JP2003301093A - Polyester composition, and hollow molded object, sheet- like product, and stretched film produced therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester composition which is excellent in crystallization control properties and long-time continuous moldability in melt molding; and a hollow molded object, a sheet-like product, and a stretched film, all produced therefrom and excellent in clarity and heat-resistant dimensional stability, especially, becoming a proper range in the shrinkage factor of the mouth plug part of the hollow molded object and hard to cause remaining nasty taste or bad smell when used as a liquid container. <P>SOLUTION: This polyester composition comprises PET (polyethylene terephthalate) chips, 0.1-5,000 ppm fine polyester powder having the same composition as the PET chips, and 0.1 ppb to 5,000 ppm at least one resin selected from the group consisting of polyolefin resins, polyamide resins, and polyacetal resins and it is characterized in that the PET contains specified amounts of a P compound, a Sb compound, and at least one metal compound selected from the group consisting of Mg compounds, Ca compounds, Co compounds, Mn compounds, and Zn compounds. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester composition preferably used as a raw material for molded products such as hollow molded containers such as beverage bottles, films and sheets, and molded products made from the same. Yes, especially,
Provided are a small hollow molded article having excellent transparency and heat-resistant dimensional stability, and a sheet-like article having excellent transparency, slipperiness, and dimensional stability after molding. The present invention also relates to a polyester composition having good mold releasability from a heat treatment mold when molding a small hollow molded article and excellent long-term continuous moldability.

[0002]

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

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

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

In the case of polyester bottles for beverages, hot sterilized beverages are hot-filled into the bottles, or the beverages are filled and then sterilized at high temperature. There is a problem that shrinkage and deformation occur in etc. As a method for improving the heat resistance of a polyester bottle, there has been proposed a method in which a bottle mouth plug is heat-treated to increase the crystallinity, or a stretched bottle is heat-fixed.

In particular, the crystallization of the mouth plug is insufficient,
Further, when the variation in crystallinity is large, the sealing property with the cap is deteriorated and the contents may leak.

Specifically, in the case of beverages such as fruit juice drinks, oolong tea and mineral water that require hot filling, a method of heat-treating the preformed or molded bottle cap to crystallize (JP-A-55-792
No. 37, JP-A-58-110221, etc.) are generally used. In such a method, that is, a method of heat-treating the plug portion and the shoulder portion to improve heat resistance, the time and temperature of the crystallization treatment greatly affect the productivity, and the treatment can be performed at a low temperature in a short time. PET with high conversion speed
Is preferred. On the other hand, the body portion is required to be transparent even when subjected to heat treatment at the time of molding so as not to deteriorate the color tone of the bottle content, and the spout portion and the body portion need to have contradictory properties.

Further, in order to improve the heat resistance of the bottle body, for example, 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 was because deposits due to PET were attached to the mold surface, resulting in mold stains, which were transferred to the bottle surface. In particular, in recent years, the molding speed has been increased along with the downsizing of bottles, and from the viewpoint of productivity, shortening the heating time for crystallizing the spout and mold fouling have become more serious problems. .

Various proposals have been made to solve such problems. For example, 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. (JP-A-57-125246, JP-A-57-
No. 207639), but these methods have a problem in practical use due to the generation of foreign matter and cloudiness. Further, there is a method of adding a treated polyester obtained by crushing a polyester molded product obtained by melt-molding the polyester to the raw material polyester (JP-A-5-105807), but this method has an extra step of melt molding and crushing. Is required, and there is a risk that impurities other than polyester are mixed in in such a post-process, which is not a preferable method in terms of economy and quality. In addition, a method of inserting a heat-resistant resin piece into the plug portion (Japanese Patent Laid-Open No. 61-259946,
JP-A-2-269638) has been proposed,
Bottle productivity is poor and recyclability is also a problem.

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

In order to solve these problems, a germanium compound or a mixture of titanium compound and titanium compound is used as a polycondensation catalyst. However, use of an expensive germanium compound has a drawback that the cost of PET becomes high.

[0012]

As a method for solving such a problem, for example, in JP-A-6-279579, transparency is improved by defining the ratio of the amount of the antimony compound and the phosphorus compound used. A method is disclosed. However, the crystallization rate of the hollow molded article from PET obtained by this method is not stable, and the fluctuation is extremely large, so that the dimension of the plug portion becomes unstable and defective capping occurs. There is also the problem that its transparency is not sufficient.

On the other hand, as a measure for improving the crystallization rate of PET, a method for modifying PET by contacting a PET chip with a polyethylene member under flowing conditions (Japanese Patent Laid-Open No. 9-7).
1639) or a method for modifying PET by contacting with a member made of polypropylene resin or polyamide resin under similar conditions (Japanese Patent Laid-Open No. 11-209492).
No.), or a polyester resin composition obtained by blending PET with 0.1 to 45 ppb polyethylene (JP-A-9-151308), or PET with 0.1 to 10 parts.
A polyester resin composition (Japanese Unexamined Patent Publication No. 9-194697) prepared by blending 00 ppm of polypropylene has been proposed. However, even if such a method is used or such a polyester resin composition is used, it is appropriate. It has a stable crystallization rate, and gives a molded product with excellent dimensional stability and transparency of the plug after heating and crystallization, and it is very difficult to obtain a polyester polymerized using an antimony catalyst. I knew it was.

The present invention solves the problems of the above-mentioned conventional polyesters, causes rapid crystallization of the plug portion, has a crystallization rate such that the shrinkage rate of the plug portion is in an appropriate range, and is transparent. An object of the present invention is to provide a polyester composition which gives a molded article excellent in heat resistance.

[0015]

To achieve the above object, the polyester composition of the present invention comprises a polyester chip whose main repeating unit is ethylene terephthalate, and a polyester chip having the same composition as the polyester chip. Fine 0.1 to 5000 ppm, and at least one resin 0.1 ppb selected from the group consisting of polyolefin resin, polyamide resin, and polyacetal resin
To 50,000 ppm, wherein the polyester comprises at least one metal compound selected from a magnesium compound, a calcium compound, a cobalt compound, a manganese compound, and a zinc compound, a phosphorus compound and an antimony compound as described below (1 ) ~ (3)
A polyester composition containing an amount satisfying 0.1 ≤ M ≤ 3.0 (1) 0.1 ≤ M / P ≤ 2.0 (2) 0.1 ≤ Sb ≤ 1.7 (3) (where M is 1 ton of polymer) Per mole of the metal atom of at least one metal compound selected from magnesium compound, calcium compound, cobalt compound, manganese compound and zinc compound, P is the number of moles of phosphorus atom of the phosphorus compound per ton of the polymer, Sb represents the number of moles of antimony atoms of the antimony compound per ton of the polymer.)

In this case, the polyester composition contains an amount of at least one metal compound selected from the group consisting of titanium compounds, germanium compounds and aluminum compounds, which satisfies the following (4) to (6). can do. 0 <Ti ≤ 0.4 (4) 0 <Ge ≤ 0.6 (5) 0 <Al ≤ 2.0 (6) (In the above formula, Ti represents the titanium atom of the titanium compound per ton of the polymer. The number of moles, Ge is the number of moles of germanium atom of the germanium compound per ton of polymer,
Al represents the number of moles of aluminum atoms of the aluminum compound per ton of the polymer. )

In this case, when the polyester fine is measured by DSC, the melting peak temperature on the highest side of the melting peak temperature can be 265 ° C. or lower.

Here, as described below, the melting point of fine is measured by a differential scanning calorimeter (DSC).
The melting peak temperature of 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”.

In this case, the content of the film-like material having the same composition as the polyester may be 10 ppm or less.

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

In this case, the cyclic trimer content may be 0.7% by weight or less. In this case, the cyclic trimer increase amount when melted at a temperature of 290 ° C. for 60 minutes can be 0.50% by weight or less.

In this case, the polyester is
In the chip forming step after the melt polycondensation, the sodium content (N), the magnesium content (M), the silicon content (S) and the calcium content (C) are the following (7).
The polyester may be chipped with cooling water that satisfies at least one of (10) to (10). N ≤ 1.0 (ppm) (7) M ≤ 0.5 (ppm) (8) S ≤ 2.0 (ppm) (9) C ≤ 1.0 (ppm) (10)

Further, in this case, the hollow molded article is
It can be formed by molding the polyester composition described above. Further, in this case, the sheet-like material may be formed by extrusion molding the above-described polyester composition. Furthermore, in this case, the stretched film may be obtained by stretching the sheet-like material in at least one direction.

