JP2003171451A - Method for producing polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester excellent in transparency and flavor, capable of providing a blow molded product scarcely containing a foreign matter and scarcely causing stain of a mold in molding and a method for producing an inexpensive polyester by which increase of filtration pressure of a filter in film formation is reduced. <P>SOLUTION: This method for producing the polyester comprises producing the polyester containing ethylene terephthalate as a main recurring unit by using at least one kind of metal compound selected from a magnesium compound, a calcium compound, a cobalt compound, a manganese compound and a zinc compound, and a phosphorus compound and an antimony compound. In the production method, polymerization is carried out in the presence of a specific amount of the metal compound and the resultant melted polycondensation polyester is formed into chips while cooling the polyester by using a cooling water in which chemical oxygen demand (COD) satisfies a specific range and then, solid phase polymerization of the chips is carried out. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention provides a hollow molded article or the like which is excellent in transparency and flavor (flavorability) and contains almost no foreign matter, and has little filter clogging during film formation. The present invention relates to a method for producing a polyester having improved operability.

[0002]

2. Description of the Related Art Polyester resins, especially polyethylene terephthalate (hereinafter simply referred to as "PET"), are excellent in transparency, mechanical strength, heat resistance, gas barrier property, and the like in carbonated beverages and juices. It is used as a material for containers such as stainless steel and mineral water, and its spread is remarkable. PE commonly used for such applications
T is mainly produced by using terephthalic acid and ethylene glycol as raw materials and using a germanium compound, an antimony compound, a titanium compound and a mixture thereof as a polycondensation catalyst.

In these applications, a polyester bottle is hot-filled with a beverage sterilized at high temperature, or is sterilized at high temperature after filling the beverage. There is a problem that shrinkage and deformation occur in etc. As a method for improving the heat resistance of a polyester bottle, a method has been proposed in which the bottle mouth plug is heat-treated to increase the crystallinity, or the stretched bottle is heat-fixed. In particular, when the crystallization of the spout is insufficient or the crystallization degree varies greatly, the sealing property with the cap may be deteriorated and the contents may leak.

In the case of beverages such as fruit juice drinks, oolong tea and mineral water which require hot filling, a method of crystallizing the preform or molded bottle by heat treating the mouth part (for example, Generally, refer to Patent Document 1 and Patent Document 2). In such a method, that is, a method of heat-treating the plug portion and the shoulder portion to improve heat resistance, the time and temperature of the crystallization treatment greatly affect the productivity, and the treatment can be performed at a low temperature in a short time. It is preferable that PET has a high rate of conversion. On the other hand, the body portion is required to be transparent even when subjected to heat treatment at the time of molding so as not to deteriorate the color tone of the bottle content, and the spout portion and the body portion need to have contradictory properties.

Among the above catalysts, the antimony catalyst is used as a catalyst for producing PET for fibers and films because of its low price. However, as compared with the case where a germanium compound or a titanium compound is used as a catalyst, the obtained PET has a higher crystallization rate and it is very difficult to obtain a hollow molded article having excellent transparency.

In order to solve these problems, a germanium compound or a mixture of this and a titanium compound is used as a polycondensation catalyst. However, the use of an expensive germanium compound has a drawback that the cost of PET increases. As a method for solving such a problem, a method is disclosed in which the transparency is improved by defining the usage ratio of the antimony compound and the phosphorus compound (for example, see Patent Document 3). However, P obtained by this method
The transparency of hollow moldings from ET is not sufficient.

Further, a continuous production method of polyester having excellent transparency using antimony trioxide, phosphoric acid and sulfonic acid compounds has been disclosed (for example, refer to Patent Document 4). However, the polyester obtained by such a method is poor in thermal stability, and the resulting hollow molded article has a high acetaldehyde content, which is a problem.

The present inventors have also proposed that an antimony compound,
Disclosed is a polyester in which the amount of metal compound such as magnesium and the amount of phosphorus compound used and the ratio of the amount used and the amount of basic nitrogen compound compounded are specified, and it is found that a molded article with improved transparency can be obtained from this polyester. (For example, refer to Patent Document 5). However, it has been found that, even when such a polyester is used, sometimes only a hollow molded article having very poor transparency and flavor (flavor) is obtained. When the solid-state polymerization treatment is carried out in order to decrease the acetaldehyde content of the melt-polycondensed polyester thus obtained and simultaneously increase the molecular weight, the transparency of the hollow molded article from the obtained solid-phase-polyester is obtained. The phenomenon that the fluctuation of the sex becomes large, the flavor property becomes very poor, and the amount of foreign matters mixed into the vessel wall of the hollow molded body becomes large frequently occurs. In particular, when solid phase polymerization treatment is carried out for a long period of time using the same equipment, there is a problem that the flavor property is poor, foreign matter is mixed in very much, and only a hollow molded product having no commercial value can be obtained. I understand.

The melt polycondensed polyester prepolymer is
After completion of the melt polycondensation, the product is extruded through the pores and made into chips while being cooled with cooling water. Using distilled water as cooling water in this chip formation process is disadvantageous in terms of cost,
It is common to use industrial water that is a simple treatment of water, groundwater, drainage, etc. from rivers. However, it has been found that when the cooling treatment is performed using industrial water, there may be a problem in that the flavor and aroma of the content of the obtained molded container are extremely deteriorated. In such a case, crystallization of the obtained polyester at the time of molding is too early, resulting in a bottle with poor transparency, and shrinkage of the plug part due to crystallization of the plug part does not fall within the specifications. There was also the problem of capping failure.

According to the results of the study conducted by the present inventors, in the chip forming step, bacteria, bacteria and the like derived from the nature contained in industrial water, organic particles and organic compounds originating from spoiled plants and animals, etc. If the content is more than a certain value, these substances may be adsorbed and penetrated into the surface of the polyester chip during the solid-state polymerization step, and further deteriorate to adversely affect the flavor and odor of the contents of the molding container. I have come to understand that there is.

Further, in the chip forming process, the above-mentioned COD attached to the surface of the chip and brought into the solid-state polymerization reactor.
The causative substance, an organic compound or a metal-containing substance, adheres to the vessel wall of the solid-state polymerization device together with a part of the surface layer of the polyester chip, which becomes a scale by long-time heating at a high temperature of about 170 ° C or higher. It adheres to the vessel wall. Then, it sometimes peels off and mixes into the polyester chip, and becomes a foreign substance in a molded article such as a bottle, which may reduce the commercial value.

[0012]

[Patent Document 1] JP-A-55-79237

[Patent Document 2] Japanese Patent Laid-Open No. 58-110221

[Patent Document 3] JP-A-6-279579

[Patent Document 4] Japanese Patent Laid-Open No. 10-36495

[Patent Document 5] Japanese Patent Laid-Open No. 2000-129102

[0013]

DISCLOSURE OF THE INVENTION The present invention is to solve the problems of the prior art, and provides a hollow molded article excellent in transparency and flavor, and the obtained molded article is a foreign substance. The present invention relates to a method for producing a polyester that contains almost no such substances and is less likely to cause mold stains during molding of a molded body.

[0014]

In order to achieve the above object, a method for producing a polyester according to the present invention comprises at least one metal compound selected from a magnesium compound, a calcium compound, a cobalt compound, a manganese compound and a zinc compound, In the method for producing a polyester, which uses a phosphorus compound and an antimony compound to produce a polyester mainly composed of an aromatic dicarboxylic acid component and a glycol component, the metal compound described above in (1) to
An amount satisfying (3) is added and a dicarboxylic acid containing an aromatic dicarboxylic acid as a main component or an ester-forming derivative thereof is reacted with a glycol or an ester-forming derivative thereof to form a low polycondensate. Obtained, and then polycondensed, and subsequently, the polyester obtained is made into chips while cooling with cooling water having a chemical oxygen demand (COD) satisfying the following (4), and then solid-phase polymerized. It is a method for producing a polyester. 0.1 ≤ Me ≤ 3 (1) 0.1 ≤ Me / P ≤ 2 (2) 0.3 ≤ Sb ≤ 3 (3) COD ≤ 2.5 (mg / l) (4) (in the above formula , Me is the number of moles of metal atom of at least one metal compound selected from magnesium compound, calcium compound, cobalt compound, manganese compound and zinc compound per ton of polymer, and P is the phosphorus compound per ton of polymer. The number of moles of phosphorus atom in Sb is polymer-1
The number of moles of antimony atom of the antimony compound per ton is shown. )

In this case, at least water treated by an ion exchange device can be used as the cooling water in the chip forming step.

In this case, the content of either the fine content of the polyester, the content of the film-like material, or the total content of the fine content and the content of the film-like material can be 5000 ppm or less.

Here, fine means JIS-Z8801.
According to JIS means fine powder of polyester that has passed through a sieve having a mesh size of 1.7 mm, and a film-like material remains on a sieve having a mesh size of 5.6 mm according to JIS-Z8801. Of polyester, it means a film-like material after two or more chips are fused or the chip-like material cut into pieces larger than the normal shape is removed, and the content thereof is measured by the following measuring method. .

In this case, as a gas which comes into contact with the polyester in at least one of the melt polycondensation step, the chip formation step, the solid phase polymerization step, and the fine removal step, particles having a particle size of 0.3 to 5 μm are 1,000,000.
It is possible to use a gas introduced from outside the system, which is equal to or less than the number of pieces / cubic foot.

In this case, the polyester is a polyester containing ethylene terephthalate as the main repeating unit, and the peak temperature on the highest side of the fine melting peak temperature contained in the polyester is 26.
It can be 5 ° C or less. Here, as described below, the melting point of fine is measured using a differential scanning calorimeter (DSC), and the melting peak temperature of DSC is called the melting point.
The melting peak representing this melting point is composed of one or more melting peaks, and in the present invention,
In the case where there is one melting peak, the peak temperature thereof, and in the case of a plurality of melting peaks, the melting peak temperature of the highest temperature side among these plural melting peaks, The peak temperature on the highest side of the fine melting peak temperature is referred to as "fine melting point" in Examples and the like.

In this case, the polyester obtained by injection molding has an intrinsic viscosity of 0.55 to 2.0 deciliter / gram, an acetaldehyde content of 10 ppm or less, and a cyclic trimer content of 0.5% by weight or less. A polyester having ethylene terephthalate as a main repeating unit, which has a haze of 15% or less, and a crystallization temperature (Tc1) measured by DSC at the time of temperature rise of the molded plate of 150 to 170 ° C. Can be

In this case, at least one resin selected from the group consisting of a polyolefin resin, a polyamide resin and a polyacetal resin can be blended with the above polyester.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the method for producing a polyester of the present invention will be specifically described below. The polyester according to the present invention is a thermoplastic polyester comprising a dicarboxylic acid containing an aromatic dicarboxylic acid as a main component or an ester-forming derivative thereof and a glycol or an ester-forming derivative thereof, and preferably an aromatic dicarboxylic acid. A thermoplastic polyester in which the acid unit contains 85 mol% or more of the acid component, more preferably a thermoplastic polyester in which the aromatic dicarboxylic acid unit contains 90 mol% or more of the acid component, and particularly preferably the aromatic dicarboxylic acid unit is the acid component. Is 95% by mole or more of the thermoplastic polyester.

