JP2003231746A - Method for producing polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polyester having excellent transparency and a moderate and stable crystallization rate, being capable of efficiently producing a molding, especially a heat-resistant blow molding having excellent dimensional stability under heat and being excellent in long-time continuous moldability because it leaves little deposit on the mold. <P>SOLUTION: The method for producing the polyester comprises bringing the polyester mainly comprising an ethylene terephthalate repeating unit into contact with at least one member selected from among a polyolefin resin member, a polyamide resin member, and a polyacetal resin member under a fluidized condition, wherein the polyester is one containing at least one metal compound selected from among a magnesium compound, a calcium compound, a manganese compound, and a zinc compound, a phosphorus compound, and an antimony compound in such amounts as to satisfy specified ranges. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing polyester used for packaging materials such as bottles and films, sheets, etc., and more specifically, it is excellent in transparency, moderate and stable crystallization. The present invention relates to a method for producing a polyester, which has a high speed and gives a molded product having excellent heat resistance and dimensional stability, and which is less likely to cause mold stains when the molded product is molded.

[0002]

BACKGROUND OF THE INVENTION Polyester is excellent in mechanical strength, heat resistance, transparency and gas barrier property, so that it is especially used for filling beverages such as juices, soft drinks, carbonated drinks, packaging films and audio. It is most suitable as a material for video films and is used in large quantities.

It is also used in large quantities on a global scale as an industrial material such as clothing fibers and tire cords.

PET generally used for such applications
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 the case of polyester bottles for beverages, hot sterilized beverages are hot-filled into the bottles, or the beverages are filled and then sterilized at high temperature. 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.

Specifically, in the case of beverages such as fruit juice, oolong tea, and mineral water that require hot filling, the preform or the bottle cap formed is heat treated. The method of crystallization is then common (see Patent Documents 1 and 2). Such a method, that is, a method of heat-treating the plug portion and the shoulder portion to improve heat resistance is
The time and temperature of crystallization treatment greatly affect productivity,
PE with high crystallization rate that can be processed at low temperature and in a short time
It is preferably T. 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.

Further, in order to improve the heat resistance of the bottle body, for example, a method of heat treatment by increasing the temperature of the stretching blow mold to a high temperature is adopted (Patent Document 3). However, if a large number of bottles are molded using the same mold by such a method, the bottles obtained with long-term operation will be whitened and the transparency will be reduced, and only bottles with no commercial value can be obtained. . It was found that this was because deposits due to PET were attached to the mold surface, resulting in mold stains, which were transferred to the bottle surface. In particular, in recent years, the molding speed has been increased along with the downsizing of bottles, and from the viewpoint of productivity, shortening the heating time for crystallizing the spout and mold fouling have become more serious problems. .

Various proposals have been made to solve such problems. For example, polyethylene terephthalate
There is a method of adding an inorganic nucleating agent such as kaolin or talc (see Patent Documents 4 and 5), and a method of adding an organic nucleating agent such as montanic acid wax salt (see Patent Documents 6 and 7). However, these methods have a problem in practical use due to the generation of foreign matter and cloudiness. Also, for the raw material polyester,
There is a method (see Patent Document 8) of adding a treated polyester obtained by crushing a polyester molded body obtained by melt molding from the polyester, but this method requires an extra step of melt molding and crushing. There is a risk of inclusion of contaminants other than polyester in the subsequent step, and this is not an economically and qualitatively preferable method. Further, a method of inserting a heat-resistant resin piece into the spout part has been proposed (see Patent Documents 9 and 10), but the productivity of the bottle is poor and the recyclability is also problematic. .

Among the above catalysts, antimony catalysts are used as catalysts for producing PET for fibers and films because of their 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 titanium compound and titanium compound is used as a polycondensation catalyst. However, use of an expensive germanium compound has a drawback that the cost of PET becomes high.

As a method of solving such a problem,
A method has been disclosed in which transparency is improved by defining the ratio of the amount of the antimony compound and the phosphorus compound used (see Patent Document 11). However, the crystallization rate of the hollow molded article from PET obtained by this method is not stable, and the fluctuation is extremely large, so that the dimension of the plug portion becomes unstable and defective capping occurs. There is also the problem that its transparency is not sufficient.

On the other hand, as a measure for improving the crystallization rate of PET, a method for modifying PET by contacting a PET chip with a polyethylene member under flowing conditions (Patent Document 12).
Or a method of modifying PET by contacting with a member made of a polypropylene resin or a polyamide resin under similar conditions (see Patent Document 13). It has a stable crystallization rate, and gives a molded product with excellent dimensional stability and transparency of the plug after heating and crystallization, and it is very difficult to obtain a polyester polymerized using an antimony catalyst. I knew it was.

[0013]

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

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

[Patent Document 3] Japanese Patent Publication No. 59-6216

[Patent Document 4] Japanese Patent Application Laid-Open No. 56-2342

[Patent Document 5] JP-A-56-21832

[Patent Document 6] Japanese Patent Laid-Open No. 57-125246

[Patent Document 7] Japanese Unexamined Patent Publication No. 57-207639

[Patent Document 8] Japanese Unexamined Patent Publication No. 5-105807

[Patent Document 9] Japanese Patent Laid-Open No. 61-259946

[Patent Document 10] Japanese Unexamined Patent Publication No. 2-269638

[Patent Document 11] JP-A-6-279579

[Patent Document 12] Japanese Unexamined Patent Publication No. 9-71639

[Patent Document 13] Japanese Patent Laid-Open No. 11-209492

[0014]

DISCLOSURE OF THE INVENTION The present invention solves the problems of the above-mentioned conventional methods, is excellent in transparency, and is suitable.
In addition, it has a stable crystallization rate and can efficiently produce molded products with excellent heat-resistant dimensional stability, especially heat-resistant hollow molded products, and is excellent in long-term continuous moldability with less contamination of the mold. It is an object to provide a method for producing polyester.

[0015]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made a polyester resin whose main repeating unit is ethylene terephthalate, which is polymerized by using an antimony catalyst, into at least one of a polyolefin resin member and a polyamide resin member. As a result of diligent study on a method for producing a polyester which is subjected to contact treatment with a kind of member under flowing conditions to give a molded article having excellent transparency and heat-resistant dimensional stability and little fluctuation in crystallization rate, magnesium compound, calcium compound, cobalt The compounding amount of at least one metal compound selected from compounds, manganese compounds and zinc compounds, phosphorus compounds and antimony compounds in the polyester is such that the transparency of the molded product from the polyester obtained by the contact treatment with the resin member. It was found that it is related to characteristics such as It was completed a light.

