the polymerization of the copolymerized polyester improves the catalytic activity of the aluminum compound and also improves the thermal stability of the polymerized polyester.

The amount of the phenolic compound to be used is 5 × 10 ^{−7 to} 0. 01 mol is preferred,
More preferably, it is 1 × 10 ^{−6 to} 0.005 mol. In the present invention, a phosphorus compound may be used together with the phenolic compound.

Further, the phenol compound is preferably a phosphorus compound. Here, that the phenol compound is a phosphorus compound means a phosphorus compound having a phenol moiety in the same molecule.

The phosphorus compound constituting the polycondensation catalyst used in the present invention is not particularly limited. The use of one or two or more compounds selected from the group consisting of compounds and phosphine compounds is preferred because the effect of improving the catalytic activity is large. Among these, the use of one or two or more phosphonic acid compounds is particularly preferable because the effect of improving the catalytic activity is particularly large.

The phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds are represented by the following formulas (5) to (10), respectively. Refers to a compound having the structure shown below.

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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Examples of the phosphonic acid compounds include, for example,
Examples include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, and the like. Examples of the phosphinic acid-based compound include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, and phenyl phenylphosphinate. Examples of the phosphine oxide-based compound include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide. Among phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds, compounds represented by the following formulas (11) to (16) are used as phosphorus compounds. Is preferred.

[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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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.

The phosphorus compounds constituting the polycondensation catalyst used in the present invention include the following general formulas (17) to (1)
The use of the compound represented by 9) is particularly preferable because the effect of improving the catalytic activity is large.

[0070]

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[0071]

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[0072]

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(In the formulas (17) to (19), R ¹ , R ⁴ , R
⁵ and R ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group or an amino group. 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. However, the hydrocarbon group may include an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. As the phosphorus compound constituting the polycondensation catalyst used in the present invention, R ¹ , R ⁴ ,
Compounds in which R ⁵ and R ⁶ are groups having an aromatic ring structure are particularly preferred.

The phosphorus compounds constituting the polycondensation catalyst used in the present invention include, for example, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, Diethyl benzylphosphonate, diphenylphosphinic acid,
Examples thereof include methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate, diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide. Of these, dimethyl phenylphosphonate and diethyl benzylphosphonate are particularly preferred.

The amount of the phosphorus compound used is 5 × 10 5 moles per mole of all the constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester.
^{-7 to} 0.01 mol, 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 used in the present invention is not particularly limited as long as it is a phosphorus compound having a phenol structure. Have,
The use of one or more compounds selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds improves the catalytic activity. The effect is large and preferable. 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 used in the present invention, when compounds represented by the following general formulas (20) to (22) are used, the catalyst is particularly preferable. It is preferable because the activity is improved.

[0078]

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[0079]

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[0080]

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(In the formulas (20) to (22), R¹Is pheno
A hydrocarbon group having 1 to 50 carbon atoms,
Is a halogen group, alkoxyl group, amino group, etc.
Having 1 to 50 carbon atoms including a substituent and a phenol moiety
Represents a hydride group. R^Four, R^Five, R ⁶Are each independently water
Element, hydrocarbon group having 1 to 50 carbon atoms, hydroxyl group or halogen
Substituents such as an alkoxy group, an alkoxyl group, or an amino group
And a hydrocarbon group having 1 to 50 carbon atoms. R^Two, R^ThreeIs
Each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, water
1 carbon atom containing a substituent such as an acid group or an alkoxyl group
Represents up to 50 hydrocarbon groups. However, the hydrocarbon group is branched
Structure, alicyclic structure such as cyclohexyl, phenyl or naph
It may contain an aromatic ring structure such as chill. R^TwoAnd R^Fourof
The ends may be linked. ) As a phosphorus compound having a phenol moiety in the same molecule
Is, for example, p-hydroxyphenylphosphonic acid, p
-Dimethyl hydroxyphenylphosphonate, p-hydro
Diethyl xyphenylphosphonate, p-hydroxyphen
Diphenylylphosphonate, bis (p-hydroxyphene)
Nyl) phosphinic acid, bis (p-hydroxyphenyl)
Methyl phosphinate, bis (p-hydroxyphenyl)
Phenyl phosphinate, p-hydroxyphenylphenyi
Ruphosphinic acid, p-hydroxyphenylphenylphosph
Methyl finate, p-hydroxyphenylphenylphos
Phenyl finate, p-hydroxyphenylphosphine
Acid, methyl p-hydroxyphenylphosphinate, p-
Phenyl hydroxyphenylphosphinate, bis (p-
Hydroxyphenyl) phosphine oxide, Tris
(P-hydroxyphenyl) phosphine oxide,
S- (p-hydroxyphenyl) methylphosphine oxa
And compounds represented by the following formulas (23) to (26)
Things. Among these, the following equation (25)
A compound represented by the formula: and p-hydroxyphenylphospho
Dimethyl phosphate is particularly preferred.

[0082]

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[0083]

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[0084]

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[0085]

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The compound represented by the above formula (25) includes SANKO-220 (manufactured by Sanko Co., Ltd.).
Can be used.

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

The amount of the phosphorus compound having a phenol moiety in the same molecule may be 5 × 10 ^{-7 based on} the total number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. It is preferably from 0.01 to 0.01 mol, more preferably from 1 × 10 ^{−6 to} 0.005 mol.

In the present invention, it is preferable to use a metal salt compound of phosphorus as the phosphorus compound. The metal salt compound of phosphorus, which is a preferred phosphorus compound constituting the polymerization catalyst used in the present invention, is not particularly limited as long as it is a metal salt of a phosphorus compound. The effect of improvement is preferable. Examples of the metal salt of a phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.

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

As the metal salt compound of phosphorus constituting the polymerization catalyst used in the present invention, it is preferable to use at least one selected from compounds represented by the following general formula (27) because the effect of improving the catalytic activity is large. .

[0092]

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(In the formula (27), 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 represents 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, carbon number 1-50
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, and l +
m is 4 or less. M represents a (l + m) -valent metal cation. n represents an integer of 1 or more. The hydrocarbon group may include an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. As the above R ¹ , for example, phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl,
2-biphenyl and the like. Examples of R ² include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, te
rt-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, substituted phenyl group or naphthyl group, —CH ₂ C
And a group represented by H ₂ OH. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion.

Among the compounds represented by the general formula (27), it is preferable to use at least one selected from the compounds represented by the following general formula (28).

[0095]

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(In the formula (28), 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 ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation. The hydrocarbon group may include an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. As the above R ¹ , for example, phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl,
2-biphenyl and the like. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion.

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

In the above formula (28), M is Li, N
a, K, Be, Mg, Sr, Ba, Mn, Ni, Cu,
It is preferable to use a material selected from Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, and Mg are particularly preferred.

Examples of the metal salt compound of phosphorus include lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [(1-naphthyl) methylphosphonate], potassium [ Ethyl (2-naphthyl) methylphosphonate], magnesium bis [(2-naphthyl) methylphosphonate], lithium [ethyl benzylphosphonate], sodium [ethyl benzylphosphonate], magnesium bis [ethyl benzylphosphonate], beryllium bis [Ethyl benzyl phosphonate], strontium bis [ethyl benzyl phosphonate], manganese bis [ethyl benzyl phosphonate], sodium benzyl phosphonate, magnesium bis [benzyl phosphonate],
Sodium [ethyl (9-anthryl) methyl phosphonate], magnesium bis [(9-anthryl) methyl phosphonate], sodium [ethyl 4-hydroxybenzyl phosphonate], magnesium bis [ethyl 4-hydroxybenzyl phosphonate], sodium [ Phenyl 4-chlorobenzylphosphonate, magnesium bis [ethyl 4-chlorobenzylphosphonate], sodium [methyl 4-aminobenzylphosphonate], magnesium bis [methyl 4-aminobenzylphosphonate], sodium phenylphosphonate, magnesium Examples include bis [ethyl phenylphosphonate] and zinc bis [ethyl phenylphosphonate]. Among these, lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [(1-naphthyl) methylphosphonate], lithium [ethyl benzylphosphonate], Sodium [ethyl benzylphosphonate], magnesium bis [ethyl benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonic acid]
Is particularly preferred.

Another preferred phosphorus compound constituting the polymerization catalyst used in the present invention, that is, a metal salt compound of phosphorus is at least one selected from compounds represented by the following general formula (29). .

[0101]

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[0102] (In the formula ^{(29), R 1, R} 2 are each independently hydrogen, .R ³ representing a hydrocarbon group having 1 to 30 carbon atoms,
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 is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a carbon atom having 1 to 5 carbon atoms including carbonyl.
Represents 50 hydrocarbon groups. 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, and l + m is 4 or less. M represents a (l + m) -valent metal cation. n represents an integer of 1 or more. The hydrocarbon group may include an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. Among these, it is preferable to use at least one selected from the compounds represented by the following general formula (30).

[0103]

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(In the formula (30), M ^{n +} represents an n-valent metal cation. N represents 1, 2, 3, or 4.) In the above formula (29) or (30), M is Li ,
Na, K, Be, Mg, Sr, Ba, Mn, Ni, C
It is preferable to use one selected from u and Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, M
g is particularly preferred.

Specific metal salt compounds of phosphorus include lithium [ethyl 3,3,5-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-
Ethyl di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5-di-ter
t-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], strontium bis [3,5-di-tert-butyl-4-hydroxy] Ethyl benzylphosphonate], barium bis [3,5-
Phenyl di-tert-butyl-4-hydroxybenzylphosphonate], manganese bis [3,5-di-tert
-Butyl-4-hydroxybenzylphosphonate], nickel bis [3,5-di-tert-butyl-
Ethyl 4-hydroxybenzylphosphonate], copper bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], zinc bis [3,5-di-te]
rt-butyl-4-hydroxybenzylphosphonate]. Among these, lithium [3,
Ethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert
-Ethyl-butyl-4-hydroxybenzylphosphonate] and magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate] are particularly preferred.

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

The aluminum salt of a phosphorus compound, which is a preferable component constituting the polymerization catalyst used in the present invention, is not particularly limited as long as it is a phosphorus compound having an aluminum portion. An aluminum salt of a phosphonic acid compound is used. And the effect of improving the catalyst activity is large, which is preferable. Examples of the aluminum salt of the phosphorus compound include a monoaluminum salt, a dialluminum salt, and a trialuminum salt.

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

The aluminum salt of a phosphorus compound constituting the polymerization catalyst used in the present invention includes the following general formula (3)
It is preferable to use at least one selected from the compounds represented by 1) because the effect of improving the catalytic activity is large.

[0110]

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(In the formula (31), 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 represents 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, carbon number 1-50
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, and l +
m is 3. n represents an integer of 1 or more. The hydrocarbon group may include an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. As the above R ¹ , for example, phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl,
2-biphenyl and the like. Examples of R ² include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, te
rt-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, substituted phenyl group or naphthyl group, —CH ₂ C
And a group represented by H ₂ OH. The above R ³ O ^-
Examples thereof include a hydroxide ion, an alcoholate ion, an ethylene glycolate ion, an acetate ion and an acetylacetone ion.