The above-mentioned polyester composition of the present invention is excellent in crystallization control property of the spout, and is excellent in transparency, heat resistance, mechanical properties, residual off-taste, no off-flavor, and aroma retention. A hollow molded article, a sheet-like material or a stretched film is provided.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The embodiments of the polyester composition of the present invention, and the hollow molded article, sheet-like material and stretched film comprising the same will be specifically described below.

The polyester according to the present invention is a polyester whose main repeating unit is ethylene terephthalate, preferably 8 ethylene terephthalate units.
It is a linear polyester containing 5 mol% or more, more preferably 90 mol% or more, and particularly preferably 95% mol or more.

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

The glycol as a copolymerization component used when the polyester is a copolymer includes diethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol and the like. Aliphatic glycols, alicyclic glycols such as cyclohexanedimethanol, bisphenol A, aromatic glycols such as alkylene oxide adducts of bisphenol A and the like can be mentioned.

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

The above-mentioned polyester is a direct esterification method in which terephthalic acid, ethylene glycol and, if necessary, the above-mentioned copolymerization components are directly reacted to distill off water to effect esterification, and then polycondensate under reduced pressure. , Or dimethyl terephthalate and ethylene glycol and, if necessary, the above-mentioned copolymerization components are reacted in the presence of an ester exchange catalyst to distill off methyl alcohol to effect transesterification, and then polycondensate under reduced pressure. Manufactured by the exchange method.

As the above-mentioned starting materials dimethyl terephthalate, terephthalic acid or ethylene glycol,
Virgin dimethyl terephthalate derived from paraxylene, terephthalic acid or ethylene glycol derived from ethylene, as well as dimethyl terephthalate and terephthalic acid recovered from used PET bottles by a chemical recycling method such as methanol decomposition or ethylene glycol decomposition. A recovered raw material such as bishydroxyethyl terephthalate or ethylene glycol can also be used as at least a part of the starting material. The quality of the recovered raw material is a purity according to the purpose of use,
It goes without saying that it must be refined to quality.

Further, solid phase polymerization may be carried out in order to increase the molecular weight of the polyester resin and reduce the acetaldehyde content. In order to accelerate crystallization before solid-phase polymerization, the molten polycondensed polyester may be adsorbed with moisture and then crystallized by heating, or steam may be directly blown onto the polyester chips to be crystallized by heating.

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

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

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

The polyester composition of the present invention comprises a polyester chip whose main repeating unit is ethylene terephthalate, fine 0.1 to 5000 ppm of polyester having the same composition as the polyester chip, a polyolefin resin and a polyamide resin. , At least one resin selected from the group consisting of polyacetal resins.
A polyester composition comprising 1 ppb to 50000 ppm, wherein the polyester is at least one metal compound selected from a magnesium compound, a calcium compound, a cobalt compound, a manganese compound, and a zinc compound, a phosphorus compound and an antimony compound as follows ( 1)
The polyester composition is characterized by containing an amount satisfying (3) to (3). 0.1 ≤ M ≤ 3.0 (1) 0.1 ≤ M / P ≤ 2.0 (2) 0.1 ≤ Sb ≤ 1.7 (3) (where M is 1 ton of polymer) Per mole of the metal atom of at least one metal compound selected from magnesium compound, calcium compound, cobalt compound, manganese compound and zinc compound, P is the number of moles of phosphorus atom of the phosphorus compound per ton of the polymer, Sb represents the number of moles of antimony atoms of the antimony compound per ton of the polymer.)

The polyester composition of the present invention contains at least one selected from the group consisting of titanium compounds, germanium compounds and aluminum compounds in the polyester composition in an amount satisfying the following (4) to (6). A polyester composition comprising a metal compound of a kind. 0 <Ti ≤ 0.4 (4) 0 <Ge ≤ 0.6 (5) 0 <Al ≤ 2.0 (6) (In the above formula, Ti represents the titanium atom of the titanium compound per ton of the polymer. The number of moles, Ge is the number of moles of germanium atom of the germanium compound per ton of polymer,
Al represents the number of moles of aluminum atoms of the aluminum compound per ton of the polymer. )

As the magnesium compound, calcium compound, cobalt compound, manganese compound and zinc compound used in the present invention, any compound can be used as long as it is a compound soluble in the reaction system.

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

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

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

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

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

The content of the magnesium compound, the calcium compound, the cobalt compound, the manganese compound, and the zinc compound represented by the general formula (1) is 0.1 to 3 as the metal atom of the metal compound per ton of polyester.
It is in the range of 0 mol, preferably in the range of 0.15 to 2.8 mol, and more preferably in the range of 0.2 to 2.6 mol.
If the amount is less than 0.1 mol per ton of polymer, the transparency of the obtained hollow molded article from the polyester, particularly the stretch-heat-fixed hollow molded article, is very poor, and the crystallization rate fluctuation becomes very large. On the other hand, if it exceeds 3.0 mol, the thermal stability of the polyester will be poor, the hue will be poor, and the content of acetaldehyde will be high, causing a problem in terms of flavor. Further, the crystallization speed fluctuation of the molded body also becomes large.

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

Examples of the phosphorus compound used in the production of the polyester according to the present invention include phosphoric acid compounds, phosphorous acid compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, Examples thereof include phosphinous acid compounds and phosphine compounds. 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, phosphorous acid trimethyl ester, phosphorous acid triethyl ester, phosphorous acid tributyl ester, methylphosphonic acid, methylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester, phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester,
Phenyl phosphonate diphenyl ester, benzyl phosphonate dimethyl, benzyl phosphonate diethyl, diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate, diphenylphosphine oxide, methyl Examples thereof include diphenylphosphine oxide and triphenylphosphine oxide, which may be used alone or in combination of two or more kinds.

The content of the phosphorus compound represented by the general formula (2) is such that the molar ratio Me / P of the metal atom of the above metal compound to the phosphorus atom of the phosphorus compound per ton of polyester finally obtained. Is in the range of 0.1 to 2.0, preferably 0.2 to 1.8, more preferably 0.3 to 1.
The range is 6. When Me / P is less than 0.1, the transparency of the hollow molded article, especially the stretch-heat-fixed hollow molded article, obtained from the obtained polyester resin is extremely deteriorated. On the other hand, when it exceeds 2.0, the thermal stability of the polyester is poor, and the content of acetaldehyde is high, which causes a problem in flavor.

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

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

The content of the antimony compound represented by the general formula (3) is 0.1 to 1 as the antimony atom of the antimony compound per ton of the obtained polyester.
7 mol range, preferably 0.2-1.6 mol,
More preferably, it is in the range of 0.3 to 1.5 mol. When the amount is less than 0.1 mol per ton of polymer, the polycondensation time becomes very long, which is a problem from the viewpoint of economical productivity. On the other hand, if the amount exceeds 1.7 mols, the transparency of the obtained hollow molded article decreases, the crystallization speed fluctuation becomes extremely large, and the color tone deteriorates, which is a problem. The timing of adding the antimony compound is not particularly limited, but may be before the esterification reaction or before the transesterification reaction.

Examples of the titanium compound used in the method for producing a polyester of the present invention include tetraalkyl titanates such as tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate and tetra-n-butyl titanate, and their partial hydrolysates. , Titanium acetate, titanyl oxalate, titanyl ammonium oxalate, sodium titanyl oxalate, potassium titanyl oxalate, calcium titanyl oxalate, titanyl oxalate compounds such as strontium titanyl oxalate, titanium trimellitate,
Titanium sulfate, titanium chloride, hydrolyzate of titanium halide, titanium oxalate, titanium fluoride, potassium hexafluorotitanate, ammonium hexafluorotitanate, cobalt hexafluorotitanate, manganese hexafluorotitanate, Examples include titanium acetylacetonate.

The content of the titanium compound represented by the general formula (4) is 0.4 mol or less, preferably 0.3 mol or less, as the titanium atom of the titanium compound per ton of the polyester resin finally obtained. is there. If the titanium content per ton of polymer exceeds 0.4 mol, the resulting hollow molded article will have a problem of reduced transparency, poor color tone, and increased acetaldehyde content. The timing of adding the titanium compound is not particularly limited.

