JP2003082209A - Polyester composition and blow molded product, sheetlike material and oriented film composed of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester composition having excellent crystallization controllability and long-time continuous moldability during melt molding and a blow molded product, a sheetlike material and an oriented film obtained therefrom, having excellent transparency and heat-resistant dimensional stability, affording especially a shrinkage percentage of a mouth plug part of the blow molded product within an appropriate range and scarcely causing residual off- tastes and off-flavors when formed into a liquid container. SOLUTION: This polyester composition comprises chips (A) of a polyester having main repeating units which are ethylene terephthalate and 0.1-300 ppm of fines (B) of a polyester. The area intensity ratio As on the chip surfaces of an absorption band due to the trans form caused by internal rotation with a carbon-carbon bond of ethylene glycol unit as an axis in an infrared absorption spectrum to an absorption band due to the gauche form is 5.50-9.00 and the ratio As/Ac of the area intensity ratio As to the area intensity ratio Ac in the chip central part satisfies 0.70-1.00.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester composition which is preferably used as a material for molded products such as hollow molded containers such as beverage bottles, films and sheets, and a molded product comprising the same. . In particular, the molded product obtained from the polyester composition of the present invention is excellent in crystallization controllability, and the resulting molded product is unlikely to have residual off taste or offensive odor, and is excellent in transparency and heat-resistant dimensional stability. And a sheet-like material and a stretched film which are excellent in transparency, slipperiness and dimensional stability after molding. The present invention also relates to a polyester composition which has good mold releasability from a heat treatment mold when molding a small hollow molded article and has excellent long-term continuous moldability.

[0002]

2. Description of the Related Art A polyester whose main repeating unit is ethylene terephthalate (hereinafter sometimes abbreviated as PET resin) is a carbonated beverage due to its excellent transparency, mechanical strength, heat resistance, gas barrier property and the like. It has been used as a material for containers such as juice, juice and mineral water, and its spread is remarkable. In these applications, polyester bottles are hot-filled with a beverage that has been sterilized at high temperature, or the beverage is sterilized at high temperature after filling, but with a normal polyester bottle, shrinkage occurs during such heat-filling treatment. Deformation occurs and becomes a problem. As a method for improving the heat resistance of a polyester bottle, a method has been proposed in which the bottle mouth plug is heat-treated to increase the crystallinity, or the stretched bottle is heat-fixed.
In particular, when the crystallization of the spout is insufficient or the crystallization degree varies greatly, the sealing property with the cap may be deteriorated and the contents may leak.

In order to improve the heat resistance of the body of the bottle, for example, as shown in Japanese Patent Publication No. 59-6216, a method of heat treatment by increasing the temperature of the stretching blow mold is adopted. 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 is because deposits due to the PET resin were attached to the mold surface, resulting in mold stains, which were transferred to the surface of the bottle. Particularly, in recent years, the molding speed has been increased along with the downsizing of bottles, and mold contamination has become a more serious problem from the viewpoint of productivity. 1
Further, in the case of a content liquid such as a fruit juice drink which needs to be hot-filled, a method of heat-treating the mouth part of a preformed or molded bottle to crystallize it (JP-A-55-79).
237, JP-A-58-110221, etc.) are generally used. 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 resin. On the other hand, the body is required to be transparent even when subjected to heat treatment during molding so that the color tone of the filling is not deteriorated, and the spout and the body need to have contradictory properties.

[0004]

Various proposals have been made to solve such problems. For example, a method of adding an inorganic nucleating agent such as kaolin and talc to polyethylene terephthalate (JP-A-56-2342, JP-A-56-21832), a method of adding an organic nucleating agent such as a montanic acid wax salt. (Japanese Patent Laid-Open No. 57-125246 and Japanese Patent Laid-Open No. 57-207639), but these methods have problems in practical use because of the generation of foreign matter and cloudiness. In addition, a method of inserting a heat-resistant resin piece into the plug portion (Japanese Patent Laid-Open No. 61-259946 and Japanese Patent Laid-Open No. 2-2).
No. 69638) has been proposed, but the bottle productivity is poor and the recyclability is also a problem.

To solve the problem of mold stains, a method of reducing the cyclic trimer, which is the main component of the deposit on the mold surface, by solid-phase polymerizing the PET resin in advance has been conventionally used. However, this method is insufficient in its effect because the cyclic trimer is regenerated during remelting and parison molding. Japanese Patent Publication No. 3-47830 discloses a method of treating a polyester resin with water at 90 to 110 ° C. to suppress the activity of the catalyst and controlling the formation of a cyclic trimer during parison molding. . However, this method requires a special apparatus and processing time for the processing, and has a problem that the manufacturing process becomes complicated. In addition, although the mold stain is reduced by the above method, it is still insufficient, and in some cases, a sufficient effect may not be obtained, and the transparency of the obtained molded body may be insufficient. there were.

The present invention solves the problems of the above-mentioned conventional polyesters, and the crystallization speed is such that the crystallization of the plug part occurs quickly and the shrinkage rate of the plug part is within an appropriate range. It is an object of the present invention to provide a polyester composition that gives an excellent molded article, and further to provide a polyester composition that does not stain the mold more than a catalyst deactivating resin by conventional water treatment. With the goal.

[0007]

In order to achieve the above object, the polyester composition of the present invention comprises a polyester chip (A) whose main repeating unit is ethylene terephthalate and a polyester chip (A) having the same composition. A polyester composition comprising 0.1 to 300 ppm of fine polyester (B), which is an absorption derived from a trans structure generated by internal rotation around a carbon-carbon bond of an ethylene glycol unit in an infrared absorption spectrum. Area intensity ratio As (T / T) of the band (T) and the absorption band (G) derived from the gouache structure on the chip surface.
G) is 5.50 to 9.00 and the area intensity ratio As is
(T / G) and the area intensity ratio Ac (T
/ G) ratio As (T / G) / Ac (T / G) is 0.70
It is characterized by satisfying ~ 1.00.

By melt-molding the polyester composition of the present invention having the above-mentioned constitution, a molded product having excellent transparency and heat-resistant dimensional stability, particularly a hollow molded product such as a container, can be easily obtained. it can. That is, an absorption band derived from a trans structure generated by internal rotation about the carbon-carbon bond of the ethylene glycol unit in the infrared absorption spectrum, which controls the amount of fine (B) of the polyester in the polyester composition ( The area intensity ratio As (T / G) on the chip surface between T) and the absorption band (G) derived from the gosh structure is 5.50 to 9.00, and the ratio As (T / G) / Ac (T / G) is 0.70
By satisfying 1.00, a polyester composition giving a molded article with excellent transparency, having a crystallization rate that causes rapid crystallization of the plug portion and a contraction rate of the plug portion within an appropriate range. Further, it is possible to obtain a polyester composition in which the mold is less polluted than the conventional catalyst deactivating resin by water treatment.

Here, in the infrared absorption spectrum, an absorption band (T) derived from a trans structure and an absorption band derived from a gosh structure (T) generated by internal rotation about a carbon-carbon bond of an ethylene glycol unit as an axis. G), the area intensity ratio As (T / G) on the chip surface, the area intensity ratio Ac (T / G) at the center of the chip, and the ratio As (T / G) / Ac (T / G) are described later. Can be obtained by the method.

In this case, the polyester is S
at least one compound selected from the group consisting of a b compound, a germanium compound, and a Ti compound, and Mg, Al,
Si, Ti, Mn, Fe, Co, Zn, Sr, Zr, S
A compound containing at least one element selected from the group consisting of n, W and Pb can be contained. In this case, the polyester may contain at least one selected from phenolic compounds.

In this case, the polyester may contain at least one selected from phosphorus compounds. In this case, the melting peak temperature on the highest side of the melting peak temperature of the polyester fine (B) may be 265 ° C or lower. In this case, the ring 3 when melted at a temperature of 290 ° C. for 60 minutes
The amount of increase of the monomer can be 0.50% by weight or less.

In this case, the polyester composition according to any one of claims 1 to 8 is further selected from the group consisting of a polyolefin resin, a polyamide resin, a polyacetal resin and a polybutylene terephthalate resin. A polyester composition comprising 0.1 ppb to 1000 ppm of at least one resin.

The above polyester composition is unlikely to cause mold stains during molding, has excellent crystallization controllability at the plug portion, and has excellent transparency, heat resistance, mechanical properties, residual off-taste, and off-flavor. And a sheet-like material excellent in transparency, slipperiness and dimensional stability after molding. Further, in this case, it may be a hollow molded article made of the polyester composition, a sheet-like material, and a stretched film stretched in at least one direction.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the polyester composition of the present invention, and a hollow molded article, a sheet-like material and a stretched film comprising the same will be specifically described below. The polyester whose main repeating unit is ethylene terephthalate in the present invention is preferably a linear polyester containing 85 mol% or more of ethylene terephthalate units,
More preferably 90 mol% or more, and particularly preferably 95
It is a linear polyester containing mol% or more.

Examples of the dicarboxylic acid used for the copolymerization of the polyester include aromatic dicarboxylic acids such as isophthalic acid, 2,6-naphthalene dicarboxylic acid, diphenylene 4,4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid and the like. Functional derivatives, oxyacids such as p-oxybenzoic acid and oxycaproic acid and functional derivatives thereof, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid and glutaric acid and functional derivatives thereof, cyclohexanedicarboxylic acid, etc. And aliphatic dicarboxylic acids and functional derivatives thereof.

As the glycol used for the copolymerization of the polyester, aliphatic glycols such as diethylene glycol, trimethylene glycol, tetramethylene glycol and neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, bisphenol A,
Examples thereof include aromatic glycols such as alkylene oxide adducts of bisphenol A.

Further, as the other copolymerization component composed of the polyfunctional compound in the polyester, trimellitic acid, pyromellitic acid and the like can be mentioned as the acidic component, and glycerin and pentaerythritol as the glycol component. You can The amount of the above copolymerization component used should be such that the polyester maintains a substantially linear shape. Also, monofunctional compounds such as benzoic acid,
You may copolymerize naphthoic acid etc.

The above polyester can be produced, for example, as follows. That is, first, terephthalic acid, ethylene glycol and, if necessary, the above-mentioned copolymerization component are directly reacted to distill off water to form an ester,
A direct esterification method in which polycondensation is carried out under reduced pressure using one or more compounds selected from Sb compounds, Ge compounds or Ti compounds as polycondensation catalysts, or dimethyl terephthalate and ethylene glycol and, if necessary, After reacting the above-mentioned copolymerization components in the presence of an ester exchange catalyst to distill off methyl alcohol for ester exchange, one or more selected from Sb compounds, Ge compounds or Ti compounds as polycondensation catalysts. A prepolymer is produced by the transesterification method in which the polycondensation is performed mainly under reduced pressure using the compound (1). Then, the prepolymer is subjected to solid phase polymerization by a continuous solid phase polymerization apparatus. In this case, the esterification reaction or transesterification reaction may be carried out in one step, or may be carried out in multiple steps. The melt polycondensation reaction may be carried out in one step or may be carried out in multiple steps. Furthermore, the melt polycondensation and the solid phase polymerization may be performed continuously or may be performed separately.