The aromatic dicarboxylic acid component constituting the polyester according to the present invention includes terephthalic acid, 2,6-
Examples thereof include aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid and diphenoxyethanedicarboxylic acid, and ester-forming derivatives thereof.

As the glycol component constituting the polyester according to the present invention, ethylene glycol, 1,3
Examples include alicyclic glycols such as trimethylene glycol, tetramethylene glycol, cyclohexanedimethanol, and the like.

The acid component used by copolymerization in the polyester is terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, diphenyl-4,4 '.
Aromatic dicarboxylic acids such as dicarboxylic acid and diphenoxyethanedicarboxylic acid, oxyacids such as p-oxybenzoic acid and oxycaproic acid, and ester-forming derivatives thereof, adipic acid, sebacic acid, succinic acid, glutaric acid, dimer Examples thereof include aliphatic dicarboxylic acids such as acids and ester-forming derivatives thereof, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid and ester-forming derivatives thereof.

The glycol component used by copolymerization in the polyester is ethylene glycol, 1,
Aliphatic glycols such as 3-trimethylene glycol, tetramethylene glycol, diethylene glycol and neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, aromatic glycols such as bisphenol A and alkylene oxide adducts of bisphenol A, polyethylene glycol- And polyalkylene glycol such as polybutylene glycol.

Further, as the polyfunctional compound as a copolymerization component used when the polyester is a copolymer, examples of the acid component include trimellitic acid and pyromellitic acid. Examples of the component include glycerin and pentaerythritol. The amount of the above copolymerization component used should be such that the polyester maintains a substantially linear shape. Further, a monofunctional compound such as benzoic acid or naphthoic acid may be copolymerized.

A preferred example of the thermoplastic polyester according to the present invention is a thermoplastic polyester whose main repeating unit is ethylene terephthalate, more preferably 85 mol% of ethylene terephthalate unit.
A linear copolymerized thermoplastic polyester containing the above and including isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedimethanol as a copolymerization component, and particularly preferably 95 ethylene terephthalate units.
It is a linear thermoplastic polyester containing at least mol%. Examples of these linear thermoplastic polyesters include polyethylene terephthalate (hereinafter abbreviated as PET), poly (ethylene terephthalate-ethylene isophthalate) copolymer, poly (ethylene terephthalate-1,4-cyclohexanedimethylene terephthalate) copolymer Examples thereof include a polymer, a poly (ethylene terephthalate-ethylene-2,6-naphthalate) copolymer, and a poly (ethylene terephthalate-dioxyethylene terephthalate) copolymer.

In another preferred example of the thermoplastic polyester according to the present invention, the main repeating unit is ethylene-
A thermoplastic polyester composed of 2,6-naphthalate, more preferably a linear thermoplastic polyester containing 85 mol% or more of ethylene-2,6-naphthalate units, particularly preferably ethylene- It is a linear thermoplastic polyester containing 95 mol% or more of 2,6-naphthalate units. Examples of these linear thermoplastic polyesters include polyethylene-2,6-naphthalate, poly (ethylene-2,6-naphthalate-ethylene terephthalate) copolymer, poly (ethylene-2,6-naphthalate-ethylene isophthalate). Copolymer, poly (ethylene-2,6-naphthalate-dioxyethylene-2,
6-naphthalate) copolymer and the like.

Another preferred example of the polyester according to the present invention is a linear polyester containing 1,3-propylene terephthalate units in an amount of 85 mol% or more, 1,4.
-Cyclohexane dimethylene terephthalate unit 85
It is a linear polyester containing not less than mol% or a linear polyester containing not less than 85 mol% of butylene terephthalate units.

The method for producing the polyester of the present invention will be described by taking polyethylene terephthalate as an example. This is to directly esterify terephthalic acid with ethylene glycol and / or a third component to distill off water and esterify. Then, a direct esterification method in which polycondensation is carried out under reduced pressure, or after dimethyl terephthalate is reacted with ethylene glycol and / or a third component to distill off methyl alcohol to effect transesterification, and then under reduced pressure. A method of producing a polyester by producing a melt polycondensed polyester by any method of transesterification method in which polycondensation is performed, then increasing the intrinsic viscosity, and then performing solid-phase polymerization to reduce the acetaldehyde content etc. Is. In order to accelerate crystallization before solid-phase polymerization, the melt-polymerized polyester may be adsorbed with moisture and then crystallized by heating, or steam may be directly blown onto the polyester chips to be crystallized by heating.

The melt polycondensation reaction may be carried out in a batch reactor or a continuous reactor.
In any of these methods, the melt polycondensation reaction may be carried out in one step or may be carried out in multiple steps. The solid phase polymerization reaction can be carried out by a batch type apparatus or a continuous type apparatus as in the melt polycondensation reaction. The melt polycondensation and solid phase polymerization may be carried out continuously or may be carried out separately.

An example of a preferable continuous production method will be described below by taking polyethylene terephthalate as an example. First, the case of producing a low polymer by an esterification reaction will be described. A slurry containing 1.02 to 1.5 mol, preferably 1.03 to 1.4 mol of ethylene glycol per 1 mol of terephthalic acid or its ester derivative was prepared, and this slurry was continuously subjected to the esterification reaction step. To supply

In the esterification reaction, water or alcohol produced by the reaction is removed from the system in a rectification column under the condition that ethylene glycol is refluxed using a multistage apparatus in which at least two esterification reactors are connected in series. While removing. The temperature of the first stage esterification reaction is 240 to
270 ° C, preferably 245-265 ° C, pressure 0.2
~ 3 kg / cm ² G, preferably 0.5-2 kg / cm ²
G. The temperature of the last stage esterification reaction is usually 25
0 to 280 ° C., preferably 255 to 275 ° C., the pressure is usually 0 to 1.5 kg / cm ² G, preferably 0 to 1.
It is 3 kg / cm ² G. When it is carried out in three or more stages, the reaction conditions for the intermediate stage esterification reaction are
It is a condition between the reaction conditions of the first stage and the reaction conditions of the final stage. The increase in the reaction rate of these esterification reactions is preferably distributed smoothly at each stage. Finally, the esterification reaction rate is 90% or more, preferably 93%
It is desirable to reach the above. A low-order condensate having a molecular weight of about 500 to 5000 is obtained by these esterification reactions.

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

Further, tertiary amines such as triethylamine, tri-n-butylamine and benzyldimethylamine, tetraethylammonium hydroxide, tetra-hydroxide.
When quaternary ammonium hydroxide such as n-butylammonium or trimethylbenzylammonium hydroxide and a basic compound such as lithium carbonate, sodium carbonate, potassium carbonate or sodium acetate are added in a small amount, the main chain of polyethylene terephthalate can be improved. It is preferable because the ratio of the dioxyethylene terephthalate component unit can be maintained at a relatively low level (5 mol% or less based on the total diol component).

Next, when a low polymer is produced by a transesterification reaction, 1.1 to 1.6 mol, preferably 1.2 to 1.5 mol of ethylene glycol is added to 1 mol of dimethyl terephthalate. The contained solution is prepared and continuously fed to the transesterification reaction step.

In the transesterification reaction, methanol produced by the reaction is removed to the outside of the system in a rectification column under the condition that ethylene glycol is distilled off using a device in which 1 to 2 transesterification reactors are connected in series. While doing. The temperature of the first-stage transesterification reaction is 180 to 250 ° C, preferably 200 to 240 ° C. The temperature of the final stage transesterification reaction is usually 230 to 270 ° C., preferably 24.
0-265 ° C., zinc as a transesterification catalyst,
Fatty acid salts such as cadmium, magnesium, manganese, cobalt, calcium, barium, carbonates, lead, zinc,
Antimony, germanium oxide, etc. are used. A low-order condensate having a molecular weight of about 200 to 500 is obtained by these transesterification reactions.

As the starting material dimethyl terephthalate, terephthalic acid or ethylene glycol, virgin dimethyl terephthalate derived from paraxylene, ethylene glycol derived from terephthalic acid or ethylene, and used PE are used.
A recovered raw material such as dimethyl terephthalate, terephthalic acid, bishydroxyethyl terephthalate or ethylene glycol recovered from a T bottle by a chemical recycling method such as methanol decomposition or ethylene glycol decomposition can also be used as at least a part of the starting material. It goes without saying that the quality of the recovered raw material must be refined to the purity and quality according to the purpose of use.

Next, the obtained low-order condensate is supplied to a multi-stage liquid phase condensation polymerization process. Regarding the polycondensation reaction conditions, the reaction temperature of the first stage polycondensation is 250 to 290 ° C., preferably 260 to 280 ° C., and the pressure is 500 to 20 Torr.
r, preferably 200 to 30 Torr, and the temperature of the final polycondensation reaction is 265 to 300 ° C., preferably 275.
The pressure is 10 to 0.1 Torr, preferably 5 to 0.5 Torr. When it is carried out in three or more stages, the reaction conditions of the polycondensation reaction in the intermediate stage are those between the reaction conditions of the first stage and the reaction conditions of the final stage. The degree of increase in intrinsic viscosity reached in each of these polycondensation reaction steps is preferably distributed smoothly.

The method for producing the polyester of the present invention comprises a magnesium compound, a calcium compound, a cobalt compound,
In the method for producing a polyester, which comprises using at least one metal compound selected from a manganese compound and a zinc compound, a phosphorus compound and an antimony compound to produce a polyester mainly composed of an aromatic dicarboxylic acid component and a glycol component, The compound is the following (1)
A low polycondensate by adding an amount satisfying (3) to (3) to react a dicarboxylic acid having an aromatic dicarboxylic acid as a main component or an ester-forming derivative thereof with a glycol or an ester-forming derivative thereof. And then polycondensed the same, followed by chipping the obtained polyester with cooling water having a chemical oxygen demand (COD) satisfying the following (4), followed by solid phase polymerization. A method for producing a polyester, which solves the above-mentioned problems of flavor and transparency. 0.1 ≤ Me ≤ 3 (1) 0.1 ≤ Me / P ≤ 2 (2) 0.3 ≤ Sb ≤ 3 (3) COD ≤ 2.5 (mg / l) (4) (in the above formula , Me is the number of moles of metal atom of at least one metal compound selected from magnesium compound, calcium compound, cobalt compound, manganese compound and zinc compound per ton of polymer, and P is the phosphorus compound per ton of polymer. The number of moles of phosphorus atom in Sb is polymer-1
The number of moles of antimony atom of the antimony compound per ton is shown. )

A magnesium compound, a calcium compound, which is used in the method for producing a polyester of the present invention,
Any cobalt compound, manganese compound, and zinc compound can be used as long as they are soluble in the reaction system.