As the aluminum salt of the phosphorus compound,
Aluminum salt of ethyl (1-naphthyl) methylphosphonate, aluminum salt of (1-naphthyl) methylphosphonic acid, aluminum salt of ethyl (2-naphthyl) methylphosphonate, aluminum salt of ethyl benzylphosphonate, aluminum salt of benzylphosphonic acid, Aluminum salt of ethyl (9-anthryl) methylphosphonate, 4
Aluminum salt of ethyl-hydroxybenzylphosphonate, aluminum salt of ethyl 2-methylbenzylphosphonate, aluminum salt of phenyl 4-chlorobenzylphosphonate, aluminum salt of methyl 4-aminobenzylphosphonate, ethyl 4-methoxybenzylphosphonate And aluminum salts of ethyl phenylphosphonate. Of these, aluminum salts of ethyl (1-naphthyl) methylphosphonate and aluminum salts of ethyl benzylphosphonate are particularly preferred.

Another embodiment of the present invention is a polyester polymerization catalyst comprising at least one selected from aluminum salts of phosphorus compounds represented by the following general formula (32). 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.

Another preferred aluminum salt of a phosphorus compound constituting the polymerization catalyst used in the present invention is one comprising at least one selected from compounds represented by the following general formula (32).

[0115]

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[0116] (In the formula ^{(32), R 1, R} 2 are each independently hydrogen, .R ³ representing a hydrocarbon group having 1 to 30 carbon atoms,
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 is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a carbon atom having 1 to 5 carbon atoms including carbonyl.
Represents 50 hydrocarbon groups. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m is 3. n represents an integer of 1 or more. The hydrocarbon group may include an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. Among these, it is preferable to use at least one selected from compounds represented by the following general formula (33).

[0117]

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(In the formula (33), R^ThreeIs hydrogen, carbon number 1
From 50 to 50 hydrocarbon, hydroxyl or alkoxyl groups.
Represents a hydrocarbon group having 1 to 50 carbon atoms. R^FourIs hydrogen,
C1-C50 hydrocarbon group, hydroxyl group or alkoxy
C1 to C50 hydrocarbon containing a carbonyl group or carbonyl
Represents a group. l is an integer of 1 or more, m is 0 or an integer of 1 or more
Represents a number, and 1 + m is 3. Hydrocarbon group
Alicyclic and branched structures such as syl and phenyl and naphthyl
Any aromatic ring structure may be included. ) R above^ThreeFor example, hydrogen, methyl group, ethyl
Group, propyl group, isopropyl group, n-butyl group, se
c-butyl group, tert-butyl group, long-chain aliphatic group,
Phenyl, naphthyl, substituted phenyl and naph
Chill group, -CH _TwoCH_TwoGroups represented by OH,
You. R above^FourO^-For example, hydroxide ion,
Alcoholate ion, ethylene glycolate ion,
Examples include acetate ion and acetylacetone ion.
It is.

The aluminum salt of the phosphorus compound of the present invention includes aluminum salt of ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
Aluminum salt of methyl di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-
Aluminum salt of isopropyl butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-
Aluminum salts of phenyl 4-hydroxybenzylphosphonate, aluminum salts of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid and the like can be mentioned. Among these, 3,5-di-tert-butyl-4
Aluminum salts of ethyl-hydroxybenzylphosphonate and aluminum salts of methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

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

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

The P which constitutes the polymerization catalyst used in the present invention
As the phosphorus compound having at least one —OH bond, it is preferable to use at least one selected from compounds represented by the following general formula (34) because the effect of improving the catalytic activity is large.

[0123]

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(In the formula (34), 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 represents 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. n represents an integer of 1 or more. The hydrocarbon group may include an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. As the above R ¹ , for example, phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl,
2-biphenyl and the like. Examples of R ² include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, te
rt-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, substituted phenyl group or naphthyl group, —CH ₂ C
And a group represented by H ₂ OH.

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

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

The preferred phosphorus compound used in the present invention is a specific phosphorus compound having at least one P-OH bond. The specific phosphorus compound having at least one P-OH bond, which is a preferable phosphorus compound constituting the polymerization catalyst of the present invention, is represented by the following general formula (35)
Means at least one compound selected from the compounds represented by

[0128]

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[0129] (In the formula ^{(35), R 1, R} 2 are each independently hydrogen, .R ³ representing a hydrocarbon group having 1 to 30 carbon atoms,
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 include an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. Among these, it is preferable to use at least one selected from the compounds represented by the following general formula (36).

[0130]

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(In the formula (36), R^ThreeIs hydrogen, carbon number 1
From 50 to 50 hydrocarbon, hydroxyl or alkoxyl groups.
Represents a hydrocarbon group having 1 to 50 carbon atoms. Hydrocarbon groups are
Alicyclic and branched structures such as kilohexyl, phenyl and na
It may contain an aromatic ring structure such as phthyl. ) R above^ThreeFor example, hydrogen, methyl group, ethyl
Group, propyl group, isopropyl group, n-butyl group, se
c-butyl group, tert-butyl group, long-chain aliphatic group,
Phenyl, naphthyl, substituted phenyl and naph
Chill group, -CH _TwoCH_TwoGroups represented by OH,
You.

The specific phosphorus compound having at least one P-OH bond of the present invention includes 3,5-di-tert.
Ethyl butyl-4-hydroxybenzylphosphonate,
Methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-
Isopropyl 4-hydroxybenzylphosphonate, 3,
Phenyl 5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4
Octadecyl hydroxybenzylphosphonate, 3,5
-Di-tert-butyl-4-hydroxybenzylphosphonic acid and the like. Of these, 3,5-di-
Ethyl tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

A preferred phosphorus compound is represented by the following formula (3)
And the phosphorus compound represented by 7).

[0134]

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[0135] (In the formula (37), R ¹ represents a hydrocarbon group having 1 to 49 carbon atoms containing a hydrocarbon group or a hydroxyl group, a halogen group, an alkoxyl group or an amino group of 1 to 49 carbon atoms, R ^2, R ³ is each independently hydrogen and carbon number 1
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group or an alkoxyl group. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. Further, more preferably, R ¹ , R ² ,
At least one of R ³ is a compound containing an aromatic ring structure.

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

[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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Further, the phosphorus compound used in the present invention having a large molecular weight has a large effect and is preferable since it is difficult to be distilled off during polymerization.

Another phosphorus compound desirably used as the polycondensation catalyst used in the present invention is at least one phosphorus compound selected from the compounds represented by the following general formula (38).

[0145]

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(In the above formula (38), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.)
R ³ and R ⁴ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, 1 to 1 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 include an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. Of the above general formula (38), it is preferable to use at least one selected from the compounds represented by the following general formula (39) because the effect of improving the catalytic activity is high.

[0147]

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(In the above formula (39), R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may include an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl.) Examples of R ³ and R ⁴ include hydrogen, methyl, butyl and the like. A short-chain aliphatic group, a long-chain aliphatic group such as octadecyl, an aromatic group such as a phenyl group, a naphthyl group, a substituted phenyl group or a naphthyl group, -CH ₂ CH ₂ OH
And the like.

The specific phosphorus compounds of the present invention include 3,3
Diisopropyl 5-di-tert-butyl-4-hydroxybenzylphosphonate, di-n-butyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4- Dioctadecyl hydroxybenzylphosphonate, 3,5-di-ter
and diphenyl t-butyl-4-hydroxybenzylphosphonate.

Among them, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

Another phosphorus compound in which it is desirable to use the polycondensation catalyst of the present invention is at least one phosphorus compound selected from the compounds represented by the chemical formulas (40) and (41).

[0152]

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[0153]

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When a phosphorus compound is used in combination, a catalyst exhibiting a sufficient catalytic effect can be obtained even if the amount of aluminum added in the polyester polymerization catalyst is small.

The amount of the phosphorus compound to be used is preferably 0.0001 to 0.1 mol% with respect to the total number of moles of the constituent units of the polycarboxylic acid component of the obtained polyester.
More preferably, it is 0.005 to 0.05 mol%. When the amount of the phosphorus compound is less than 0.0001 mol%, the effect of addition may not be exhibited, and when the amount exceeds 0.1 mol%, the catalytic activity as a polyester polymerization catalyst may be reduced. , The trend of decline is
It changes depending on the amount of aluminum used.

This is a technique in which an aluminum compound is used as a main catalyst component without using a phosphorus compound. In this technique, the amount of the aluminum compound used is reduced, and a cobalt compound is added to make the heat stable when the aluminum compound is used as a main catalyst. Although there is a technique for preventing coloring due to a decrease in the properties, if the cobalt compound is added to such an extent that it has a sufficient catalytic activity, the thermal stability also decreases. Therefore, it is difficult to achieve both using this technique.

According to the present invention, the use of the phosphorus compound having the above-mentioned specific chemical structure does not cause problems such as a decrease in thermal stability and the generation of foreign matters, and the addition amount of the metal-containing component as aluminum is small. However, a polymerization catalyst having a sufficient catalytic effect can be obtained, and the use of this polymerization catalyst improves the thermal stability during melt molding of polyester. Even if a phosphoric acid ester such as phosphoric acid or trimethyl phosphoric acid is added in place of the phosphorus compound, the effect of addition is not seen, and it is not practical. Further, 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, or a germanium compound within the range of the addition amount of the present invention, the effect of promoting the melt polymerization reaction is recognized. I can't.

It is preferable that the thermal stability parameter (TS) of polyethylene terephthalate having an IV of 0.65 polymerized using the polymerization catalyst used in the present invention satisfies the following formula (1).

TS <0.30 (1) where TS has an intrinsic viscosity ([IV] _i ) of about 0.65 d
1 g of 1 / g PET was placed in a glass test tube at 130 ° C. for 1 g.
After vacuum drying for 2 hours, 300 ° C. in a non-circulating nitrogen atmosphere
Intrinsic viscosity ([IV]) after maintaining in a molten state for 2 hours at
_f ) is a numerical value calculated by the following equation.

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 becomes 100 Torr after the pressure reduction and nitrogen sealing are repeated at least five times. Is sealed with nitrogen. TS = 0.245 ° [IV] _f ^-1.47- [IV] _i ^{-1.47 使用} The use of the catalyst having such a structure can improve the melting heat stability with respect to the heat melting when manufacturing molded products such as films, bottles, and fibers. A polyester which is excellent and gives a molded article with less coloring and less generation of foreign matter can be obtained.

[0161] TS is more preferably 0.25 or less, particularly preferably 0.20 or less.

IV polymerized with the catalyst: 0.65
Activity parameters of polyethylene terephthalate (A
P) preferably satisfies the following expression (2).