The polyester composition of the present invention comprises a polyester chip (A) whose main repeating unit is ethylene terephthalate, and a polyester fine (B) having the same composition as the polyester chip (A) 0.1 to 300.
ppm of a polyester composition, wherein the carbon of ethylene glycol unit in the infrared absorption spectrum is
Area intensity ratio A on the chip surface of the absorption band (T) derived from the trans structure and the absorption band (G) derived from the gosh structure generated by the internal rotation about the carbon bond
s (T / G) is 5.50 to 9.00, and the area intensity ratio As (T / G) and the area intensity ratio A at the center of the chip are
A polyester composition characterized in that the ratio As (T / G) / Ac (T / G) of c (T / G) satisfies 0.70 to 1.00.

In the polyester production process, in the step of forming the melt-polymerized polymer into chips, the solid-phase polymerization step, the step of transporting the melt-polymerized polymer chips or the solid-state polymerized polymer chips, etc., the size originally set at the time of granulation Granules, powder, etc., which are considerably smaller than those of chips, are generated. Here, such fine particles and powder are referred to as fine. In the process of producing polyester, in addition to using high-purity raw materials and auxiliary materials, filtration of molten polycondensation polymer, filtration of cooling water for polyester chips, filtration of water introduced from outside the system for water treatment of chips, Since a measure is taken to prevent foreign matters and contaminants other than the polyester used from mixing by filtering the gas used for transportation and the like, it is possible to prevent the fines from containing foreign matters and contaminants other than polyester.

Such fines have the property of promoting crystallization, and when present in a large amount, molded articles molded from such polyester compositions, especially bottles, have very poor transparency. The shrinkage amount at the time of crystallization of the bottle mouth plug part does not fall within the specified range, and the cap cannot be sealed.

The content of the fine (B) polyester of the present invention in the polyester composition is 0.1 to 300 pp.
m, preferably 0.2 to 250 ppm. When the blending amount is less than 0.1 ppm, the crystallization rate becomes very slow, and the crystallization of the plug portion of the hollow molding container becomes insufficient,
Therefore, the amount of contraction of the spout does not fall within the specified range,
Capping becomes impossible, and the stretch heat-fixing mold for molding the heat-resistant hollow molded container is heavily contaminated, so that it is necessary to frequently clean the mold to obtain a transparent hollow molded container. If it exceeds 300 ppm, the crystallization rate will be high and the crystallization of the plug part of the hollow molding container will be excessive, so that the shrinkage amount of the plug part will not fall within the specified range and Capping failure will occur, the contents will leak, and the preform for hollow molding will be whitened, which makes normal stretching impossible.

In the present invention, the intrinsic viscosity of the polyester fine (B) is usually 0.55 to 1.10,
Preferably 0.57 to 1.00, more preferably 0.
It is 58-0.90. If the intrinsic viscosity is less than 0.55, the resulting molded article will have poor transparency and the shrinkage of the plug portion will be too large. Further, it is preferable that it is the same as the intrinsic viscosity of the polyester chips, or in the range of from the intrinsic viscosity of the polyester chips to 0.2 higher than the intrinsic viscosity of the polyester chips. The same composition as the polyester chip (A) means that the fine (B) copolymerization component and the content of the copolymerization component are the same as those of the polyester chip (A).

The fine peak constituting the polyester composition of the present invention has a melting peak temperature of 265 ° C. or less, preferably 263 ° C. or less, more preferably on the highest temperature side of the melting peak temperature measured by DSC. Needs to be 260 ° C. or lower. When the fine particles having a melting peak temperature exceeding 265 ° C. are included, the crystals do not completely melt under the normally used melt molding conditions and remain as crystal nuclei. For this reason, when the hollow molded article plug portion is heated, the crystallization speed is increased, and thus the crystallization of the plug portion becomes excessive. As a result, the amount of contraction of the plug portion does not fall within the specified value range, resulting in defective capping of the plug portion and leakage of contents. 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. Also, the obtained sea
Since the sheet-like material has poor transparency and a high crystallization rate, normal stretching is impossible, and only a stretched film with large thickness unevenness and poor transparency can be obtained.

However, when it is desired to obtain a hollow-molding preform or sheet having good transparency and stretchability from a polyester composition containing fine particles having a melting peak temperature of more than 265 ° C. It must be melt-molded at a high temperature of 300 ° C or higher. However, such 300 ℃
At the above-mentioned high temperatures, the thermal decomposition of polyester becomes severe, and a large amount of by-products such as acetaldehyde and formaldehyde are generated, resulting in a great influence on the flavor of contents such as molded products. is there. In addition, when the polyester composition of the present invention contains at least one resin selected from the group consisting of the following polyolefin resins, polyamide resins, polyacetal resins, and polybutylene terephthalate resins, these are generally used. Since the thermoplastic resin is often inferior in thermal stability to the polyester according to the present invention, in the molding at a high temperature of 300 ° C. or higher as described above, thermal decomposition causes a large amount of by-products, The flavor of the obtained molded product or the like will have a greater effect.

Here, as described below, the melting point of fine is measured by a differential scanning calorimeter (DSC).
The melting peak temperature of C 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, the melting peak temperature on the highest temperature side among these plural melting peaks is defined as "the peak temperature on the highest temperature side of the fine melting peak temperature". In the examples and the like, it is referred to as “fine melting point”.

The area strength ratio As (T / T / T) on the surface of the chip (A) constituting the polyester composition of the present invention.
G) is 5.50 to 9.00, preferably 5.70 to 8.
80, more preferably 5.90 to 8.50. When the area intensity ratio As (T / G) on the surface is less than 5.50, the crystals are easily melted during the melt molding of the molded body, and crystal nuclei having a crystallization promoting action are not generated, and the crystals are The conversion speed becomes very slow. Therefore, when the plugged portion of the hollow molded body is crystallized, crystallization becomes insufficient, and the shrinkage amount of the plugged portion does not fall within the specified value range, resulting in poor capping. On the other hand, when the area intensity ratio As (T / G) on the surface exceeds 9.00, a dense crystal is generated in the chip surface layer, and the crystallinity becomes too high.
Crystals do not melt completely during melt molding and remain as crystal nuclei. As a result, the crystallization rate during heating becomes faster, and the crystallization of the plug part of the hollow molding container becomes excessive, and the shrinkage amount of the plug part does not fall within the specified value range. Next, the contents may leak.

The chip (A) constituting the polyester composition of the present invention has an absorption band derived from a trans structure produced by internal rotation centering on a carbon-carbon bond of an ethylene glycol unit in an infrared absorption spectrum. The ratio As of the area intensity ratio As (T / G) on the chip surface between (T) and the absorption band (G) derived from the gosh structure and the area intensity ratio Ac (T / G) on the chip central portion.
(T / G) / Ac (T / G) is 0.70 to 1.00, preferably 0.72 to 0.98, and more preferably 0.7.
It satisfies 3 to 0.96. Ratio As (T / G)
When / Ac (T / G) is less than 0.70, the crystals are easily melted during the melt-molding of the molded body, and crystal nuclei having a crystallization-accelerating action are not generated, resulting in a very high crystallization rate. I'll be late. Therefore, when the plugged portion of the hollow molded body is crystallized, crystallization becomes insufficient, and the shrinkage amount of the plugged portion does not fall within the specified value range, resulting in poor capping. On the other hand, the ratio As (T / G) / Ac (T / G) is 1.0.
When it exceeds 0, a dense crystal is generated on the surface layer of the chip,
In addition, the crystallinity becomes too high, and the crystals do not completely melt during melt molding and remain as crystal nuclei. As a result, the crystallization rate during heating becomes faster, and the crystallization of the plug part of the hollow molding container becomes excessive, and the shrinkage amount of the plug part does not fall within the specified value range. Next, the contents may 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.

The "chip surface" in the present invention means a thickness of 0.05 from the outer surface of the chip using a microtome.
mm refers to a layer obtained by cutting out a sample, and "the center of the chip" refers to a layer obtained by cutting out a sample having a thickness of 0.05 mm from the center of the chip using a microtome.

The above-mentioned polyester composition of the present invention can be produced, for example, as follows. That is, the melt-polycondensed prepolymer is produced by solid-phase polymerization in a continuous solid-state polymerization process in which the impact force is not applied to the chips, and the prepolymer chips are prepared by solid-state polymerization equipment including pre-crystallization equipment. When transporting polyester chips after solid-state polymerization to a sieving process or storage tank, the plug transport system or bucket system is performed while maintaining the chip temperature at a level not exceeding about 60 to 70 ° C. Adopt a conveyor transportation system, and use a screw feeder to extract chips from the crystallizer or solid-state polymerization reactor, so that the impact of chips with process equipment and transportation pipes can be minimized. By using a manufacturing apparatus capable of suppressing the above, the area strength ratio A on the chip surface is
s (T / G) within the range of 5.50 to 9.00 and the ratio As (T / G) / Ac (T / G) within the range of 0.70 to 1.00.
Can be within the range of. When a device such as a batch type rotary tumbler that exerts a large impact force on the chip is used as the solid-state polymerization device, the area strength ratio As (T / G) or the ratio As (T / G) / Ac ( T /
G) falls outside the above range.

As a method for adjusting the fine content of polyester within the above range, fine polyester chips having a high fine content which have not been subjected to a sieving step and fine particles through a sieving step and a fine removing step by an air stream are used. In addition to the method of mixing polyester chips with a very low content in an appropriate ratio, it can be adjusted by changing the opening of the sieve of the decoration in the fine removal step, or by changing the sieve dividing speed, etc. Any method can be used.

Next, the polycondensation catalyst and stabilizer used in producing the polyester according to the present invention will be described. Examples of the Sb compound used as the polycondensation catalyst in the present invention include antimony trioxide, antimony acetate, antimony tartrate, potassium antimony tartrate, antimony oxychloride, antimony glycolate, antimony pentoxide, triphenyl antimony and the like. . The Sb compound is
50-250 ppm as Sb residual amount in the produced polymer
To be in the range of.

Ge used as a polycondensation catalyst in the present invention
Examples of the compound include amorphous germanium dioxide, crystalline germanium dioxide, germanium chloride, germanium tetraethoxide, germanium tetra-n-butoxide, and germanium phosphite. When a Ge compound is used, the amount used is 5 to 150 ppm, preferably 10 to 100, as the Ge residual amount in the polyester.
ppm, and more preferably 15 to 70 ppm.