Examples of the magnesium compound include magnesium hydride, magnesium oxide, lower fatty acid salts such as magnesium acetate, and alkoxides such as magnesium methoxide.

Examples of calcium compounds include lower fatty acid salts such as calcium hydride, calcium hydroxide and calcium acetate, and alkoxides such as calcium methoxide.

Examples of the cobalt compound include lower fatty acid salts such as cobalt acetate, organic acid salts such as cobalt naphthenate and cobalt benzoate, chlorides such as cobalt chloride, and cobalt acetylacetonate.

As the manganese compound, manganese acetate,
Examples thereof include organic acid salts such as manganese benzoate, chlorides such as manganese chloride, alkoxides such as manganese methoxide, and manganese acetylacetonate.

Examples of the zinc compound include organic acid salts such as zinc acetate and zinc benzoate, chlorides such as zinc chloride, alkoxides such as zinc methoxide and zinc acetylacetonate.

The addition amount of the magnesium compound, calcium compound, cobalt compound, manganese compound, and zinc compound represented by the general formula (1) is 0.1 to 3 mol as the metal atom of the metal compound per ton of polyester. The range is 0.15 to 2.5 mol, and more preferably 0.2 to 2.0 mol. If the amount of the polymer is less than 0.1 mol per ton, the transparency of the obtained hollow molded product from the polyester, particularly the stretch-heat-fixed hollow molded product, will be extremely poor. On the other hand, if it exceeds 3 mol, the thermal stability of the polyester is poor and the content of acetaldehyde becomes high, which causes a problem in flavor.

A magnesium compound, a calcium compound, which is used in the method for producing a polyester of the present invention,
Cobalt compounds, manganese compounds and zinc compounds are
In the case of transesterification reaction, it is preferably added before the transesterification reaction. In the case of esterification reaction, the timing of adding these metal compounds is not particularly limited.

Examples of the phosphorus compound used in the method for producing the polyester of the present invention include phosphoric acid, phosphorous acid, phosphonic acid and their derivatives. Specific examples include phosphoric acid, phosphoric acid trimethyl ester, phosphoric acid triethyl ester, phosphoric acid tributyl ester, phosphoric acid triphenyl ester, phosphoric acid monomethyl ester,
Phosphoric acid dimethyl ester, phosphoric acid monobutyl ester,
Phosphoric acid dibutyl ester, phosphorous acid, phosphorous acid trimethyl ester, phosphorous acid triethyl ester, phosphorous acid tributyl ester, methylphosphonic acid, methylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester, phenylphosphonic acid dimethyl ester, phenyl-
Luphosphonic acid diethyl ester, phenylphosphonic acid diphenyl ester and the like, which may be used alone or in combination of two or more kinds.

The addition amount of the phosphorus compound represented by the general formula (2) is such that the molar ratio Me / P of the metal atom of the above metal compound to the phosphorus atom of the phosphorus compound per ton of polyester finally obtained. Is in the range of 0.1 to 2, preferably 0.2 to 1.9, and more preferably 0.3 to 1.8. When Me / P is less than 0.1, the transparency of the hollow molded article, especially the stretch-heat-fixed hollow molded article, obtained from the obtained polyester resin is extremely deteriorated. On the other hand, when it exceeds 2, the thermal stability of the polyester is poor and the content of acetaldehyde becomes high, which causes a problem in flavor.

The phosphorus compound used in the method for producing the polyester of the present invention is preferably added after the transesterification reaction in the case of the transesterification reaction.
In the case of esterification reaction, the timing of adding these phosphorus compounds is not particularly limited. It may be added at least twice.

Examples of the antimony compound used in the method for producing a polyester of the present invention include antimony trioxide, antimony acetate, antimony tartrate, antimony tartrate potassium, antimony oxychloride, antimony glycolate, antimony pentoxide, triphenyl antimony and the like. Is mentioned.

The content of the antimony compound represented by the general formula (3) is in the range of 0.3 to 3 moles, preferably 0.5 to 3, as the antimony atom of the antimony compound per ton of the obtained polyester. The amount is 2.5 mol, more preferably 0.8 to 2.3 mol. If the amount of the polymer is less than 0.3 mol per ton, the polycondensation time becomes very long, which is a problem from the viewpoint of economical productivity. Also,
If it exceeds 3 mol, the transparency of the obtained hollow molded article may be deteriorated or the color tone may be deteriorated, which is a problem.

The timing of adding the antimony compound is not particularly limited, but may be before the esterification reaction or before the transesterification reaction.

In the method for producing a polyester of the present invention, it is preferable to further use a basic nitrogen compound.
The basic nitrogen compound may be any of aliphatic, alicyclic, aromatic and heterocyclic nitrogen compounds. Specific examples include triethylamine, tributylamine, dimethylaniline, dimethylaniline, pyridine, quinoline, dimethylbenzylamine, piperidine, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, triethylbenzylammonium hydroxide, imidazole and imidazoline. Can be mentioned. These compounds may be used in a free form, or may be used as a salt of a lower fatty acid or TPA. Further, these compounds may be used alone or in combination of two or more kinds.

The blending amount of these basic nitrogen compounds is 0.01 to 1 mol%, preferably 0.0
It is 5 to 0.7 mol%, more preferably 0.1 to 0.5 mol%. 0.01 mol% of basic nitrogen compound
When it is less than 1, the transparency of the obtained hollow molded article from the polyester, particularly the stretch-heat-fixed hollow molded article, becomes extremely poor. Further, if it exceeds 1 mol%, the color tone of the polyester becomes poor.

The addition of the basic nitrogen compound used in the method for producing the polyester of the present invention to the reaction system can be appropriately selected at any stage until the completion of the initial polycondensation reaction, and may be performed alone. However, it may be performed at the same time as other additives.

In the method for producing a polyester of the present invention, as described above, the obtained melt polycondensed polyester is first made into chips while cooling with cooling water satisfying the above (4), and then solidified. It is necessary to carry out phase polymerization. COD ≤ 2.5 (mg / l) (4)

The COD of the cooling water used in the chip forming step is 0.1 to 2.5 mg / l, preferably 0.1 to 2.0 m.
g / l, more preferably 0.1-1.5 mg / l. If the COD of the cooling water used in the chip formation step is less than 0.1 mg / l, the equipment cost may increase and economical chip formation may not be possible. Further, when the COD of the cooling water used in the chip forming step exceeds 2.5 mg / l, the flavor property of the content of the molded body may be deteriorated, which is a problem.

Magnesium compound, calcium compound,
At least one metal compound selected from a cobalt compound, a manganese compound and a zinc compound, a P compound and an antimony compound are polycondensed using an amount satisfying the above (1) to (3), and then the above ( C that satisfies 4)
Transparency and flavor of a molded product of a polyester mainly composed of an aromatic dicarboxylic acid component and a glycol component, which is obtained by solid-state polymerization of a molten polycondensed polyester chipped while cooling with OD cooling water, The operability is very excellent, and in particular, the transparency and crystallization rate of the hollow molded article made of polyester containing ethylene terephthalate as the main repeating unit are stable with very little fluctuation.

Solid-state polymerization of polyester chipped while cooling with cooling water that deviates from the above conditions causes organic substances and the like in cooling water adhering to the chip surface and brought into the solid-state polymerization reactor in the chipping step. It is presumed that the impurities in the above are deteriorated by heating at high temperature for a long time. Due to this, the flavor property of the polyester molded product obtained under such conditions is deteriorated. Further, the impurities adhering to the chip surface and brought into the solid-state polymerization reaction device adhere to the vessel wall of the solid-state polymerization device together with a part of the surface layer of the polyester chip, and become a scale with a high metal content. It adheres to the vessel wall. Further, there is a problem that the product is sometimes peeled off and mixed in the polyester chip to become a foreign substance in a molded body such as a bottle, which lowers the commercial value.

Further, when the sheet is manufactured, the scale is clogged in the molten polymer filtration filter at the time of film formation, so that the filtration pressure of the filter increases sharply, resulting in poor operability and productivity. There is also the problem of becoming.

The cooling water C used in the chip forming process is described below.
A method for reducing OD is exemplified, but the present invention is not limited thereto.

In order to reduce the COD of the cooling water used in the chipping process, the COD of water is reduced to at least one place in the process until industrial water is sent to the chipping process in order to supply it to the chipping process. Install a device to
Further, a device for reducing COD may be installed in at least one or more places in the process until the water discharged from the chipping process is returned to the chipping process again. Examples of a device for reducing COD include a device that performs microfiltration, coagulation and sedimentation, and activated carbon treatment.

Further, in the method for producing a polyester of the present invention, the sodium content, magnesium content, silicon content and calcium content in the introduction water introduced into the chipping step are respectively set to N, M and S. , C, it is desirable that the melt polycondensed polyester be chipped so as to satisfy at least one of the following (5) to (8). N ≤ 1.0 (ppm) (5) M ≤ 0.5 (ppm) (6) S ≤ 2.0 (ppm) (7) C ≤ 1.0 (ppm) (8)

The sodium content (N) in the introduced water is preferably N ≦ 0.5 ppm, more preferably N
≦ 0.1 ppm. The magnesium content (M) in the introduced water is preferably M ≦ 0.3 ppm, more preferably M ≦ 0.1 ppm. The content (S) of silicon in the introduced water is preferably S ≦ 0.5 ppm, more preferably S ≦ 0.3 ppm. Further, the calcium content (C) in the introduced water is preferably C ≦ 0.5 ppm, more preferably C ≦ 0.1.
It is ppm.

The lower limits of the sodium content (N), magnesium content (M), silicon content (S) and calcium content (C) in the introduced water are N ≧
0.001ppm, M ≧ 0.001ppm, S ≧ 0.0
2 ppm and C ≧ 0.001 ppm. In order to make it below such a lower limit value, enormous capital investment is required, and the operating cost becomes very high, so that economical production is difficult.

The sodium content (N), the magnesium content (M), the silicon content (S) and the calcium content (C) are at least 1 of the above (5) to (8).
In particular, the transparency and flavor of the molded product from the polyester obtained by solid-phase polymerizing the melt polycondensed polyester chipped while cooling with introduced water satisfying all of the above are very excellent, and Filter during film formation-Few clogging and very stable operability.