AP (min) <2T (min) (2) By setting the activity parameter AP within the above range, the reaction speed is high and the time for producing a polyester by polycondensation is reduced. AP is more preferably 1.5T or less, further preferably 1.3T or less,
It is particularly preferred that it is 1.0T or less.

[0164] However, AP can be obtained by using a predetermined amount of catalyst.
Inherent viscosity of 0.65d at 5 ° C and 0.1 Torr
1 / g indicates the time (min) required to polymerize polyethylene terephthalate, and T was added using antimony trioxide as a catalyst so that the amount of antimony was 0.05 mol% with respect to the acid component in the produced polyethylene terephthalate. AP in the case.

In the present invention, antimony trioxide used for comparison is a commercially available diantimony trioxide, for example, Antimony (III) manufactured by ALDRICH.
Oxide, purity 99.999%, and this was added to ethylene glycol to a concentration of about 10 g / l.
The solution dissolved by stirring at 50 ° C. for about 1 hour is added so that the acid content in the produced polyethylene terephthalate becomes 0.05 mol% as antimony atom. This is common to antimony trioxide elsewhere in this specification.

The method of measuring AP is specifically as follows. 1) (BHET production process) Terephthalic acid and a 2-fold molar amount of ethylene glycol are used, and the esterification ratio is 95
% Bis (2-hydroxyethyl) terephthalate (B
HET) and a mixture of oligomers (hereinafter referred to as a BHET mixture). 2) (Catalyst addition step) A predetermined amount of a catalyst is added to the above BHET mixture, and the mixture is stirred at 245 ° C. for 10 minutes under a normal pressure under a nitrogen atmosphere, and then heated to 275 ° C. in 50 minutes. Is gradually reduced to 0.1 Torr. 3) (Polycondensation step) A polycondensation reaction is performed at 275 ° C. and 0.1 Torr, and polymerization is performed until the intrinsic viscosity (IV) of polyethylene terephthalate reaches 0.65 dl / g. 4) The polymerization time required for the polycondensation step is defined as AP (min).

These are carried out using a batch type reaction apparatus. The production of the BHET mixture in 1) (BHET production step) is performed by a known method. For example, terephthalic acid and a 2-fold molar amount of ethylene glycol are charged into a batch type autoclave equipped with a stirrer, and the esterification reaction is performed while distilling water out of the system at 245 ° C. under a pressure of 0.25 MPa. It is manufactured by

By setting the activity parameter AP within the above range, the reaction rate is high, and the time for producing a polyester by polycondensation is reduced. The AP is more preferably 1.5 T or less, further preferably 1.3 T or less, and particularly preferably 1.0 T or less.

2) The "predetermined amount of catalyst" in the (catalyst addition step) means the amount of the catalyst used in a variable amount according to the activity of the catalyst. With catalysts, the amount is higher. The amount of the catalyst used is at most 0.1 mol% as an aluminum compound based on the number of moles of terephthalic acid. If it is added more than this, the residual amount in the polyester is large and it is not a practical catalyst.

The PET resin chips used for measuring TS, TOS, HS, and Haze are as described in 1) to 3) above.
After passing through the step, a product produced by rapid cooling from a molten state is used. The shape of the resin chip used for these measurements is, for example, about 3 mm in length and about 2 m in diameter.
Use a m-shaped cylindrical resin tip. Further, as the resin chip for color measurement, after passing through the above steps 1) to 3), a substantially amorphous resin chip produced by rapid cooling from a molten state is used. As a method of obtaining a substantially amorphous resin chip, for example, when taking out the polymer from the reaction system after melt polymerization, quenching with cold water immediately after discharging the polymer from the discharge port of the reaction system, then sufficient cooling For example, a method of holding in cold water for a time and then cutting it into chips may be used. The resin chip thus obtained is transparent in appearance without whitening due to crystallization. The resin chip thus obtained is air-dried on a filter paper or the like at room temperature for about 24 hours, and then used for color measurement. After the above-mentioned operation, the resin chip remains transparent without any whitening due to crystallization.
It should be noted that no additive affecting the appearance such as titanium dioxide is used for the resin chip for color measurement. As the shape of the resin tip used for color measurement, for example, a cylindrical resin tip having a length of about 3 mm and a diameter of about 2 mm is used.

Polyethylene terephthalate (PE) polymerized with the polymerization catalyst used in the present invention and having an IV of 0.65
The hydrolysis resistance parameter (HS) of T) is represented by the following formula (3):
It is preferable to satisfy the following.

HS <0.10 (3) (HS has an intrinsic viscosity of about 0.65 d obtained by melt polymerization.
1 / g (before the test: [IV] _i ) PET chips were frozen and pulverized into powder having a size of 20 mesh or less at 130 ° C. for 12 minutes.
After vacuum drying for 1 hour, 1 g of the solution was put into a beaker together with 100 ml of pure water, heated to 130 ° C. in a closed system, and stirred under pressurized conditions for 6 hours, followed by intrinsic viscosity ([IV] _f2 ).
Is a numerical value calculated by the following equation. HS = 0.245 ° [IV] _f2 ^-1.47- [I
V] _i ^-1.47 _i ) Use a beaker that does not elute acids or alkalis for the measurement of HS. Specifically, it is preferable to use a stainless beaker or a quartz beaker.

By using the catalyst having such a structure,
A polyester giving a molded article having excellent hydrolysis resistance can be obtained.

HS is more preferably 0.09 or less, particularly preferably 0.085 or less.

The thermal oxidation stability parameter (TOS) of polyethylene terephthalate (PET) having an IV of 0.65 polymerized using the polymerization catalyst used in the present invention preferably satisfies the following formula (4).

TOS <0.10 (4) In the above formula, TOS has a melt-polymerized IV of about 0.65 dl.
/ G PET resin chip is freeze-ground to obtain powder having a size of 20 mesh or less, vacuum-dried at 130 ° C. for 12 hours, placed in a glass test tube, vacuum-dried at 70 ° C. for 12 hours, and dried with silica gel. 230 ° C under 1
It is determined from the IV after heating for 5 minutes using the following formula.

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.

As a method for heating under air dried with silica gel, for example, a method in which a drying tube containing silica gel is connected to the upper part of a glass test tube and heated under dry air can be exemplified.

By using the polyester polymerization catalyst having the above structure, a polyester excellent in heat aging resistance can be obtained. T
OS is more preferably 0.09 or less, further preferably 0.08 or less.

IV polymerized with the catalyst: 0.65
Of polyethylene terephthalate, the PET
It is preferable that the solution haze value (Haze) of Formula (1) satisfies the following expression (5).

Haze <3.0 (%) (5) In the above formula, Haze has a melt-polymerized intrinsic viscosity of about 0.6.
A 5 dl / g polyethylene terephthalate (PET) resin chip was treated with p-chlorophenol / 1,1,2,2-
The value measured by using a haze meter is shown by dissolving in a 3/1 mixed solvent (weight ratio) of tetrachloroethane to make a solution of 8 g / 100 ml. The measurement of the haze was performed using a cell length of 1 cm.
The above-mentioned solution was filled using the cell of No. 1 and the measurement was performed.

[0182] With such a structure, the catalyst gives a polyester having excellent transparency when formed into a molded article such as a film or a hollow molded article. Haze is more preferably 2.0 or less, further preferably 1.0 or less.

IV polymerized with the catalyst: 0.65
Of polyethylene terephthalate, the PET
Is the color delta b value parameter (Δb) of the following equation (6)
It is preferable to satisfy the following.

Δb <4.0 (6) In the above formula, Δb is a value obtained by using a colorimeter using a polyethylene terephthalate (PET) resin chip having an intrinsic viscosity of about 0.65 dl / g melt-polymerized using a predetermined catalyst. A 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. However, antimony trioxide is 0.05 mol% as antimony atom based on the acid component in the produced polyethylene terephthalate.
Added.

With such a constitution, the catalyst provides a polyester which further improves the color tone of the melt molded article. Δb
The value is more preferably 3.0 or less, still more preferably 2.5 or less.

In the polymerization catalyst used in the present invention, the color delta Lg value parameter (△ Lg) of polyethylene terephthalate having an IV of 0.65 polymerized using the catalyst is represented by the following formula (7). The parameter (△ bg) preferably satisfies the following expression (8).

ΔLg> −2.0 (7) In the above formula, ΔLg is a PET resin chip having an intrinsic viscosity of about 0.65 dl / g melt-polymerized using a predetermined amount of a catalyst, and a color difference meter is used. From the L value of the hunter measured
The value obtained by subtracting the L value when germanium dioxide is used as a catalyst is shown. However, germanium dioxide is added in an amount of 0.03 mol% as germanium atoms to the acid component in the produced polyethylene terephthalate. As the germanium dioxide used for comparison in the present invention, a commercially available compound, for example, germanium dioxide manufactured by GEMCO Co., Ltd., having a purity of 97% or more, is used to adjust the concentration of water to about 8 g / l. A solution obtained by stirring at 80 ° C. for about 1 hour and dissolving the solution is added so that the content of germanium atoms is 0.03 mol% with respect to the acid component in the produced polyethylene terephthalate. This is common to germanium dioxide elsewhere in this specification.

Δbg <4.5 (8) In the above formula, Δbg is obtained by using a PET resin chip having an intrinsic viscosity of about 0.65 dl / g melt-polymerized using a predetermined amount of a catalyst and using a color difference meter. From the hunter's b value measured by
The value obtained by subtracting the b value when germanium dioxide is used as a catalyst is shown. However, germanium dioxide is added in an amount of 0.03 mol% as germanium atoms to the acid component in the produced polyethylene terephthalate.

The above-mentioned polyester polymerization catalyst does not contain an antimony compound or a germanium compound as a main component of the catalyst, contains aluminum as a main metal component, and gives a polyester molded article having a good color tone.

As the above-mentioned resin chip for color measurement, a substantially amorphous resin chip produced by rapid cooling from a molten state is used. As a method for obtaining a substantially amorphous resin chip, for example, when removing a polymer from the reaction system after melt polymerization, the polymer is rapidly cooled with cold water immediately after discharging the polymer from the discharge port of the reaction system, and then sufficiently cooled. It can be obtained by holding in cold water for a long time and then cutting it into chips.
The resin chip thus obtained is transparent in appearance without whitening due to crystallization.

The resin chip thus obtained is
It is used for color measurement after air-drying on filter paper at room temperature for about 24 hours. After the above-mentioned operation, the resin chip remains transparent without any whitening due to crystallization. It should be noted that no additive affecting the appearance such as titanium dioxide is used in the resin chip for color measurement. ΔLg is more preferably −1.0 or more,
It is particularly preferred that it is 0.0 or more. Δbg is 4.0
It is more preferably at most 3.5, particularly preferably at most 3.5.