Ti used as a polycondensation catalyst in the present invention
Examples of the compound include tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate.
Tetraalkyl titanate such as tetra-n-butyl titanate and partial hydrolysates thereof, titanyl oxalate, titanyl ammonium oxalate, sodium titanyl oxalate, potassium titanyl oxalate, titanyl calcium oxalate,
A titanyl oxalate compound such as titanyl strontium oxalate,
Examples include titanium trimellitate, titanium sulfate, and titanium chloride. The Ti compound is added so that the amount of Ti remaining in the produced polymer is in the range of 0.1 to 10 ppm. The catalyst compound can be added at any stage of the polyester formation reaction step.

Further, various phosphorus compounds can be used as stabilizers. Examples of the phosphorus compound used in the present invention include phosphoric acid, phosphorous acid, phosphonic acid and their derivatives. Specific examples thereof 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, and phosphorous acid. Phosphoric acid, phosphorous acid trimethyl ester, phosphorous acid triethyl ester, phosphorous acid tributyl ester, methylphosphonic acid, methylphosphonic acid dimethyl ester,
Examples include ethylphosphonic acid dimethyl ester, phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, and phenylphosphonic acid diphenyl ester, which may be used alone or in combination of two or more kinds. Good. The phosphorus compound is 5 to 160 ppm, preferably 10 to 10 ppm as the residual amount of phosphorus in the produced polymer.
It is added at any stage of the above-mentioned polyester forming reaction step so as to be in the range of 100 ppm.

The polyester according to the present invention is Sb
At least one compound selected from the group consisting of compounds, germanium compounds and Ti compounds, and Mg, Al, S
i, Ti, Mn, Fe, Co, Zn, Sr, Zr, S
A compound containing at least one element selected from the group consisting of n, W and Pb is added in the above-mentioned esterification or transesterification step and / or melt polycondensation step to prepare a prepolymer in the same manner as described above. It can also be produced by solid-phase polymerization of the prepolymer.

Mg, Al, Si, T used in the present invention
i, Mn, Fe, Co, Zn, Sr, Zr, Sn, W,
Examples of the compound containing at least one element selected from the group consisting of Pb (referred to as a second group of metal compounds) include saturated aliphatic carboxylic acid salts such as acetates of these elements, and unsaturated such as acrylates. Aliphatic carboxylic acid salts, aromatic carboxylic acid salts such as benzoic acid, halogen-containing carboxylic acid salts such as trichloroacetic acid, hydroxycarboxylic acid salts such as lactate, inorganic acid salts such as carbonates, 1-propanesulfonic acid salts, etc. And organic sulfates such as lauryl sulfate, oxides, hydroxides, chlorides, alkoxides, chelate compounds with acetylacetonate, etc., and powders, aqueous solutions, ethylene glycol Solution, ethylene glycol slurry, etc. are added to the reaction system.

These metal compounds of the second group can be added to the reaction system at any stage of the polymerization reaction. For example, it can be added to the reaction system at any stage before and during the esterification reaction or transesterification reaction or immediately before the polycondensation reaction or at any stage during the polycondensation reaction.

Mg, Al, Si, Ti, Mn, Fe, C
A compound containing at least one element selected from the group consisting of o, Zn, Sr, Zr, Sn, W, and Pb is 0.005 as an element with respect to the acid component of the polyester.
1 to 0.5 mol%, preferably 0.003 to 0.3 mol%, and more preferably 0.005 to 0.1 mol%. When such a range is satisfied, it is possible to obtain a polyester composition having a suitable crystallization rate and giving a molded article with little fluctuation in crystallization rate. When the content of the compound containing these elements is less than 0.001 mol%, the crystallization acceleration effect becomes poor, and the crystallization cycle time of the spout part is increased in order to increase the productivity and reduce the cost during the production of the molded body. If you try to shorten the length, the amount of shrinkage of the plug part will not fall within the specified range due to insufficient crystallization of the plug part of the hollow molded body, resulting in poor capping and leakage of contents. Or
On the other hand, if it exceeds 0.5 mol%, the crystallization rate will be too fast and the mouthpiece of the hollow molded article will be excessively crystallized, so that the amount of contraction and shrinkage of the mouthpiece will not fall within the specified range. Therefore, the capping becomes defective and the content leaks, and the preform for the hollow molded body is whitened, which makes normal stretching impossible.

When the second group metal compound is used in combination with at least one compound selected from the group consisting of Sb compounds, germanium compounds and Ti compounds, at least one compound selected from phenol compounds Is preferably used.

The phenol compound used in the present invention is not particularly limited as long as it is a compound having a phenol structure, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and 2,6- Di-tert-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-
Diisopropyl-4-ethylphenol, 2,6-di-tert-amyl-4-methylphenol, 2,6-di-tert-octyl-4-n-
Propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-tert-butylphenol, 2-tert-butyl-2-ethyl-6-tert-octylphenol, 2-isobutyl-4 -Ethyl-6-tert-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,3-tris (2- Methyl-4-hydroxy-5
-tert-butylphenyl) butane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-
Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylene bis [3-
(3,5-di-tert-butyl-4,4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert
-Butyl-4-hydroxy-hydrocinnamide), 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5- Di-tert-
Butyl-4-hydroxybenzyl) isocyanurate, 1,
3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tris (4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, tetrakis [methylene (3,5-
Di-tert-butyl-4-hydroxy) hydrocinnamate]
Methane, bis [(3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid) glycol ester, N, N'-bis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionyl] hydrazine, 2,2'-Ogizamide bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-
Methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl
-2,4,6-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl 2- {β- (3-t
ert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2- (3 , 5-di-tert-
Butyl-4-hydroxycinnamoyloxy)) ethoxyphenyl] propane, β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester, tetrakis- [methyl-3- (3 ′, 5 '-Di-tert-butyl-4-hydroxyphenyl) propionate] methane, octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-
Butylphenyl) butane, thiodiethylene-bis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3- (5-tert-
Butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethyleneglycol-bis-[-3- (3 ' -tert-Butyl-4-hydroxy-5-methylphenyl)] propionate, 1,1,3-tris [2-methyl-4- [3- (3,
Examples thereof include 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane. These may be used in combination of two or more at the same time. Of these, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis- [methyl-3- (3 ', 5' -Di-tert-butyl
-4-Hydroxyphenyl) propionate] Methane, thiodiethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] are preferred.

By adding these phenolic compounds during the polymerization of polyester, the catalytic activity of the polycondensation catalyst is improved and the thermal stability of the polymerized polyester is also improved. The amount of the phenolic compound used in the present invention is 5 × 10 ⁻⁵ to 1 mol% relative to the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. It is more preferably 1 × 10 ^{−4 to} 0.5 mol%.

In the present invention, a phenol compound may be used together with a phosphorus compound. The more preferable phosphorus compound used in the present invention is at least one selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. Is a phosphorus compound. By using these phosphorus compounds during the polymerization of the polyester, the effect of improving the catalytic activity and the effect of improving the thermal stability of the polyester can be seen. Among these, it is preferable to use a phosphonic acid compound because the effect of improving the catalytic activity and the effect of improving the thermal stability of the polyester are large. Among the above-mentioned phosphorus compounds, it is preferable to use a compound having an aromatic ring structure because the effect of improving the catalytic activity and the effect of improving the thermal stability of the polyester are large.

The phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds and phosphine compounds referred to in the present invention are represented by the following formulas (1) to (6), respectively. A compound having a structure represented by

[0045]

[Chemical 1]

[0046]

[Chemical 2]

[0047]

[Chemical 3]

[0048]

[Chemical 4]

[0049]

[Chemical 5]

[0050]

[Chemical 6]

Examples of the phosphonic acid compounds used in the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate and the like. Is mentioned. Examples of the phosphinic acid compound used in the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, and phenyl phenylphosphinate. Examples of the phosphine oxide compound used in the present invention include diphenylphosphine oxide, methyldiphenylphosphine oxide,
Examples thereof include triphenylphosphine oxide.

Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds and phosphine compounds, the following formula (7)
It is preferable to use the compounds represented by (12) to (12).

[0053]

[Chemical 7]

[0054]

[Chemical 8]

[0055]

[Chemical 9]

[0056]

[Chemical 10]

[0057]

[Chemical 11]

[0058]

[Chemical 12]

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

As the phosphorus compound used in the present invention, it is preferable to use the compounds represented by the following general formulas (13) to (15) because the effect of improving the catalytic activity is particularly large.

[0061]

[Chemical 13]

[0062]

[Chemical 14]

[0063]

[Chemical 15]

(In the formulas (13) to (15), R ¹ , R ⁴ and R
⁵ and R ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group-containing hydrocarbon group having 1 to 50 carbon atoms. R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the phosphorus compound used in the present invention,
In the above formulas (13) to (15), compounds in which R ¹ , R ⁴ , R ⁵ , and R ⁶ are groups having an aromatic ring structure are particularly preferable.

The phosphorus compound used in the present invention includes
For example, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenyl Examples thereof include phosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate, diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide. Of these, dimethyl phenylphosphonate and diethyl benzylphosphonate are particularly preferable.

Among the above-mentioned phosphorus compounds, it is particularly preferable to use a phosphorus compound having a phenol moiety in the same molecule as the phosphorus compound used in the present invention. As a phosphorus compound having a phenol part in the same molecule,
It is not particularly limited as long as it is a phosphorus compound having a phenol structure, but has a phenol portion in the same molecule, phosphonic acid compound, phosphinic acid compound, phosphine oxide compound, phosphonous acid compound, phosphinic acid compound It is preferable to use one kind or two or more kinds of compounds selected from the group consisting of phosphine compounds, because the effect of improving the catalytic activity is large. Among these, it is preferable to use a phosphonic acid compound having one or more phenol moieties in the same molecule, because the effect of improving the catalytic activity is particularly large.

Further, as the phosphorus compound used in the present invention having a phenol moiety in the same molecule, compounds represented by the following general formulas (16) to (18) are preferably used because the catalytic activity is particularly improved.

[0069]

[Chemical 16]

[0070]

[Chemical 17]

[0071]

[Chemical 18]

(In the formulas (16) to (18), R ¹ includes a phenol moiety-containing hydrocarbon group having 1 to 50 carbon atoms, a substituent such as a hydroxyl group, a halogen group, an alkoxyl group or an amino group, and a phenol moiety. Represents a hydrocarbon group having 1 to 50 carbon atoms, wherein R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, an amino group or the like. Represents a hydrocarbon group having 1 to 50 carbon atoms, wherein R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, and 1 to 50 carbon atoms containing a substituent such as a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may contain a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl, etc. The ends of R ² and R ⁴ are bonded to each other. May be.)

Examples of the phosphorus compound having a phenol moiety in the same molecule used in the present invention include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate and p-hydroxyphenyl. Diphenyl phosphonate, bis (p-hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, phenyl bis (p-hydroxyphenyl) phosphinate,
p-Hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, phenyl p-hydroxyphenylphenylphosphinate, p-
Hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, bis (p-hydroxyphenyl) phosphine oxide, tris (p-hydroxyphenyl) phosphine oxide, bis (p-hydroxyphenyl) methylphosphine Oxide, and the following formula (1
Examples thereof include compounds represented by 9) to (22). Among these, the compound represented by the following formula (21) and dimethyl p-hydroxyphenylphosphonate are particularly preferable.