When the introduced water that deviates from the above conditions is used, the metal-containing substance attached to the chip surface and brought into the solid-state polymerization reactor in the chip forming step is one of the surface layers of the polyester chip. It adheres to the vessel wall of the solid-state polymerization apparatus together with the part, and this becomes a scale with a high metal content and adheres to the vessel wall by long-term heating at a high temperature of about 170 ° C. or higher. Then, it sometimes peels off and mixes into the polyester chip, and becomes foreign matter in the molded body such as a bottle, which may reduce the commercial value.

The method for suppressing the sodium content, magnesium content, silicon content, and calcium content of the introduced water within the above ranges will be illustrated below, but the present invention is not limited thereto.

In order to reduce sodium, magnesium, calcium, and silicon in the introduced water, a device for removing sodium, magnesium, calcium, and silicon is installed at at least one place in the process until industrial water is sent to the chip forming process. To do. A filter is installed to remove clay minerals such as particulate silicon dioxide and aluminosilicate. Examples of the device for removing sodium, magnesium, calcium, and silicon include an ion exchange device, an ultrafiltration device, and a reverse osmosis membrane device. Further, the particle size existing in the introduced water introduced from outside the system is 1 to 25 μm.
It is desirable to use water having m particles of 50,000 particles / 10 ml or less. The number of particles having a particle size of 1 to 25 μm in the introduced water is preferably 10,000 particles / 10 ml or less,
It is more preferably 1000 pieces / 10 ml or less, and particularly preferably 100 pieces / 10 ml or less.

The lower limit value of particles having a particle size of 1 to 25 μm is 1 particle / 10 ml or more. To reduce the particle size to the lower limit value or less, enormous equipment investment is required, and the operating cost becomes very high. Economical production is difficult.

Particles having a particle size exceeding 25 μm in the introduced water are
Although not particularly specified, preferably 2000 /
It is 10 ml or less, more preferably 500 pieces / 10 ml or less, further preferably 100 pieces / 10 ml, and particularly preferably 10 pieces / 10 ml or less.

The particles having a particle size of less than 1 μm in the introduced water are not particularly specified in the present invention, but in order to obtain a transparent molded product or a polyester which gives a molded product having an appropriate crystallization rate. The smaller the number, the better. Particle size 1
The number of particles less than μm is preferably 100,000 /
10 ml or less, more preferably 50,000 pieces / 10 ml
Or less, more preferably 20,000 pieces / 10 ml or less,
Particularly preferably, it is 10,000 pieces / 10 ml or less. 1
As a method for removing and controlling particles having a size of μm or less from water, a microfiltration method or an ultrafiltration method using a membrane such as a ceramic membrane or an organic membrane can be used.

50,000 particles / 10 ml of particles having a particle size of 1 to 25 μm in the introduced water to be introduced in the chip forming step below.
The control method is illustrated below, but the present invention is not limited to this.

As a method for reducing the number of particles in water to 50,000 particles / 10 ml or less, an apparatus for removing particles is installed at at least one place until natural water such as industrial water is supplied to the chip forming step. Preferably, from a natural water sampling port, a device for removing particles is installed during the chip formation step, and the water is supplied to the chip formation step.
The content of particles having a particle size of 1 to 25 μm is 50,000 / 10
It is preferably less than or equal to ml. Examples of the device for removing particles include a filter filtration device, a membrane filtration device, a sedimentation tank, a centrifuge, and a foam entrainment treatment device. For example, in the case of a filter filtration device, examples thereof include a belt filter system, a bag filter system, a cartridge filter system, a centrifugal filtration system and the like. Among them, the belt filter method, centrifugal filtration method,
A bag filter type filtration device is suitable. If it is a belt filter type filtering device,
Examples include paper, metal and cloth. Further, the size of the mesh of the filter is 5 to 100 μm, preferably 10 to 70 μm, and more preferably 15 to 40 μm in order to remove particles and efficiently introduce water.

Further, it is preferable to use the cooling water for the chips while repeatedly recycling them, from the viewpoint of improving economical efficiency and productivity. A filter, a temperature controller, a device for removing impurities such as acetaldehyde, and the like can be provided during the cooling water recycling process. Further, a device for removing the above particles, sodium, magnesium, calcium, and silicon can be provided.

The intrinsic viscosity of the polyester obtained from the final polycondensation reactor of the melt polycondensation is 0.30 to 0.80.
Deciliter / gram, preferably 0.35 to 0.75
Deciliter / gram, more preferably 0.40
It is preferably in the range of 0.70 deciliters / gram. If the intrinsic viscosity is less than 0.30 deciliter / gram, the degree of crystallinity becomes too high in the pre-crystallization before solid phase polymerization, which slows down the solid phase polymerization rate, making economical production impossible. Also, due to the brittleness of the chips, a large amount of polyester fines are generated in the pre-crystallization and solid-state polymerization steps as described later, the crystallization rate is very fast, and the fluctuation of the rate is very large. Only polyester can be obtained. Further, when the intrinsic viscosity exceeds 0.80 deciliter / gram, the acetaldehyde content of the solid-phase polymerized polyester obtained from such melt polycondensed polyester cannot be reduced to 10 ppm or less. Therefore, the flavor and odor of the content of the molded product obtained from such solid-phase polymerized polyester are adversely affected. In addition, the hue also becomes very yellow, which reduces the commercial value of the obtained molded product.

In the chip forming step, the molten polycondensed polyester is extruded into the water through the pores of the die and cut in water, or is extruded into the air and immediately cut while cooling with cooling water. Chiped by etc.

In the manufacturing method of the present invention, the shape of the polyester chips may be any of cylinder type, square type, spherical type or flat plate type. Its average particle size is usually 1.5
˜5 mm, preferably 1.6 to 4.5 mm, more preferably 1.8 to 4.0 mm. For example, in the case of a cylinder type, the length is 1.5 to 4 mm and the diameter is 1.5.
It is practically about 4 mm. In the case of spherical particles, it is practical that the maximum particle size is 1.1 to 2.0 times the average particle size and the minimum particle size is 0.7 times or more the average particle size. Further, it is practical that the weight of the chip is in the range of 10 to 30 mg / piece.

The melt polycondensed polyester thus obtained is solid-phase polymerized by a conventionally known method in the solid-phase polymerization step. First, the melt polycondensed polyester to be subjected to solid-phase polymerization is heated at a temperature of 100 to 210 ° C. for 1 to 5 hours under an inert gas or under reduced pressure, or an atmosphere of steam or an inert gas containing steam. Pre-crystallized. Then, solid phase polymerization is performed at a temperature of 190 to 230 ° C. for 1 to 30 hours in an inert gas atmosphere or under reduced pressure. In the case of polyester having an intrinsic viscosity of 1.0 or more used for direct blow, the solid phase polymerization time may exceed 30 hours. After solid phase polymerization, if necessary, under reduced pressure or an inert gas atmosphere, about 150
It is cooled to -50 ° C or lower.

The polyester melt-polycondensed as described above is chipped and then transported through the transportation pipe to a storage silo or a solid phase polymerization step. When such chips are transported by, for example, a forced low-density transportation method using air, a large impact force is applied to the surface of the polyester chips due to a collision with a pipe, and as a result, fines or film-like substances are generated. It occurs in large quantities. Such fine or film-like material has the effect of promoting the crystallization of polyester, and when it is present in a large amount, the transparency of the obtained molded product becomes extremely poor. In addition, such fines and film-like substances have a melting point whose peak temperature on the highest side of the melting peak temperature measured as described below is higher than the normal melting point by about 10 to 20 ° C. or more. Things are included. Also, when the solid phase polymerization is carried out using a rotary type solid phase polymerization apparatus, or when a feeder for applying impact force or shearing force to the polyester chips is used as a transportation method to the next step, the melting peak is also used. A very large amount of fine or film-like substances having a melting point whose peak temperature on the highest temperature side is higher than the normal melting point by about 10 to 20 ° C. or more are generated. It is presumed that this is because the chip heats up due to a large force such as an impact force applied to the chip surface, and at the same time, oriented crystallization of polyester occurs on the chip surface, resulting in a dense crystal structure.

The fine or film-like material of polyester having a melting point of about 10 to 20 ° C. higher than the normal melting point of the peak temperature of the highest melting peak temperature as described above is solid-phase polymerized with polyester chips. Upon treatment, these melting points are even higher than before treatment. Further, the peak temperature on the highest side of the melting peak temperature is about 10 ° C from the normal melting point.
Even fine or film-like materials with melting points not too high,
The above-mentioned treatments make these melting points have a melting point higher than the normal melting point by about 10 to 20 ° C. or more.
It is presumed that this is because the crystal structure is changed to a more dense crystal structure by these treatments.

A polyester containing fine or film-like material having a melting point having a melting point higher than the normal melting point by about 10 to 20 ° C. or more is molded under normal molding conditions. In this case, such a high melting point crystal is not completely melted during melt molding and remains as a crystal nucleus. As a result, the crystallization rate at the time of heating becomes very fast, and the crystallization of the plug part of the hollow molding container becomes excessive, so that the shrinkage amount of the plug part does not fall within the specified value range, and The problem of capping failure and leakage of contents occurs. In addition, the hollow-molding preform is whitened, which makes normal stretching impossible, resulting in uneven thickness, and the high crystallization rate results in poor transparency of the obtained hollow-molded product and also in transparency. Fluctuation also becomes a big problem.

A hollow-molding spare having good transparency and stretchability from polyester containing fines having a melting point whose peak temperature on the highest side of the melting peak temperature is about 10 to 20 ° C. higher than the normal melting point. In order to obtain a molded product or a sheet-like product, it must be melt-molded at a temperature higher than the normal melting point by about 30 to 50 ° C or more. However, at such a high temperature, thermal decomposition of polyester becomes severe,
A large amount of by-products such as acetaldehyde and formaldehyde are generated, and as a result, the flavor and the like of the resulting contents such as molded products are greatly affected. Further, when the polyester obtained by the production method of the present invention is blended with a resin such as the following polyolefin resin, since these resins are often inferior in thermal stability to the polyester of the present invention, the above About 30 ~ than the normal melting point
In the case of molding at a temperature higher than 50 ° C., thermal decomposition occurs and a large amount of by-products are generated, so that the flavor of the obtained molded product or the like has a greater effect.

In general, the melt polycondensed polyester and the solid-state polyester described below depend on the production method, but some fine or film-like substances having a melting point higher than the normal melting point by about 10 to 20 ° C. or more as described above. About 1 including fine
It is contained in an amount of about 00 ppm to about several wt% and, moreover, such fines are not present in the melt polycondensed polyester chips in a uniform mixed state but are unevenly distributed.