The germanium compound used in the method for producing a polyester of the present invention includes amorphous germanium dioxide, crystalline germanium dioxide, germanium tetroxide, germanium hydroxide, germanium oxalate, germanium chloride, germanium tetraethoxide, germanium tetra- Examples include n-butoxide and germanium phosphite.

The content of the germanium compound represented by the general formula (5) is 0.6 mol or less, preferably 0.5 mol or less, as the germanium atom of the germanium compound per ton of the polyester resin finally obtained. is there. The germanium content per ton of polymer is 0.
If it exceeds 6 moles, the thermal oxidation stability of the obtained polymer deteriorates, and the transparency of the hollow molded article decreases.
Then, the cost of the obtained resin becomes high, which is a problem. The timing of adding the germanium compound is not particularly limited.

Aluminum compounds used in the production of the polyester according to the present invention include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate and benzoic acid. Carboxylates such as aluminum, aluminum trichloroacetate, aluminum lactate, aluminum citrate, and salicylate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, polyaluminum chloride, aluminum nitrate,
Inorganic acid salts such as aluminum sulfate, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t
-Aluminum alkoxides such as butoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate, aluminum chelate compounds such as diiso-propoxide, organoaluminum compounds such as trimethylaluminum, triethylaluminum and parts thereof. Hydrolyzate, aluminum oxide, etc. are mentioned. Of these, carboxylates,
Inorganic acid salts and chelate compounds are preferable, and among these, basic aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, polyaluminum chloride and aluminum acetylacetonate are particularly preferable.

The content of the aluminum compound represented by the general formula (6) is 2.0 mol or less, preferably 1.9 mol or less, as the aluminum atom of the aluminum compound per ton of the finally obtained polyester resin. is there. Aluminum content per ton of polymer is 2.
If it exceeds 0 mol, the thermal oxidation stability of the obtained polymer will deteriorate, and the transparency of the hollow molded article will also decrease.
Then, the hue of the obtained resin deteriorates, which is a problem. The timing of adding the aluminum compound is not particularly limited.

Further, metal compounds other than the above can also be used within a range that does not affect the characteristics of the polyester composition of the present invention. Specific examples include lithium, sodium, potassium, copper, beryllium, strontium, barium, boron, gallium, indium, silicon, zirconium, tin, hafnium, lead, niobium, tantalum, bismuth, chromium, molybdenum, tellurium, tungsten. ,
Examples thereof include oxides, halides, hydroxides, carbonates, sulfates, alkoxides and aliphatic or aromatic carboxylates of iron, nickel and the like.

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

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

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

In the polyester resin composition of the present invention,
It is necessary to contain 0.1 ppb to 50,000 ppm of at least one resin selected from the group consisting of polyolefin resin, polyamide resin and polyacetal resin. The blending ratio of the resin used in the present invention into the polyester is 0.1 ppb to 50,000 ppm, preferably 0.3 ppb to 10,000 ppm, more preferably 0.5 ppb to 100 ppm, further preferably 1.0 ppb to 1 ppm, and particularly preferably. 1.0 ppb
~ 45 ppb. If the compounding amount is less than 0.1 ppb, the crystallization speed will be very slow and the mouthpiece of the hollow molded article will not be sufficiently crystallized. Therefore, if the cycle time is shortened, the amount of shrinkage of the mouthpiece will be regulated. Capping failure occurs because it does not fall within the value range, and the stretch heat-fixing mold for molding the heat-resistant hollow molded product is heavily contaminated, and the mold is frequently cleaned when trying to obtain a transparent hollow molded product. There must be. If it exceeds 50,000 ppm, the crystallization rate will be high and the crystallization of the plug part of the hollow molded article will be excessive, and the amount of shrinkage and shrinkage of the plug part will not fall within the specified range, resulting in poor capping. Leakage of the product occurs and the preform for the hollow molded body is whitened, which makes normal stretching impossible. Further, in the case of a sheet-like material, if it exceeds 50,000 ppm, the transparency becomes extremely poor and the stretchability becomes poor so that normal stretching is impossible, and only a stretched film with large thickness unevenness and poor transparency is obtained. I can't.

Examples of the polyolefin resin blended in the polyester composition of the present invention include polyethylene resin, polypropylene resin, and α-olefin resin. 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.

As the α-olefin resin blended in the polyester composition of the present invention, homopolymers of α-olefins having about 2 to 8 carbon atoms such as 4-methylpentene-1 and their α-olefins can be used. 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 C _2-
Examples thereof include copolymers with C ₁₈ α-olefins.

As the polyamide resin to be blended with the polyester composition of the present invention, for example, lactam polymers such as butyrolactam, δ-valerolactam, ε-caprolactam, enantolactam, ω-laurolactam, 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.

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

In the production of the polyester composition in which the above-mentioned polyolefin resin or the like is blended in the present invention, a resin such as the above-mentioned polyolefin resin or the like is directly added to the polyester having the above-mentioned characteristics so that the content thereof falls within the above-mentioned range, and the mixture is melted. In addition to a conventional method such as a method of kneading or a method of melt kneading by adding as a master-batch, the resin is used in the production step of the polyester, for example, during melt polycondensation, immediately after melt polycondensation, immediately after pre-crystallization. , During the solid phase polymerization, immediately after the solid phase polymerization, or in the process from the end of the production step to the molding step, etc., or added directly as a powder or the polyester. By mixing chips by contacting them with the resin member under flowing conditions, or by melting and kneading after the contact treatment. It can be.

Here, as a method of bringing the polyester chip into contact with the resin member under flowing conditions, it is preferable to bring the polyester chip into collision contact with the member in a space where the resin member exists. Specifically, for example, immediately after melt polycondensation of polyester, immediately after pre-crystallization, immediately after solid-phase polymerization, during the manufacturing process, and when filling / discharging a transport container at the transportation stage as a product of polyester chips, In addition, at the time of loading the molding machine at the molding stage of the polyester chip, pneumatic transportation pipe, gravity transportation pipe, etc.
A part of the silo, the magnet part of the magnet catcher, etc. is made of the resin, the resin film, the sheet, the molded body or the like is attached, or the resin is lined, or in the transfer path. A method of transferring the polyester chips by, for example, installing the resin member having a rod-like shape or a net-like shape may be used. The contact time of the polyester chip with the member is usually an extremely short time of about 0.01 seconds to several minutes, but a small amount of the resin can be mixed into the polyester.

In the production process of polyester, 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 and the solid-state polymerized polymer chips, etc., the size originally set at the time of granulation Granules and powder that are considerably smaller than the chips of Here, such fine particles and powder are referred to as fine, and a thin film having a thickness of about 0.5 mm or less is referred to as a film. 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, Take measures to prevent foreign substances and contaminants other than polyester from being mixed by filtering the gas used for transportation, etc., so that the fine and film-like substances should not contain foreign substances and contaminants other than polyester. You can

Such fine or film-like material has a property of promoting crystallization, and when it is present in a large amount, a molded article molded from such a polyester composition, especially a bottle, is very transparent. Or the amount of shrinkage during crystallization of the bottle mouth plug does not fall within the specified range and the cap cannot be sealed.

The fine content of the polyester having the same composition as the polyester in the polyester composition of the present invention is 0.1 to 5000 ppm, preferably 0.1 to 3 ppm.
000 ppm or less, more preferably 0.1 to 1000 p
pm or less, more preferably 0.1 to 500 ppm or less, most preferably 0.1 to 100 ppm or less.
If the blending amount is less than 0.1 ppm, the crystallization rate will be very slow and the mouthpiece of the hollow molding container will be insufficiently crystallized. Therefore, the amount of shrinkage of the mouthpiece will fall within the specified range. It does not fit, capping becomes impossible, and the stretch heat fixing mold for molding the heat resistant hollow molding container is heavily soiled,
To obtain a transparent hollow molded container, the mold must be frequently cleaned. On the other hand, when it exceeds 5000 ppm, the crystallization rate becomes fast and the fluctuation of the rate becomes large. Therefore, in the case of a sheet-like material, the transparency and surface condition are poor, and when it is stretched, unevenness in thickness is poor. In addition, the degree of crystallinity of the plug part of the hollow molded article becomes excessive and fluctuates too much, so that the shrinkage amount of the plug part does not fall within the specified value range and capping of the plug part fails and leakage of contents occurs. In addition, the preform for hollow molding is whitened, which makes normal stretching impossible. In particular, the fine content of the polyester composition for hollow molding,
0.1 to 500 ppm is preferable.