[0074]

[Chemical 19]

[0075]

[Chemical 20]

[0076]

[Chemical 21]

[0077]

[Chemical formula 22]

As the compound represented by the above formula (21), SANKO-220 (manufactured by Sanko Co., Ltd.) can be used.

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

Among the above-mentioned phosphorus compounds, in the present invention, it is particularly preferable to use a phosphorus metal salt compound as the phosphorus compound. The metal salt compound of phosphorus is not particularly limited as long as it is a metal salt of a phosphorus compound, but it is preferable to use a metal salt of a phosphonic acid compound because the catalytic activity improving effect is large. Examples of metal salts of phosphorus compounds include monometal salts, dimetal salts, trimetal salts and the like.

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

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

[0083]

[Chemical formula 23]

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

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

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

[0087]

[Chemical formula 24]

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

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

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

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

As the phosphorus metal salt compound used in the present invention, lithium [(1-naphthyl) methylphosphonate ethyl], sodium [(1-naphthyl) methylphosphonate ethyl], magnesium bis [(1-naphthyl) methylphosphonate] Ethyl], potassium [(2-naphthyl)
Ethyl methylphosphonate], magnesium bis [(2-
Naphthyl) methylphosphonate], lithium [benzylphosphonate], sodium [benzylphosphonate], magnesium bis [benzylphosphonate], beryllium bis [benzylphosphonate], strontium bis [benzylphosphonate], Manganese bis [ethyl benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonic acid], sodium [(9-anthryl) methylphosphonate ethyl], magnesium bis [(9-anthryl) methylphosphonate ethyl], sodium [4
-Ethyl hydroxybenzylphosphonate], magnesium bis [ethyl 4-hydroxybenzylphosphonate],
Sodium [phenyl 4-chlorobenzylphosphonate], magnesium bis [ethyl 4-chlorobenzylphosphonate], sodium [methyl 4-aminobenzylphosphonate], magnesium bis [methyl 4-aminobenzylphosphonate], sodium phenylphosphonate , Magnesium bis [ethyl phenylphosphonate], zinc bis [ethyl phenylphosphonate] and the like. Among these, lithium [(1-naphthyl) methylphosphonate ethyl], sodium [(1-naphthyl) methylphosphonate ethyl], magnesium bis [(1-naphthyl) methylphosphonate ethyl], lithium [benzylphosphonate ethyl], Sodium [benzyl phosphonate], magnesium bis [ethyl benzyl phosphonate], sodium benzyl phosphonate, magnesium bis [benzyl phosphonate] are particularly preferred.

Among the above phosphorus compounds, in the present invention, it is particularly preferable to use, as the phosphorus compound, at least one selected from the specific metal salt compounds of phosphorus represented by the following general formula (25).

[0094]

[Chemical 25]

(In the formula (25), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group or an alkoxyl group or carbonyl. Examples of R ⁴ O ⁻ include hydroxide ion, alcoholate ion, acetate ion and acetylacetone ion. l
Is an integer of 1 or more, m is 0 or an integer of 1 or more, l + m
Is 4 or less. M represents a (l + m) -valent metal cation. n
Represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

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

[0097]

[Chemical formula 26]

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

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

Specific metal salt compounds of phosphorus used in the present invention include lithium [3,5-di-tert-butyl-4-
Ethyl hydroxybenzylphosphonate], sodium [ethyl 3,5, -di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], potassium [ 3,5
-Di-tert-butyl-4-hydroxybenzylphosphonate ethyl], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], magnesium bis [3,5-di-tert-butyl] -4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di-ter]
t-Butyl-4-hydroxybenzylphosphonate methyl], strontium bis [3,5-di-tert-butyl-4]
-Hydroxybenzylphosphonate], barium bis [3,5-di-tert-butyl-4-phenylphenyl hydroxybenzylphosphonate], manganese bis [3,5-di-tert-
Butyl-4-hydroxybenzylphosphonate ethyl],
Nickel bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], copper bis [3,5-di-tert
-Butyl-4-hydroxybenzylphosphonate ethyl], zinc bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl] and the like. Among these, lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], sodium [3,5
-Di-tert-butyl-4-hydroxybenzylphosphonate ethyl], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl] are particularly preferred.

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

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

As the phosphorus compound having at least one P-OH bond used in the present invention, it is preferable to use at least one compound selected from the compounds represented by the following general formula (27) because the catalytic activity improving effect is large. .

[0104]

[Chemical 27]

(In the formula (27), R ¹ is hydrogen and the number of carbon atoms is ^{1 to 1} ).
It represents a hydrocarbon group having 50, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group and a hydrocarbon group having 1 to 50 carbon atoms. R ² is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and 1 to 5 carbon atoms.
Represents a hydrocarbon group of 0. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

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

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

The phosphorus compound having at least one P—OH bond used in the present invention includes (1-naphthyl)
Ethyl methylphosphonate, (1-naphthyl) methylphosphonic acid, ethyl (2-naphthyl) methylphosphonate, ethyl benzylphosphonate, benzylphosphonic acid, (9-
Anthryl) methylphosphonate ethyl, 4-hydroxybenzylphosphonate ethyl, 2-methylbenzylphosphonate ethyl, 4-chlorobenzylphosphonate phenyl,
Methyl 4-aminobenzylphosphonate, ethyl 4-methoxybenzylphosphonate and the like can be mentioned. Among these, ethyl (1-naphthyl) methylphosphonate and ethyl benzylphosphonate are particularly preferable.

Among the above-mentioned phosphorus compounds, in the present invention, it is particularly preferable to use a specific phosphorus compound having at least one P—OH bond as the phosphorus compound. P-OH
The specific phosphorus compound having at least one bond means at least one compound selected from the compounds represented by the following general formula (28).

[0110]

[Chemical 28]

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

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

[0113]

[Chemical 29]

(In the formula (29), R ³ is hydrogen and has 1 carbon atom.
It represents a hydrocarbon group of ˜50, a hydrocarbon group of 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

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

Specific phosphorus compounds having at least one P—OH bond used in the present invention include 3,5-di-t
ert-Butyl-4-hydroxybenzylphosphonate ethyl, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate methyl, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate isopropyl, 3, 5-di-tert-
Butyl-4-hydroxybenzylphosphonate phenyl,
Octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid and the like can be mentioned. Among these, ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferable.

The preferred phosphorus compound used in the present invention is the phosphorus compound represented by the chemical formula (30).

[0118]

[Chemical 30]

[0119] (In the formula (30), R ¹ represents a hydrocarbon group having 1 to 49 carbon atoms containing a hydrocarbon group or a hydroxyl group or a halogen group, an alkoxyl group, or an amino group, of 1 to 49 carbon atoms, R ² , R ³ are independently hydrogen and 1 to 1 carbon atoms.
It represents a hydrocarbon group of 50, a hydrocarbon group of 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain an alicyclic structure, a branched structure or an aromatic ring structure. )

Further, more preferably, a compound in which at least one of R ¹ , R ² and R ^{3 in} the chemical formula (30) contains an aromatic ring structure.

Specific examples of these phosphorus compounds are shown below.

[0122]

[Chemical 31]

[0123]

[Chemical 32]

[0124]

[Chemical 33]

[0125]

[Chemical 34]

[0126]

[Chemical 35]

[0127]

[Chemical 36]

The phosphorus compound used in the present invention is
A polymer having a larger molecular weight is preferable because it is more likely to be distilled off during the polymerization and thus has a larger effect.

Among the above phosphorus compounds, in the present invention, it is preferable to use at least one phosphorus compound selected from the specific phosphorus compounds represented by the following general formula (37) as the phosphorus compound.

[0130]

[Chemical 37]

(In the above formula (37), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
R ³ and R ⁴ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and 1 to 1 carbon atoms.
It represents 50 hydrocarbon groups. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl and naphthyl. )

Among the above-mentioned general formula (37), it is preferable to use at least one selected from the compounds represented by the following general formula (38) because the catalytic activity improving effect is high.

[0133]

[Chemical 38]

(In the formula (38), R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

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

Specific phosphorus compounds used in the present invention include diisopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-tert-butyl-4.
-Hydroxybenzylphosphonate di-n-butyl, 3,5
Examples include dioctadecyl-di-tert-butyl-4-hydroxybenzylphosphonate and diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.
Among these, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-
Diphenyl butyl-4-hydroxybenzylphosphonate is particularly preferred.

Among the above-mentioned phosphorus compounds, the phosphorus compound particularly preferably used in the present invention is represented by the chemical formula (3
9) and at least one phosphorus compound selected from the compounds represented by (40).

[0138]

[Chemical Formula 39]

[0139]

[Chemical 40]

As the compound represented by the chemical formula (39), Irganox 1222 (manufactured by Ciba Specialty Chemicals) is commercially available, and as the compound represented by the chemical formula (40), Irganox1.
425 (manufactured by Ciba Specialty Chemicals) is commercially available and can be used.

As the aluminum compound or phosphorus compound used in the present invention, it is preferable to use at least one selected from aluminum salts of phosphorus compounds. The aluminum salt of a phosphorus compound is not particularly limited as long as it is a phosphorus compound having an aluminum portion, but it is preferable to use an aluminum salt of a phosphonic acid compound because the effect of improving the catalytic activity is large. Examples of aluminum salts of phosphorus compounds include monoaluminum salts, dialuminum salts, and trialuminum salts.

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

As the aluminum salt of the phosphorus compound used in the present invention, it is preferable to use at least one selected from the compounds represented by the following general formula (41) because the catalytic activity improving effect is large.

[0144]

[Chemical 41]

(In the formula (48), R ¹ is hydrogen and the number of carbon atoms is 1
Represents a hydrocarbon group having 50 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group and having 1 to 50 carbon atoms. R ² is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and 1 to 1 carbon atoms.
It represents 50 hydrocarbon groups. R ³ is hydrogen, having 1 to 5 carbon atoms
It represents a hydrocarbon group of 0, a hydroxyl group, an alkoxyl group, or a carbonyl-containing hydrocarbon group of 1 to 50 carbon atoms. l
Is an integer of 1 or more, m is 0 or an integer of 1 or more, l + m
Is 3. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

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

Examples of the aluminum salt of the phosphorus compound used in the present invention include aluminum salts of ethyl (1-naphthyl) methylphosphonate, aluminum salts of (1-naphthyl) methylphosphonic acid, and aluminum salts of ethyl (2-naphthyl) methylphosphonate. An aluminum salt of ethyl benzylphosphonate, an aluminum salt of benzylphosphonic acid, an aluminum salt of ethyl (9-anthryl) methylphosphonate, an aluminum salt of ethyl 4-hydroxybenzylphosphonate, an aluminum salt of ethyl 2-methylbenzylphosphonate, Aluminum salt of phenyl 4-chlorobenzylphosphonate, aluminum salt of methyl 4-aminobenzylphosphonate, aluminum salt of ethyl 4-methoxybenzylphosphonate, aluminum salt of ethyl phenylphosphonate Such as salt-free, and the like. Among these, aluminum salts of ethyl (1-naphthyl) methylphosphonate and aluminum salts of ethyl benzylphosphonate are particularly preferable.