Therefore, the polyester and the solid-phase polymerized polyester which have been melt-polycondensed in the melt polycondensation step and then made into chips are transported to a fine etc. removal step for separating and removing fines and / or film-like matters, and It is important to remove as much of these as possible before they are processed in the process.

Examples of the method for removing fine particles include a vibrating screen step separately installed immediately before or after the solid phase polymerization step, a method for air flow classification by an air flow, a gravity type classification step and the like. . You may add these processes further.

The fine content, film content, or fine content and film content of the melt polycondensed polyester prepolymer after the fine and / or film-like material is removed by the fine removal step. Of the total content of 500pp
The above-mentioned problems are solved by making m or less, and it is desirable to reduce to 300 ppm or less, more preferably 100 ppm or less, and further preferably 50 ppm or less.

The fine content of the polyester after solid phase polymerization is set to 5000 ppm or less to solve the above problems, and preferably 3000 pp.
m or less, more preferably 1000 ppm or less, further preferably 500 ppm or less, most preferably 100 pp
It is desirable to reduce it to m or less.

In the case of a polyester whose main repeating unit is ethylene terephthalate, most of the melting peak temperature of the fine and / or film-like substances contained in the polyester treated by the fine removing step is the most. When the melting peak temperature on the high temperature side is 265 ° C., the crystallization rate of the polyester obtained by the above-mentioned reason becomes too fast, or its fluctuation becomes very large, and the obtained hollow molding The pre-molded body is whitened, which makes normal stretching impossible, resulting in uneven thickness, poor transparency of the obtained hollow molded body, and large fluctuation of transparency, which is a serious problem.

Therefore, in the case of the polyester having ethylene terephthalate as the main repeating unit obtained by the present invention, the highest melting peak temperature of fine contained in the polyester treated by the fine removing step is the highest temperature. The melting peak temperature of 265 ° C. or less solves the above problems.

In the present invention, the melting point of chips or fines is measured by the following method using a differential scanning calorimeter (DSC). The melting peak temperature of DSC is called the melting point. The melting peak representing this melting point is composed of one or more melting peaks. In the present invention, when there is one melting peak, the peak temperature is
When there are a plurality of melting peaks, the melting peak temperature on the highest temperature side among the plurality of melting peaks is defined as "the peak on the highest temperature side of the fine melting peak temperature". In the examples, etc., it is referred to as "melting temperature of fine".

Further, as a method for preventing the inclusion of fines having a melting peak temperature on the highest side of the melting peak temperature exceeding 265 ° C., the following method can be mentioned. That is, after melt polycondensation, the molten polyester is extruded into water from a die and cut in water, or extruded into the air and immediately cut with cooling water while cutting into chips, and then formed into chips. After the chips are drained, chips, fines and film-like substances with a shape other than the prescribed size are removed by a vibrating screen process and an air flow classification process using an air flow, and the chips are sent to a storage tank by a plug transport system or a bucket type conveyor-transport system. . Use the screw to remove the chips from the tank.
With a formula feeder, it is transported to the next process by a plug transportation system or a bucket conveyor transportation system, and an air flow classification process by an air flow or a vibrating sieving process etc. is provided immediately before the solid-state polymerization process. Perform removal processing. Further, the melt polycondensed polyester which has been subjected to the removal treatment of the fine or film-like material described above is again subjected to an air stream classification step by an air flow immediately before the solid-state polymerization step, or a vibrating sieving step, etc. It is also possible to carry out the removal and directly add it to the solid phase polymerization step. When transporting the melt-polycondensed prepolymer chips to the solid-state polymerization equipment or when transporting the polyester chips after the solid-state polymerization to the sieving process, heat treatment process, storage tank, etc., most of these transports are plugged. Adopting a transportation method or a bucket type conveyor transportation method, and using a screw feeder to withdraw chips from the crystallization device or the solid-state polymerization reactor, equipment for chips and processes, transportation piping, etc. Use a device that can minimize the impact with.

According to the method for producing a polyester of the present invention, regardless of whether a batch type solid phase polymerization apparatus or a continuous type solid phase polymerization apparatus is used, continuous production is carried out for a period of from half a year to one or more. However, transparency and flavor
Properties of the solid-phase polymerized polyester that does not deteriorate the properties, contains almost no foreign matter, and provides an economical hollow molded product, etc., and a solid phase with improved filterability and economical efficiency during film formation. It is possible to obtain a polymerized polyester.

According to the method for producing a polyester of the present invention, the intrinsic viscosity is 0.55 to 2.0 deciliter / gram, the acetaldehyde content is 10 ppm or less, and the cyclic 3
The content of the polymer is 0.5% by weight or less, the haze of the molded plate obtained by injection molding is 15% or less, and the crystallization temperature (Tc1) of the molded plate measured by DSC is 150 to 17
It is possible to obtain an inexpensive polyester having ethylene terephthalate as a main repeating unit in the range of 0 ° C.

The intrinsic viscosity of the polyester whose main repeating unit is ethylene terephthalate obtained by the production method of the present invention is preferably 0.60 to 0.60.
1.50 deciliters / gram, more preferably 0.
It is in the range of 65 to 1.30 deciliters / gram. When the intrinsic viscosity is less than 0.55 deciliter / gram, the mechanical properties of the obtained molded product and the like are poor. On the other hand, if it exceeds 2.0 deciliters / gram, the resin temperature becomes high when melted by a molding machine or the like, and thermal decomposition becomes violent, resulting in an increase in free low-molecular-weight compounds that affect aroma retention, or a molded product. Will be colored yellow.

The polyester obtained by the production method of the present invention has an acetaldehyde content of 10 ppm or less, preferably 8 ppm or less, more preferably 5 ppm.
Hereinafter, the formaldehyde content is 7 ppm or less, preferably 6 ppm or less, and more preferably 4 ppm or less. If the acetaldehyde content exceeds 10 ppm or if the formaldehyde content disappears below 7 ppm,
The flavor, smell and the like of the contents such as molded articles obtained from such polyesters are deteriorated.

Further, the amount of diethylene glycol copolymerized with the polyester obtained by the production method of the present invention is 1.0 of the glycol component constituting the polyester.
˜5.0 mol%, preferably 1.3 to 4.5 mol%, more preferably 1.5 to 4.0 mol%. If the amount of diethylene glycol exceeds 5.0 mol%, the thermal stability becomes poor, the molecular weight decreases significantly during molding, and the acetaldehyde content and formaldehyde content increase undesirably. If the content of diethylene glycol is less than 1.0 mol%, the transparency of the obtained molded product will be poor.

The content of the cyclic trimer of the polyester obtained by the production method of the present invention is 0.5% by weight or less, preferably 0.45% by weight or less, more preferably 0.40% by weight or less. . When a heat-resistant hollow molded article or the like is molded from the polyester of the present invention, heat treatment is carried out in a heating mold, but when the content of the cyclic trimer is 0.5% by weight or more, the heating mold is heated. Adhesion of oligomers to the surface sharply increases, and the transparency of the obtained hollow molded article is extremely deteriorated.

The haze of the molded plate obtained from the polyester whose main repeating unit is ethylene terephthalate obtained by the production method of the present invention is preferably 1.
0% or less, more preferably 8% or less, and the crystallization temperature (Tc1) at the time of heating is preferably 155 to 16
The temperature is 8 ° C, more preferably 158 to 165 ° C.

When the haze of the molded plate exceeds 15%,
The obtained hollow molded article has poor transparency, which is a problem particularly in the case of a stretched hollow molded article. Also, Tc1 is 17
If the temperature exceeds 0 ° C., the crystallization rate by heating becomes very slow, the crystallization of the plug portion of the hollow molded body becomes insufficient, and the problem of leakage of the contents occurs. Further, when Tc1 is less than 150 ° C., the transparency of the hollow molded article decreases, which becomes a problem.

Further, in the hollow molded article, the plug portion is subjected to heat crystallization treatment depending on the application, but it may be difficult to control crystallization due to variation of molding conditions or heating conditions, and a large number of defective products. May occur. In order to solve such a problem, in the production method of the present invention, it is desirable that at least one resin selected from the group consisting of a polyolefin resin, a polyamide resin, and a polyacetal resin is blended with the polyester. The compounding ratio of the above-mentioned polyolefin resin is 0.1 ppb.
~ 50,000 ppm, preferably 0.3 ppb-100
00 ppm, more preferably 0.5 ppb to 100 pp
m, more preferably 1.0 ppb to 1 ppm, particularly preferably 1.0 ppb to 45 ppb. If the compounding amount is less than 0.1 ppb, the crystallization speed will be very slow and the mouthpiece of the hollow molded article will not be sufficiently crystallized. Therefore, if the cycle time is shortened, the amount of shrinkage of the mouthpiece will be regulated. Capping failure occurs because it does not fall within the value range, and the stretch heat-fixing mold for molding the heat-resistant hollow molded product is heavily contaminated, and the mold is frequently cleaned when trying to obtain a transparent hollow molded product. There must be. Also 50,000p
If it exceeds pm, the crystallization speed becomes fast, and the crystallization of the plug part of the hollow molded body becomes excessive, so that the shrinkage / shrinkage amount of the plug part does not fall within the specified range, resulting in poor capping. Of the hollow molded body and the preformed body for the hollow molded body is whitened, which makes normal stretching impossible. Further, in the case of a sheet-like material, if it exceeds 50,000 ppm, the transparency becomes extremely poor and the stretchability becomes poor so that normal stretching is impossible, and only a stretched film with large thickness unevenness and poor transparency is obtained. I can't. Further, when the above-mentioned polyolefin resin or the like is used alone, it is hardly effective in preventing stains on the heating die, but it has been found that coexistence with a specific amount of fine is very effective on stains on the die.

In the method for producing polyester of the present invention, examples of the polyolefin resin blended with the polyester include polyethylene resin, polypropylene resin, and α-olefin resin. Further, these resins may be crystalline or amorphous.

In the method for producing a polyester of the present invention, examples of the polyethylene resin blended with the polyester include a homopolymer of ethylene, ethylene and propylene, butene-1,3-methylbutene-1, pentene-1, Other α having about 2 to 20 carbon atoms such as 4-methylpentene-1, hexene-1, octene-1, and decene-1
-Copolymers with olefins and vinyl compounds such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, and styrene can be mentioned. Specifically, for example, low / medium / high density polyethylene (branched or linear) ethylene homopolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-4-methyl, etc. Pentene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-octene-1 copolymer, ethylene-vinyl acetate copolymer,
Examples thereof include ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-ethyl acrylate copolymers, and other ethylene-based resins.