That is, in the method for producing a polyester of the present invention, the polyester whose main repeating unit is ethylene terephthalate is mixed with at least one member selected from a polyolefin resin member and a polyamide resin member under flowing conditions. A method for producing a polyester to be contact-treated, wherein the polyester has the following (1)
A polyester containing at least one metal compound selected from the group consisting of magnesium compound, calcium compound, cobalt compound, manganese compound and zinc compound, phosphorus compound and antimony compound. Is a manufacturing method. 0.1 ≤ M ≤ 2.0 (1) 0.1 ≤ M / P ≤ 1.8 (2) 0.3 ≤ Sb ≤ 2.2 (3) (where M is 1 ton of polymer) Per mol of the metal atom of at least one metal compound selected from the magnesium compound, the calcium compound, the cobalt compound, the manganese compound and the zinc compound, P is the phosphorus atom (P) of the phosphorus compound per ton of the polymer. The number of moles, Sb is
The number of moles of antimony atom (Sb) of the antimony compound per ton of polymer is shown. )

In this case, when the polyester before the contact treatment is subjected to the chip forming step after the melt polycondensation, the content of sodium (N), the content of magnesium (M), the content of silicon (S) and the content of calcium are The content (C) of the above can be a polyester chipped with cooling water satisfying at least one of the following (4) to (7). N ≤ 1.0 (ppm) (4) M ≤ 0.5 (ppm) (5) S ≤ 2.0 (ppm) (6) C ≤ 1.0 (ppm) (7)

In this case, the content of either the fine content of the polyester before the contact treatment, the content of the film-like material, or the total content of the fine content and the content of the film-like material is 500 ppm or less. It is preferable.

Here, fine means JIS-Z8801.
According to JIS-Z8801 means a fine polyester powder that has passed through a sieve with a mesh size of 1.7 mm, and a film-like material remains on a sieve with a mesh size of 5.6 mm according to JIS-Z8801. Of polyester, two or more chips are fused together, or the chip-shaped product cut into pieces larger than the normal shape is removed, and the thickness is about 0.5 mm.
The following film-like materials are meant, and their contents are measured by the following measuring methods.

In this case, the peak temperature on the highest side of the melting peak temperature of fine contained in the polyester before and / or after the contact treatment is
It is preferably 265 ° C or lower.

Further, as described below, the melting point of fine is measured by 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. In the present invention, when there is one melting peak, the peak temperature and the melting peak are determined. -In the case of a plurality of melting peaks, among these plural melting peaks,
The melting peak temperature on the highest temperature side is defined as "Fine melting peak
The peak temperature on the highest temperature side is referred to as "peak temperature on the highest temperature side" and is referred to as "fine melting point" in Examples and the like.

In this case, the member is at least one member selected from the group consisting of polyester pneumatic transportation pipes, polyester gravity transportation pipes, rod-shaped, plate-shaped or mesh-shaped bodies installed in the polyester transportation path. Is preferred.

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.

[0024]

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 polyester whose main repeating unit is ethylene terephthalate, which is produced from terephthalic acid or its ester-forming derivative and ethylene glycol or its ester-forming derivative as raw materials, It is preferably a linear polyester containing 85 mol% or more of ethylene terephthalate units, more preferably 90 mol% or more, and particularly preferably 95% or more.

The dicarboxylic acid as a copolymerization component used when the polyester is a copolymer is
Aromatic dicarboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and functional derivatives thereof, p-oxybenzoic acid, oxycaproic acid, etc. Oxyacids and their functional derivatives, adipic acid, sebacic acid, succinic acid, glutaric acid and other aliphatic dicarboxylic acids and their functional derivatives, cyclohexanedicarboxylic acid and other aliphatic dicarboxylic acids and their functional derivatives, etc. .

The glycol used as a copolymerization component when the polyester is a copolymer is diethylene glycol or 1,3-trimethylene glycol.
, Tetramethylene glycol, neopentyl glyco-
Alicyclic glycol such as cyclohexyl dimethanol, aromatic glycol such as bisphenol A, alkylene oxide adduct of bisphenol A, polyethylene glycol, etc. Polybutylene glyco
Examples thereof include polyalkylene glycol such as alcohol.

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.

In the method for producing a polyester of the present invention, terephthalic acid is directly reacted with ethylene glycol and / or a third component to distill off water to effect esterification, and then polycondensation is carried out under reduced pressure. Either an esterification method or a transesterification method in which dimethyl terephthalate is reacted with ethylene glycol and / or a third component to distill off methyl alcohol for transesterification, and then polycondensation is performed under reduced pressure. It is a method for producing a melt polycondensed polyester by the above method.

If necessary, the intrinsic viscosity is increased,
This is a method for producing a polyester in which solid phase polymerization is performed in order to reduce the acetaldehyde content and the like. In order to accelerate crystallization before solid-phase polymerization, the molten polycondensed 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 using 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, 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 by 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.

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 by 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.

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 magnesium compounds include magnesium hydride, lower fatty acid salts such as magnesium oxide and 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 content of the magnesium compound, the calcium compound, the cobalt compound, the manganese compound, and the zinc compound represented by the general formula (1) is 0.1 to 3 as the metal atom of the metal compound per ton of polyester.
It is in the range of 0 mol, preferably in the range of 0.15 to 2.8 mol, and more preferably in the range of 0.2 to 2.6 mol.
If the amount is less than 0.1 mol per ton of polymer, the transparency of the hollow molded article made of the obtained polyester, particularly the stretch-heat-fixed hollow molded article, becomes extremely poor. On the other hand, if it exceeds 3.0 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 a 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 content 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 1.8, preferably 0.2 to 1.6, more preferably 0.3 to 1.
The range is 5. 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 1.8, the thermal stability of the polyester is poor and the content of acetaldehyde is 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, potassium antimony tartrate, 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 0.3-1.10 as the antimony atom of the antimony compound per ton of the obtained polyester.
7 mol range, preferably 0.5-1.6 mol,
More preferably, it is in the range of 0.8 to 1.5 mol. When the amount is less than 0.3 mol per ton of polymer, the polycondensation time becomes very long, which is a problem from the viewpoint of economical productivity. On the other hand, if it exceeds 1.7 moles, the transparency of the obtained hollow molded article will be deteriorated and the color tone will be deteriorated, which will be a problem. The timing of adding the antimony compound is not particularly limited,
It 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.

The melt polycondensed polyester obtained as described above is extruded through the pores after completion of the melt polycondensation, and is made into chips while being cooled with cooling water.