In the present invention, as a method for adjusting the fine content of polyester within the above range, for example, polyester chips having a high fine content, which have not been subjected to a sieving step, and a sieving step and fine removal by an air stream are carried out. In addition to the method of mixing polyester chips with a very small amount of fine through the process at an appropriate ratio, it can also be adjusted by changing the opening of the decoration in the fine removal process, and the sieving speed Any method such as by changing can be used.

The fine peak constituting the polyester composition of the present invention has a melting peak temperature of 265 ° C. or lower, preferably 263 ° C. or lower, 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. Further, since the obtained sheet-like material has poor transparency and a high crystallization rate, normal stretching is impossible, and only a stretched film having large thickness unevenness and poor transparency can be obtained.

However, when it is desired to obtain a preform for blow molding or a sheet-like product having good transparency and stretchability from a polyester composition containing fines 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. Further, 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, and polyacetal resins, these resins generally correspond to the present invention. In many cases, it is inferior to polyester in thermal stability.
In molding at a high temperature of 00 ° C. or higher, thermal decomposition is caused to generate a large amount of by-products, so that the flavor of the obtained molded product or the like has a greater effect.

The content of the film-like material having the same composition as the polyester in the polyester composition of the present invention is 10 ppm or less, preferably 5 ppm or less, more preferably 1 ppm or less. The film-like substance has a higher crystallization-promoting effect than fine film, probably because it is oriented and crystallized, and therefore the lower limit of the compounding amount that does not have a bad influence is lowered. If the blending amount exceeds 10 ppm, the crystallization rate becomes very high, and the crystallization of the mouth plug portion of the hollow molding container becomes excessive, so that the shrinkage amount of the mouth plug portion does not fall within the specified value range, The capping of the spout becomes defective, the content leaks, and the preform for hollow molding is whitened, which makes normal stretching impossible. In addition, the lower limit of the content of the film-like substance is 0.
It is preferably 1 ppm.

The melting peak temperature of the film-like material in the polyester composition of the present invention on the highest side of the melting peak temperature measured by DSC is the same as or higher than that of fine, 260 ° C to about 290 ° C. Two
In the film-like material having a melting peak temperature of more than 65 ° C., the crystals do not completely melt under the normally used melt molding conditions and remain as crystal nuclei. When the shape is large, it is not completely melt-dispersed and is present in a streak shape in the obtained molded product, and the part is whitened or the transparency is deteriorated because crystallization is extremely promoted. Or

A specific example of the method for preventing the polyester composition of the present invention from containing such fines having a high melting point will be described below. In the case of melt polycondensation polyester, after melt polycondensation, the melt polyester is extruded into water from a die and cut in water, or extruded into the air and immediately cut into chips while cooling with cooling water. After draining the polyester chips that have been formed into chips, chips other than the prescribed size, fine or film-like substances are removed by a vibration sieving process, a vibration sieving process, or an airflow classification process using an air flow, and a plug transport system or bucket system is used. It is sent to a storage tank by a conveyor transportation method. Chips are extracted from the tank by a screw feeder, and transported to the next process by a plug transportation system or a bucket conveyor system, and fine removal treatment is performed immediately before or immediately after the next process by an airflow classification process using an air flow. To do.

When solid-phase polymerization is carried out, if necessary, the melt-polycondensed polyester from which the fine or film-like matter has been removed is again subjected to a vibrating sieving step or a vibrating sieving step immediately before the solid-state polymerization step. Fines and film-like substances are removed by an airflow classification process using an air flow and the mixture is fed to the solid phase polymerization process. As the solid-state polymerization device, a chip,
In particular, it is important to use a device whose surface is not impacted or sheared. When transporting the melt-polycondensed prepolymer chips to a solid-state polymerization facility or when transporting the polyester chips after solid-state polymerization to a sieving step, the contact treatment step or a storage tank, most of these transportations are Adopting a plug transport system or a bucket type conveyor transport system, and using a screw feeder to extract chips from the crystallization device or solid-state polymerization reactor, the impact between chips and process equipment, transportation pipes, etc. Use a device that can suppress

When the melt polycondensed polyester or solid-phase polymerized polyester is subjected to contact treatment with water or steam as described below, a vibrating sieving step, a vibrating sieving step, an air stream classification step by an air flow, etc. are performed immediately before the treatment. Fines and film-like substances are removed by installing them, and the plug transportation method or bucket type conveyor transportation method is adopted for transportation to the next process. Then, similarly to the above, just before filling the container as a product, fines and the like are removed by a vibrating sieving process, a vibrating sieving process, an airflow classification process using an air flow, or the like.

The polyester according to the present invention has a sodium content, a magnesium content, a silicon content and a calcium content in the cooling water in the chipping step, which are N, M, S and C, respectively. , (7) to (1 below
It is preferable that the polyester is chipped after melt polycondensation so as to satisfy at least one, and preferably all of 0). N ≤ 1.0 (ppm) (7) M ≤ 0.5 (ppm) (8) S ≤ 2.0 (ppm) (9) C ≤ 1.0 (ppm) (10)

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

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

When cooling water that deviates from the above conditions is used, these metal-containing compounds adhere to the surface of the polyester chip, the crystallization rate of the obtained polyester is very fast, and its fluctuation is large, which is preferable. Absent. The content of the metal in industrial water fluctuates considerably throughout the year, and the content of the metal adhering to the polyester fluctuates in accordance with this fluctuation, or at least one of the above (10) to (13). As compared with the case where cooling water satisfying the above conditions is used, the transparency of the molded product from the polyester obtained by using industrial water as the cooling water at the time of chip formation is poor, and its fluctuation is very large. In addition, it is preferable that all of the above items (10) to (13) are satisfied.

Further, when solid-state polymerization of the molten polycondensed polyester that was made into chips while cooling with cooling water that deviates from the above conditions, it was attached to the chip surface in the chip-forming step and brought into the solid-state polymerization reactor. The above-mentioned metal-containing substance adheres to the wall of the solid-state polymerization device together with a part of the surface layer of the polyester chip, and this becomes a scale with a high metal content by long-time heating at a high temperature of about 170 ° C or higher. It adheres to the vessel wall. Then, this is sometimes peeled off and mixed in the polyester chip, and becomes a foreign substance in a molded article such as a bottle, which lowers the commercial value.

Further, when a sheet is produced, the above-mentioned scale is clogged with the molten polymer filtration filter during film formation, so that the filtration pressure of the filter rises sharply, resulting in poor operability and productivity. There is also the problem of becoming.

A method for suppressing the sodium content, magnesium content, silicon content, and calcium content of the cooling water of the chips to the above ranges will be illustrated below, but the present invention is not limited thereto.

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

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

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

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

Further, the polyester composition of the present invention
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 polymer is increased, the adhesion of the oligomer to the surface of the heating mold is rapidly increased, and the transparency of the obtained hollow molded product is extremely deteriorated.

The polyester composition of the present invention in which the amount of the cyclic trimer increased by 0.50 wt% or less when melted at a temperature of 290 ° C. for 60 minutes was obtained after melt polycondensation or after 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, steam, or a steam-containing gas after melt polycondensation or after solid-phase polymerization.

A method of contacting the polyester chips with water, steam or a gas containing steam in order 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 applying 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 temperature of water is 20 to 180 ° C., preferably 40 to 150.
C., more preferably 50 to 120.degree.

The method of industrially performing water treatment is 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 the polyester chips are subjected to water treatment in a batch system, a silo type treatment tank can be used. 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.

Whether the water treatment method is continuous or batchwise, the number of particles having a particle size of 1 to 25 μm existing in the water introduced from outside the system is X,
The content of sodium is N, the content of magnesium is M,
When the content C of calcium is S and the content of silicon is S, at least one, preferably all of the following (11) to (15) are satisfied, and the water treatment is performed. 1 ≤ X ≤ 50,000 (pieces / 10 ml) (11) 0.001 ≤ N ≤ 1.0 (ppm) (12) 0.001 ≤ M ≤ 0.5 (ppm) (13) 0.001 ≤ C ≤ 1 0.0 (ppm) (14) 0.01 ≤ S ≤ 2.0 (ppm) (15)

By setting any of the number of particles in the water introduced into the water treatment tank and the content of sodium, magnesium, calcium, or silicon within the above range, a metal-containing substance such as oxide or hydroxide called scale. May float in the treated water, settle, or adhere to the walls of the processing tank or piping, which may adhere to the polyester chips and permeate to promote crystallization during molding, resulting in a poorly transparent bottle. Can be prevented.