In the method for producing a polyester of the present invention, examples of the polypropylene resin to be blended with the polyester include homopolymers of propylene, propylene and ethylene, butene-1,3-methylbutene-1,
Pentene-1,4-methylpentene-1, hexene-
Other α-olefins having about 2 to 20 carbon atoms such as 1, octene-1, and decene-1, and vinyl compounds such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, and styrene. And the like. Specific examples thereof include propylene-based resins such as propylene homopolymer, propylene-ethylene copolymer, and propylene-ethylene-butene-1 copolymer.

Further, in the method for producing a polyester of the present invention, the α-olefin resin blended with the polyester is, for example, 4-methylpentene-1 homopolymer of α-olefin having about 2 to 8 carbon atoms, And other α-olefins having about 2 to 20 carbon atoms such as ethylene, propylene, butene-1, 3-methylbutene-1, pentene-1, hexene-1, octene-1, and decene-1. And the like. Specifically, for example, butene-1 homopolymer, 4-methylpentene-1
Homopolymer, butene-1-ethylene copolymer, butene-
Examples thereof include butene-1 type resins such as 1-propylene copolymers and copolymers of 4-methylpentene-1 and C _{2 to} C ₁₈ α-olefins.

Further, in the method for producing a polyester of the present invention, examples of the polyamide resin blended with the polyester include butyrolactam, δ-valerolactam,
Polymers of lactams such as ε-caprolactam, enantolactam and ω-laurolactam, 6-aminocaproic acid,
Polymers of aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, undecamethylenediamine,
Aliphatic diamines such as 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-
Alicyclic diamines such as bis (aminomethyl) cyclohexane and bis (p-aminocyclohexylmethane), diamine units such as aromatic diamines such as m- or p-xylylenediamine, and glutaric acid, adipic acid, suberic acid, Polycondensates with aliphatic dicarboxylic acids such as sebacic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, dicarboxylic acid units such as aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and copolymers thereof Specifically, for example, nylon 4, nylon 6, nylon 7, nylon 7, nylon 8, nylon 9, nylon 11, nylon 12, nylon 66, nylon 69, nylon 610,
Nylon 611, Nylon 612, Nylon 6T, Nylon 6I, Nylon MXD6, Nylon 6 / MXD6,
Nylon MXD6 / MXDI, Nylon 6/66, Nylon 6/610, Nylon 6/12, Nylon 6/6
T, nylon 6I / 6T and the like. Further, these resins may be crystalline or amorphous.

Further, in the method for producing a polyester of the present invention, examples of the polyacetal resin blended with the polyester include polyacetal homopolymers and copolymers. As the polyacetal homopolymer, A
The density measured by STM-D792 is 1.4.
Polyacetal having a melt flow ratio (MFR) of 0 to 1.42 g / cm ³ , measured by ASTM D-1238 at 190 ° C. and a load of 2160 g of 0.5 to 50 g / 10 minutes is preferable.

Further, as the polyacetal copolymer,
The density measured by the method of ASTM-D792 is 1.
38 to 1.43 g / cm ³ , a polyacetal copolymer having a melt flow ratio (MFR) measured at 190 ° C. and a load of 2160 g of 0.4 to 50 g / 10 min by the measuring method of ASTMD-1238 was obtained. preferable. Examples of these copolymerization components include ethylene oxide and cyclic ethers.

As a method of blending the thermoplastic resin such as the above-mentioned polyolefin resin with the polyester, a method of directly adding the thermoplastic resin to the polyester so that the content thereof is in the above range and melt-kneading Or, in addition to a conventional method such as a method of adding as a master-batch and melt-kneading, the above-mentioned thermoplastic resin is used in the production step of the polyester, for example, during melt polycondensation, immediately after melt polycondensation, immediately after pre-crystallization. , During solid phase polymerization, immediately after solid phase polymerization, etc., or during the period from the end of the manufacturing stage to the molding stage, etc., as a powder or granules, or polyester chips It is also possible to use a method in which the above-mentioned thermoplastic resin member is mixed under such a flow condition as described above and then mixed and then melt-kneaded.

Here, as a method for bringing the polyester chip-shaped body into contact with the above-mentioned thermoplastic resin member under a flow condition, the polyester chip-like member is placed in an empty space where the above-mentioned thermoplastic resin member is present. It is preferable to bring the members into collisional contact with each other. Specifically, for example, during a production process such as immediately after melt polycondensation of polyester, immediately after pre-crystallization, immediately after solid-phase polymerization, or at a transportation stage as a product of polyester chips. Part of the aerodynamic transport pipe, gravity transport pipe, silo, magnet part of the magnet catcher, etc. when filling / discharging the transport container of Or lining with the above-mentioned thermoplastic resin, or the above-mentioned thermoplastic resin part such as a rod-shaped or net-like body in the transfer path. The by, for example installation, and a method of transferring the polyester chips. The contact time of the polyester chip with the member is usually an extremely short time of about 0.01 second to several minutes, but a small amount of the thermoplastic resin can be mixed into the polyester.

Further, in the present invention, in order to produce a polyester having an appropriate crystallization rate and giving little variation in crystallization rate, the polyester is contact-treated with a member made of the above-mentioned thermoplastic resin. In addition, by treating the polyester in a sieving process for removing fines and film-like substances and a removal process such as fines by an air stream, the fine content of polyester, the film-like substance content, or the fine content and film-like substance content. It is desirable to reduce the content of any one of the total content to 500 ppm or less.

On the other hand, when the member made of the thermoplastic resin and the polyester are contact-treated, it is preferable that the thermoplastic resin is present in a state of being adhered to the surface of the polyester chip. The thermoplastic resin member may be a polyester chip depending on the magnitude of the impact force when it collides with the member, the pressure force when contacting the member, or the impact resistance and peeling resistance of the thermoplastic resin member. There is also a state in which it is mixed with the above-mentioned contact-treated polyester chip in a state where it does not adhere to, that is, in a state independent of the polyester chip. The molded product obtained from the polyester in such a mixed state has a too high crystallization rate, or has a very large fluctuation in the rate.
In the case of a preformed body for a hollow molded body, only a hollow molded body having a large transparency and whitening and transparency unevenness, normal stretching is impossible, and large thickness unevenness and poor transparency can be obtained. Usually, the above contact-treated polyester is present as fine fine particles, but sometimes in the form of granules or agglomerates having an average particle diameter of about 0.5 to several mm, independent of the polyester chips. It may be mixed in. In such a case, the thermoplastic resin becomes a foreign substance in the obtained molded body, and as a result, the resulting molded body has unevenness in thickness, pores,
There are many defects such as whitening. Therefore, it is desirable to remove the fine particles, particles or lumps of the thermoplastic resin existing independently of the polyester chips before molding.

The following methods may be mentioned as a method for separating and removing the fine particles, particles or lumps of the thermoplastic resin from the polyester which has been contact-treated with the member made of the thermoplastic resin. That is, after melt-polycondensed polyester or solid-phase polymerized polyester is contact-treated with a member made of the above-mentioned thermoplastic resin, it is treated by a vibration sieving step and a stream classification step by an air flow, or a washing step with ion-exchanged water. The thermoplastic resin in the form of fine granules, granules and lumps is removed by a method such as the method described above, or a method of performing a floating selection treatment. The method of separating and removing the fine particles, particles or lumps of the thermoplastic resin as described above is also effective as a method of removing the polyester fines or film-like materials described below.

In the production process of polyester, a silo, a hopper of a molding machine, and transportation are carried out through each step such as a melt polycondensation step to a solid phase polymerization step, or a solid phase polymerization step to a sieving step, an air stream classification step, and the like. Although it is filled in a container such as a container for use in transporting and drying the polyester between these processes, air around the treatment facility is generally taken into the process by a blower or the like and used. Conventionally, such air is either left untreated or used according to JIS.
It was generally used only after being processed by a cleaner equipped with a low-performance filter unit such as type 3 defined in B 9908 (1991). However, when the air treated in such a process is used, there is a problem that only a molded product having poor transparency can be obtained.

Therefore, in the method for producing a polyester of the present invention, from the step of transporting the polyester chips obtained in the melt polycondensation step to the next step, as the gas that comes into contact with the polyester in the subsequent steps,
It is desirable to use a gas having a particle size of 0.3 to 5 μm that is introduced from outside the system of 1,000,000 (pieces / cubic foot) or less.

Particles having a particle diameter of less than 0.3 μm in a gas are not particularly specified, but a smaller amount is preferable in order to obtain a resin giving a transparent molded body.
The number of particles having a particle size of less than 0.3 μm is preferably 100.
It is 00000 (pieces / cubic feet) or less, more preferably 5,000,000 (pieces / cubic feet) or less, and further preferably 2000000 (pieces / cubic feet or less).

A method for controlling the number of particles having a particle size of 0.3 to 5 μm in the gas introduced from outside the system to 1,000,000 (particles / cubic foot) or less is illustrated below, but the present invention is not limited to this. Not something to do. As a method for reducing the number of particles having a particle size of 0.3 to 5 μm in the gas introduced from outside the system to 1,000,000 (particles / cubic foot) or less, a step of contacting the gas introduced from the outside with the polyester chips A cleaning device for removing the particles is installed at at least one place inside. In the case where the gas is air in the vicinity of processing equipment, during the process until the air introduced by the blower from the air inlet comes into contact with the polyester chips,
Format 1 specified in JIS B 9908 (1991)
Alternatively, it is preferable to install a gas cleaning device equipped with a type 2 filter unit and set the number of particles having a particle size of 0.3 to 5 μm in the air to 1,000,000 (pieces / cubic feet) or less. . In addition, JIS is installed in the air sampling port.
It is possible to extend the life of the filter unit by installing a gas cleaning device equipped with a type 3 filter unit defined in B 9908 (1991) and using it together with the gas cleaning device equipped with the filter unit. It is possible.

JIS B 99 for removing particles in gas
As a material of the ultra-high performance filter (hereinafter referred to as HEPA filter) unit of type 1 defined in 08 (1991), a filter paper made of glass fiber can be mentioned.

In addition, JIS B 9908 (1991)
Examples of the material for the high-performance filter unit of the type 2 defined in 1. include a filter made of polypropylene fiber, a filter made of a laminate of Teflon (R) film and PET fiber cloth, and the like. Generally, an electrostatic filter made of polypropylene fiber is used.

In addition, JIS B 9908 (1991)
Examples of the material of the low-performance filter unit of the type 3 defined in 1. include non-woven fabric made of PET or polypropylene.

The polyester obtained by the production method of the present invention is a PET obtained by using a raw material such as dimethyl terephthalate or terephthalic acid recovered by purifying a used PET bottle by a chemical recycling method as at least a part of the starting material, Flake PE that is used PET bottle purified by mechanical recycling method and collected
It can be used as a mixture with T or PET in the form of chips.