Then, in order to lower the acetaldehyde content and increase the intrinsic viscosity, the above polyester is solid-phase polymerized by a conventionally known method.
First, the polyester to be subjected to solid-phase polymerization is pre-crystallized by heating at a temperature of 100 to 210 ° C. for 1 to 5 hours under an inert gas, a reduced pressure, or an atmosphere of steam or a steam-containing inert gas. It Then, at a temperature of 190 to 230 ° C. under an inert gas atmosphere or under reduced pressure, 1
Solid phase polymerization is carried out for about 30 hours.

The shape of the polyester chips according to the present invention may be any of cylinder type, square type, spherical type or flat plate type, and the average particle size thereof is usually 1.5 to 5 mm, preferably 1. 6 to 4.5 mm, more preferably 1.8
The range is up to 4.0 mm. For example, in the case of a cylinder type, it is practical that the length is 1.5 to 4 mm and the diameter is about 1.5 to 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. Also,
It is practical that the weight of the chip is in the range of 10 to 30 mg / piece.

The intrinsic viscosity of the melt polycondensed polyester according to the present invention is 0.55 to 1.30 deciliter / gram,
Preferably 0.58 to 1.20 deciliters / gram,
More preferably, it is in the range of 0.60 to 0.90 deciliter / gram. Intrinsic viscosity is 0.55 deciliters /
When the amount is less than gram, the mechanical properties of the obtained molded product and the like are poor. On the other hand, when it exceeds 1.30 deciliters / gram, the resin temperature becomes high when melted by a molding machine or the like and the thermal decomposition becomes violent, resulting in an increase in free low molecular weight compounds which affect the aroma retention, Will be colored yellow.

In the case of solid-state polymerization subsequent to melt polycondensation, the intrinsic viscosity of the polyester obtained from the final polycondensation reactor for melt polycondensation has an intrinsic viscosity of 0.30 to 0.80 deciliter / gram, preferably 0.1. It is preferably in the range of 35 to 0.75 deciliter / gram, more preferably 0.40 to 0.70 deciliter / gram. If the intrinsic viscosity is less than 0.30, the degree of crystallinity becomes too high in the pre-crystallization before the 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 fine polyester is generated in the pre-crystallization and solid-state polymerization steps as will be described later, and the crystallization rate is very fast, and the rate fluctuation is very large. I can't. Further, when the intrinsic viscosity exceeds 0.80, 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 order to accelerate the crystallization rate of the molded product obtained from the above polyester and suppress the fluctuation thereof, the polyester obtained by the melt polycondensation as described above, or the melt polycondensation and the subsequent solid phase polymerization. The polyester obtained in this manner is subjected to contact treatment under flow conditions with at least one member selected from the group consisting of a polyolefin resin member, a polyamide resin member and a polyacetal resin member in the form of chips.

As a method of contacting the polyester with at least one member selected from the group consisting of a polyolefin resin member, a polyamide resin member and a polyacetal resin member, polyester is added in a space where the polyolefin resin member is present. It is preferable to bring the members into collisional contact, and specifically, for example, immediately after melt polycondensation of polyester or immediately after solid-state polymerization, and at the time of filling into a container for transportation at the transportation stage of the polyester as a product or the like. Pipes for pneumatic transportation, pipes for gravity transportation, silos, magnet catchers when discharged from the container or when the molding machine is loaded at the polyester molding stage, etc.
The part of the magnet portion, etc., of the polyolefin resin, polyamide resin, polyacetal resin, or lining any of the polyolefin resin, polyamide resin, polyacetal resin, or the transfer A method of transferring polyester by, for example, installing a member of a polyolefin resin member, a polyamide resin member, or a polyacetal resin member in the shape of a rod, a plate, or a net in the path, and the like can be given. . The contact time of the polyester with the member is usually a short time of about 0.01 second to several minutes, but at least one kind of the above-mentioned polyolefin resin, polyamide resin and polyacetal resin can be blended in the polyester in a trace amount. .

Further, in the method for producing polyester of the present invention, the polyester is mixed with at least one member selected from the above-mentioned polyolefin resin member, polyamide resin member and polyacetal resin member under flowing conditions. Ratio A of surface area of member (cm ² ) and throughput of the polyester per unit time (ton / hour)
However, it is more preferable to satisfy the following formula.

A = [Surface area (cm ² ) of the member to be contact-treated with polyester] / [Processing amount of polyester per unit time (ton / hour)] = 10 to 3000 (8)

The ratio A between the surface area (cm ² ) of the member and the throughput (ton / hour) of the polyester per unit time.
Is preferably 15 to 2500, more preferably 20.
~ 2300. Surface area (cm ² ) of the member and throughput of the polyester per unit time (ton / hour)
When the ratio A is less than 10, the compounding amount of the resin in the polyester becomes small, and thus the crystallization rate of the obtained molded body is insufficient and its variation becomes large. Then, crystallization of the plug portion of the hollow molded body becomes insufficient, and thus the shrinkage amount of the plug portion does not fall within the specified value range, so that a capping phenomenon occurs.

If the ratio A of the surface area (cm ² ) of the member to the throughput (ton / hour) of the polyester per unit time exceeds 3000, the blending amount of the resin into the polyester becomes excessive, Moreover, the variation in the compounding amount becomes very large. For this reason, the crystallization rate of the obtained molded body becomes fast, and the fluctuation thereof becomes very large. Then, the crystallization of the plug part of the hollow molded body becomes excessive, and the shrinkage amount of the plug part does not fall within the specified value range. The preform for use is whitened, which makes normal stretching impossible. As the resin forming the resin member used for the contact treatment of polyester in the present invention, at least one resin selected from polyolefin resins, polyamide resins, and polyacetal resins can be mentioned.

Examples of the polyolefin resin used for the resin member for contact treatment in the present invention include polyethylene resin, polypropylene resin, and α-olefin resin. Further, these resins may be crystalline or amorphous.

As the polyethylene resin used in the present invention, for example, ethylene homopolymer, ethylene and propylene, butene-1,3-methylbutene-
1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1 and other α-olefins having about 2 to 20 carbon atoms, vinyl acetate, vinyl chloride,
Examples thereof include acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, styrene, and copolymers with vinyl compounds such as unsaturated epoxy compounds. Specifically, for example, ultra-low / low / medium / high-density polyethylene (branched or linear) ethylene homopolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene- 4-methylpentene-1 copolymer, ethylene-
Hexene-1 copolymer, ethylene-octene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, etc. An ethylene resin can be used.

Examples of the polypropylene resin used in the present invention include propylene homopolymer, propylene and ethylene, butene-1,3-methylbutene-1, pentene-1,4-methylpentene-1,
2 carbon atoms such as hexene-1, octene-1, decene-1
To about 20 other α-olefins, copolymers with vinyl compounds such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, styrene, hexadiene, octadiene,
Examples thereof include copolymers with diene such as decadiene and dicyclopentadiene. Specific examples include propylene-based resins such as propylene homopolymers (atactic, isotactic, syndiotactic polypropylene), propylene-ethylene copolymers, propylene-ethylene-butene-1 copolymers.