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 the group consisting of an alkali metal, an alkaline earth metal, and a compound thereof coexist as the second metal-containing component in addition to aluminum or its compound. is there. The coexistence of such a second metal-containing component in the catalyst system increases the catalytic activity in addition to the effect of suppressing the production of diethylene glycol, and 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. The use of such a known catalyst can provide a polyester having excellent thermal stability. However, the known catalyst using an alkali metal compound or an alkaline earth metal compound in combination requires an addition amount thereof in order to obtain practical catalytic activity. Is required, and when an alkali metal compound is used, the amount of foreign matters caused by the use of the alkali metal compound increases. In addition, when an alkaline earth metal compound is used in combination, the thermal stability and thermal oxidative stability of the obtained polyester are reduced in order to obtain practical activity, the coloring due to heating is large, and the amount of foreign matter generated is also small. More.

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

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

When strong alkalis such as hydroxides are used among these alkali metals, alkaline earth metals or compounds thereof, they tend not to be easily dissolved in 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 easily colored, and the hydrolysis resistance is also reduced. Tend to. Accordingly, the alkali metal or a compound thereof or an alkaline earth metal or a compound thereof according to the present invention is preferably a saturated aliphatic carboxylate, an unsaturated aliphatic carboxylate, or an aromatic salt of an alkali metal or an alkaline earth metal. Group carboxylate, halogen-containing carboxylate, hydroxycarboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid,
Inorganic acid salts selected from hydrochloric acid, hydrobromic acid, chloric acid, and bromic acid, organic sulfonates, organic sulfates, chelating compounds,
And oxides. Of these, from the viewpoint of ease of handling and availability, it is preferable to use a saturated aliphatic carboxylic acid salt of an alkali metal or an alkaline earth metal, particularly an acetate.

The polyester according to the present invention further comprises:
In a preferred embodiment, the cobalt compound is added as a cobalt atom in an amount of less than 10 ppm to the polyester.

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

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

The addition amount of the cobalt compound is such that the total of aluminum atoms and cobalt atoms is 50 ppm or less and 10 pp of cobalt atoms with respect to the finally obtained polymer.
It is preferably less than m. More preferably, the total of aluminum atoms and cobalt atoms is 40 ppm or less,
The cobalt atom is 8 ppm or less, more preferably the total of the aluminum atom and the cobalt atom is 25 ppm or less, and the cobalt atom is 5 ppm or less.

From the viewpoint of the thermal stability of the polyester, it is preferred that the total of aluminum atoms and cobalt atoms is less than 50 ppm, and that the content of cobalt atoms is 10 ppm or less. In order to have sufficient catalytic activity, the total amount of aluminum atoms and cobalt atoms is 0.01 ppm.
More is preferred.

The polyester of the present invention can be produced by a method including conventionally known steps except that the polyester polymerization catalyst of the present invention is used as a catalyst. For example, PE
In the case of producing T, terephthalic acid and ethylene glycol are directly reacted to remove water and esterified, and then subjected to polycondensation under reduced pressure, or a direct esterification method in which dimethyl terephthalate and ethylene are used. It is produced by a transesterification method in which a glycol is reacted to distill off methyl alcohol and transesterified, followed by polycondensation under reduced pressure. If necessary, solid-state polymerization may be performed in order to increase the intrinsic viscosity and reduce the acetaldehyde content and the like. In order to promote crystallization before solid-phase polymerization, the melt-polymerized polyester may be heated and then crystallized after moisture absorption, or steam may be directly blown onto the polyester chip for heat crystallization.

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

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

The polymerization catalyst used in 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, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation 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 the present invention may be a powdery or neat addition, or a slurry or solution addition of a solvent such as ethylene glycol. Well, there is no particular limitation.
Further, a mixture of aluminum metal or a compound thereof and another component, preferably a phenolic compound or a phosphorus compound, may be added in advance, or they may be added separately. Further, the aluminum metal or its compound and another component, preferably a phenolic compound or a phosphorus compound, may be added to the polymerization system at the same time, or they may be added at different times.

The polymerization catalyst used in the present invention includes other polymerization catalysts such as an antimony compound, a titanium compound, a germanium compound, and a tin compound. It is advantageous and advantageous to use coexistence within the range of an addition amount that does not cause a problem in the product when the productivity is improved by shortening the polymerization time.

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

The titanium compound can be added in a range of 10 ppm or less based on the polymer obtained by polymerization. More preferably, it is added in an amount of 5 ppm or less, further preferably 2 ppm or less. When the added amount of titanium is more than 10 ppm, the thermal stability of the obtained resin is significantly reduced.

As a germanium compound, 60 pp as germanium atoms in a polyester obtained by polymerization was used.
m or less. More preferably, it is added in an amount of 40 ppm or less. If the amount of germanium added is more than 60 ppm, it is disadvantageous in terms of cost, which is not preferable.

The germanium compound can be added so that the amount of germanium atoms remaining in the polyester obtained by polymerization becomes 30 ppm or less. A more preferred residual 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.

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

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

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

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

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

After the polymerization of the polyester according to the method of the present invention, the catalyst is removed from the polyester or the catalyst is deactivated by adding a phosphorus compound or the like, thereby further improving the thermal stability of the polyester. it can.

The polyester referred to in the present invention is a polyester whose main repeating unit is ethylene terephthalate, and preferably has 7 ethylene terephthalate units.
It is a linear polyester containing 0 mol% or more, more preferably 80 mol% or more, particularly preferably 95 mol% or more.

Examples of the dicarboxylic acid as a copolymer component used when the polyester is a copolymer include:
Orthophthalic acid, isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5
-Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl-4,4-dicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 1,2-bis (phenoxy) ethane-
aromatic dicarboxylic acids such as p, p′-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and functional derivatives thereof, lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or a functional derivative thereof, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, Decanedicarboxylic acid, dodecanedicarboxylic acid,
Examples thereof include aliphatic dicarboxylic acids such as tetradecane dicarboxylic acid and functional derivatives thereof, and alicyclic dicarboxylic acids such as 1,3-cyclohexane dicarboxylic acid and 1,4-cyclohexane dicarboxylic acid and functional derivatives thereof.

The glycol as a copolymer component used when the polyester is a copolymer includes diethylene glycol, triethylene glycol,
-Propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,10-decamethylene glycol,
Aliphatic glycols such as 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,
Alicyclic glycols such as 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 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-hydroxy And aromatic glycols such as phenyl) ethane, bisphenol A, and alkylene oxide adducts of bisphenol A.

Examples of the cyclic ester used for the copolymerization of the polyester include ε-caprolactone, β-propion lactone, β-methyl-β-propion lactone,
γ-valerolactone, glycolide, lactide and the like.

Further, examples of the polyfunctional compound as a copolymer component used when the polyester is a copolymer include trimellitic acid and pyromellitic acid as an acid component, and a glycol component as a glycol component. Glycerin and pentaerythritol can be mentioned.
The amount of the above-mentioned copolymer component to be used must be such that the polyester maintains a substantially linear shape. Further, a monofunctional compound such as benzoic acid or naphthoic acid may be copolymerized.

The polyester 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-carboxyethyl) phenylphosphinic acid, 9,
10-dihydro-10-oxa- (2,3-carboxypropyl) -10-phosphaphenanthrene-10-oxide. By including these phosphorus compounds as copolymer components, it is possible to improve the flame retardancy and the like of the obtained polyester.

Further, the polyester 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-carboxyethyl) 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.

It should be noted that mold contamination at the time of molding a hollow molded article and roll contamination at the time of molding a sheet-like material can be achieved by reducing the content of the cyclic trimer to 0.5% by mass or less. Further, it is possible to further improve mold fouling by reducing as much as possible the regeneration amount of the cyclic trimer in the molten state during molding of the molded product.

As a measure for preventing mold fouling, the content of the polyester cyclic trimer is set to 0.50% by mass or less, preferably 0.45% by mass or less, more preferably 0.40% by mass or less.
There is a method of reducing the amount to less than mass%. When molding a heat-resistant hollow molded article from polyester, heat treatment is performed in a heating mold. However, when the content of the cyclic trimer is 0.50% by mass or more, the heat treatment is performed on the surface of the heating mold. The adhesion of the oligomer is rapidly increased, and the transparency of the obtained hollow molded article or the like is extremely deteriorated.

The polyester was treated at a temperature of 290 ° C. for 3 hours.
It is also possible to adopt a method of reducing the amount of increase of the cyclic trimer (ΔCT amount) when melted for 0 minute to 0.50 mass% or less. The amount of increase of the cyclic trimer is preferably 0.3% by mass.
Or less, more preferably 0.2% by mass or less, particularly preferably. 1% by mass or less. When the amount of the cyclic trimer increased by melting at a temperature of 290 ° C. for 30 minutes exceeds 0.50% by mass, the amount of the cyclic trimer increases at the time of melting the resin for molding, and the oligomer on the surface of the heating mold is increased. Adhesion sharply increases, and the transparency of the obtained hollow molded article or the like is extremely deteriorated.

As a method of reducing the content of the cyclic trimer, there is a method of solid-phase polymerization of a melt-polymerized polyester prepolymer having an IV of 0.40 to 0.60. Further, there is a method in which a polyester having a predetermined IV is subjected to a heat treatment under an inert gas atmosphere or a reduced pressure under a condition that the IV does not substantially change.

A method for reducing the increase in cyclic trimer to 0.50% by mass or less when melted at a temperature of 290 ° C. for 30 minutes is described below. In order to suppress regeneration of the cyclic trimer in the molten state during molding as much as possible, it is important to reduce the amount of the active polymerization catalyst remaining in the polyester as much as possible. A typical method for reducing the amount of such an active polymerization catalyst is as follows.

One method is to inactivate the polymerization catalyst by contacting the polyester with water.

As a method for deactivating the polyester polycondensation catalyst, there is a method in which the polyester chip is subjected to a contact treatment with water, steam or a steam-containing gas after melt polycondensation or after solid phase polymerization.

Examples of the water treatment method include a method of immersing in water and a method of spraying water on a chip with a shower.
The processing time is 5 minutes to 2 days, preferably 10 minutes to 1 day.
Days, more preferably 30 minutes to 10 hours, and the temperature of water is 20 to 180 ° C, preferably 40 to 150 ° C,
More preferably, it is 50 to 120 ° C.

The following is an example of a method for industrially performing water treatment, but the method is not limited thereto. The treatment method may be either a continuous method or a batch method, but the continuous method is preferable for industrial use.

In the case of treating polyester chips with water in a batch system, a silo-type treatment tank may be used. That is, the chips of the polyester are received in the silo in a batch system and water treatment is performed. In the case of treating the polyester chips with water in a continuous manner, the polyester chips can be continuously or intermittently received in the tower-type treatment tank from above and subjected to water treatment.

When the polyester chips are brought into contact with water vapor or a gas containing water vapor for the treatment, 50 to 50%
Steam or steam-containing gas or steam-containing air at a temperature of 150 ° C., preferably 50 to 110 ° C., is preferably supplied or present in an amount of 0.5 g or more as steam per kg of granular polyethylene terephthalate. The granular polyethylene terephthalate is brought into contact with steam.