The polyester obtained by the production method of the present invention may optionally contain other additives such as known ultraviolet absorbers, antioxidants, oxygen absorbers, oxygen scavengers,
A lubricant added from the outside or a lubricant that is internally precipitated during the reaction,
You may mix | blend various additives, such as a mold release agent, a nucleating agent, a stabilizer, an antistatic agent, and a pigment.

When the polyester obtained by the production method of the present invention is used for a sheet or the like, in order to improve handling properties such as slipperiness, winding property, blocking resistance, etc. Calcium carbonate,
Inorganic particles such as magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, and magnesium phosphate, organic salt particles such as terephthalate salts such as calcium and calcium oxalate, barium, zinc, manganese, and magnesium, and divinyl. Inert particles such as crosslinked polymer particles such as homopolymers or copolymers of benzene, styrene, acrylic acid, methacrylic acid, vinyl monomers of acrylic acid or methacrylic acid can be contained.

The hollow molded article using the polyester obtained by the production method of the present invention can be manufactured by a commonly used melt molding method,
That is, it can be molded by a method such as an injection blow, a direct blow, and a stretching blow.

When a stretched hollow molded article is produced, a transparent hollow molded article having excellent heat resistance can be produced from the polyester of the present invention by using a known method such as the hot parison method or the cold parison method. I can.

When a stretched hollow molded article is produced using the polyester obtained by the production method of the present invention, a preformed article is first formed by injection molding and then stretch blow-molded to form a bottle. Injection molding is generally performed at an injection temperature of about 265 to about 300 ° C., about 30 to about 70 kg.
It is carried out at an injection pressure of / cm 2 to form a preform. The plug portion of this preform is heat-treated to crystallize it. The preformed body thus obtained is preheated to about 80 to about 120 ° C. in the cold parison method and cooled to about 80 to about 120 ° C. in the hot parison method. Approximately 120 times this preform in a blow mold.
Stretch blow-molded at about 210 ° C, then about 0.5-
Heat treatment for about 30 seconds. The stretching ratio is usually 1.3 to 3.5 times in the machine direction and 2 to 6 times in the circumferential direction.
The polyester obtained by the production method of the present invention can also be used for a multilayer hollow molded article.

[0130]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The method of measuring the main characteristic values will be described below.

(1) Intrinsic viscosity (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) Diethylene glycol content (hereinafter referred to as "DEG content") Decomposition with methanol, the DEG amount was quantified by gas chromatography, and expressed as a ratio (mol%) to all glycol components. did.

(3) Acetaldehyde content (hereinafter referred to as "A
"A content") Resin pellet sample / distilled water = 1 g / 2 ml is put in a glass ampoule with nitrogen substitution, the upper part is sealed, and it is heated at 160 ° C. for 2 hours.
After time extraction treatment, after cooling, the acetaldehyde in the extract is measured by high-sensitivity gas chromatography and the concentration is pp
Displayed in m.

(4) Cyclic trimer content of polyester resin A resin pellet sample was added to hexafluoroisopropanol /
Dissolve in the chloroform mixture and add more chloroform to dilute. To this is added methanol to precipitate the polymer, which is then filtered. The filtrate was evaporated to dryness, adjusted to a constant volume with dimethylformamide, and quantified by liquid chromatography.

(5) Measurement of fine content and film-like material content Approximately 0.5 kg of resin was used as a sieve (A) with a wire mesh having a nominal size of 5.6 mm according to JIS-Z8801 and a nominal size of 1.7.
A sieve (diameter 20 cm) (B) having a metal mesh of mm was placed on the sieve in which the two stages were combined, and sieved with a rocking type sieving tow machine SNF-7 manufactured by Terraoka at 1800 rpm for 1 minute. This operation was repeated, and a total of 20 kg of the resin was sieved.

When, in addition to the film-like material, two or more chips fused to each other or a chip-like material cut into a size larger than the normal shape are trapped on the sieve (A). The remaining film-like material from which these had been removed and the fines sieved off under the sieve (B) were separately washed with ion-exchanged water, filtered with a G1 glass filter manufactured by Iwaki Glass Co., Ltd., and collected. These were dried together with the glass filter in a dryer at 100 ° C. for 2 hours, cooled and weighed. The same operation of washing with ion-exchanged water and drying was repeated again to confirm that the weight became constant, and the weight of the glass filter was subtracted from this weight to obtain the fine weight and the weight of the film-like material. Fine content or film-like material content is fine weight or film-like material weight /
The total weight of resin screened. The total content is calculated from these values.

(6) Measurement of fine peak temperature of fine particles Differential scanning calorimeter (DS) manufactured by Seiko Denshi Kogyo KK
C), measured using RDC-220. In (5),
Fines collected from 20 kg of polyester were dried under reduced pressure at 25 ° C for 3 days, and a sample of 4 m was used for each measurement.
DSC measurement at a temperature rising rate of 20 ° C./min using g,
The melting peak temperature on the highest side of the melting peak temperature is determined. The measurement is performed on a maximum of 10 samples, and the average value of the melting peak temperatures on the highest temperature side is obtained.

(7) Crystallization temperature (Tc
1) Differential thermal analyzer (DS) manufactured by Seiko Electronics Co., Ltd.
C), measured with RDC-220. Using 10 mg of a sample from the center of a 2 mm-thick plate of the following (12) molded plate. The temperature is raised at a temperature rising rate of 20 ° C./minute, and the peak temperature of the crystallization peak observed during the heating is measured and used as the crystallization temperature during heating (Tc1).

(8) Average Density of Polyester Chip, Density of Preform Mouth Portion The density was measured at 30 ° C. with a density gradient tube of a calcium nitrate / water mixed solution. The plug density was determined as an average value of 10 samples crystallized by the method (11).

(9) Haze (% haze) A sample was cut from the body (wall thickness: about 0.45 mm) of the following (12) molded body (wall thickness 5 mm) and (13) hollow molded body, and Measured with a haze meter manufactured by Color Co., Ltd.

(10) Foreign matter of hollow molded article Three hollow molded articles of the following (13) were visually observed, averaged, and evaluated as follows. ◎: There is no foreign matter ○: Very small amount of foreign matter (3 or less foreign matter having a size of 0.5 mm or less per hollow molded body) △: 0.5 mm or more per hollow molded body 5 to 10 foreign matter x: Very large number (more than 10 foreign matter having a size of 0.5 mm or more per hollow molding)

(11) Density increase due to heating of preform plug part The preform plug part was heat treated for 60 seconds by a home-made infrared heater, and a sample was taken from the top surface to measure the density.

(12) Molding of molded body The dried polyester resin was subjected to 1 molding at a cylinder temperature of 290 ° C. using an M-100 injection molding machine manufactured by Meiki Seisakusho.
Molding is performed with a stepped flat plate die cooled to 0 ° C. to obtain a stepped molded body. This step-formed body is 2, 3, 4, 5, 6, 7, 8,
It is provided with a molded plate having a thickness of 9, 10, 11 mm and a size of about 3 cm × about 5 cm square. That is, 11 mm on the resin supply port side and 1
Starting from 0mm both thickness forming plates, 3mm and 2mm
Both of the molded plates are sequentially provided in a stepwise manner, and the weight of one piece is about 146 g. A molded plate having a thickness of 2 mm is cut out for use in measuring the crystallization temperature (Tc1) during heating, and a molded plate having a thickness of 5 mm is cut out for use in measuring haze (% of haze).

(13) Molding of Hollow Molded Body M-1 manufactured by Meiki Seisakusho using dried polyester resin
A preform was molded at a resin temperature of 290 ° C. using an 00 injection molding machine. The plug part of this preform was heated and crystallized by a home-made cap part crystallization device, and then biaxially stretched using a LB-01 stretch blow molding machine manufactured by Co-Poplast.
Molded and then heat set in a mold set to about 145 ° C, and 1500 ml hollow molding container (body wall average thickness 0.4
5 mm).

(14) Leakage Evaluation of Contents from Hollow Molded Body The hollow molded body molded in (13) above was filled with 90 ° C. hot water, capped with a capping machine, and then the container was laid down and left to stand. I investigated the leak. In addition, the state of deformation of the spout after capping was also examined.

(15) Sensory test The biaxially stretched blow hollow molded article molded in the above (13) was subjected to 9
Distilled water at 5 ° C. was placed therein, and the bottle was sealed and held for 30 minutes, cooled to room temperature and left at room temperature for 1 month. Distilled water is used as a blank for comparison. The sensory test was carried out by 10 panelists according to the following criteria, and the average values were compared. (Evaluation criteria) 0: No off-taste or odor 1: Slight difference from blank 2: Slight difference from blank 3: Sensible difference from blank 4: Very large difference from blank feel

(16) Sodium content, calcium content, magnesium content and silicon content in the introduced water introduced into the chip forming step, the introduced water was collected, and the 1G1 glass filter manufactured by Iwaki Glass Co., Ltd.
After filtering with, the filtrate was measured with an inductively coupled plasma emission spectrometer manufactured by Shimadzu Corporation.

(17) Particle Size and Number of Particles in Introduced Water Introduced into Chiping Process Light-shielding type particle measuring instrument HIAC / ROYCO. Counter 4
The measurement was performed using a 100 type and a sampler 3000 type.

(18) Chemical oxygen demand (COD) (mg / l) of the cooling water used in the chip forming step The cooling water filtered by the glass filter used in (16) above is specified in JIS-K0101. Measure according to the method.

(19) Measurement of the Number of Particles in Gas Contacting Polyester The gas sent by a blower for forcibly sending the gas and passing through the gas cleaning device is branched from the main gas stream before contacting with the polyester. It is introduced into a particle measuring instrument and measured.
The measurement is repeated 5 times, the average value is obtained, and the number per 1 cubic foot of gas is calculated. As the particle measuring instrument, a light scattering type particle measuring instrument KC-01B manufactured by Rion Co., Ltd. was used.