The α-olefin resins used in the present invention include homopolymers of α-olefins having about 2 to 8 carbon atoms such as 4-methylpentene-1, and those α-olefins, ethylene and propylene. , Butene-
1,3-methylbutene-1, pentene-1, hexene-
Examples thereof include copolymers with other α-olefins having about 2 to 20 carbon atoms such as 1, octene-1, and decene-1. Specifically, for example, butene-1 resin such as butene-1 homopolymer, 4-methylpentene-1 homopolymer, butene-1-ethylene copolymer, butene-1-propylene copolymer and 4 - methylpentene-1 and C ₂ -C ₁₈ copolymer of α- olefins, and the like. The polyamide resin used in the present invention includes, for example, butyrolactam, δ-valerolactam, ε-caprolactam, enanthlactam, lactam polymers such as ω-laurolactam, 6-aminocaproic acid, 11-aminoundecanoic acid, Polymers of aminocarboxylic acids such as 12-aminododecanoic acid, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, undecamethylenediamine, 2,2,4- or 2,
Aliphatic diamines such as 4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl)
Aliphatic diamines such as cyclohexane and bis (p-aminocyclohexylmethane), diamine units such as aromatic diamines such as m- or p-xylylenediamine, and fats such as glutaric acid, adipic acid, suberic acid, and sebacic acid. Group dicarboxylic acids, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, polycondensates with dicarboxylic acid units such as aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and copolymers thereof, and the like. For example, nylon 4, nylon 6, 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 M
XD6, Nylon 6 / MXD6, Nylon MXD6 / M
XDI, Nylon 6/66, Nylon 6/610, Nylon 6/12, Nylon 6 / 6T, Nylon 6I / 6T
Etc. Further, these resins may be crystalline or amorphous.

Further, examples of the polyacetal resin used in the present invention include polyacetal homopolymers and copolymers. As the polyacetal homopolymer, the density measured by the measuring method of ASTM-D792 is 1.40 to 1.42 g / cm ³ , and ASTM D-12.
Melt flow ratio (MFR) measured at a temperature of 190 ° C. and a load of 2160 g by the measuring method of 38 is 0.5 to 50 g / 10.
Polyacetals in the minutes range are preferred.

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 by the measuring method of ASTM D-1238 of 0.4 to 50 g / 10 min was obtained. preferable. Examples of these copolymerization components include ethylene oxide and cyclic ethers.

The blending ratio of the resin used in the present invention to the polyester is 0.1 ppb-50.
000ppm, preferably 0.3ppb-10000p
pm, more preferably 0.5 ppb to 100 ppm, further preferably 1.0 ppb to 1 ppm, particularly preferably 1.0 ppb to 45 ppb. Compounding amount is 0.1p
When it is less than pb, the crystallization rate becomes very slow and the crystallization of the plug part of the hollow molded article becomes insufficient. Therefore, if the cycle time is shortened, the shrinkage amount of the plug part falls within the specified range. There is no capping because it does not exist,
The stretch-heat-fixing mold for molding the heat-resistant hollow molded body is heavily contaminated, and the mold must be frequently cleaned to obtain a transparent hollow molded body. If it exceeds 50,000 ppm, the crystallization rate will be high and the crystallization of the plug part of the hollow molded article will be excessive, and the amount of shrinkage and shrinkage of the plug part will not fall within the specified range, resulting in poor capping. Leakage of the product occurs and the preform 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.

When the member made of the resin and the polyester are contact-treated, it is desirable that the resin exists in a state of being adhered to the surface of the polyester chip. However, the impact force when the polyester chip collides with the member or Depending on the magnitude of the pressure force when contacting, or by the properties such as impact resistance and peeling resistance of the resin member, the resin is not attached to the polyester chip, that is, a state independent of the polyester chip, For example, some fine particles are in a state of being mixed with the above-mentioned contact-treated polyester chips. The molded product obtained from the polyester in the state in which the fine resin particles are mixed as described above has a very high crystallization rate, and a very large fluctuation in the rate. In the case of a preformed body for a hollow molded body, the preformed body has severe whitening and transparency unevenness, and normal stretching cannot be performed, resulting in large thickness unevenness, and only a hollow molded article having poor transparency is obtained. I can't. 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 resin becomes a foreign substance in the obtained molded product, and as a result, the resulting molded product has many defects such as uneven thickness, voids, and whitening. Therefore, it is desirable to remove the fine particles, particles or lumps of the resin existing independently of the polyester chips before molding.

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

Further, in the present invention, the cooling water in the chip forming step has the following sodium content (N), magnesium content (M), silicon content (S) and calcium content (C): It is even more preferable that the molten polycondensed polyester is chipped using cooling water that satisfies at least one of (4) to (7), and preferably all of them. N ≤ 1.0 (ppm) (4) M ≤ 0.5 (ppm) (5) S ≤ 2.0 (ppm) (6) C ≤ 1.0 (ppm) (7)

The sodium content (N) in the waste water is preferably N ≦ 0.5 ppm, more preferably N ≦ 0.5.
It is 0.1 ppm.

The magnesium content (M) in the cooling water is
M ≦ 0.3 ppm is preferable, and M ≦ 0.1 ppm is more preferable.

The content (S) of silicon in the cooling water is
S ≦ 0.5 ppm is preferable, and S ≦ 0.3 ppm is more preferable.

Further, the calcium content (C) in the cooling water is preferably C ≦ 0.5 ppm, more preferably C ≦ 0.1 ppm.

The lower limits of the sodium content (N), magnesium content (M), silicon content (S) and calcium content (C) in the cooling 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.

When cooling water that deviates from the above conditions is used, these metal-containing compounds adhere to the surface of the polyester chip, the crystallization rate of the obtained polyester is very fast, and its fluctuation is large, which is preferable. Absent. Also,
Solid-state polymerization of molten polycondensed polyester that has been made into chips while cooling with cooling water that deviates from the above conditions causes the above-mentioned metal-containing substance that adheres to the chip surface and is brought into the solid-state polymerization reactor in the chipping process Adheres to the vessel wall of the solid-state polymerization equipment together with a part of the surface layer of the polyester chip, and this becomes a scale with a high metal content due to long-term heating at a high temperature of about 170 ° C. or higher, and is deposited on the vessel wall. It will adhere. Then, this is sometimes peeled off and mixed in the polyester chip, and becomes a foreign substance in a molded article such as a bottle, which lowers the commercial value.