The contact between the polyester chips and water vapor is usually carried out for 10 minutes to 2 days, preferably for 20 minutes to 2 days.
Performed for 10 hours.

The following is an example of a method for industrially carrying out contact treatment between granular polyethylene terephthalate and steam or a steam-containing gas, but the method is not limited thereto. The processing method may be either a continuous method or a batch method.

When a polyester chip is subjected to a contact treatment with steam in a batch system, a silo-type treatment apparatus may be used. That is, a polyester chip is received in a silo, and steam or a steam-containing gas is supplied in a batch system to perform a contact treatment.

When the polyester chips are continuously subjected to the contact treatment with steam, the granular polyethylene terephthalate is continuously received in a tower type treating apparatus from above, and steam is continuously supplied in parallel or countercurrent to contact with the steam. Can be processed.

As described above, when treated with water or steam, the granular polyethylene terephthalate is drained, if necessary, with a draining device such as a vibrating sieve or a simmon cutter, and then the conveyor is used for the next drying step. Transfer.

For drying the polyester chips which have been subjected to contact treatment with water or steam, a commonly used polyester drying treatment can be used. As a method for continuous drying, a hopper-type through-air dryer that supplies a polyester chip from the upper portion and allows a drying gas to flow from the lower portion is usually used.

As a dryer for drying by a batch method, drying may be performed under atmospheric pressure while passing a drying gas.

As the dry gas, atmospheric air may be used, but dry nitrogen and dehumidified air are preferred from the viewpoint of preventing molecular weight reduction due to hydrolysis or thermal oxidative decomposition of polyester.

As another means, there is a method in which a phosphorus compound is added to a melt of polyester after melt polycondensation or after solid phase polymerization and mixed to inactivate a polymerization catalyst such as an Al catalyst.

In the case of the melt-polymerized polyester, the polyester after the completion of the melt polymerization reaction is mixed with a polyester resin containing a phosphorus compound in a device such as a line mixer capable of mixing in a molten state, thereby deactivating the Al catalyst. Method.

Examples of the method of blending the phosphorus compound with the solid-phase polymerized polyester include a method of dry blending the phosphorus compound with the solid-phase polymerized polyester, a polyester master batch chip in which the phosphorus compound is melt-kneaded and blended, and a solid-state polymerized polyester. A method in which a predetermined amount of a phosphorus compound is blended with polyester by a method of mixing chips and then melted in an extruder or a molding machine to inactivate the Al catalyst is exemplified.

The amount of the phosphorus compound required to completely deactivate the Al catalyst is at least 5 times the molar amount of the remaining Al content in the polyester.

The phosphorus compounds used include phosphoric acid,
Examples thereof include phosphorous acid, phosphonic acid, and derivatives thereof. Specific examples include phosphoric acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, monomethyl phosphate, dimethyl phosphate, monobutyl phosphate, dibutyl phosphate, and dibutyl phosphate. Phosphoric acid, trimethyl phosphite, triethyl phosphite, tributyl phosphite, methylphosphonic acid,
Methyl dimethyl phosphonate, ethyl dimethyl phosphonate, dimethyl phenyl phosphonate, diethyl phenyl phosphonate, diphenyl phenyl phosphonate, and the like. May be used in combination.

The limiting viscosity of the polyester of the present invention is 0.5
5 to 1.50 deciliter / gram, preferably 0.5
The range is from 8 to 1.30 deciliter / gram, and more preferably from 0.60 to 1.00 deciliter / gram. If the intrinsic viscosity is less than 0.55 deciliter / gram, the mechanical properties of the obtained molded article and the like are poor. Also, 1.
If it exceeds 50 deciliters / gram, the resin temperature rises during melting by a molding machine or the like, and thermal decomposition becomes severe, free low-molecular-weight compounds that affect fragrance retention increase, or the molded product is colored yellow. Problems occur.

The acetaldehyde content of the polyester of the present invention is 10 ppm or less, preferably 8 ppm.
Or less, more preferably 6 ppm or less, still more preferably 4 ppm or less. Acetaldehyde content is 10p
If it is not less than pm, the contents and contents of containers and the like molded from the polyester will have poor flavor and odor.

The amount of diethylene glycol copolymerized in the polyester of the present invention is preferably 0.5 to 5.0 mol%, more preferably 1.0 to 4.0 mol%, of the glycol component constituting the polyester. It is 5 mol%, and more preferably 1.5 to 4.0 mol%. When the amount of diethylene glycol exceeds 5.0 mol%, the thermal stability becomes poor,
The decrease in molecular weight during molding and the increase in the acetaldehyde content and the formaldehyde content are undesirably large. When the content of diethylene glycol is less than 0.5 mol%, the transparency of the obtained molded article is deteriorated.

The polyester of the present invention may contain an organic, inorganic, or organometallic toner, a fluorescent whitening agent, and the like. Coloring such as yellowing can be suppressed to a more excellent level. In addition, other optional polymers, antistatic agents, antifoaming agents, dyes, pigments, matting agents, optical brighteners, stabilizers, antioxidants, and other additives may be contained. As the antioxidant, an aromatic amine-based or phenol-based antioxidant can be used, and as the stabilizer, a phosphorus-based, sulfur-based, amine-based stabilizer such as phosphoric acid or phosphate ester-based can be used. Can be used.

The method for producing the hollow molded article according to the present invention includes:
Stretch blow molding in which a bottomed preform is stretch blow-molded, direct blow molding, extrusion blow molding and the like can be used. The hollow molded body is manufactured by drying the polyester chips obtained by melt polymerization or solid state polymerization by vacuum drying, etc., and then molding by a molding machine such as an injection molding machine, or molding the melt after melt polymerization as it is Direct molding method in which a parison, which is a preform of a hollow molded body, is produced by introducing it into a machine and is referred to as a direct parison method. Further, as the sheet-like substance according to the present invention, extrusion molding can be used.

Examples of the hollow molded body include aseptic bottles for juices, heat-resistant pressure bottles for tea, carbonated drinks, alcoholic drinks bottles such as shochu and whiskey, beer bottles, household detergents, and hairdressing agents. It is used as a bottle for such applications.

Further, such a container may have a multilayer structure in which an intermediate layer is provided with a gas barrier resin layer such as polyvinyl alcohol or polymethaxylylenediamine adipate, a light-shielding resin layer or a recycled polyester layer. is there. Further, polymetaxylylenediamine adipate and the like can be blended. In addition, evaporation and CV
Using a method such as D (chemical vapor deposit),
It is also possible to coat the inside and outside of the container with a layer of metal such as aluminum or diamond-like carbon.

In order to enhance the crystallinity of the plug portion of the hollow molded body, other resins such as polyethylene and an inorganic nucleating agent such as talc may be added.

Further, the sheet is processed by vacuum forming, pressure forming, embossing or the like, and trays and containers for foods and miscellaneous goods, cups, blister packs, carrier tapes for electronic parts,
Used as an electronic component delivery tray. The sheet can be used as various cards.

Polyester is used in vacuum molded articles for food packaging, sheets for compressed air molded articles, blister packs for miscellaneous goods, and the like. Antimony catalysts are inexpensive and have excellent catalytic activity. When this is used as a main component, that is, in an amount of addition at which a practical polymerization rate is exhibited, metal antimony precipitates during polycondensation,
Darkening and foreign matter are generated in the polyester, compared with the case where a germanium compound or a titanium compound is used as a catalyst,
The crystallization rate of the obtained PET is high, and it is difficult to obtain a sheet having excellent transparency. Particularly, a sheet having a thickness of 1 mm or more is very difficult. Under these circumstances, polyesters containing no antimony at all or containing no antimony as the main component of the catalyst are invaluable.

[0260]

EXAMPLES (1) Intrinsic viscosity of polyester (IV) It was determined from the solution viscosity at 30 ° C. in a 1,1,2,2-tetrachloroethane / phenol (2: 3 weight ratio) mixed solvent.

(2) Polyethylene diethylene glyco-
The content was decomposed with methanol and the amount of DEG was quantified by gas chromatography and expressed as a ratio (mol%) to the total glycol components.

(3) Density: Measured at 30 ° C. using a density gradient tube of calcium nitrate / water mixed solution.

(4) Content of cyclic trimer of polyester (hereinafter referred to as "CT content") A 300 mg sample was dissolved in 3 ml of a mixed solution of hexafluoroisopropanol / chloroform (volume ratio = 2/3). Add 30 ml to dilute.
To this, 15 ml of methanol was added to precipitate a polymer, followed by filtration. The filtrate was evaporated to dryness, the volume was adjusted to 10 ml with dimethylformamide, and the amount of cyclic trimer was determined by high performance liquid chromatography.

(5) Increase in cyclic trimer during melting of polyester (ΔCT amount) 3 g of dried polyester chip was placed in a glass test tube, immersed in an oil bath at 290 ° C. for 30 minutes under a nitrogen atmosphere, and melted. Let it. The amount of increase of the cyclic trimer at the time of melting is determined by the following equation.

Increase in cyclic trimer during melting (% by mass) = content of cyclic trimer after melting (% by mass)-content of cyclic trimer before melting (% by mass) (6) Acetaldehyde content (%) (Hereinafter referred to as “AA content”) Sample / distilled water = 1 g / 2 cc placed in a glass ampoule purged with nitrogen, sealed, extracted at 160 ° C. for 2 hours, and cooled to reduce acetaldehyde in the extract. The concentration was measured by gas chromatography and the concentration was expressed in ppm.

(7) Haze (% haze) A sample was cut from the body (thickness: about 0.40 mm) of the molded article (thickness: 5 mm) and the hollow molded article (9) below, and Color haze meter, model ND
Measured with H2000.

(8) Molding of Stepped Molded Plate The dried polyester was obtained from M-150C (D
M) Stepped plate mold (surface temperature of about 2) cooled by water at 10 ° C at a cylinder temperature of 290 ° C by an injection molding machine.
(2 ° C.). The resulting stepped plate is 2,
A plate having a thickness of about 3 cm × about 5 cm square having a thickness of 3, 4, 5, 6, 7, 8, 9, 10, 11 mm is provided in a stepwise manner, and each piece weighs about 146 g. A plate having a thickness of 5 mm was used for measuring haze (% haze).

(9) Evaluation of Mold Stain The polyester was dried with a dryer using dehumidified nitrogen, and a preform was molded at a resin temperature of 295 ° C. using an M-150C (DM) injection molding machine manufactured by Koki Seisakusho. The plug portion of this preform was heated and crystallized with a home-made plug portion crystallizer, and then biaxially stretched and blow-molded using an LB-01E stretch blow molding machine manufactured by Corpoplast Co., Ltd.
Heat fix for about 7 seconds in a mold set at 1000 ° C, 1000cc
(The body was circular). The stretch blow molding was continuously performed under the same conditions, and the stain on the mold was evaluated by the number of moldings until the transparency of the molded body was impaired by visual judgment. Further, as a sample for haze measurement, a body portion of a molded body after continuous molding for 3000 times was provided.