(Example 1) An EG slurry of TPA adjusted to a molar ratio of EG to TPA of 1.7 was continuously supplied to the system in the first esterification reaction apparatus where the reaction product is present, and the reaction was carried out continuously. The reaction was carried out under pressure at an average residence time of 4 hours at a temperature of 255 ° C. This reaction product was continuously taken out of the system and supplied to the second esterification reactor, and reacted at atmospheric pressure at a temperature of 260 ° C. for an average residence time of 2.5 hours in each tank. Then, the esterification reaction product was continuously taken out from the second esterification reactor and continuously supplied to the continuous polycondensation reactor. From a plurality of polycondensation catalyst supply pipes connected to the esterification reaction product transportation pipes, an amount of phosphorus of 0.6 mol (about 19 ppm relative to the produced polyester resin) as a phosphorus atom per ton of the produced polyester resin was obtained. EG solution of acid, EG solution of magnesium acetate tetrahydrate in an amount such that 0.6 mol of magnesium atom per ton of produced polyester resin (about 15 ppm based on produced polyester resin), and 1 ton of produced polyester resin An EG solution of antimony trioxide in an amount of 1.6 mol per atom of antimony (about 195 ppm with respect to the produced polyester resin) is supplied to the esterification reaction product, and the mixture is stirred at about 265 ° C. at 25 torr. 1 hour, then with stirring in the second polycondensation reactor at about 265 ° C., 3
1 hour at torr and with stirring in the final polycondensation reactor,
Polycondensation was performed at about 275 ° C. and 0.5 to 1 torr. The intrinsic viscosity of the melt polycondensation prepolymer was 0.60 dl / g.

The molten polycondensation reaction product was obtained by treating industrial water (derived from river underflow water) with a filter-filtration device and an ion exchange device, COD of 1.0 to 1.5 mg / l, and particle size of 1 to 1.
Approximately 700 particles / 10 ml of 25 μm particles, sodium content 0.03 ppm, magnesium content 0.01
ppm, calcium content 0.01 ppm, and silicon content 0.11 ppm with cooling water having a chip temperature of about 40
After chipping while cooling to below ℃, it is transported to a storage tank, and then fine and film-like substances are removed by a vibrating sieving step and an air stream classifying step to reduce the fine content to about 40 ppm or less. did. Then, it is sent to a crystallizer by a plug transport method, continuously crystallized under a nitrogen gas flow at about 155 ° C. for 3 hours, and then charged into a tower type solid-phase polymerizer and under a nitrogen gas flow for about 208 hours.
Solid phase polymerization was continuously carried out at 0 ° C. to obtain solid phase polymerized polyester. After the solid phase polymerization, fines and film-like substances were removed by continuous treatment in a sieving step and a fines removing step, and stored in a storage tank under a nitrogen stream.

The PET thus obtained had an intrinsic viscosity of 0.81 deciliter / gram, a DEG content of 2.7 mol%, a cyclic trimer content of 0.32 wt%, and an average density of 1.41.
The peak temperature was 50 g / cm ³ , the AA content was 3.8 ppm, the fine content was about 40 ppm, and the peak temperature on the highest side of the melting peak temperature was 245 ° C. The residual amount of Sb measured by atomic absorption spectrometry was about 180 ppm.
In addition, in the solid-state polymerization reaction of Example 1 to Comparative Example 2, in each of the Examples and Comparative Examples, a continuous solid-state polymerization apparatus which was overheated and cleaned was used, and continuous production was started. The solid-state polymerization PET of the 3rd month was used for molding evaluation and bottle molding evaluation. In addition, as the air for sending the melt polycondensation PET chips to the solid-state polymerization step, and the air that comes into contact with the chips before the solid-state polymerization PET chips are filled in the storage container, JIS
B 9908 (1991) Type 3 PET non-woven filter unit equipped with an air purifier and JIS B
Air filtered by an air purifier equipped with a HEPA filter unit of 9908 (1991) type 1 particle collection rate of 99% or more (the number of particles having a particle size of 0.3 to 5 μm is about 500 / cubic foot) It was used. Also in Examples 2-3 and Comparative Examples 1 and 2, air filtered in the same manner was used.

The PET was evaluated using a molded plate and a biaxially stretched molded bottle. The results are shown in Table 1. The haze of the molded plate was 5.9%, and the Tc1 of the molded plate was 164 ° C. The AA content of the bottle was 23.5 ppm, and the sensory test was 0.5, which was a problem-free value. The body haze of the bottle was as good as 1.1%. Foreign matter on the bottle is "◎
(There is no foreign substance) ”, and there was no problem. Also,
The density at the mouth of the bottle was 1.379 g / cm ^3, which was a value with no problem, and there was no problem in the leak test of the contents, and the mouth part was not deformed.

(Examples 2 and 3) PET resins were obtained in the same manner as in Example 1 except that the addition amounts and ratios of magnesium acetate tetrahydrate and phosphoric acid were changed as shown in Table 1.
The results are shown in Table 1. The characteristics of the obtained PET and the characteristics of the bottle were good and there was no problem.

(Comparative Example 1) Magnesium acetate tetrahydrate,
The amount and ratio of phosphoric acid were the same as in Example 3, and as cooling water for chip formation of the molten polycondensed polyester, industrial water was directly cooled for chip formation without using a filter-filtration device and an ion exchange device. Solid-state polymerized PET was obtained in the same manner as in Example 1 except that water was used as water. In addition,
COD contained in the industrial water used as the cooling water at the time of chip formation is 5.5 to 6.5 mg / l, and the particle size is 1 to 25 μm.
Particles of about 60000 to 70000/10 ml, sodium content of 2.0 to 3.0 ppm, magnesium content of 0.8 to 1.5 ppm, calcium content of 1.0
.About.2.5 ppm, and the silicon content was 2.0 to 3.5 ppm.

This PET was evaluated using a molded plate and a biaxially stretched molded bottle. The results are shown in Table 1. The sensory test result of the obtained bottle was very bad. In addition, the transparency of the bottle was poor, and the amount of foreign substances in the wall of the bottle was very large, and the bottle had no commercial value. When the foreign matter was taken out and analyzed by X-ray microanalyzer, metals such as calcium, silicon and antimony were detected. Moreover, the deformation of the mouth plug and the leakage of the contents were examined.
Leakage of contents was recognized.

(Comparative Example 2) The amounts and ratios of antimony trioxide, magnesium acetate tetrahydrate and phosphoric acid were changed as shown in Table 1, and as a cooling water at the time of chip formation of the melt polycondensed polyester, a filter was used. -A solid-state polymerized PET was obtained in the same manner as in Example 1 except that industrial water was used as it was as cooling water for chip formation without using a filtration device and an ion exchange device. In addition, COD contained in the industrial water used as cooling water at the time of chip formation is 12.5 to 13.
Particles with a particle size of 5 mg / l and a particle size of 1 to 25 μm are approximately 80,000 to
90000 pieces / 10ml, sodium content 5.0 ~
7.0ppm, magnesium content 1.8-2.5p
pm, the calcium content was 1.8 to 3.5 ppm, and the silicon content was 4.0 to 5.8 ppm.

The PET was evaluated using a molded plate and a biaxially stretched molded bottle. The results are shown in Table 1. The sensory test result of the obtained bottle was very bad. In addition, the transparency of the bottle was poor, and the amount of foreign substances in the wall of the bottle was very large, and the bottle had no commercial value. When the foreign matter was taken out and analyzed by X-ray microanalyzer, metals such as calcium, silicon and antimony were detected. Moreover, the deformation of the mouth plug and the leakage of the contents were examined.
Leakage of contents was recognized.

[0160]

[Table 1]

[0161]

EFFECTS OF THE INVENTION According to the method for producing a polyester of the present invention, a hollow molded article having excellent transparency and flavor can be provided, and the molded article contains a polyester containing almost no foreign matter and a filter-filtration pressure increase is small. Therefore, inexpensive polyester can be advantageously obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshitaka Eto             20 No. 248 Takashiro, Shiga Town, Shiga District, Shiga Prefecture (72) Inventor Hiroshi Hashimoto             2-3 Imazu Shoyodai, Imazu Town, Takashima District, Shiga Prefecture             Two F term (reference) 4J029 AA03 AB05 AC01 AC02 AD01                       AE01 BA03 BA07 BB13A                       BB13B BD03A BF25 CB06A                       CB10A CC05A JE043 JE133                       JE182 JE203 JF131 JF141                       JF361 JF471 JF541 JF571                       KD17 KE02 KH08 KJ06

Claims (7)

[Claims] 1. Using at least one metal compound selected from a magnesium compound, a calcium compound, a cobalt compound, a manganese compound and a zinc compound, a phosphorus compound and an antimony compound, mainly from an aromatic dicarboxylic acid component and a glycol component. In the method for producing a polyester for producing the following polyester, a dicarboxylic acid containing an aromatic dicarboxylic acid as a main component or its ester-forming property is obtained by adding the metal compound in an amount satisfying the following (1) to (3). The derivative is reacted with a glycol or an ester-forming derivative thereof to obtain a low polycondensate, which is then polycondensed, and then the obtained polyester is subjected to a chemical oxygen demand (COD) of the following. Chiping is performed while cooling with cooling water that satisfies (4), and then solid phase polymerization is performed. A method for producing a characteristic polyester. 0.1 ≤ Me ≤ 3 (1) 0.1 ≤ Me / P ≤ 2 (2) 0.3 ≤ Sb ≤ 3 (3) COD ≤ 2.5 (mg / l) (4) (in the above formula , Me is the number of moles of metal atom of at least one metal compound selected from magnesium compound, calcium compound, cobalt compound, manganese compound and zinc compound per ton of polymer, and P is the phosphorus compound per ton of polymer. The number of moles of phosphorus atom in Sb is polymer-1
The number of moles of antimony atom of the antimony compound per ton is shown. ) 2. The method for producing a polyester according to claim 1, wherein at least water treated by an ion exchange device is used as cooling water in the chipping step. 3. The fine content of the polyester, the film-like material content, or the total content of the fine content and the film-like material content is 5000 p.
It is below pm, The manufacturing method of the polyester in any one of Claim 1 or 2 characterized by the above-mentioned. 4. A gas contacting with polyester in at least one of a melt polycondensation step, a chip forming step, a solid phase polymerization step, and a fine removal step, etc., wherein 1,000,000 particles having a particle size of 0.3 to 5 μm / Cubic field
The method for producing a polyester according to any one of claims 1 to 3, wherein the following gas introduced from outside the system is used. 5. A polyester comprising ethylene terephthalate as a main repeating unit,
The method for producing a polyester according to any one of claims 1 to 4, wherein the peak temperature on the highest temperature side of the fine melt peak temperature contained in the polyester is 265 ° C or lower. 6. The polyester has an intrinsic viscosity of 0.55.
2.0 deciliter / gram, acetaldehyde content of 10 ppm or less, cyclic trimer content of 0.5% by weight or less, haze of a molded plate obtained by injection molding was 15% or less, and measured by DSC. 7. A polyester having ethylene terephthalate as a main repeating unit, which has a crystallization temperature (Tc1) in the range of 150 to 170 ° C. when the molded plate is heated, and is a polyester according to claim 1. Method. 7. The polyester according to claim 1, wherein the polyester is blended with at least one resin selected from the group consisting of a polyolefin resin, a polyamide resin, and a polyacetal resin. Manufacturing method.