Further, when a sheet is produced, the above-mentioned scale is clogged with 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.

A method for suppressing the sodium content, magnesium content, silicon content, and calcium content of the cooling water of the chips to 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 cooling 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 cooling 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, 500 particles having a particle size of 1 to 25 μm existing in water introduced from outside the system as chip cooling water are used.
It is desirable to use water made up to 100 pieces / 10 ml or less. The number of particles having a particle size of 1 to 25 μm in the cooling water is preferably 10,000 particles / 10 ml or less, more preferably 1000 particles / 10 ml or less. Particle size in introduced water 25
The number of particles exceeding μm is not particularly limited, but preferably 2000 particles / 10 ml or less, more preferably 5 particles.
00 pieces / 10 ml or less, more preferably 100 pieces / 1
0 ml, 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 giving 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 efficiently remove particles and efficiently introduce water.

In addition, it is preferable that the cooling water for the chips is repeatedly recycled for use from the viewpoint of improving economy 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 melt-polycondensed polyester is, after being made into chips, transported to a silo or the like in a transport pipe for storage, or transported to a solid-state polymerization step. Similarly, solid-state polymerized polyester chips are also transported to the next step or silo. 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. A part of the fines and most of the film-like materials thus produced have a very high melting peak temperature of over 265 ° C. Also, when 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 chip is used as a transportation method to the next step, Fines and film-like substances having a melting peak temperature exceeding 265 ° C. 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 peak temperature of above 265 ° C. is melted by subjecting it to solid-state polymerization treatment with polyester chips and then water treatment. The peak temperature becomes higher than that before the treatment. Fines and film-like substances having a melting peak temperature of 265 ° C. or less, but much higher than the normal melting peak temperature, have a melting peak temperature of more than 265 ° C. by the above-mentioned treatments. It has a melting peak temperature. It is presumed that this is because the crystal structure is changed to a more dense crystal structure by these treatments.

265 ° C. higher than the normal melting point
When a polyester containing a fine or film-like substance having a melting point peak of more than 100 is molded under normal molding conditions, the crystals do not completely melt during melt molding and remain as crystal nuclei.
As a result, the crystallization rate at the time of heating becomes 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 range and the capping of the plug part is defective. Next, there arises a problem that the contents leak. 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. Fluctuations will be large.

When it is desired to obtain a preform for blow molding or a sheet having good transparency and stretchability from polyester containing fines having a melting peak temperature exceeding 265 ° C, 300 ° C. It must be melt-molded at the above high temperature. However, at such a high temperature of 300 ° C. or higher, thermal decomposition of the polyester becomes severe, and a large amount of by-products such as acetaldehyde and formaldehyde are generated,
As a result, the flavor and the like of the obtained molded product or the like will be greatly affected. Further, when the polyester obtained by the production method of the present invention contains the resin, the resin is often inferior in thermal stability to the polyester of the present invention, and thus molding at a high temperature of 300 ° C. or higher as described above. In the above, since thermal decomposition is caused to generate a large amount of by-products, the flavor and the like of the content of the obtained molded product or the like will be further affected.

Generally, the polyester contains about 100 ppm to about several weight% of the above-mentioned fines and fines including film-like substances, and such fines are evenly distributed on the polyester chip. It is unevenly distributed rather than existing in a mixed state. Therefore, when such a polyester is subjected to a contact treatment with a member made of a resin such as a polyolefin resin under flowing conditions, the crystallization rate is further increased, but only the polyester having a very varied rate is obtained, which is a problem. .

In the present invention, the content of the fine content of the polyester before the contact treatment with the member, the content of the film-like material, or the total content of the fine content and the content of the film-like material is 500 ppm or less, preferably 300 ppm or less, more preferably 100 pp
The above-mentioned problems can be further solved by lowering it to m or less, more preferably 50 ppm or less.

Further, in the present invention, the content of any one of the fine content, the film-like material content or the total content of the fine content and the film-like material content of the polyester after the contact treatment is set to 5000 ppm or less. This solves the above problems and is preferably 3
It is desirable to lower it to 000 ppm or less, more preferably 1000 ppm or less, still more preferably 500 ppm or less, and most preferably 100 ppm or less. 500
If it exceeds 0 ppm, the crystallization rate of the obtained molded product from polyester at the time of heating will be high, resulting in excessive crystallization of the plug part of the hollow molding container, and thus the amount of shrinkage of the plug part will be the specified value. It will not fit within the range, and there will be a problem that capping of the spout will occur and the contents will leak. 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. Fluctuations will be large. In particular, when the capacity of the hollow molded body is larger than 1500 cc or in the case of the high heat resistant hollow molded body, the tendency becomes remarkable, and only the hollow molded body having no commercial value can be obtained. Therefore, when used for such applications, their content is especially 500 ppm.
It is important to keep the following: Further, by reducing the content of fines and the like as described above, it is possible to remove the above-mentioned resin granules or agglomerates existing independently of the above-mentioned polyester chips.

Further, in the present invention, the peak temperature on the highest side of the melting peak temperature of fine contained in the polyester before and / or after the contact treatment with the member is 265 ° C. or less. The present invention solves the above problems even further.

Examples of the method for separating and removing the fine and / or film-like substances from the polyester before and / or after the contact treatment with the member include the following methods. That is, immediately before the solid-state polymerization step and immediately before or after the step of contact-treating with the member made of the resin, the vibrating and sieving steps separately installed, or the vibrating and sieving step and the airflow classifying step by an air flow, etc. are treated. Methods and the like.

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., a step of removing fines as described above after the contact treatment with the resin is carried out. There is a method of treating with.

By using the polyester obtained by the above-mentioned production method, a molded article having excellent transparency and little fluctuation in crystallization rate can be obtained, but for the above reason, contact treatment with a member made of the resin is carried out. It is also necessary to pay attention to the content of the fine or film-like substances contained in the previous polyester and their properties.