(10) Sensory test [0269] Distilled water at 90 ° C was put in the above hollow container, sealed, kept for 30 minutes, cooled to room temperature, allowed to stand at room temperature for one month, opened, and tested for flavor, smell, etc. Was. Distilled water was used as a blank for comparison. The sensory test was carried out by 10 panelists according to the following criteria and compared with the average value.

(Evaluation Criteria) 0: No off-taste or smell is felt 1: A slight difference from the blank is felt 2: A difference from the blank is felt 3: A considerable difference from the blank is felt 4: Very much different from the blank A large difference is felt. (11) Acid value 0.1 g of polyester was dissolved by heating in 10 ml of benzyl alcohol, and then titrated using a solution of 0.1 N NaOH in methanol / benzyl alcohol = 1/9.

(12) Diethylene glycol content (DE
G) 0.1 g of polyester in 250 ml of methanol at 250 ° C.
And then quantitatively determined by gas chromatography.

(13) Differential Scanning Calorimetry (DSC) Measurement was performed using a DSC 2920 manufactured by TA Instruments. Put 10.0mg of polyester into aluminum pan,
Heat to 280 ° C at a heating rate of 50 ° C / min.
And then quenched in liquid nitrogen immediately after holding for 1 minute. Thereafter, the temperature was raised from room temperature to 300 ° C. at a rate of 20 ° C./min, and the crystallization temperature Tc1 and the melting point Tm at the time of temperature rise were determined. After maintaining at 300 ° C. for 2 minutes, the temperature was decreased at a rate of 10 ° C./min.
I asked. Tc1, Tm, and Tc2 were the temperatures of the local maximums of the respective peaks.

(14) Hue of polyethylene terephthalate having an IV of 0.65 When a predetermined stirring torque was reached in the melt polymerization, nitrogen was introduced into the autoclave, the pressure was returned 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 manufactured by Tokyo Denshoku Co., Ltd.).
TC-1500MC-88) using Hunter's L
It measured as a value, a value, and b value.

(15) Thermal stability parameter (TS) The melt-polymerized IV was about 0.65 dl / g (before the melting test;
[IV] 1 g of PET resin chip of _i )
After placing in a glass test tube of 12 mm and vacuum drying at 130 ° C. for 12 hours, setting in a vacuum line and repeating vacuuming and nitrogen filling at least 5 times, sealing with 100 mmHg of nitrogen, sealing, and placing in a 300 ° C. salt bath After being immersed and maintained in a molten state for 2 hours, the sample was taken out, freeze-pulverized and vacuum-dried, and the IV (after the melting test; IV] _f2 ) was measured and determined by the following formula. The formula was quoted from a previous report (Ueyama et al .: The Journal of the Rubber Society of Japan, Vol. 63, No. 8, page 497, 1990). TS = 0.245 ｛[IV] _f2 ^-1.47- [I
V] _i ^-1.47 ｝ (16) Thermal oxidation stability parameter (TOS) A melt-polymerized PET resin chip having an IV of about 0.65 dl / g is freeze-pulverized into a powder having a size of 20 mesh or less, and the powder is obtained at 130 ° C. for 12 hours. 300 mg of the dried in a vacuum 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] _{f 1} 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 ｝ (17) 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 7) 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 (TypeMC manufactured by Texam Giken Co., Ltd.).
12. ELB). 1 g of the above powder is added to pure water 1
The mixture was placed in a dedicated stainless steel beaker together with 00 ml, and a dedicated stirring blade was further placed therein. The system was closed, set in a mini-color device, and stirred at 130 ° C. for 6 hours while being heated and pressurized. 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 ｝ (18) Solution haze value (Haze) A melt-polymerized IV resin tip having an IV of about 0.65 dl / g was mixed with p-chlorophenol / 1,1,2,2-tetrachloroethane in 3 / It was dissolved in one mixed solvent (weight ratio) to make a solution of 8 g / 100 ml, and the solution was measured at room temperature using a turbidimeter 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 (1), and Haze (%) was determined from the calculation formula Haze (%) = (DF / TT) × 100.

(19) ¹ H-NMR Measurement The compound was dissolved in CDCl ₃ or DMSO and measured at room temperature using a Varian GEMINI-200.

(20) Melting Point Measurement The compound was placed on a cover glass, and the
RO MELTINGPOINT APPARATUS
Was measured at a heating rate of 1 ° C./min.

(21) Elemental Analysis The phosphorus was analyzed by molybdenum blue colorimetry after wet decomposition of a PET resin chip. Other metals were subjected to high-frequency plasma emission analysis and atomic absorption analysis after incineration / acid dissolution.

(Example 1) (Synthesis example of phosphorus compound) A phosphorus compound represented by the following formula (42) (phosphorus compound A)
Synthesis of

[0280]

Embedded image

(1) Sodium (O-ethyl)
3,5-di-tert-butyl-4-hydro
Synthesis of xybenzylphosphonate 6.5 g of a 50% aqueous sodium hydroxide solution (84 mmo)
l) and 6.1 ml of methanol in a mixed solution
yl (3,5-di-tert-butyl-4-hy
(doxybenzyl) phosphonate 5
g (14 mmol) of a methanol solution (6.1 ml) was added, and the mixture was heated and refluxed for 24 hours under a nitrogen atmosphere. After the reaction,
While cooling the reaction mixture, 7.33 g of concentrated hydrochloric acid (70 mm
ol), and the precipitate was collected by filtration, washed with isopropanol, and the filtrate was distilled off under reduced pressure. The obtained residue was dissolved in hot isopropanol, the insoluble matter was collected by filtration, the isopropanol was distilled off under reduced pressure, and the residue was washed with hot heptane, dried and dried.
dium (O-ethyl 3,5-di-tert-
butyl-4-hydroxybenzylphos
3.4 g (69%) were obtained.

Shape: white powder Melting point: 294-302 ° C. (decomposition) ¹ H-NMR (DMSO, δ): 1.078 (3H,
t, J = 7 Hz), 1.354 (18H,
s), 2.711 (2H, d), 3.724 (2
H, m, J = 7 Hz), 6.626 (1H,
s), 6.9665 (2H, s) Elemental analysis (theoretical values in parentheses): Na 6.36%
(6.56%), P 9.18% (8.84%) (2) O-ethyl 3,5-di-tert-bu
tyl-4-hydroxybenzylphosphh
Synthesis of sonic acid (phosphorus compound A) Sodium (O-ethyl 3,5-di-t)
ert-butyl-4-hydroxybenzyl
Phosphonate 1.5 g of concentrated hydrochloric acid was added to 20 ml of an aqueous solution of 1 g (2.8 mmol), and the mixture was stirred for 1 hour. 150 ml of water was added to the reaction mixture, and the precipitated crystals were collected by filtration, washed with water, and dried to obtain O-ethyl 3,5-di-.
tert-butyl-4-hydroxybenzy
826 mg of lphosphonic acid (88
%)Obtained.

Shape: plate-like crystal Melting point: 126-127 ° C. ¹ H-NMR (CDCl ₃ , δ): 1.207 (3H,
t, J = 7 Hz), 1.436 (18H, s),
3.013 (2H, d), 3.888 (2H, d)
m, J = 7 Hz. ), 7.088 (2H, s),
7.679-8.275 (1H, br) (Polyester polymerization example) A high-purity terephthalic acid and a 2-fold molar amount of ethylene glycol were charged into a heating medium circulation type 2-liter stainless steel autoclave equipped with a stirrer, and triethylamine was acidified. 0.3 mol% is added to the components,
An esterification reaction was performed for 120 minutes while distilling water out of the system at 245 ° C. under a pressure of 0.25 Mpa, and a mixture of bis (2-hydroxyethyl) terephthalate (BHET) and an oligomer having an esterification rate of 95% (hereinafter referred to as “BET”). , BHE
T mixture). 2.5 parts of aluminum trisacetylacetonate were added to the BHET mixture.
g / l of ethylene glycol solution with respect to the acid component in the polyester as 0.015 mol as aluminum atom
In addition, an ethylene glycol solution of 10 g / l of the above phosphorus compound A was added as 0.04 mol% of the phosphorus compound A to the acid component in the polyester, and the mixture was stirred at 245 ° C. for 10 minutes under a normal pressure under a nitrogen atmosphere. . Then, the temperature of the reaction system was gradually lowered while raising the temperature to 275 ° C. over 50 minutes to obtain 0.1 Torr.
A polycondensation reaction was performed at rr. Table 1 shows the polymerization time (AP) required until the IV of polyethylene terephthalate reached 0.65 dlg ^-1 .

The polyethylene terephthalate having an IV of 0.65 dlg ^-1 obtained by the above polycondensation was formed into chips according to a conventional method. Various physical properties were measured using this PET resin chip. The results are shown in Tables 1 and 2.

[0285]

[Table 1]

[0286]

[Table 2]

PET having an intrinsic viscosity of 0.50 dl / g obtained by melt polymerization under the same conditions as above with a shortened polymerization time.
After crystallizing the resin chip surface at 160 ° C. under a nitrogen stream, the resin chip is dried at about 160 to 170 ° C. under a nitrogen stream in a stationary solid-state polymerization tower, and then solid-phase polymerized at 210 ° C., IV
Obtained PET of 0.74 dl / g.

This PET has a DEG content of 2.0 mol%, an acetaldehyde content of 2.3 ppm, a cyclic trimer content of 0.29 mass%, and a density of 1.422 g / cm.
^{Was 3} .

Next, a step-formed plate and a stretched hollow formed body were obtained by the methods described in the above (8) and (9). The haze of the molded plate molded using this PET was 3.9%, which was no problem.

The acetaldehyde content of the stretched hollow molded article at the time of the initial molding was 19.0 ppm, the cyclic trimer content was 0.37% by mass, the haze was 0.9%, and there was no problem. The value was no problem.

Further, 3,000 or more continuous stretch blow moldings were carried out, but no stain was found on the molds. The haze of the stretched hollow molded article was as low as 1.5%, and the transparency was good.

(Example 2) (Synthesis example of phosphorus compound) Synthesis of magnesium salt of phosphorus compound (phosphorus compound B) represented by the following formula (43)

[0293]

Embedded image

(1) Sodium (O-ethyl)
3,5-di-tert-butyl-4-hydro
Synthesis of xybenzylphosphonate (phosphorus compound B) 6.5 g of a 50% aqueous sodium hydroxide solution (84 mmo)
l) and 6.1 ml of methanol in a mixed solution
yl (3,5-di-tert-butyl-4-hy
(doxybenzyl) phosphonate 5
g (14 mmol) of a methanol solution (6.1 ml) was added, and the mixture was heated and refluxed for 24 hours under a nitrogen atmosphere. After the reaction,
While cooling the reaction mixture, 7.33 g of concentrated hydrochloric acid (70 mm
ol), and the precipitate was collected by filtration, washed with isopropanol, and the filtrate was distilled off under reduced pressure. The obtained residue was dissolved in hot isopropanol, the insoluble matter was collected by filtration, the isopropanol was distilled off under reduced pressure, and the residue was washed with hot heptane, dried and dried.
dium (O-ethyl 3,5-di-tert-
butyl-4-hydroxybenzylphos
3.4 g (69%) were obtained.