When the polyester chips are contacted with steam or a gas containing steam, the treatment is carried out at 50 to 50%.
Steam or steam-containing gas or steam-containing air at a temperature of 150 ° C., preferably 50 to 110 ° C. is preferably supplied or present as steam in an amount of 0.5 g or more per 1 kg of granular polyethylene terephthalate. The granular polyethylene terephthalate is contacted with steam. The contact between the polyester chips and steam is usually 10 minutes to 2 days, preferably 20 minutes to 10 days.
Done on time.

The method of industrially carrying out the contact treatment between the particulate polyethylene terephthalate and steam or a gas containing steam will be illustrated 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 the contact treatment with steam in a batch system, a silo type treatment apparatus 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 polyester chips are continuously contacted with steam, granular polyethylene terephthalate should be continuously received from the upper part in a tower type processing device, and steam should be continuously supplied in cocurrent or countercurrent to contact with steam. You can

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

For drying the polyester chips which have been contact-treated with water or steam, a commonly used polyester drying process can be used. As a method for continuously drying, a hopper-type aeration dryer in which polyester chips are supplied from the upper part and a drying gas is aerated from the lower part is usually used.

As a dryer for batch-type drying, drying may be carried out 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.

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

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

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.

Further, as the gas which comes into contact with the polyester after the melt polycondensation step or the solid phase polymerization step, the particle size is 0.3.
~ 5μm particles 1,000,000 (pieces / cubic feet)
The following, preferably 500000 (pieces / cubic feet)
Below, more preferably 100,000 (pieces / cubic sheet)
G) It is desirable to use the following gases introduced from outside the system. The particles having a particle size of more than 5 μm in the gas are not particularly limited, but preferably 5 (pieces / cubic sheet).
G)) or less, more preferably 1 (pieces / cubic foot) or less.

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

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

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

A method for controlling the number of particles having a particle size of 0.3 to 5 μm in the gas introduced from outside the system to 1,000,000 (particles / cubic foot) or less is illustrated below, but the present invention is not limited to this. Not something to do. As a method for reducing the number of particles having a particle diameter of 0.3 to 5 μm in the gas introduced from outside the system to 1,000,000 (particles / cubic foot) or less, a step of contacting the gas introduced from the outside with the polyester chips A cleaning device for removing the particles is installed at least at one or more places inside. When the gas is air near the processing equipment,
During the process until the air introduced by the blower from the air inlet comes into contact with the polyester chip, JIS
Form 1 or / specified in B 9908 (1991)
Further, it is preferable to install a gas purifying apparatus equipped with a type 2 filter unit and set the number of particles having a particle size of 0.3 to 5 μm in the air to 1,000,000 (pieces / cubic foot) or less. In addition, JIS B 99 is installed in the air intake port.
It is possible to extend the life of the filter unit by installing the gas cleaning device equipped with the filter unit of the type 3 defined in 08 (1991) and using it together with the gas cleaning device equipped with the filter unit. Is.

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

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

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

The intrinsic viscosity of the polyester composition of the present invention is preferably 0.55 to 1.50 deciliter / gram, more preferably 0.58 to 1.20 deciliter / gram. When the intrinsic viscosity of the polyester is less than 0.55 deciliter / gram, the transparency, heat resistance, mechanical properties, etc. of the molded product obtained by melt-molding the polyester composition of the present invention may not be sufficiently satisfied. When the intrinsic viscosity exceeds 1.50 deciliters / gram, the resin temperature rises during melting by a molding machine or the like, and thermal decomposition becomes severe, 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 composition of the present invention is 50 ppm or less, preferably 3 ppm.
0 ppm or less, more preferably 10 ppm or less, further preferably 5 ppm or less, the formaldehyde content is
It is 20 ppm or less, preferably 10 ppm or less, more preferably 8 ppm or less, and further preferably 4 ppm or less. When the acetaldehyde content is 50 ppm or more and / or the formaldehyde content is 20 ppm or more, the taste and odor of the contents of containers formed from this polyester are deteriorated.

The amount of diethylene glycol copolymerized in the polyester of the present invention is preferably 0.5 to 5.0 mol%, more preferably 1.0 to 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 cyclic 3 of the polyester composition of the present invention
The content of the monomer is preferably 0.7% by weight or less, more preferably 0.50% by weight or less, and further preferably 0.4
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 content of the cyclic trimer exceeds 0.7% by weight, the heating metal mold is used. Adhesion of the oligomer to the mold surface sharply increases, and the transparency of the obtained hollow molded article is extremely deteriorated.

In the present invention, the shape of the polyester chips may be any of cylinder type, square type, spherical type or flat plate type. The average particle size is usually 1.5-5 mm,
Preferably 1.6 to 4.5 mm, more preferably 1.
It is in the range of 8 to 4.0 mm. For example, in the case of a cylinder type, it is practical that the length is 1.5 to 4 mm and the diameter is about 1.5 to 4 mm. In the case of spherical particles, it is practical that the maximum particle size is 1.1 to 2.0 times the average particle size and the minimum particle size is 0.7 times or more the average particle size. Further, it is practical that the weight of the chip is in the range of 10 to 30 mg / piece.

The polyester composition of the present invention is obtained by injection molding the molded plate having a thickness of 5 mm and having a haze of 15% or less, and from a molded product having a thickness of 2 mm obtained by injection molding. Crystallization temperature when the test piece is heated (hereinafter "Tc1"
Is referred to as “)” in the range of 150 to 168 ° C. The haze of the molded plate is preferably 10% or less, more preferably 8% or less, and the crystallization temperature (Tc1) at the time of heating is preferably 153 to 165 ° C, more preferably 155 to 163 ° C. Is.

When the haze of the molded plate exceeds 15%,
The obtained hollow molded article has poor transparency, which is a problem particularly in the case of a stretched hollow molded article. Also, Tc1 is 16
If it exceeds 8 ° C., the heating crystallization rate becomes very slow, the crystallization of the plug portion of the hollow molded body becomes insufficient, and the problem of leakage of the contents occurs. Further, when Tc1 is less than 150 ° C., the transparency of the hollow molded article decreases, which becomes a problem.

The polyester composition of the present invention is a PET obtained by using a raw material such as dimethyl terephthalate or terephthalic acid recovered by purifying a used PET bottle by a chemical recycling method as at least a part of the starting raw material.
And PET flakes and chip PET that are used PET bottles purified and collected by the mechanical recycling method
It can be used as a mixture with.

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 saturated fatty acid monoamides 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.

Metal salt compounds of aliphatic monocarboxylic acids having 8 to 33 carbon atoms such as naphthenic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid,
Stearic acid, behenic acid, montanic acid, melissic acid,
It is also possible to concurrently use a lithium salt, a sodium salt, a potassium salt, a magnesium salt, a calcium salt, a cobalt salt or the like of a saturated or unsaturated fatty acid such as oleic acid or linoleic acid. The compounding amount of these compounds is 10 p
It is in the range of pb to 300 ppm.

The polyester composition of the present invention can be preferably used as a hollow molded article, a tray, a packaging material such as a biaxially stretched film, a film for coating a metal can, and the like. Further, the polyester composition of the present invention can be used as one component layer such as a multilayer molded product or a multilayer film.

The polyester composition of the present invention can be used to form films, sheets, containers and other packaging materials by using a commonly used melt molding method. Also,
Mechanical strength can be improved by stretching PET in at least a uniaxial direction. The stretched film made of the polyester composition of the present invention is a sheet-like product obtained by injection molding or extrusion molding, and can be any of uniaxial stretching, sequential biaxial stretching, and simultaneous biaxial stretching that are usually used for stretching PET. It is molded using a stretching method. Also pressure molding,
It can also be formed into a recup shape or a tray shape by vacuum forming.