A specific example of a method for preventing the polyester before the contact treatment with the resin member from containing such fines having a high melting point will be described below. In the case of melt polycondensation polyester, after melt polycondensation, the melt polyester is extruded into water from a die and cut in water, or extruded into the air and immediately cut into chips while cooling with cooling water. After draining the polyester chips formed into chips, a vibrating screen process and an air flow classification process using an air flow,
Alternatively, chips, fines, and film-like substances having a shape other than a predetermined size are removed by a water washing treatment step and sent to a storage tank by a plug transportation method or a bucket type conveyor-transportation method. Chips are taken out from the tank by a screw feeder, and transported to the next step by a plug transportation method or a bucket conveyor transportation method, and air flow classification by an air flow immediately before or after the contact treatment step. Fine removal processing is performed depending on the process. Then, the molten polycondensed polyester that has been subjected to the fine or film-like matter removal treatment is again removed by the airflow classification step using an air stream immediately before the solid-state polymerization step, and the solid-state polymerization step is performed. throw into. When transporting the melt-polycondensed prepolymer chips to a solid-state polymerization facility or when transporting the polyester chips after solid-state polymerization to a sieving step, the contact treatment step or a storage tank, most of these transportations are performed. Adopting a plug transportation system or a bucket type conveyor transportation system, and using a screw feeder to extract chips from the crystallization device or solid-state polymerization reactor, the equipment of chips and process and the transportation piping Use a device that can suppress the impact with the like.

As a gas for contacting the polyester after the melt polycondensation step or the solid phase polymerization step, or the polyester after the contact treatment with the member made of the resin, 1,000,000 particles having a particle size of 0.3 to 5 μm (pieces / piece) It is desirable to use a gas introduced from outside the system, which is less than or equal to cubic feet, preferably less than or equal to 500,000 (pieces / cubic feet), and more preferably less than or equal to 100,000 (pieces / cubic feet). Particles exceeding 5 μm in gas are
Although not particularly limited, it is preferably 5 (pieces / cubic foot) or less, more preferably 1 (pieces / cubic foot).
G) The following.

In the polyester manufacturing process, a container such as a silo, a hopper of a molding machine, a container for transportation, etc. is passed through each process such as a melt polycondensation process, a solid phase polymerization process, etc., such as a sieving process and an air flow classification process. In order to transport and dry the polyester during these steps, air around the treatment equipment is generally taken into the steps by a blower or the like and used. Conventionally, such air is either left untreated or used according to JIS B 9908 (199).
It was generally used only after being treated by a cleaner equipped with a low-performance filter unit such as type 3 defined in 1). However, the polyester treated in such a process may cause a problem that only a molded product having poor transparency can be obtained. In particular, before and after the contact treatment step with the member made of the resin, when the air having the quality as described above is used as the gas that comes into contact with the polyester, the crystallization rate and the transparency of the obtained molded product largely vary. There is a high possibility that it will become a problem.

Therefore, in the method for producing polyester by contact treatment with the resin member of the present invention, after the melt polycondensation, the solid phase polymerization, the water treatment or the contact treatment with the resin member, Among the polyesters, at least one polyester has a particle size of 0.3 to 5 as a gas to be contacted in any one of a transporting step to the next step, a sieving step, a storing step and a container filling step.
It is desirable to use a gas having a particle diameter of μm of 1,000,000 (particles / cubic foot) or less, which is introduced from outside the system.

Particles having a particle size of less than 0.3 μm in a gas are not particularly specified, but the smaller the number is preferable in order to obtain a resin which gives a transparent molded product.
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 shown below, but the present invention is not limited to this. Not something to do.

Particle size in gas introduced from outside the system 0.3 to 5
As a method of reducing the number of particles of μm to 1,000,000 (pieces / cubic foot) or less, cleaning by removing the particles at least at one or more places during the process until the gas introduced from outside the system contacts the polyester chips Install the device. When the gas is air in the vicinity of the treatment facility, JIS B 9908 is used during the process in which the air introduced by the blower from the air inlet comes into contact with the polyester chips.
A gas purifier equipped with a type 1 or / and type 2 filter unit defined in (1991) is installed, and the number of particles having a particle size of 0.3 to 5 μm in the air is set to 1,000,000.
(Individual / cubic foot) It is preferable to make it below. Also,
According to JIS B 9908 (199)
It is possible to extend the life of the filter unit by installing the gas cleaning device equipped with the type 3 filter unit defined in 1) and using it together with the gas cleaning device equipped with the filter unit. .

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.

Also, according to 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.

According to the method for producing a polyester of the present invention, the intrinsic viscosity is 0.65 to 2.0 deciliter / gram, the density is 1.37 cm ³ / g or more, the acetaldehyde content is 10 ppm or less, and the cyclic trimer content is Crystallization temperature of 0.6% by weight or less, haze of a 5 mm thick molded plate obtained by injection molding and 15% or less, and temperature rise of a molded plate of 2 mm thickness obtained by injection molding (Tc1) is 15
Polyesters in the range 0-165 ° C can be obtained.

The intrinsic viscosity of the polyester whose main repeating unit is ethylene terephthalate obtained by the production method of the present invention is preferably 0.68 to
1.50 deciliters / gram, more preferably 0.
It is in the range of 70 to 1.30 deciliters / gram. When the intrinsic viscosity is less than 0.65 deciliter / gram, the mechanical properties of the obtained molded product 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 acetaldehyde content of the polyester obtained by the production method of the present invention is 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.

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 polyester obtained by the production method of the present invention is 0.6% by weight or less, preferably 0.5% by weight or less, more preferably 0.40% by weight or less. . When molding a heat-resistant hollow molded article or the like from the polyester of the present invention, heat treatment is carried out in a heating mold, but when the content of the cyclic trimer exceeds 0.6% by weight, the surface of the heating mold is Adhesion of oligomers to the resin rapidly increases, and the transparency of the obtained hollow molded article is extremely deteriorated.

The haze of the molded plate made of polyester obtained by the production method of the present invention is preferably 10.
% Or less, more preferably 8% or less, and the crystallization temperature (Tc1) at the time of heating is preferably 153-163.
C., more preferably 155 to 162.degree.

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 16
If it exceeds 5 ° C., the heating crystallization rate 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.

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 raw 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, it is added to the polyester in order to improve handling properties such as slipperiness, winding property and blocking resistance. 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 the 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 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. About 120 to about 2 of this preform in a blow mold.
Stretch blow molding at 10 ° C, then about 0.5 to about 30
Heat treat for seconds. The draw ratio is usually 1.3 to 10 in the machine direction.
It is preferably 3.5 times 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.

[0123]

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) of polyester 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 of polyester
Content (hereinafter referred to as "DEG content") It was decomposed with methanol and the amount of DEG was quantified by gas chromatography, and expressed as a ratio (mol%) to all glycol components.

(3) Content of Polyester Cyclic Trimer (hereinafter referred to as "CT Content") A sample is dissolved in a hexafluoroisopropanol / chloroform mixture solution, and chloroform is further added to dilute it. 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 the cyclic trimer composed of ethylene terephthalate units was quantified by liquid chromatography.

(4) Acetaldehyde content of polyester (hereinafter referred to as “AA content”) Sample / distilled water = 1 g / 2 cc A glass ampoule with nitrogen substitution was sealed with the upper part and extracted at 160 ° C. for 2 hours. After treatment and cooling, acetaldehyde in the extract was measured by high sensitivity gas chromatography and the concentration was expressed in ppm.