As the aluminum compound or phosphorus compound used in the present invention, it is particularly preferable to use at least one selected from the aluminum salts of specific phosphorus compounds represented by the following general formula (42).

[0149]

[Chemical 42]

((In the formula (42), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. R
³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group or an alkoxyl group or carbonyl. l is an integer greater than or equal to 1, m is
It represents 0 or an integer of 1 or more, and l + m is 3. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

Among these, it is preferable to use at least one selected from the compounds represented by the following general formula (43).

[0152]

[Chemical 43]

(In the formula (43), R ³ is hydrogen or carbon number 1)
It represents a hydrocarbon group of ˜50, a hydrocarbon group of 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. R ⁴ is hydrogen,
It represents a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms and containing carbonyl. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m is 3. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

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

The aluminum salt of the specific phosphorus compound used in the present invention includes an aluminum salt of ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
Aluminum salt of methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, aluminum salt of isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert- Butyl-4-hydroxybenzylphosphonic acid phenyl aluminum salt, 3,5-
Examples thereof include aluminum salts of di-tert-butyl-4-hydroxybenzylphosphonic acid. Among these, 3,
Aluminum salt of ethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4
Particularly preferred is the aluminum salt of methyl hydroxybenzylphosphonate. Further, in order to control the amount of diethylene glycol copolymerized in the polyester according to the present invention, a basic compound, for example, a compound of an alkali metal or an alkaline earth metal, a tertiary amine such as triethylamine, or hydroxylation is used. A quaternary ammonium salt such as tetraethylammonium can be added. Of these, compounds of alkali metals and alkaline earth metals are preferable.

An alkali metal used in the present invention,
As alkaline earth metals, Li, Na, K, Rb, C
At least one selected from s, Be, Mg, Ca, Sr and Ba is preferable, and the use of an alkali metal or a compound thereof is more preferable. When using an alkali metal or a compound thereof, use of Li, Na and K is particularly preferable.

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

Further, the polyester composition of the present invention is
It is necessary that the amount of increase of the cyclic trimer when melted at a temperature of 0 ° C. for 60 minutes is 0.50% by weight or less. Ring 3
The increase amount of the monomer is preferably 0.3% by weight or less, more preferably 0.1% by weight or less. 290
If the amount of increase of the cyclic trimer when melted at a temperature of 60 ° C. for 60 minutes exceeds 0.50% by weight, the cyclic trimer is melted when the resin for molding is melted.
The amount of the monomers increases, the amount of oligomers attached to the surface of the heating mold rapidly increases, and the transparency of the obtained hollow molded product is extremely deteriorated.

The polyester composition of the present invention, in which the amount of cyclic trimer increased by 0.50% by weight or less when melted at a temperature of 290 ° C. for 60 minutes, was obtained after melt polycondensation or solid phase polymerization. It can be produced by deactivating the polyester polycondensation catalyst.

Examples of the method for deactivating the polyester polycondensation catalyst include a method in which the polyester chips are subjected to contact treatment with water, water vapor or a gas containing water vapor after melt polycondensation or after solid phase polymerization.

A method of contacting the polyester chips with water, steam or a gas containing steam to achieve the above object will be described below. Examples of the hot water treatment method include a method of immersing in hot water and a method of spraying water on the chips with a shower. The treatment time is 5 minutes to 2 days, preferably 10 minutes to 1 day, more preferably 30 minutes to 10 hours, and the water temperature is 20 to 180 ° C., preferably 40.
To 150 ° C, more preferably 50 to 120 ° C.

The method of industrially performing water treatment will be illustrated below, but the method is not limited to this. The treatment method may be either a continuous method or a batch method, but the continuous method is preferable for industrial use. When water treatment of polyester chips in batch method,
A silo-type treatment tank is included. That is, the polyester chips are received in silos in a batch system and treated with water. When the polyester chips are treated with water continuously, the polyester chips can be continuously or intermittently received from the upper portion of the tower-type treatment tank for water treatment. This conceptual diagram is shown in FIG.

In the polyester composition of the present invention, the content of calcium element in the polyester composition is C (pp
m), the content of magnesium element is M (ppm), and the content of silicon element is S (ppm), the following (1)
It is a polyester composition characterized by satisfying any one of formulas (4) to (4). (1) 0.001 ≤ N ≤ 5 (ppm) (2) 0.001 ≤ C ≤ 5 (ppm) (3) 0.001 ≤ M ≤ 5 (ppm) (4) 0.001 ≤ S ≤ 5 ( ppm)

N, C, M and S are preferably each 0.005 to 1 ppm, more preferably each 0.0.
1 to 0.5 ppm, more preferably 0.01 to 0.3
It is ppm.

All the values of N, C, M and S are 0.00.
If it is less than 1 ppm, the crystallization rate will be very slow, and the plugging part of the hollow molding container will be insufficiently crystallized. Therefore, the shrinkage amount of the plugging part will not fall within the specified value range, so that the capping failure phenomenon will occur. May occur, or a sheet-like material having poor dimensional stability after molding the container may be given. Furthermore, when the values of N, C, M, and S are set to less than 0.001 ppm, sodium such as distilled water or water treated with a reverse osmosis membrane or water subjected to highly ion exchange treatment is used for water treatment, Since it is necessary to use water having a very low content of calcium, magnesium and silicon, it is not economically preferable.

When the values of N, C, M, and S exceed 5 ppm, the crystallization rate 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 is reduced. Since it does not fall within the specified value range, the capping of the spout becomes defective and the content leaks, and the preform for hollow molding is whitened, which makes normal stretching impossible.
The values of N, C, M and S are all preferably 5 ppm or less. In addition, it is preferable that N, C, M, and S satisfy all the upper limits of these formulas (1) to (4). Since the above-mentioned sodium, calcium, magnesium, and silicon are mainly derived from treated water, these metals are often present on the surface of the polyester chip or the surface layer having a thickness within about 0.5 mm from the chip surface. .

When the polyester chips are industrially treated with water, natural water (industrial water) or waste water is often reused because the amount of water used for the treatment is large. Usually, this natural water is taken from river water, groundwater, etc., and is said to have undergone treatment such as sterilization and removal of foreign substances without changing the shape of water (liquid). In addition, natural water generally used for industrial purposes is derived from natural sources such as silicates, aluminosilicates, and other inorganic compounds such as clay minerals, bacteria, bacteria, and spoiled plants and animals. It contains a large amount of organic compounds having When water treatment is performed using these natural waters, metal-containing substances such as sodium, magnesium, calcium and silicon dioxide adhere to and permeate the polyester chips and polyester fines to form crystal nuclei. It was found that the transparency of the hollow molded product which had been used was extremely deteriorated.

Regardless of whether the water treatment method is continuous type or batch type, if all or most of the treated water discharged from the treatment tank is treated as industrial waste water, a large amount of new water is needed. Not only that, there is concern about the impact on the environment due to an increase in the amount of drainage. That is, by returning at least a part of the treated water discharged from the treatment tank to the water treatment tank and reusing it, it is possible to reduce the necessary amount of water, and it is possible to reduce the effect on the environment due to the increase in the amount of drainage. As long as the wastewater returned to the water treatment tank maintains a certain temperature, the heating amount of the treated water can be reduced.

From the economical and environmental viewpoints, the treated water is repeatedly used in the case of batch-type water treatment, and the treated water discharged from the water treatment tank is reused in the case of continuous water treatment. Although it is returned and reused, in any case, metal-containing substances such as sodium, magnesium, calcium, and silicon dioxide in the treated water or fines derived from polyester chips adhere to the treatment tank or piping of the water treatment device, and This may cause stains on the processing equipment.

A method for reducing the sodium content, magnesium content, calcium content, silicon dioxide content, etc. of the treated water in the treatment tank will be exemplified below.
It is not limited to this. In order to reduce the sodium content, magnesium content, calcium content, silicon dioxide content, etc. of the treated water in the treatment tank, at least in the process until industrial water is sent to the treatment tank for supply to the treatment tank. Sodium, magnesium in one or more places,
Install a device to remove calcium, silicon dioxide, etc.
Further, a device for removing sodium, magnesium, calcium, silicon dioxide or the like may be installed at least at one or more places in the process until the treated water discharged from the treating tank is returned to the treating tank again. As an apparatus for removing sodium, magnesium, calcium, silicon dioxide, etc., an ion exchange apparatus, a chemical precipitation apparatus, an electrolytic desiliconization apparatus, etc. may be mentioned. The sodium content, magnesium content, calcium of treated water introduced from outside the system. In order to reduce the content of each to less than 0.001 ppm, it is necessary to distill water or to repeat filtration by a reverse osmosis membrane, which increases the cost of water and may be economically undesirable.

When the polyester chips and steam or a gas containing steam are contacted for treatment, 50 to 15
Steam or steam-containing gas at a temperature of 0 ° C., preferably 50 to 110 ° C., or steam-containing air is preferably supplied or present in an amount of 0.5 g or more as steam per 1 kg of granular polyethylene terephthalate. And contact with steam. This contact between polyester chips and water vapor
It is usually carried out for 10 minutes to 2 days, preferably 20 minutes to 10 hours.

The method for industrially carrying out the contact treatment between the particulate polyethylene terephthalate and steam or a steam-containing gas is shown below, but the method is not limited to this. Further, the treatment method may be either a continuous method or a batch method. When the polyester chips are subjected to a contact treatment with steam in a batch system, a silo type treatment device can be used. That is, the polyester chips are received in a silo, and steam or a steam-containing gas is supplied in a batch method to perform contact treatment.

When the polyester chips are continuously contacted with steam, granular polyethylene terephthalate may be continuously received from the upper part in a tower type processing apparatus, and steam may be continuously supplied in a cocurrent or countercurrent to contact with steam. it can. The water-treated polyester chips are vibrating screener,
Drain with a drainer such as Simon Carter and transfer to the drying process. As a matter of course, the water separated from the polyester chips by the water draining device is sent to a fine removing device such as a filter-type filtering device and a centrifugal separator, and can be used again for water treatment.

The polyester chips can be dried by using a continuous drying process for polyester chips which is usually used. As a continuous drying method, a hopper-type aeration dryer in which polyester chips are supplied from the upper part and a dry gas is aerated from the lower part is usually used. A silo-type dryer is used as a dryer for performing batch-type drying, and the dryer may be dried under atmospheric pressure while ventilating a drying gas.