Shape: white powder Melting point: 294-302 ° C. (decomposition) ¹ H-NMR (DMSO, δ): 1.078 (3H,
t, J = 7 Hz), 1.354 (18H,
s), 2.711 (2H, d), 3.724 (2
H, m, J = 7 Hz), 6.626 (1H,
s), 6.9665 (2H, s) Elemental analysis (theoretical values in parentheses): Na 6.36%
(6.56%), P 9.18% (8.84%) (2) Magnesium bis (O-ethyl)
3,5-di-tert-butyl-4-hydro
Synthesis of xybenzylphosphonate (phosphorus compound B) Sodium (O-ethyl 3,5) under stirring at room temperature
-Di-tert-butyl-4-hydroxyb
benzylphosphonate) 500mg
(1.4 mmol) aqueous solution (4 ml), magnesium nitrate hexahydrate (192 mg, 0.75 mmol) aqueous solution 1
ml was added dropwise. After stirring for 1 hour, the precipitate was collected by filtration, washed with water,
Dry to Magnesium bis (O-ethyl
3,5-di-tert-butyl-4-hydr
oxybenzylphosphonate) to 359
mg (74%).

Shape: white powder Melting point:> 300 ° C. ¹ H-NMR (DMSO, δ): 1.0820 (6H,
t, J = 7 Hz), 1.3558 (36H,
s), 2.8338 (4H, d), 3.8102
(4H, m, J = 7 Hz), 6.6328 (2
(H, s), 6.9917 (4H, s) (Polyester polymerization example) A high-purity terephthalic acid and twice the molar amount of ethylene glycol were charged into a 2-liter stainless steel autoclave equipped with a stirrer and triethylamine was added. 0.3 mol% is added to the acid component,
An esterification reaction was performed for 120 minutes while distilling water out of the system at 245 ° C. under a pressure of 0.25 Mpa, and a mixture of bis (2-hydroxyethyl) terephthalate (BHET) and an oligomer having an esterification rate of 95% (hereinafter referred to as “BET”). , BHE
T mixture). 2.5 g / l of aluminum acetylacetonate was added to this BHET mixture.
0.015 mol% as an aluminum atom with respect to the acid component in the polyester was added to the acid component in the polyester, and the above-mentioned phosphorus compound B was added to the acid component in an amount of 0.02 mol%.
Then, the mixture was stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Then, over 50 minutes, the pressure of the reaction system was gradually lowered while the temperature was raised to 275 ° C. to 0.1 Torr, and the polycondensation reaction was further performed at 275 ° C. and 0.1 Torr. Polyethylene terephthalate IV is 0.65 dl
Table 3 shows the polymerization time (AP) required to reach g ⁻¹ .

Further, polyethylene terephthalate having an IV of 0.65 dlg ^-1 obtained by the above polycondensation was formed into chips according to a conventional method. Various physical properties were measured using this PET resin chip. The results are shown in Tables 3 and 4.

[0298]

[Table 3]

[0299]

[Table 4]

PET having an intrinsic viscosity of 0.50 dl / g obtained by melt polymerization under the same conditions as above with a shortened polymerization time.
After crystallizing the resin chip surface at 160 ° C. under a nitrogen stream, the resin chip is dried at about 160 to 170 ° C. under a nitrogen stream in a stationary solid-state polymerization tower, and then solid-phase polymerized at 210 ° C., IV
Obtained PET of 0.74 dl / g.

The PET content of this PET was 2.0 mol%, the acetaldehyde content was 2.4 ppm, the cyclic trimer content was 0.29 mass%, and the density was 1.423 g / cm.
^{Was 3} .

Next, a stepped plate and a stretched hollow molded body were obtained by the methods described in (8) and (9) above.

The haze of the formed plate was 3.7%, which was no problem. The acetaldehyde content of the stretched hollow molded article during the initial molding was 18.3 ppm, and the cyclic trimer content was 0.3.
The content was 7% by mass, the haze was 0.7%, which was no problem, and the sensory test was 1.5, which was no problem.

The P obtained by using the polycondensation catalyst of the present invention
A hollow molded article molded using ET is excellent in transparency and flavor.

[0305] Continuous stretch blow molding of 3000 or more tubes was carried out, but no mold contamination was observed. The haze of the stretched hollow molded article was as low as 1.5%, and the transparency was good.

Example 3 (Synthesis Example of Aluminum Salt of Phosphorus Compound) O-ethyl 3,5-di-tert-butyl
-4-hydroxybenzylphosphona
Synthesis of aluminum salt of te (aluminum salt A) (1) Sodium (O-ethyl 3,5-di-
tert-butyl-4-hydroxybenzy
Synthesis of 50% sodium hydroxide aqueous solution 6.5 g (84 mmo)
l) and 6.1 ml of methanol in a mixed solution
yl (3,5-di-tert-butyl-4-hy
(doxybenzyl) phosphonate 5
g (14 mmol) of a methanol solution (6.1 ml) was added, and the mixture was heated and refluxed for 24 hours under a nitrogen atmosphere. After the reaction,
While cooling the reaction mixture, 7.33 g of concentrated hydrochloric acid (70 mm
ol), and the precipitate was collected by filtration, washed with isopropanol, and the filtrate was distilled off under reduced pressure. The obtained residue was dissolved in hot isopropanol, the insoluble matter was collected by filtration, the isopropanol was distilled off under reduced pressure, and the residue was washed with hot heptane, dried and dried.
dium (O-ethyl 3,5-di-tert-
butyl-4-hydroxybenzylphos
3.4 g (69%) were obtained.

Shape: white powder Melting point: 294-302 ° C. (decomposition) ¹ H-NMR (DMSO, δ): 1.078 (3H,
t, J = 7 Hz), 1.354 (18H,
s), 2.711 (2H, d), 3.724 (2
H, m, J = 7 Hz), 6.626 (1H,
s), 6.9665 (2H, s) Elemental analysis (theoretical values in parentheses): Na 6.36%
(6.56%), P 9.18% (8.84%) (2) O-ethyl 3,5-di-tert-bu
tyl-4-hydroxybenzylphosphh
Synthesis of Onate Aluminum Salt (Aluminum Salt A) Sodium (O-ethyl 3,5
-Di-tert-butyl-4-hydroxyb
benzylphosphonate 1g (2.8m
5 mol of an aqueous solution of 364 mg (0.97 mmol) of aluminum nitrate 9 hydrate was added dropwise to 7.5 ml of an aqueous solution of the same. After stirring for 3 hours, the precipitate was collected by filtration, washed with water, and dried to obtain O-ethyl 3,5-di-tert-butyl.
l-4-hydroxybenzylphosphon
860 mg of aluminum salt of ate were obtained.

Shape: white powder Melting point: 183-192 ° C. (Example of polyester polymerization) A high-purity terephthalic acid and twice the molar amount of ethylene glycol were charged into a 2-liter stainless steel autoclave equipped with a stirrer, and triethylamine was added. Is added to the acid component by 0.3 mol%,
An esterification reaction was performed for 120 minutes while distilling water out of the system at 245 ° C. under a pressure of 0.25 Mpa, and a mixture of bis (2-hydroxyethyl) terephthalate (BHET) and an oligomer having an esterification rate of 95% (hereinafter referred to as “BET”). , BHE
T mixture). To the BHET mixture, 0.02 mol% of the above-mentioned aluminum salt A as an aluminum atom was added to the acid component in the polyester, and the mixture was stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Then, the temperature of the reaction system was gradually decreased while raising the temperature to 275 ° C. over 50 minutes to 0.1 Torr to further increase the pressure to 275 ° C.
The polycondensation reaction was performed at 0.1 ° C. and 0.1 Torr. The polymerization time (AP) required for the IV of polyethylene terephthalate to reach 0.65 dlg ^-1 was 98 minutes.

Further, polyethylene terephthalate having an IV of 0.65 dlg ^-1 obtained by the above polycondensation was formed into chips according to a conventional method.

The PET resin chip had a thermal stability parameter (TS) of 0.16, a hydrolysis resistance parameter (HS) of 0.05, and a thermal oxidation parameter (TOS) of less than 0.01.

PET having an intrinsic viscosity of 0.50 dl / g obtained by melt polymerization under the same conditions as above with a shortened polymerization time.
After crystallizing the resin chip surface at 160 ° C. under a nitrogen stream, the resin chip is dried at about 160 to 170 ° C. under a nitrogen stream in a stationary solid-state polymerization tower, and then solid-phase polymerized at 210 ° C., IV
Obtained PET of 0.74 dl / g.

The PET had a DEG content of 2.0 mol%, an acetaldehyde content of 2.3 ppm, a cyclic trimer content of 0.29 mass%, and a density of 1.423 g / cm.
^{Was 3} .

Then, a step-formed plate and a stretched hollow formed body were obtained by the methods described in the above (8) and (9).

The haze of the formed plate was 3.8%, which was no problem. The acetaldehyde content of the stretched hollow molded article during the initial molding was 20.0 ppm, and the cyclic trimer content was 0.3.
The content was 8% by mass and the haze was 0.9%, which was no problem, and the sensory test was 1.5, which was no problem.

The P obtained by using the polycondensation catalyst of the present invention
A hollow molded article molded using ET is excellent in transparency and flavor.

[0316] Further, continuous stretch blow molding of 3,000 or more pieces was carried out, but no mold staining was observed. The haze of the stretched hollow molded article was as low as 1.5%, and the transparency was good.

Example 4 13 g of aluminum chloride was used as a polycondensation catalyst for a mixture of bis (2-hydroxyethyl) terephthalate and an oligomer produced from high-purity terephthalic acid and ethylene glycol according to a conventional method.
/ L of an ethylene glycol solution in an amount of 0.015 mol% as an aluminum atom with respect to the acid component in the polyester
And Irganox 1425 (a compound of chemical formula (41), manufactured by Ciba Specialty Chemicals) at 10 g /
l Add ethylene glycol solution to Irgan
0.02 mol% was added as ox1425, and the mixture was stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Then, the pressure of the reaction system was gradually lowered while raising the temperature to 275 ° C. over 50 minutes to 13.3 Pa (0.1 Torr), and the polycondensation reaction was further performed at 275 ° C. and 13.3 Pa.
Note that Irganox 1425 (manufactured by Ciba Specialty Chemicals) is a compound of the formula 41.

The IV obtained by the above polycondensation is 0.65
dl / g of polyethylene terephthalate was formed into chips according to a conventional method.

The PET resin chip had a thermal stability parameter (TS) of 0.17, a hydrolysis resistance parameter (HS) of 0.05, and a thermal oxidation parameter (TOS) of less than 0.01.