(5) Measurement of content of fines and content of film-like substance About 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. Apart from the film-like material having a thickness of about 0.5 mm or less, two or more chips are fused to each other on the sieve (A), or a chip-like material cut into a size larger than the normal shape. When the fine particles that have been captured are removed, the remaining film-like material having a thickness of about 0.5 mm or less and the fines that have been sieved off under the sieve (B) are washed separately with ion-exchanged water and then washed with Iwaki. It was collected by filtering with a G1 glass filter manufactured by Glass Co. These are put together with the glass filter in a dryer at 100 ° C.
After drying for 2 hours, it was 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 content is fine weight or film weight / total screened resin weight. The total content is calculated from these values.

(6) Measurement of fine melt peak temperature 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) Average Density of Polyester Chip, Density of Preform Plug Portion and Density Deviation of Plug Portion Measurement was carried out at 30 ° C. with a density gradient tube of calcium nitrate / water mixed solution. Further, the density of the plug portion was obtained as an average value of 10 samples crystallized by the method (9), and the density deviation of the plug portion was obtained from these 10 values.

(8) Haze (% haze) and molded plate haze unevenness Samples from the body of the following (11) (wall thickness 5 mm) and the body of the hollow molded body (12) (wall thickness about 0.45 mm) Cut out, Haze meter manufactured by Nippon Denshoku Co., Ltd., model NDH
Measured at 2000. In addition, a forming plate formed 10 times in succession
The haze (wall thickness 5 mm) was measured, and the unevenness of the molded plate haze was determined by the following. Molded plate haze unevenness (%) = maximum haze value (%)-minimum haze value (%)

(9) Density increase due to heating of preform mouthpiece The preform mouthpiece 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.

(10) Crystallization temperature (T
c1) Differential thermal analyzer (DS
C), measured with RDC-220. A 10 mg sample from the center of a 2 mm thick plate of the following (11) molded plate was used. 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).

(11) Molding of Stepped Molded Plate A dried polyester is manufactured by Meiki Seisakusho M-150C (D
M) A stepped flat plate mold (surface temperature of about 2 ° C.) cooled with water at 10 ° C. at a cylinder temperature of 290 ° C. by an injection molding machine.
2 ° C.) for molding. The obtained step forming plate is 2,
A plate having a thickness of 3, 4, 5, 6, 7, 8, 9, 10, and 11 mm and a size of about 3 cm × about 5 cm square was provided stepwise, and the weight of one piece was about 146 g. The plate with a thickness of 2 mm is used for measuring the crystallization temperature (Tc1) at the time of heating, and the plate with a thickness of 5 mm is used for measuring the haze (% of haze).

(12) Molding of Hollow Molded Body Polyester was dried by a dryer using dehumidified air, and a preform was molded at a resin temperature of 290 ° C. by an M-150C (DM) injection molding machine manufactured by each machine manufacturer. . This prefor
The mouth plug part of the glass was heated and crystallized by a home-made mouth part crystallizer. Next, this preform was biaxially stretched and blown at a ratio of about 2.5 times in the longitudinal direction and about 3.8 times in the circumferential direction with an LB-01E molding machine manufactured by COPOPLAST Co., and subsequently about 150 times.
The container was heat-set in a mold set to 0 ° C. to form a container (body thickness 0.45 mm) having a capacity of 2000 cc. The stretching temperature was controlled to 100 ° C.

(13) Evaluation of Leakage of Contents from Hollow Molded Body The hollow molded body molded in (12) 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.

(14) Sodium Content, Calcium Content, Magnesium Content, and Silicon Content of Cooling Water in the Chipping Step The cooling water that had undergone particle removal and ion exchange was sampled with a 1G1 glass filter manufactured by Iwaki Glass Co., Ltd. After filtration, the filtrate was measured with an inductively coupled plasma emission spectrometer manufactured by Shimadzu Corporation.

(15) Measurement of the Number of Particles in Cooling Water in the Chip Making Step PAC manufactured by Seishin Enterprise Co., Ltd., which is a particle measuring device using the light-blocking method for cooling water that has undergone particle removal and ion exchange
The number of particles was measured by using 150, and the number of particles was expressed as particles / 10 ml.

(16) Measurement of the Number of Particles in Gas Contacting Polyester Chips 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 coming into contact with the chips. Then, 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 in which the reaction product was present, and the reaction was usually performed. The reaction was carried out under pressure at an average residence time of 4 hours at a temperature of 255 ° C. This reaction product is continuously taken out of the system and supplied to the second esterification reaction apparatus, and the temperature is set to 260 at normal pressure.
The reaction was carried out at ° C. 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 1.4 mol as antimony atom per unit (about 170 p for the produced polyester resin)
EG) of EG solution of antimony trioxide is fed to the esterification reaction product and stirred to about 265
Polycondensation was carried out at 25 ° C. and 25 to 3 torr, and further, polycondensation was carried out at about 275 ° C. and 0.5 to 1 torr with stirring in the final polycondensation reactor. The intrinsic viscosity of the melt polycondensation prepolymer is 0.5.
It was 5 dl / g.

The molten polycondensation reaction product was treated with industrial water (derived from river runoff water) by a filter-filtration device and an ion exchange device, and about 500 particles / 10 particles having a particle size of 1 to 25 μm were used.
ml, sodium content 0.02 ppm, magnesium content 0.01 ppm, calcium content 0.0
After cooling into chips with cooling water containing 1 ppm and silicon content of 0.11 ppm so that the chip temperature is about 40 ° C. or less, the chips are transported to a storage tank, and then finely divided by a vibrating sieving process and an air stream classification process. And by removing the film-like material, the fine content is about 40p.
It was pm or less. Then, it is sent to a crystallizer by a plug transport method, continuously crystallized at about 155 ° C. for 3 hours under a nitrogen gas flow, and then charged into a tower type solid-phase polymerizer and continuously at about 207 ° C. under a nitrogen gas flow. Solid-state polymerization was performed to obtain solid-state polymerization PET. 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.

This PET was processed by a vibrating sieving process and an airflow classifying process to obtain a fine content of about 50 pp.
m. Next, a linear low-density polyethylene (MI = about 0.9 g / m) was attached to a part of the SUS304 transportation pipe connected to the transportation container filling step installed after the airflow classification step.
10 minutes, density = about 0.923 g / cm ³ ) inner diameter 70
mm was transported at a rate of about 3 tons / hour in a transportation pipe to which a cylindrical pipe having a length of 700 mm was connected, and contact treatment was performed under flowing conditions. Treated amount of polyester per unit time (ton /
The ratio A of the surface area (cm ² ) of the cylindrical pipe to the
It was about 513. After the contact treatment, it was further treated in the airflow classification step. Fine content of PET after treatment is about 50
ppm, peak at the highest melting peak temperature of fine
Temperature is 245 ° C, polyethylene content is about 10 ppb
Met.