In producing a stretched film, the stretching temperature is usually 80 to 130 ° C. The stretching may be uniaxial or biaxial, but biaxial stretching is preferable from the viewpoint of practical physical properties of the film. In the case of uniaxial stretching, the stretching ratio is usually 1.1 to 10 times, preferably 1.5 to 8 times, and in the case of biaxial stretching, it is usually 1.1 to 8 times in each of the machine direction and the transverse direction. , Preferably 1.5 to 5 times. Also, the vertical / horizontal ratio is usually 0.5.
˜2, preferably 0.7 to 1.3. The obtained stretched film can be further heat-fixed to improve heat resistance and mechanical strength. Heat fixation is usually under tension, 120 ° C
~ 240, preferably 150 ~ 230 ℃, usually several seconds ~
It is performed for several hours, preferably several tens of seconds to several minutes.

In producing the hollow molded article, a briform molded from the PET composition of the present invention is stretch blow molded, and an apparatus conventionally used for PET blow molding can be used. Specifically, for example, a preform is once molded by injection molding or extrusion molding, and as it is or after processing the plug portion and the bottom portion, it is reheated, and biaxial stretch blow molding such as hot parison method or cold parison method. The law applies. The molding temperature in this case, specifically the temperature of each part of the cylinder and nozzle of the molding machine, is usually in the range of 260 to 290 ° C. The stretching temperature is usually 70 to 120 ° C, preferably 90 to 110 ° C.
The stretching ratio is usually 1.5 to 3.5 times in the longitudinal direction and 2 to 5 times in the circumferential direction. The obtained hollow molded article can be used as it is, but in the case of beverages such as fruit juice and oolong tea which require heat filling, generally, heat-setting treatment is further performed in a blow mold to obtain heat resistance. It is used by imparting sex. The heat setting is usually 100 to 200 ° C., preferably 120 to 180 ° C. under tension such as compressed air.
At a temperature of several seconds to several hours, preferably several seconds to several minutes.

In order to impart heat resistance to the spout,
The plug part of the preform obtained by injection molding or extrusion molding is crystallized in an oven equipped with a far infrared or near infrared heater, or the plug part is molded with the above heater after bottle molding. Crystallize.

In the polyester composition of the present invention, if necessary, known ultraviolet absorbers, antioxidants, oxygen scavengers,
A lubricant added from the outside or a lubricant that is internally precipitated during the reaction,
You may mix | blend various additives, such as a mold release agent, a nucleating agent, a stabilizer, an antistatic agent, and a pigment. Further, when the polyester composition of the present invention is used for film use, calcium carbonate, magnesium carbonate, barium carbonate is added to the polyester composition in order to improve handling properties such as slipperiness, winding property and blocking resistance. , Inorganic particles of calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, etc., organic salt particles of terephthalate such as calcium or calcium oxalate, barium, zinc, manganese, magnesium, etc., divinylbenzene, styrene, acrylic Inert particles such as crosslinked polymer particles such as homopolymers or copolymers of vinyl monomers of acid, methacrylic acid, acrylic acid or methacrylic acid can be contained. In addition, the measuring method of the main characteristic value in this invention is demonstrated below.

[0136]

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

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

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

(3) Content of cyclic trimer of polyester (hereinafter referred to as "CT content") A sample is dissolved in a hexafluoroisopropanol / chloroform mixture, 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.

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

(5) Measurement of fine content and film-like material content 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.

On the above-mentioned sieve (A), the thickness is about 0.5 mm.
Apart from the following film-like material, if two or more chips are fused to each other or a chip-like material cut to a size larger than the normal shape is captured, the remaining after removing these, The film-like material having a thickness of about 0.5 mm or less and the fines sieved under the sieve (B) were separately washed with ion-exchanged water, filtered with a G1 glass filter manufactured by Iwaki Glass Co., Ltd., and collected. These were dried together with the glass filter in a dryer at 100 ° C. for 2 hours, then 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-like material content is fine weight or film-like material weight /
The total weight of resin screened. The total content is calculated from these values.

(6) Measurement of fine melting peak temperature (hereinafter referred to as "fine melting point") Differential scanning calorimeter (DS) manufactured by Seiko Instruments Inc.
C), measured using RDC-220. In (5),
Fines collected from 20 kg of polyester were dried under reduced pressure at 25 ° C for 3 days, and a sample of 4 m was used for each measurement.
DSC measurement at a temperature rising rate of 20 ° C./min using g,
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.

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

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

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

(10) Crystallization temperature (T
c1) Differential thermal analyzer (DS) manufactured by Seiko Instruments Inc.
C), measured with RDC-220. Using a 10 mg sample from the center of the 2 mm thick plate of the following (11) molded plate. The temperature is raised at a temperature rising rate of 20 ° C./min, the peak temperature of the crystallization peak observed during the heating is measured, and the measured crystallization temperature (Tc1) is set.

(11) Molding of Stepped Molded Plate In molding the stepped molded plate according to the description of this patent, polyester chips dried under reduced pressure at 160 ° C. for about 16 hours using a vacuum dryer are injection molded by Meiki Seisakusho. Machine M-150C
-With a DM type injection molding machine, having a gate portion (G) as shown in FIGS. 1 and 2, 2 mm to 11 mm (thickness of A portion = 2
mm, thickness of B part = 3 mm, thickness of C part = 4 mm, thickness of D part = 5 mm, thickness of E part = 10 mm, thickness of F part =
A step-formed plate having a thickness of 11 mm) was injection-molded. A polyester chip previously dried under reduced pressure using a vacuum dryer DP61 type manufactured by Yamato Kagaku Co., Ltd. was used, and a dry inert gas (nitrogen gas) was purged in the molding material hopper in order to prevent moisture absorption of the chip during molding. As the plasticizing conditions by the M-150C-DM injection molding machine, the feed screw rotation speed = 70%, the screw rotation speed = 120 rpm, the back pressure 0.5 MPa, and the cylinder temperature is 4 in order from directly below the hopper.
The temperature was set to 5 ° C., 250 ° C., and thereafter 290 ° C. including the nozzle. The injection conditions are as follows: the injection speed and the holding pressure are 20%, and the injection pressure and the holding pressure are adjusted so that the weight of the molded product is 146 ± 0.2g, and the holding pressure is 0.5MP with respect to the injection pressure.
a Adjusted lower. The upper limits of the injection time and the pressure holding time are set to 10 seconds and 7 seconds, respectively, and the cooling time is set to 50 seconds, and the total cycle time including the molded product take-out time is about 75 seconds. Cooling water having a water temperature of 10 ° C. is constantly introduced into the mold to adjust the temperature, but the mold surface temperature at the time of stable molding is about 22 ° C. The test plate for evaluating the characteristics of the molded product was arbitrarily selected from the stable molded products of 11 to 18 shots from the start of molding after introducing the molding material and replacing the resin. The 2 mm thick plate (A in FIG. 1) was measured for crystallization temperature (Tc1) during heating, and the 5 mm thick plate (FIG. 1) was used.
Is used for measuring haze (% haze).

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

(13) Evaluation of Leakage of Contents from Hollow Molded Body The hollow molded body molded in (12) above was filled with 90 ° C. hot water, capped with a capping machine, the container was laid down, and the contents were left. I investigated the leak. In addition, the state of deformation of the spout after capping was also examined.

(14) Sodium Content, Calcium Content, Magnesium Content, and Silicon Content of Cooling Water in the Chip Making Step The cooling water that has undergone particle removal and ion exchange is collected and filtered with a 1G1 glass filter manufactured by Iwaki Glass Co., Ltd. After that, the filtrate was measured by an atomic absorption method (Na) and an inductively coupled plasma optical emission spectrometer (Ca, Mg, Si) manufactured by Shimadzu Corporation.

(15) Measurement of Number of Particles in Cooling Water in Chiping Step Particle removal and ion-exchanged cooling water is a particle measuring device by light interception method PAC manufactured by Seishin Enterprise Co., Ltd.
The number of particles was measured by using 150, and the number of particles was expressed as particles / 10 ml.

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

(Example 1) An EG slurry of TPA adjusted to a molar ratio of EG to TPA of 1.7 was continuously fed to the system in the first esterification reactor where the reaction product was present, and the reaction was carried out under normal pressure. Was reacted at an average residence time of 4 hours at a temperature of 255 ° C.