Although atmospheric air may be used as the dry gas, dry nitrogen and dehumidified air are preferable from the viewpoint of preventing a decrease in molecular weight due to hydrolysis or thermal oxidative decomposition of the polyester. By subjecting the polyester to water or steam treatment as described above, 29
It is possible to suppress an increase in the amount of oligomers after heating and melting at a temperature of 0 ° C.

As another means for deactivating the polycondensation catalyst, there may be mentioned a method of inactivating the polymerization catalyst by adding and mixing the phosphorus compound to the melt of the polyester after melt polycondensation or after solid phase polymerization. .

In the case of the melt polycondensation polyester, the polyester after completion of the melt polycondensation reaction and the polyester resin containing the phosphorus compound are mixed in an apparatus such as a line mixer capable of being mixed in a melted state to obtain a polycondensation catalyst. The method of inactivating is mentioned.

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

The phosphorus compound used is phosphoric acid,
Examples include 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, Phosphoric acid, trimethyl phosphite, triethyl phosphite, tributyl phosphite, methylphosphonic acid,
Methylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester, phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid diphenyl ester, and the like, which may be used alone or in combination of two or more. You may use together.

As a method for producing the polyester composition of the present invention by subjecting the polyester after solid phase polymerization to contact with water or steam, the chips after solid phase polymerization are transported from a solid phase polymerization device or a storage tank to a water treatment device. When transporting the polyester after water treatment to the sieving process or storage tank, all of these transportations adopt the plug transportation method or bucket type conveyor transportation method, and also from the water treatment tank or dryer. A method of using a manufacturing apparatus capable of suppressing the impact between the chip and the transportation pipe or the like by using a screw feeder for the extraction of the chip can be mentioned.

When the polyester chips are treated with water as described above, the following method is practical as a method for adjusting the fine content of the polyester composition to the range of 0.1 to 300 ppm. That is, first, in the water treatment step, it is preferable that at least a part of the water for treatment is water that has been discharged from the treatment tank and returned to the treatment tank and is repeatedly used. By reusing water, it is possible to control the amount of fine powder in the treated water, and it is easy to control the fine content of polyester. When water with a fine powder amount of 0 is used for water treatment, fines attached to the polyester chips may be washed away by water and fall below 0.1 ppm. Furthermore, the amount of fine powder in the treated water is 1000p
It is preferable to carry out while adjusting so as to be pm or less, preferably 500 ppm or less. The amount of fine powder is 1000pp
When water exceeding m is used, the fine content of polyester may exceed 300 ppm.

The polyester composition of the present invention is obtained by adding at least one resin selected from the group consisting of a polyolefin resin, a polyamide resin, a polyacetal resin and a polybutylene terephthalate resin to the above polyester composition. A polyester composition comprising 1 ppb to 1000 ppm blended. The blending ratio of the above-mentioned polyolefin resin and the like in the polyester composition of the present invention is 0.1 ppb to 1000 ppm, preferably 0.1.
3 ppb to 100 ppm, more preferably 0.5 ppb
~ 1 ppm, more preferably 0.5 ppb-45 pp
b. If the compounding amount is less than 0.1 ppb, the crystallization speed will be very slow and the mouthpiece of the hollow molded article will not be sufficiently crystallized. Therefore, if the cycle time is shortened, the amount of shrinkage of the mouthpiece will be regulated. Capping failure occurs because it does not fall within the value range, and the stretch heat-fixing mold for molding the heat-resistant hollow molded product is heavily contaminated, and the mold is frequently cleaned when trying to obtain a transparent hollow molded product. There must be.
If it exceeds 1000 ppm, the crystallization speed will be high and the crystallization of the plug part of the hollow molded article will be excessive, and the shrinkage / shrinkage amount of the plug part will not fall within the specified range, resulting in poor capping. Things may leak,
Further, the preform for the hollow molded body is whitened, which makes normal stretching impossible. In the case of a sheet-like material, 100
If it exceeds 0 ppm, the transparency becomes extremely poor, and the stretchability becomes poor so that normal stretching is impossible and only a stretched film having large thickness unevenness and poor transparency can be obtained. Also,
When the above-mentioned polyolefin resin or the like is used alone, it has almost no effect on the prevention of stains on the heating die, but it has been found to be very effective on the stains on the die by coexistence with a specific amount of fines.

Examples of the polyolefin resin blended in the polyester composition of the present invention include polyethylene resins, polypropylene resins, and α-olefin resins. Further, these resins may be crystalline or amorphous.

Examples of the polyethylene resin blended in the polyester composition of the present invention include 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,
Examples thereof include copolymers with vinyl compounds such as vinyl chloride, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, styrene and 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, Examples thereof include ethylene-based resins such as ethylene-methacrylic acid copolymer and ethylene-ethyl acrylate copolymer.

Examples of the polypropylene resin blended in the polyester composition of the present invention include homopolymers of propylene, propylene, ethylene and butene.
1,3-methylbutene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, decene-
Copolymers with other α-olefins having about 2 to 20 carbon atoms such as 1 and vinyl compounds such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester and styrene, or hexadiene ,
Examples thereof include copolymers with diene such as octadiene, 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 resin blended in the polyester composition of the present invention includes homopolymers of α-olefins having about 2 to 8 carbon atoms such as 4-methylpentene-1 and their α-olefins. And ethylene, propylene, butene-1, 3-methylbutene-1, pentene-
Examples thereof include copolymers with other α-olefins having about 2 to 20 carbon atoms such as 1, hexene-1, octene-1, and decene-1. Specifically, for example, butene-1 homopolymer, 4-methylpentene-1 homopolymer, butene-1-
Butene-1 type resins such as ethylene copolymer and butene-1-propylene copolymer, and 4-methylpentene-1 and C2
Examples thereof include a C18 copolymer with an α-olefin.

Examples of the polyamide resin blended in the polyester composition of the present invention include butyrolactam, δ-valerolactam, ε-caprolactam, enantolactam, ω-laurolactam, and other polymers of lactam, and 6-aminocapron. Acid, polymers of aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine,
Undecamethylenediamine, 2,2,4- or 2,4
Aliphatic diamines such as 4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane)
Alicyclic diamines such as, diamine units such as aromatic diamines such as m- or p-xylylenediamine, and glutaric acid,
Aliphatic dicarboxylic acids such as adipic acid, suberic acid and sebacic acid, 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 these And the like. Specific examples thereof include 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 MXD
6, nylon 6 / MXD6, nylon MXD6 / MXD
I, nylon 6/66, nylon 6/610, nylon 6/12, nylon 6 / 6T, nylon 6I / 6T and the like. Further, these resins may be crystalline or amorphous.

The polyacetal resin blended in the polyester composition of the present invention includes, for example, polyacetal homopolymers and copolymers. Polyacetator
As the homopolymer, the density measured by the method of ASTM-D792 is 1.40 to 1.42 g / cm ³ , A
According to the measuring method of STMD-1238, 190 ℃, load 2
Melt flow ratio (MFR) measured at 160 g is 0.5
Polyacetal in the range of up to 50 g / 10 min is preferred.
Further, as the polyacetal copolymer, ASTM-D
The density measured by the measuring method of 792 is 1.38 to 1.4.
3 g / cm3, according to ASTM D-1238,
A polyacetal copolymer having a melt flow ratio (MFR) measured at 190 ° C. and a load of 2160 g of 0.4 to 50 g / 10 min is preferable. Examples of these copolymerization components include ethylene oxide and cyclic ethers.

As the polybutylene terephthalate resin to be blended with the polyester composition of the present invention, for example, a polybutylene terephthalate homopolymer composed of terephthalic acid and 1,4-butanediol or a polybutylene terephthalate homopolymer thereof can be used. In addition, a copolymer obtained by copolymerizing naphthalene dicarboxylic acid, diethylene glycol, 1,4-cyclohexane dimethanol, etc. can be mentioned. Further, the production of the thermoplastic resin blended polyester composition such as the polyolefin resin in the present invention,
In addition to the conventional method such as a method of directly adding and melt-kneading the thermoplastic resin to the polyester so that the content thereof is in the above range, or a method of adding as a master-batch and melt-kneading, The thermoplastic resin of, the production step of the polyester, for example, during melt polycondensation, immediately after melt polycondensation, immediately after pre-crystallization, during solid phase polymerization, immediately after solid phase polymerization, or the like, or From the end to the molding stage, etc., is directly added as a powder or granular material, or is mixed by a method such as contacting the thermoplastic resin member under the flowing conditions of the polyester chips. It is also possible to use a method of melt-kneading after heating.

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

Polyester Chip (A) According to the Present Invention
The intrinsic viscosity of the polyester that forms the resin is 0.55 to 0.
Preferably 90 deciliters / gram, 0.5
More preferably, it is 8 to 0.87 deciliter / gram. The intrinsic viscosity of polyester chips (A) is 0.5
When it is less than 5 deciliters / gram, the transparency of a molded article obtained by melt molding the polyester composition of the present invention,
The heat resistance and mechanical properties may not be sufficiently satisfied. If the intrinsic viscosity exceeds 0.90 deciliters / gram, the resin temperature rises during melting by a molding machine and the thermal decomposition becomes more intense, and free low-molecular weight compounds that affect aroma retention increase. However, there arises a problem that the molded body is colored yellow.

The acetaldehyde content of the polyester according to the present invention is 50 ppm or less, preferably 30 ppm.
ppm or less, more preferably 10 ppm or less, further preferably 5 ppm or less, the formaldehyde content is 2
It is 0 ppm or less, preferably 10 ppm or less, more preferably 8 ppm or less, and further preferably 4 ppm or less. Acetaldehyde content is 50 ppm or more and /
Alternatively, if the formaldehyde content is 20 ppm or more, the flavor and odor of the contents such as a container formed from this polyester are deteriorated.

The amount of diethylene glycol copolymerized in the polyester according to the present invention is preferably 0.5 to 5.0 mol%, more preferably 1.0 to 5.0 mol% of the glycol component constituting the polyester. It is 4.5 mol%, and more preferably 1.5 to 4.0 mol%. When the amount of diethylene glycol exceeds 5.0 mol%, the thermal stability is deteriorated, the molecular weight is greatly reduced during molding, and the acetaldehyde content and the formaldehyde content are increased, which is not preferable. If the content of diethylene glycol is less than 0.5 mol%, the transparency of the obtained molded product will be poor.

The content of the polyester cyclic trimer according to the present invention is preferably 0.50% by weight or less, more preferably 0.45% by weight or less, and further preferably 0.4% by weight or less.
It is 0% by weight or less. When a heat-resistant hollow molded article or the like is molded from the polyester composition of the present invention, heat treatment is carried out in a heating mold, but when the cyclic trimer content is 0.50% by weight or more, heating is performed. Oligomer attachment to the surface of the mold rapidly increases, and the transparency of the obtained hollow molded article is extremely deteriorated.