The PET thus obtained had an intrinsic viscosity of 0.75 deciliter / gram, a DEG content of 3.0 mol%, a cyclic trimer content of 0.30 wt%, and an average density of 1.40.
70 g / cm3, AA content was 3.8 ppm, fine content was about 50 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 170 ppm.

For the transportation of the melt polycondensation PET chips in the manufacturing process, the plug type transportation system and the bucket type conveyor transportation system were used in all of Examples 1 to 2. In addition, as air for sending the melt polycondensation PET chip to the solid-state polymerization step, and air for contacting the solid-state polymerization PET chip with the chip before filling the storage container, JIS B 99
08 (1991) Type 3 PET non-woven filter unit equipped with an air purifier and JIS B 9908
HEP with (1991) type 1 particle collection rate of 99% or more
Air filtered by an air cleaner equipped with the A filter unit (the number of particles having a particle size of 0.3 to 5 μm is about 500 / cubic foot) was used. Examples 2-3 and Comparative Examples 1-2
However, similarly filtered air was used.

The PET was evaluated using a molded plate and a biaxially stretched molded bottle. The results are shown in Table 1. Molded plate haze is 4.8%, molded plate haze unevenness is 0.2%,
The Tc1 of the molded plate was 165 ° C. The density of the bottle cap is 1.378 g / cm3, and the density deviation of the cap is 0.00
The value was 1 g / cm3, which was a problem-free value, and the body haze of the bottle was 1.0%, which was good. When the bottle was visually observed, no foreign matter was present. In addition, in the leak test of the contents, there was no problem and the mouth plug was not deformed. Bottle A
The A content was 23.0 ppm, which was a value with no problem.

(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) The amounts and ratios of antimony trioxide, magnesium acetate tetrahydrate and phosphoric acid were changed as shown in Table 1, and a filter was used as cooling water for chip formation of the melt polycondensed polyester. -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. The particles having a particle size of 1 to 25 μm contained in the industrial water used as the cooling water at the time of chipping are about 60,000 to 80,000 particles / 10 ml, the sodium content is 3.0 to 5.0 ppm, and the magnesium content is 0. ．
8-1.0ppm, calcium content 1.0-2.5p
The pm and silicon contents were 3.0 to 3.8 ppm. The PET was evaluated using a molded plate and a biaxially stretched molded bottle. The results are shown in Table 1. The transparency of the obtained bottle was poor, and foreign matter was visually observed, and deformation of the spout and leakage of the contents were examined, but leakage of the contents was observed.

(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. It should be noted that particles having a particle size of 1 to 25 μm contained in the industrial water used as the cooling water at the time of chip formation are about 80,000 to 90,000 particles / 10 ml, the sodium content is 5.0 to 7.0 ppm, and the magnesium content is 1 ．
8-2.5ppm, calcium content 1.8-3.5p
The pm and silicon contents were 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 transparency of the obtained bottle was poor, and foreign matter was visually observed, and deformation of the spout and leakage of the contents were examined, but leakage of the contents was observed.

[0149]

[Table 1]

[0150]

EFFECT OF THE INVENTION According to the method for producing a polyester of the present invention, a molded article having excellent transparency, a suitable and stable crystallization rate, and excellent heat-resistant dimensional stability, particularly a heat-resistant hollow molded article, can be obtained. It is possible to advantageously obtain polyesters having improved and improved runnability.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshitaka Eto             20 No. 248 Takashiro, Shiga Town, Shiga District, Shiga Prefecture F-term (reference) 4J029 AA03 AB05 AC01 AC02 AE01                       BA03 BA05 BA10 BB13A                       BD03A BF20 CA04 CA05                       CA06 CB05A CB06A CB10A                       CC06A CD03 CE01 CF15                       FC03 FC08 FC35 FC36 HA01                       HB01 JC412 JF131 JF141                       JF471 JF541 JF571 LB05                       LB10

Claims (6)

[Claims] 1. A polyester in which a polyester whose main repeating unit is ethylene terephthalate is contact-treated with at least one member selected from a polyolefin resin member, a polyamide resin member, and a polyacetal resin member under flowing conditions. The manufacturing method of
The polyester contains at least one metal compound selected from magnesium compounds, calcium compounds, cobalt compounds, manganese compounds and zinc compounds, a phosphorus compound and an antimony compound in an amount satisfying the following (1) to (3). A method for producing a polyester, comprising: 0.1 ≤ M ≤ 2.0 (1) 0.1 ≤ M / P ≤ 1.8 (2) 0.3 ≤ Sb ≤ 2.2 (3) (where M is 1 ton of polymer) Per mol of the metal atom of at least one metal compound selected from the magnesium compound, the calcium compound, the cobalt compound, the manganese compound and the zinc compound, P is the phosphorus atom (P) of the phosphorus compound per ton of the polymer. The number of moles, Sb is
The number of moles of antimony atom (Sb) of the antimony compound per ton of polymer is shown. ) 2. The polyester before the contact treatment, in the chip forming step after melt polycondensation, contains sodium (N), magnesium (M), silicon (S) and calcium. The amount (C) is from (4) to
The method for producing polyester according to claim 1, wherein the polyester is chipped with cooling water satisfying at least one of (7). N ≤ 1.0 (ppm) (4) M ≤ 0.5 (ppm) (5) S ≤ 2.0 (ppm) (6) C ≤ 1.0 (ppm) (7) 3. The content of any one of the fine content, the film-like material content, or the total content of the fine content and the film-like material content of the polyester before the contact treatment is 500 ppm or less. The method for producing a polyester according to claim 1, wherein the polyester is produced. 4. The fine melting point fine contained in the polyester before and / or after the contact treatment.
The peak temperature on the highest temperature side is 265 ° C. or lower, and the method for producing polyester according to claim 1. 5. The pipe is a pipe for pneumatic transportation of a polyester chip, a pipe for gravity transportation of a polyester chip,
The method for producing polyester according to any one of claims 1 to 4, wherein the polyester is at least one selected from the group consisting of rod-shaped, plate-shaped, and net-shaped bodies installed in a transfer path of polyester chips. 6. A gas contacting with polyester in at least one of a melt polycondensation step, a chip formation 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 5, characterized in that a gas introduced from outside the system below is used.