This reaction product was continuously taken out of the system and supplied to the second esterification reaction apparatus, and the temperature was adjusted to 26 at atmospheric pressure.
The reaction was carried out at 0 ° C. Then, the esterification reaction product was continuously taken out from the second esterification reactor and continuously supplied to the continuous polycondensation reactor. From a plurality of polycondensation catalyst supply pipes connected to the esterification reaction product transportation pipe, 0.6 ton of phosphorus atom was obtained per ton of the produced polyester resin.
An EG solution of phosphoric acid in an amount such that the amount is about 19 mol (about 19 ppm based on the produced polyester resin), and 0.6 mol (about 15 ppm based on the produced polyester resin) as a magnesium atom per ton of the produced polyester resin. Solution of magnesium acetate tetrahydrate in an amount of EG, and 1.4 mol of antimony atom per ton of the produced polyester resin (about 170 p for the produced polyester resin).
EG) of EG solution of antimony trioxide is fed to the esterification reaction product and stirred to about 265
Polycondensation was carried out at 25 ° C. and 25 to 3 torr, and further, polycondensation was carried out at about 275 ° C. and 0.5 to 1 torr with stirring in the final polycondensation reactor. The intrinsic viscosity of the melt polycondensation prepolymer is 0.5
It was 5 dl / g.

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

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

The PET composition thus obtained had an intrinsic viscosity of 0.7.
5 deciliters / gram, DEG content 3.0 mol%, cyclic trimer content 0.30% by weight, average density 1.407 g / cm3, AA content 3.8 ppm,
The fine content was about 50 ppm, the peak temperature on the highest temperature side of the melting peak temperature was 248 ° C., and there was no film. The residual amount of Sb measured by atomic absorption spectrometry was about 165 ppm.

For the transportation of the melt polycondensation PET chips in the manufacturing process, the plug type transportation system and the bucket type conveyor transportation system were all used in Examples 1 to 2. In addition, as air for sending the melt-polycondensed PET chips to the solid-state polymerization step, and air for contacting the chips until the solid-state polymerization PET chips are filled in the storage container, JIS B990 is used.
8 (1991) type 3 PET non-woven filter unit equipped with an air cleaner and JIS B 9908
HEP with (1991) type 1 particle collection rate of 99% or more
Air filtered by an air purifier equipped with an A filter unit (the number of particles having a particle size of 0.3 to 5 μm is about 500 particles / cubic foot) was used. Examples 2-8 and Comparative Examples 1-2
However, similarly filtered air was used. This PET
The composition 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 4.6%, the haze unevenness of the molded plate was 0.2%, and the Tc1 of the molded plate was 165 ° C. The density of the bottle mouth part was 1.378 g / cm3, the density deviation of the mouth part was 0.001 g / cm3, which was a problem-free value, and the body haze of the bottle was as good as 1.0%. In addition, in the leak test of the contents, there was no problem and the mouth plug was not deformed. The AA content of the bottle was 23.0 ppm, which was a value with no problem.

(Example 2) Magnesium acetate tetrahydrate,
A PET composition was obtained in the same manner as in Example 1 except that the addition amount and ratio of phosphoric acid were changed as shown in Table 1. The results are shown in Table 1. The characteristics of the obtained PET composition and the characteristics of the bottle were good, and there was no problem.

Example 3 Magnesium acetate tetrahydrate,
A PET composition was obtained in the same manner as in Example 1 except that the addition amounts and ratios of phosphoric acid and antimony trioxide were changed as shown in Table 1. The results are shown in Table 1. Obtained PE
The properties of the T composition and the properties of the bottle were good, and there was no problem.

(Example 4) Magnesium acetate tetrahydrate,
The amounts and ratios of phosphoric acid and antimony trioxide added were changed as shown in Table 1, and the EG solution of tetrabutyl titanate was esterified in such an amount that 0.01 mol of titanium atom was obtained per ton of the produced polyester resin. PE was prepared in the same manner as in Example 1 except that it was added to the product and polycondensed.
A T composition was obtained. The results are shown in Table 1. The characteristics of the obtained PET composition and the characteristics of the bottle were good, and there was no problem.

(Example 5) Magnesium acetate tetrahydrate,
The amounts and ratios of phosphoric acid and antimony trioxide added were changed as shown in Table 1, and the EG solution of crystalline germanium dioxide was esterified with an amount of 0.28 mol of germanium atoms per ton of produced polyester resin. A PET composition was obtained in the same manner as in Example 1, except that the polycondensation was carried out by adding to the chemical product. The results are shown in Table 1. The characteristics of the obtained PET composition and the characteristics of the bottle were good, and there was no problem.

(Example 6) Magnesium acetate tetrahydrate,
The amounts and ratios of phosphoric acid and antimony trioxide added were changed as shown in Table 1, and an EG solution of aluminum acetate was esterified to produce 0.37 mol of aluminum atom per ton of produced polyester resin. PE in the same manner as in Example 1 except that polycondensation was carried out by adding it to the product.
A T composition was obtained. The results are shown in Table 1. The characteristics of the obtained PET composition and the characteristics of the bottle were good, and there was no problem.

(Example 7) Toyobo nylon resin, T60
0 (polyamide resin obtained from metaxylylenediamine and adipic acid, Ny-MXD6) and PE of Example 1
T was kneaded in the same manner as in Example 1 to produce a PET master. A PET composition (IV of 0.75 deciliter / gram, DEG content of 2.7) obtained by mixing the PET of Example 1 with the master so that the nylon resin was about 1% by weight. Mol%, AA content is 3.8 ppm, cyclic trimer content is 0.34 wt%,
The fine content was about 50 ppm, the film-like substance was not contained, and the fine melting point was 245 ° C.) was evaluated using a molded plate and a biaxially stretched molded bottle.

The haze of the molded plate was 11.2%, the haze unevenness of the molded plate was 0.9%, and the Tc1 of the molded plate was 153 ° C.
The density of the bottle cap part is 1.383 g / cm3, and the density deviation of the cap part is 0.003 g / cm3, which is a value with no problem.
The body haze of the bottle was as good as 2.6%.

In the leak test of the contents, no problem was found and the mouth plug was not deformed. The AA content of the bottle was 9.2 ppm.

(Example 8) After separating and removing a bottle made of a different resin, a used polyethylene terephthalate bottle from which a label and a cap have been removed is crushed and washed with water to recover recovered flakes with ethylene glycol in the presence of a depolymerization catalyst. The crude dimethyl terephthalate obtained by polymerization and then transesterification with methanol was purified by distillation, and the purified dimethyl terephthalate thus obtained was hydrolyzed to obtain high-purity terephthalic acid.

A slurry of terephthalic acid and ethylene glycol (virgin product) (molar ratio of ethylene glycol / terephthalic acid = 1.6) was charged with bis (hydroxyethyl) terephthalate and kept at a temperature of 250 ° C. and normal pressure. The esterification reaction was supplied to the esterification reaction tank, and the esterification reaction was carried out for 4 hours while distilling out water produced as a by-product, and 100 kg of this esterification reaction product was transferred to the polycondensation tank. Subsequently, in the polycondensation tank to which the esterification reaction product was transferred, from a plurality of polycondensation catalyst supply pipes, 0.6 mol of phosphorus atoms per ton of produced polyester resin (about 19 ppm relative to produced polyester resin). An EG solution of phosphoric acid in an amount such that the amount is 0.6 mol of magnesium atom per ton of the produced polyester resin (about 15 ppm with respect to the produced polyester resin), and an EG solution of magnesium acetate tetrahydrate , And 1.4 mol of antimony atom per ton of the produced polyester resin (about 170 p for the produced polyester resin).
After adding an EG solution of antimony trioxide in an amount such that
The temperature is raised to 5 ° C and the atmospheric pressure is reduced to 350 Pa in 1 hour.
Then, it was subjected to melt polycondensation under a reduced pressure of 150 Pa at 278 ° C. for a time such that the obtained resin had an intrinsic viscosity of 0.56 dl / g. It is extracted in a strand form from an extraction port provided at the bottom of the polycondensation tank, and is made into chips while being cooled with ion-exchanged water of the same quality as used in Example 1, and then fine and film-like substances are removed by a vibrating screener. As a result, the fine content was reduced to about 50 ppm or less.