PET having an intrinsic viscosity of 0.50 dl / g obtained by melt polymerization under the same conditions as above with a shortened polymerization time.
After crystallizing the resin chip surface at 160 ° C. under a nitrogen stream, the resin chip is dried at about 160 to 170 ° C. under a nitrogen stream in a stationary solid-state polymerization tower, and then solid-phase polymerized at 210 ° C., IV
Obtained PET of 0.74 dl / g.

This PET had a DEG content of 2.5 mol%, an acetaldehyde content of 2.4 ppm, a cyclic trimer content of 0.29 mass%, and a density of 1.423 g / cm.
^{Was 3} .

Next, a step-shaped molded plate and a stretched hollow molded body were obtained by the methods described in the above (8) and (9).

The haze of the formed plate was 3.6%, which was no problem. The acetaldehyde content of the stretched hollow molded article at the time of the initial molding was 20.1 ppm, and the cyclic trimer content was 0.3.
The content was 8% by mass and the haze was 0.9%, which was no problem, and the sensory test was 1.5, which was no problem.

The P obtained by using the polycondensation catalyst of the present invention
A hollow molded article molded using ET is excellent in transparency and flavor.

[0325] Further, continuous stretching blow molding of 3,000 or more pieces was carried out, but no mold contamination was observed, and the haze of the stretched hollow molded article was as low as 1.5%, and the transparency was good.

Example 5 The solid-phase polymerized PET (IV = 0.74 dl / g) obtained in Example 1 was dried under dehumidified nitrogen, and dry-blended with phosphoric acid. The mixture was melt-extruded to prepare a phosphoric acid-containing master chip.

The solid-phase polymerized PET of Example 1 and the above-mentioned master chip were mixed so that the phosphorus content derived from phosphoric acid became 150 ppm, dried under dehumidified nitrogen, and then subjected to the above (8) and (9). ) A step-shaped molded plate and a stretched hollow molded body were obtained by the method described in (1).

The haze of the formed plate was 4.5%, which was no problem. The acetaldehyde content of the stretched hollow molded article at the time of initial molding was 14.2 ppm, and the cyclic trimer content was 0.3.
1% by mass, haze was 1.1%, which was no problem, and the sensory test was 0.8, which was a problem-free value.

Separately, the solid-phase polymerized PET of Example 1 and the above-mentioned master chip were mixed with each other so that the phosphorus content derived from phosphoric acid was
After mixing to 0 ppm, the mixture was dried under dehumidified nitrogen, extruded with a melt extruder to form chips, and the amount of increase in cyclic trimer was measured by the method described in (5).
% By mass.

The P obtained by using the polycondensation catalyst of the present invention
A hollow molded article molded using ET is excellent in transparency and flavor.

[0331] Further, continuous stretch blow molding of 3000 or more tubes was carried out, but no stain on the mold was observed. The haze of the stretched hollow molded article was as low as 1.0%, and the transparency was good.

Example 6 The solid-phase polymerized PET (IV = 0.74 dl / g) obtained in Example 1 was dried under dehumidified nitrogen, and then dry-blended with phosphoric acid. The mixture was melt-extruded to prepare a phosphoric acid-containing master chip.

The solid-phase polymerized PET of Example 1 and the above-mentioned master chip were mixed so that the phosphorus content derived from phosphoric acid became 25 ppm, dried under dehumidified nitrogen, and then subjected to the above (8) and (9). ) A step-shaped molded plate and a stretched hollow molded body were obtained by the method described in (1).

The haze of the formed plate was 4.7%, which was no problem. The acetaldehyde content of the stretched hollow molded article at the time of initial molding was 15.8 ppm, and the cyclic trimer content was 0.3.
The value was 4% by mass, the haze was 1.0%, no problem, and the sensory test was 0.9, which was no problem.

Separately, the solid-phase polymerized PET of Example 1 and the above-mentioned master chip were mixed with each other to have a phosphorus content derived from phosphoric acid of 25%.
After mixing to give ppm, the mixture was dried under dehumidified nitrogen, extruded with a melt extruder to form chips, and the amount of increase in cyclic trimer was measured by the method described in (5). %Met.

The P obtained by using the polycondensation catalyst of the present invention
A hollow molded article molded using ET is excellent in transparency and flavor.

In addition, continuous stretch blow molding of 3,000 or more tubes was carried out, but no mold contamination was observed. The haze of the stretched hollow molded article was as low as 1.2%, and the transparency was good.

(Comparative Example 1) Melt polycondensation was carried out under the same conditions as in Example 1; the intrinsic viscosity was 0.74 dl / g, the DEG content was 2.0 mol%, and the acetaldehyde content was 98 p.
pm, the cyclic trimer content is 1.05% by mass, and the density is 1.
336 g / cm ³ of PET was obtained.

Next, a step-formed plate and a stretched hollow formed body were obtained by the methods described in the above (8) and (9). The haze of the molded plate molded using this PET was 6.8%, which was no problem.

However, the stretched hollow molded article at the time of initial molding had a high acetaldehyde content of 95 ppm, a cyclic trimer content of 1.10% by mass, and a haze of 4.6%. In addition, the sensory test was as high as 3.9, and the off-flavor and off-flavor was very serious.

A mold stain test was carried out, but the mold became severely stained after 300 continuous moldings, and the molding was stopped. The haze of the stretched product at this time was as high as 12.5%.

(Comparative Example 2) A catalyst was prepared in the same manner as in Example 1 except that antimony trioxide was used in an amount of 0.05 mol% as an antimony atom based on an acid component in PET as a catalyst. PET was manufactured.

The PET had an IV of 0.74 dl / g and a D
The EG content was 2.5 mol%, the acetaldehyde content was 2.9 ppm, the cyclic trimer content was 0.30% by mass, and the density was 1.422 g / cm ³ .

Next, a step-shaped molded plate and a stretched hollow molded body were obtained by the methods described in the above (8) and (9). The haze of the molded plate molded using this PET was as high as 18.1%.

The stretched hollow molded article at the time of initial molding had an acetaldehyde content of 22.5 ppm and a cyclic trimer content of 0.40% by mass, but had a very high haze of 9.2%. However, the sensory test was 1.2, which was a satisfactory value.

(Example 7) The solid phase polymerized PET of Example 1 and the phosphoric acid-containing master chip of Example 5 were mixed so that the phosphorus content derived from phosphoric acid became 10 ppm, and then dried under dehumidified nitrogen. Then, a stepped molded plate and a stretched hollow molded body were obtained by the methods described in the above (8) and (9).

The haze of the formed plate was as good as 4.8%. The acetaldehyde content of the stretched hollow molded article at the time of initial molding was 18.9 ppm, and the cyclic trimer content was 0.1.
36% by mass and haze were as good as 1.1%, and the sensory test was 0.9 which was a satisfactory value.

[0348] Separately, the solid-phase polymerized PET of Example 1 and the above-mentioned master chip were combined with each other at a phosphorus content derived from phosphoric acid of 10 p.
pm, dried under dehumidified nitrogen, extruded with a melt extruder to form chips, and the increase in cyclic trimer was measured by the method described in (5). %Met.

The P obtained by using the polycondensation catalyst of the present invention
The hollow molded body molded using ET is excellent in transparency and flavor. In addition, continuous stretch blow molding of 3,000 or more was performed, but almost no mold dirt was recognized.
The haze of the stretched hollow molded article was as low as 1.5%, and the transparency was good.

It should be understood that the embodiments and examples disclosed this time are illustrative in all aspects and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

[0351]

The present invention does not contain an antimony compound or a germanium compound as a main component of a catalyst, uses aluminum as a main metal component, has excellent catalytic activity, and is capable of preventing heat deterioration during melt molding without deactivating or removing the catalyst. A polyester which was effectively suppressed, was excellent in thermal stability, generated little foreign matter, was excellent in transparency, and was excellent in color tone was obtained.

 ──────────────────────────────────────────────────の Continued on the front page (72) Shoichi Katamai 2-1-1 Katata, Otsu-shi, Shiga F-term in Toyobo Co., Ltd. Research Laboratory 4F071 AA46 AF30 AH05 BA01 BB05 BB06 BB09 BC01 BC03 BC04 4J029 AA02 AC01 AD01 AE01 AE03 BA04 BA05 BA10 BB05A BB12A BB13A BD03A BD04A BF09 BF14A BF25 BH02 CA01 CA02 CA03 CA04 CA05 CB04A CB05A CB10 J CB12A CC05A CC06A CC07 CD01 JE01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB12 JC461 JC471 JC551 JC561 JC571 JF021 JF031 JF041 JF051 JF121 JF131 JF141 JF151 JF161 JF221 JF571 KE02 KE03 KH08

Claims (13)

[Claims] 1. A polyester containing ethylene terephthalate as a repeating unit, which is synthesized by a catalyst containing at least one of aluminum and an aluminum compound and a phenolic compound, and which contains a cyclic trimer. A polyester having an amount of 0.5% by mass or less. 2. A polyester containing ethylene terephthalate as a repeating unit, which is synthesized by a catalyst containing at least one of aluminum and an aluminum compound and a phosphorus compound, and has a cyclic trimer content. Is 0.5% by mass or less. 3. The polyester according to claim 1, wherein a phosphorus compound is further used as the catalyst. 4. The phosphorous compound is at least one of a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphonous acid compound, a phosphinous acid compound, or a phosphine compound. The polyester according to claim 2 or 3, wherein the polyester is contained. 5. The phosphorous compound represented by the following general formula (1)
The polyester according to any one of claims 2 to 4, comprising at least one of the compounds represented by (3). Embedded image Embedded image Embedded image (In the formulas (1) to (3), R ¹ , R ⁴ , R ⁵ , and R ⁶ each independently include hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. Represents a hydrocarbon group having 1 to 50 carbon atoms, 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. However, the hydrocarbon group may contain an alicyclic structure or an aromatic ring structure.) 6. The polyester according to claim 2, wherein the phosphorus compound contains at least one of a phosphorus acid and a metal salt compound. 7. The polyester according to claim 2, wherein the phosphorus compound contains at least a portion represented by the following chemical formula (4). Embedded image 8. The polyester according to claim 1, wherein the amount of the cyclic trimer increased by melting at a temperature of 290 ° C. for 30 minutes is 0.50% by mass or less. 9. The polyester according to claim 1, wherein the content of acetaldehyde in the polyester is 10 ppm or less. 10. The polyester has an intrinsic viscosity of 0.5.
The polyester according to any one of claims 1 to 9, wherein the polyester content is 5 to 1.50 deciliter / gram. 11. The polyester according to claim 1, wherein the polyester is a linear polyester containing 95 mol% or more of ethylene terephthalate as a repeating unit.
Polyester according to any one of the above. 12. A hollow molded article obtained by molding the polyester according to any one of claims 1 to 11. 13. A sheet-like substance obtained by molding the polyester according to any one of claims 1 to 11.