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

It is also possible to use a saturated fatty acid monoamide, an unsaturated fatty acid monoamide, a saturated fatty acid bisamide, an unsaturated fatty acid bisamide and the like at the same time in the polyester composition of the present invention.

Examples of the saturated fatty acid monoamide include lauric acid amide, palmitic acid amide, stearic acid amide and behenic acid amide. Examples of unsaturated fatty acid monoamides include oleic acid amide, erucic acid amide ricino-acid amide, and the like. Examples of the saturated fatty acid bisamide include methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebisbehenic acid amide, hexamethylenebisstearic acid amide, and hexamethylenebisbehenic acid. Examples include amides. Examples of unsaturated fatty acid bisamides include ethylenebisoleic acid amide and hexamethylenebisoleic acid amide. Preferable amide compounds are saturated fatty acid bisamide, unsaturated fatty acid bisamide and the like. The compounding amount of such an amide compound is 1
It is in the range of 0 ppb to 1 × 10 ⁵ ppm.

The polyester composition of the present invention may also contain a metal salt compound of an aliphatic monocarboxylic acid having 8 to 33 carbon atoms such as naphthenic acid, caprylic acid, capric acid, lauric acid,
Lithium salts, sodium salts, potassium salts, magnesium salts, calcium salts, and cobalt of saturated and unsaturated fatty acids such as myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid, melissic acid, oleic acid, and linoleic acid. It is also possible to use salt and the like together. The compounding amount of these compounds is in the range of 10 ppb to 300 ppm.

The polyester composition of the present invention can be preferably used as a hollow molding, a packaging material such as a tray, a biaxially stretched film, a film for coating a metal can, and the like.
Further, the polyester composition of the present invention can also be used as a constituent layer of a multilayer molded body, a multilayer film or the like. In the polyester composition of the present invention, a known ultraviolet absorber, a lubricant added from the outside or a lubricant internally deposited during the reaction, a release agent, a nucleating agent, a stabilizer, an antistatic agent, a dye, etc. You may mix | blend various additives, such as a pigment.

[0200]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.
In addition, the measuring method of the main characteristic value in this invention is demonstrated 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 content (hereinafter referred to as [DEG content]) Decomposition with methanol, the DEG content was quantified by gas chromatography, and expressed as a ratio (mol%) to all glycol components. expressed.

(3) Acetaldehyde content (hereinafter referred to as "A
"A content") Sample / distilled water = 1 g / 2 ml is put in a glass ampoule that has been purged with nitrogen, the upper part is sealed and extracted at 160 ° C for 2 hours, and after cooling, acetaldehyde in the extract is a highly sensitive gas. It was measured by chromatography and the concentration was expressed in ppm.

(4) Content of cyclic trimer of polyester (CT content) A sample is dissolved in a hexafluoroisopropanol / chloroform mixture solution, and chloroform is further added to dilute it. Methanol is added to this to precipitate the polymer, which is then filtered. The filtrate was evaporated to dryness, the volume was made constant with dimethylformamide, and the cyclic trimer composed of ethylene terephthalate units was quantified by liquid chromatography.

(5) Increasing amount of cyclic trimer during melting of polyester (ΔCT amount) 3 g of dried polyester chips were placed in a glass test tube and immersed in an oil bath at 290 ° C. for 60 minutes under a nitrogen atmosphere to melt. Let The amount of cyclic trimer increase during melting is determined by the following formula. Increase of cyclic trimer at melting (wt%) = cyclic 3 after melting
Content of monomer (% by weight) -Content of cyclic trimer before melting (% by weight)

(6) As (T /
G) and Ac (T / G) measurement and As (T / G)
/ Ac (T / G) calculation A 0.050 mm thick surface cut with a microtome
And FT-IR (free
The infrared spectrum was measured with a conversion infrared spectrometer. Profit
Derived from the T (trans) structure
972 cm as an absorption band^-1And G (Gorsch)
1042 cm as an absorption band derived from the structure ^-1Choose
And the high and low wavenumber ends of each absorption band.
Measure the area strength of the area surrounded by the tangent line (base line)
Decided T-absorbent van obtained for surface and center
And As (T / G)
And Ac (T / G), then As (T / G) / Ac (T
/ G) was calculated.

(7) Fine content measurement 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. Put these 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 determine 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.

(7) Measurement of fine melting peak temperature (hereinafter referred to as "fine melting point") Differential scanning calorimeter (DS) manufactured by Seiko Denshi Kogyo Co., Ltd.
C), measured using RDC-220. In (6),
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,
Obtain the melting peak temperature on the highest side of the melting peak temperature. 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. Melting peak is 1
In the case of two, the temperature is calculated.

(9) Average Density of Polyester Chip, Density of Preform Mouth Portion and Density Deviation of Mouth Portion A density gradient tube of a calcium nitrate / water mixed solution was used to measure the density. The density of the plug portion was calculated as an average value of 10 samples crystallized by the method (11), and the density deviation of the plug portion was calculated from the density values of these 10 samples.

(10) Haze (% haze) and haze unevenness Samples were cut from the body (wall thickness 5 mm) of the following (13) and the body (wall thickness approximately 0.4 mm) of the hollow molded body of (14). Measured with a haze meter manufactured by Nippon Denshoku Co., Ltd. Also, 1
The haze of a molded plate (wall thickness 5 mm) molded continuously 0 times was measured, and the haze unevenness was determined by the following. Haze spot = maximum haze value / minimum haze value

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

(12) Thickness variation of bottle Samples (3 cm × 3 cm) at four locations were randomly cut from the center of the body of the hollow molded article of (14) described below, and the thickness was measured with a digital thickness meter (in the same sample). Was measured at 5 points each, and the average was taken as the sample thickness). Thickness unevenness was determined by the following. Thickness unevenness = maximum thickness / minimum thickness

(13) Molding of Stepped Molded Plate A dried polyester is manufactured by Meiki Seisakusho M-150C (D
M) Molded by an injection molding machine at a cylinder temperature of 290 ° C. using a stepped flat plate mold cooled to 10 ° C. The obtained stepped molded plate was 2, 3, 4, 5, 6, 7, 8,
It is equipped with 9,3,11 mm thick plates of about 3 cm x about 5 cm square in a stepwise manner, and the weight of one piece is about 146.
It is g. A plate having a thickness of 5 mm is used for measuring haze (% haze).

(14) Evaluation of mold stains The polyester composition was dried with a drier using nitrogen, and a preform was molded with a M-150C (DM) injection molding machine manufactured by Meiki Seisakusho at a resin temperature of 290 ° C. The plug part of this preform is heated and crystallized by a homemade plug part crystallization device, and then biaxially stretch blow molded using a LB-01 stretch blow molding machine manufactured by Co-Poplast Co., Ltd.
It was heat-set in a mold set at 0 ° C. to obtain a 500 cc hollow molded body. Stretch blow molding was continuously carried out under the same conditions, and the mold stain was evaluated by the number of moldings until the transparency of the container was impaired by visual observation. As the haze measurement sample, the body of the container after continuous molding for 8000 times was used.

(15) Leakage Evaluation of Contents from Hollow Molded Body The hollow molded body molded in (14) 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.

Example 1 IV0.51 dl / g polyethylene terephthalate prepolymer obtained by melt polycondensation using crystalline germanium dioxide as a polycondensation catalyst and phosphoric acid as a stabilizer was chipped. , Send it to the crystallization device by the plug transportation method, and about 15 under nitrogen gas flow.
It is continuously crystallized at 5 ° C. for 3 hours, then charged into a tower-type solid-phase polymerization vessel, and solid-phase polymerized at about 209 ° C. under a nitrogen gas flow.
A solid-phase polymerized polyester was obtained. After the solid phase polymerization, fines 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 polyester was treated with water as follows. For water treatment of polyester chips, the apparatus shown in FIG. 1 is used, and the raw material chip supply port (1) at the upper part of the treatment tank, the overflow discharge port (2) located at the upper limit level of the treated water in the treatment tank, A discharge port (3) for the mixture of polyester chips and treated water in the lower part of the treatment tank, treated water discharged from this overflow outlet, treated water discharged from the treatment tank, and discharge of the lower portion of the treatment tank. The pipe (6) in which the treated water discharged from the drainage device (4) is sent to the water treatment tank again via the fine powder removing device (5) which is a continuous filter having a filter medium made of paper and having a thickness of 30 μm. ),
An internal volume of about 50 m ³ equipped with an inlet (7) for the treated water from which the fine powder has been removed, an adsorption tower (8) for adsorbing acetaldehyde in the treated water to which the fine powder has been removed, and an inlet (9) for new ion-exchanged water. The tower-type processing tank was used.

The treated water was continuously charged into a water treatment tank controlled at a temperature of 95 ° C. at a rate of 50 kg / hour from a supply port (1) at the upper part of the treatment tank, and treated water having a fine powder content of about 95 ppm was used. With water treatment time of 4 hours, PET chips were continuously withdrawn at a rate of 50 kg / hour from the outlet (3) at the bottom of the treatment tank together with the treated water. In addition, the amount of fine powder in the treated water is measured from the treated water discharge port of the treated layer to the JIS standard (JIS
-1000 ml of treated water that has passed through a filter having a nominal size of 850 μm according to Z-8801) is collected and used as a 1G1 glass filter manufactured by Iwaki Glass Co., Ltd. (pores 100 to 120 μm).
After filtration with, dried at 100 ° C. for 2 hours and cooled at room temperature, the weight is measured and calculated. The PET obtained had an intrinsic viscosity of 0.75 deciliters / gram and a DEG content of 2.6.
Mol%, content of cyclic trimer is 0.30% by weight, cyclic trimer increase is 0.05% by weight, average density is 1.4029 g
/ Cm ³ , As (T / G) and Ac (T / G) of the chip are 7.33, 8.30, As (T / G) / Ac, respectively.
(T / G) was 0.88, AA content was 2.5 ppm, fine content was 10 ppm, and the peak temperature of the highest melting peak temperature (fine melting point) was 265 ° C. or lower. It was The Ge residual amount measured by atomic absorption spectrometry was 50 ppm, and the P residual amount was 33 ppm. In the manufacturing process, melt-polymerized prepolymer chips, solid-state polymerized chips, and water-treated chips are all transported by a plug-type transportation method while maintaining the temperature of the chips at a temperature not exceeding about 60 to 70 ° C. A screw type feeder was used to extract the chips from the storage layer.

The PET was evaluated using a molded plate and a biaxially stretched molded bottle. The results are shown in Table 1. The haze of the molded plate is 2.9%, and the density of the plug part is 1.371 g.
/ Cm ³ is a value that does not cause a problem, and continuous stretch blow molding of 5000 or more was performed, but no mold stain was observed,
The transparency of the bottle was also good. In addition, in the leak test of the contents, there was no problem and the mouth plug was not deformed. The body haze of the obtained bottle was 0.7%, and the haze unevenness was 1.
1, the thickness unevenness was as good as 1.04. Further, the number of times of molding until the mold was soiled was 11,000, which was not a problem. The AA content of the bottle was 16.0 ppm, which was a value with no problem.