Subsequently, the polyester resin chip obtained above was crystallized by a stirring flow type crystallizer held at about 160 ° C., and then transferred to a packed column type solid phase polymerization column, and nitrogen was passed under a nitrogen stream 210. Solid phase polymerization was carried out at 0 ° C., and then fine particles were removed by treatment in a sieving step and a fine removing step so that the fine content was about 50 ppm.

Then, in the same manner as in Example 1, PE containing about 10 ppb of the same linear low-density polyethylene was blended.
A T composition was obtained. The obtained PET composition (IV is 0.7
5 deciliters / gram, DEG content is 3.2 mol%, AA content is 4.5 ppm, cyclic trimer content is 0.33% by weight, fine content is about 50 ppm, film-like material is not included. (Fine melting point is 248 ° C)
Was evaluated using a molded plate and a biaxially stretched molded bottle.

The haze of the molded plate was 9.7%, the haze unevenness of the molded plate was 0.3%, and the Tc1 of the molded plate was 159 ° C. The density of the bottle mouth part was 1.380 g / cm3, the density deviation of the mouth part was 0.003 g / cm3, which was a problem-free value, and the body haze of the bottle was 1.5%, which was good. In addition, in the leak test of the contents, there was no problem and the mouth plug was not deformed. The AA content of the bottle was 22.4 ppm.

(Comparative Example 1) Magnesium acetate tetrahydrate,
The amount and ratio of phosphoric acid were the same as in Example 3, and as cooling water for chip formation of the melt polycondensed polyester, industrial water was used as it was as cooling water for chip formation without using a filter filtration device and an ion exchange device. A solid-state polymerization PET composition was obtained in the same manner as in Example 1 except that the above composition was used as.
The particles having a particle size of 1 to 25 μm contained in the industrial water used as the cooling water at the time of chip formation are about 60,000 to 80
000 pieces / 10 ml, sodium content 3.0-5.
0 ppm, magnesium content 0.8-1.0 pp
m, calcium content was 1.0 to 2.5 ppm, and silicon content was 3.0 to 3.8 ppm. The PET composition was evaluated using a molded plate and a biaxially stretched molded bottle. The results are shown in Table 1. The content of the film-like material was 10 ppm or more. The transparency of the obtained bottle was poor, and the deformation of the spout and leakage of the contents were examined, and leakage of the contents was found.

(Comparative Example 2) The amounts and ratios of antimony trioxide, magnesium acetate tetrahydrate and phosphoric acid were changed as shown in Table 1, and a filter was used as cooling water for chip formation of the melt polycondensed polyester. A solid-state polymerized PET composition was obtained in the same manner as in Example 1 except that industrial water was used as it was as cooling water for chip formation without using a filtration device and an ion exchange device. It should be noted that particles having a particle size of 1 to 25 μm contained in the industrial water used as the cooling water at the time of chip formation are about 80,000 to 90,000 particles / 10 ml, the sodium content is 5.0 to 7.0 ppm, and the magnesium content is 1 0.8-2.5 ppm, calcium content 1.8-
It was 3.5 ppm and the silicon content was 4.0 to 5.8 ppm.

This PET composition was evaluated using a molded plate and a biaxially stretched molded bottle. The results are shown in Table 1. The content of the film-like material was 10 ppm or more. The transparency of the obtained bottle was poor, and the deformation of the spout and leakage of the contents were examined, and leakage of the contents was found.

Comparative Example 3 The melt polycondensation prepolymer of Comparative Example 2 was directly charged into a rotary tumbler by a low density transportation system without fine removal treatment, and crystallized and solid-phased under reduced pressure while rotating. Polymerized. Got
A linear low-density polyethylene (MI = about 0.9 g / 10 min, density = about 0.
Made of 923 g / cm ³ ) inner diameter 70 mm, length 700 mm
It was transported at a rate of about 3 tons / hour in the transportation pipe connected to the cylindrical pipe, and subjected to contact treatment under flowing conditions.

This PET composition was evaluated using a molded plate and a biaxially stretched molded bottle. The results are shown in Table 1. The content of the film-like material was 10 ppm or more. The transparency of the obtained bottle was very poor, and the deformation of the spout and the leakage of the contents were examined, and the leakage of the contents was found.

[0179]

[Table 1]

[0180]

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 plan view of a stepped molding plate used in Examples.

FIG. 2 is a side view of the step forming plate of FIG.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // B29K 67:00 B29L 7:00 B29L 7:00 B65D 1/00 A (72) Inventor Yoshitaka Eto Shiga 20F Term, No. 248, Takagi, Shiga-cho, Shiga Prefecture (reference) 3E033 AA01 BA17 CA07 CA18 FA02 FA03 3E086 AB01 AD04 AD05 AD06 AD30 BB21 BB67 CA11 CA13 4F210 AA03 AA23 AA24 AA29 AG01 AG07 QC05 QG01 QG18 4002 002 CF003 BB002 GS00 4J029 AA03 AB04 AB07 AC01 AD01 AD07 AD10 AE01 AE03 BA03 CB06A HA01 HB01 JA041 JA091 JA111 JA201 JA251 JA261 JB131 JB151 JB171 JC551 JC571 JC581 JC751 JF131 JF221 KF04 K02 K02 K02 K02 K02 K02 K03 K02 K02 KKD07 K02 K02 KKD07 K02 K02 K02 K07 K02 K02 K03 K02 K02 K02 K03 K02 K02 K03 K02 K03 K02 K02 K03 K02 K03 K02 K02 K03 K02 K02 K03 K04

Claims (10)

[Claims] 1. A polyester chip whose main repeating unit is ethylene terephthalate, and a polyester fine 0.1 to 0.1 having the same composition as the polyester chip.
A polyester composition comprising 5000 ppm and 0.1 ppb to 50000 ppm of at least one resin selected from the group consisting of a polyolefin resin, a polyamide resin and a polyacetal resin, wherein the polyester is a magnesium compound, a calcium compound or cobalt. A polyester composition comprising at least one metal compound selected from a compound, a manganese compound and a zinc compound, a phosphorus compound and an antimony compound in an amount satisfying the following (1) to (3). 0.1 ≤ M ≤ 3.0 (1) 0.1 ≤ M / P ≤ 2.0 (2) 0.1 ≤ Sb ≤ 1.7 (3) (where M is 1 ton of polymer) Per mole of the metal atom of at least one metal compound selected from magnesium compound, calcium compound, cobalt compound, manganese compound and zinc compound, P is the number of moles of phosphorus atom of the phosphorus compound per ton of the polymer, Sb represents the number of moles of antimony atoms of the antimony compound per ton of the polymer.) 2. An at least one metal compound selected from the group consisting of titanium compounds, germanium compounds and aluminum compounds, in an amount satisfying the following (4) to (6). 2. The polyester composition according to 1. 0 <Ti ≤ 0.4 (4) 0 <Ge ≤ 0.6 (5) 0 <Al ≤ 2.0 (6) (In the above formula, Ti represents the titanium atom of the titanium compound per ton of the polymer. The number of moles, Ge is the number of moles of germanium atom of the germanium compound per ton of polymer,
Al represents the number of moles of aluminum atoms of the aluminum compound per ton of the polymer. ) 3. When the fineness of the polyester is measured by DSC, the melting peak on the highest temperature side of the melting peak temperature.
A temperature of less than 265 ° C.
The polyester composition according to. 4. The polyester composition according to claim 1, wherein the content of the film-like material is 10 ppm or less. 5. The polyester composition according to claim 1, wherein the cyclic trimer content is 0.7% by weight or less. 6. The polyester composition according to claim 1, wherein the cyclic trimer increase amount when melted at a temperature of 290 ° C. for 60 minutes is 0.50% by weight or less. . 7. The content of sodium (N), the content of magnesium (M), the content of silicon (S) and the content of calcium (C) of the polyester in a chip forming step after melt polycondensation. Is a polyester chipped with cooling water satisfying at least one of the following (7) to (10), and the polyester composition according to any one of claims 1 to 5. N ≤ 1.0 (ppm) (7) M ≤ 0.5 (ppm) (8) S ≤ 2.0 (ppm) (9) C ≤ 1.0 (ppm) (10) 8. A hollow molded article obtained by molding the polyester composition according to claim 1. 9. A sheet obtained by extruding the polyester composition according to any one of claims 1 to 7.
Grit. 10. A stretched film obtained by stretching the sheet-like material according to claim 8 in at least one direction.