Example 2 Example 1 was repeated except that the same prepolymer as in Example 1 was used to shorten the solid phase polymerization time.
Solid phase polymerization using the same equipment under the same conditions as
Water treatment was carried out under the same conditions. The characteristics of the obtained PET, the molded plate obtained by molding the PET, and the biaxially stretched molded bottle are shown in Table 1.
Shown in. The result was fine.

Example 3 A slurry of high-purity terephthalic acid and ethyl glycol was continuously fed to a first esterification reactor containing a reactant in advance, and tetraisopropyl titanate ethylene was used. The glycol solution and the crystalline germanium dioxide were dissolved in water by heating, and ethylene glycol was added thereto, and the solution was heat-treated individually and continuously, while stirring, at about 250 ° C., 0.5 kg / cm 2.
^The reaction was carried out at ² G with an average residence time of 3 hours. The reaction product was sent to the second esterification reactor and stirred at about 260 ° C.
The reaction was carried out at 0.05 kg / cm ² to a predetermined degree of reactivity. The ethylene glycol solution of phosphoric acid is then added to this second
It was continuously fed into the transportation pipe from the esterification reactor to the first polycondensation reactor. The esterification reaction product was continuously fed to the first polycondensation reactor and stirred at about 265 ° C. for 25 hours.
1 hour at torr and then with stirring in the second polycondensation reactor,
Polyethylene terephthalate prepolymer of IV 0.51 dl / g was obtained by polycondensation at about 265 ° C. for 3 hours at 3 torr and for 1 hour at the final polycondensation reactor under stirring at about 275 ° C. for 0.5 to 1 torr. Got

Then, in the same manner as in Example 1, water treatment was carried out after solid phase polymerization. The PET obtained had an intrinsic viscosity of 0.
74 deciliters / gram, DEG content 2.7 mol%, cyclic trimer content 0.35% by weight, cyclic trimer increase 0.07% by weight, average density 1.4028 g / c
m ³ , chip As (T / G), Ac (T / G) are 7.60, 8.90, As (T / G) / Ac (T / G), respectively.
G) was 0.85, the AA content was 2.9 ppm, the fine content was 8 ppm, and the peak temperature (fine melting point) on the highest side of the melting peak temperature was 265 ° C or lower. The amount of Ge remaining measured by atomic absorption spectrometry is 27 pp
m, Ti residual amount is 1 ppm, P residual amount is 10 ppm
Met. The transportation and extraction of the chips in the manufacturing process were performed in the same manner by using the same device as in Example 1.

The PET was evaluated using a molded plate and a biaxially stretched molded bottle. The results are shown in Table 1. The haze of the molded plate is 3.4%, and the density of the plug part is 1.374 g.
/ Cm ³ and the density deviation of the plug portion are 0.001 g / cm ^{3, which} is a problem-free value, and continuous stretch blow molding of 5000 or more pieces was carried out, but no mold stain was observed, and the bottle was transparent. The property was also good. Also, in the leak test of the contents,
There was no problem and there was no deformation of the mouth plug. The body haze of the obtained bottle was 0.8%, the haze unevenness was 1.1, and the thickness unevenness was 1.03. In addition, the number of times of molding until the mold was soiled was 10,000 times, which was not a problem. The AA content of the bottle was 19.7 ppm, which was a problem-free value.

Example 4 A slurry of high-purity terephthalic acid and ethyl glycol was continuously fed to a first esterification reactor containing a reactant in advance, and the mixture was stirred to about 2
The reaction was carried out at 50 ° C. and 0.5 kg / cm ² G with an average residence time of about 3 hours. This reaction product was sent to the second esterification reactor, and reacted under stirring at about 260 ° C. and 0.05 kg / cm ² G to a predetermined reactivity. Crystalline germanium dioxide was dissolved in water by heating, and ethylene glycol was added to the solution, and the solution was heat-treated to obtain 0.022 mol% germanium atom based on the acid component in the polyester. An ethylene glycol solution of aluminum acetylacetonate was used as the polyester. 0.015 mol% as an aluminum atom with respect to the acid component in, and Irganox 142
An ethylene glycol solution of 5 (manufactured by Ciba Specialty Chemicals) was used as Irganox 1 for the acid component.
0.01 mol% as 425 was separately fed continuously to this second esterification reactor. The esterification reaction product was continuously fed to the first polycondensation reactor and stirred at about 265 ° C. at 25 torr for about 1 hour, and then stirred at the second polycondensation reactor at about 265 ° C. at 3 torr. About an hour,
Furthermore, while stirring in the final polycondensation reactor, at about 275 ° C., 0.5
Polycondensation at about 1 torr for about 1 hour gives IV 0.51d
1 / g of polyethylene terephthalate prepolymer was obtained.

Then, in the same manner as in Example 1, after solid phase polymerization, water treatment was carried out. The PET obtained had an intrinsic viscosity of 0.
74 deciliters / gram, DEG content 2.7 mol%, cyclic trimer content 0.35% by weight, cyclic trimer increment 0.08% by weight, average density 1.4027 g / c
m ³ , chip As (T / G), Ac (T / G) are 7.55, 8.50, As (T / G) / Ac (T /
G) was 0.89, the AA content was 2.9 ppm, the fine content was 8 ppm, and the peak temperature (fine melting point) on the highest side of the melting peak temperature was 265 ° C or lower. The residual Ge amount measured by atomic absorption spectrometry is about 38p.
It was pm (about 0.010 mol% with respect to the acid component).
In addition, the transportation and extraction of chips in the manufacturing process
It carried out by the same method using the apparatus similar to Example 1. The PET was evaluated using a molded plate and a biaxially stretched molded bottle. The results are shown in Table 1.

The haze of the molded plate was 3.1%, the density of the plug portion was 1.376 g / cm ³ , and the density deviation of the plug portion was 0.001.
The value was g / cm ^3, which was a problem-free value, and continuous stretch blow molding of 5,000 or more was performed, but no mold stain was observed and the transparency of the bottle was good. In addition, in the leak test of the contents, there was no problem and the mouth plug was not deformed. The obtained bottle had good haze of 1.0%, uneven haze of 1.1, and uneven thickness of 1.03. In addition, the number of times of molding until the mold was soiled was 10,000 times, which was not a problem. The AA content of the bottle was 19.8 ppm, which was a value without problems.

(Comparative Example 1) The prepolymer obtained in Example 1 was put into a rotary tumbler, crystallized at 140 ° C under reduced pressure while rotating, and solid-phase polymerized at 210 ° C. After the solid phase polymerization, fine particles were removed in a sieving process. The transportation to the solid-state polymerization apparatus and the transportation after the solid-state polymerization were all performed by the low-density transportation method. The chip temperature during transportation or immediately after transportation increased to about 80 ° C or higher. Obtained PE
Water treatment was performed on T under the same conditions as in Example 1. Table 1 shows the characteristics of the obtained PET, the molded plate obtained by molding the PET, and the biaxially stretch-molded bottle. The transparency of the obtained bottle was poor, and the deformation of the stopper and the leakage of the contents were examined.
Leakage of contents was recognized.

[0227]

[Table 1]

[0228]

According to the polyester composition of the present invention,
It has excellent crystallization controllability during melt molding and long-term continuous moldability, and the hollow molded article, sheet-like material and stretched film obtained therefrom have excellent transparency and heat-resistant dimensional stability. The shrinkage rate of the plug portion of the hollow molded body is in an appropriate range, and residual off taste and offensive odor hardly occur when the liquid container is formed.

[Brief description of drawings]

FIG. 1 is a schematic view of an apparatus used in a method for producing polyester used in Examples.

[Explanation of symbols]

1 Raw material chip supply port 2 Overflow outlet 3 Polyester chips and treated water outlet 4 drainer 5 Fine powder remover 6 piping 7 Treated water inlet 8 adsorption tower 9 Ion exchange water inlet

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/13 C08K 5/49 5/49 C08L 101: 00 // (C08L 67/02 B65D 1/00 A (11:00) (72) Inventor Keisuke Suzuki 10-24 Toyocho, Tsuruga City, Fukui Prefecture Toyobo Co., Ltd.Tsuruga Factory (72) Inventor Shumu Kimura 26-21 Akao-cho, Shiga F Term (reference) ) 3E033 AA01 BA18 BB04 CA20 FA02 4F071 AA46 AA87 AF29Y AH04 AH05 BA01 BB06 BC01 BC04 4J002 BB003 CB003 CF061 CF06 JA JA JA JA JA 261 JA03 EJ0 BBJ BBJA01 EJ027 EJ027 EJ027 EJ027 EJ027 JF183 JF223 JF321 JF333 JF361 JF471 JF543 JF563 JF573 KE12 KH03 KH05 KH08

Claims (10)

[Claims] 1. A polyester composition comprising a polyester chip (A) whose main repeating unit is ethylene terephthalate and a polyester fine (B) having the same composition as the polyester chip (A) in an amount of 0.1 to 300 ppm. Between the absorption band (T) derived from the trans structure and the absorption band (G) derived from the gosh structure generated by the internal rotation about the carbon-carbon bond of the ethylene glycol unit in the infrared absorption spectrum. The area intensity ratio As (T / G) on the chip surface is 5.50 to
9.00 and the ratio As (T) of the area intensity ratio As (T / G) and the area intensity ratio Ac (T / G) at the center of the chip.
/ G) / Ac (T / G) satisfies 0.70 to 1.00. 2. The polyester comprises at least one compound selected from the group consisting of Sb compounds, germanium compounds and Ti compounds, and Mg, Al, Si, Ti and M.
The polyester composition according to claim 1, further comprising a compound containing at least one element selected from the group consisting of n, Fe, Co, Zn, Sr, Zr, Sn, W and Pb. 3. The polyester composition according to claim 2, wherein the polyester contains at least one selected from phenolic compounds. 4. The polyester composition according to claim 1, wherein the polyester contains at least one selected from phosphorus compounds. 5. The melting peak temperature on the highest side of the melting peak temperature of the polyester fine (B) is 265 ° C.
It is the following, The polyester composition in any one of Claims 1-4. 6. The polyester composition according to claim 1, wherein the amount of cyclic trimer increase when melted at a temperature of 290 ° C. for 60 minutes is 0.50% by weight or less. . 7. The polyester composition according to claim 1, further comprising at least one selected from the group consisting of a polyolefin resin, a polyamide resin, a polyacetal resin, and a polybutylene terephthalate resin. A polyester composition comprising 0.1 ppb to 1000 ppm of a resin. 8. A hollow molded article comprising the polyester composition according to any one of claims 1 to 7. 9. A sheet-like material obtained by extrusion-molding the polyester composition according to claim 1. 10. A stretched film obtained by stretching the sheet-like material according to claim 9 in at least one direction.