JP2003306601A - Polyester composition, and hollow molded material, sheet material and stretched film obtained from the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester composition excellent in economic efficiency, crystallization-controlling property on melt-molding, and long time continuous molding property, and a hollow molded material, sheet material and stretched film obtained from the same, excellent in transparency, heat-resistant dimensional stability, especially having an appropriate range of shrinkage at a mouth part of a hollow molded material and hardly generating a residual foul taste or foul smell on using it as a liquid container. <P>SOLUTION: This polyester composition comprises chips of a polyester having main recurring unit of ethylene terephthalate and 0.1-500 ppm polyester fine. The polyester contains at least 1 kind of metal compound selected from the group consisting of Al, Si, Mg, Fe, Co, Zn, Ga, Sr, Zr, Sn, W and Pb. The polyester fine exhibits ≤265°C melting peak temperature at the highest temperature side of the melting peak temperature in the case of measuring with a DSC. <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 preferably used as a raw material for molded articles such as hollow molded containers such as beverage bottles, films and sheets, and a molded article composed of the polyester. TECHNICAL FIELD The present invention relates to a polyester having good mold releasability from a heat treatment mold when molding a small hollow molded article and excellent in long-term continuous moldability. In particular, the molded product obtained from the polyester of the present invention is excellent in crystallization controllability, and the resulting molded product is unlikely to have residual off taste or odor, and is excellent in transparency and heat-resistant dimensional stability. Provided are a hollow molded article, a sheet-like material and a stretched film which are excellent in transparency, slipperiness and dimensional stability after molding.

[0002]

BACKGROUND OF THE INVENTION Polyester such as polyethylene terephthalate has a high industrial value because of its excellent mechanical properties and chemical properties, and it has high industrial value.
Widely used as bottles.

As a material for containers such as seasonings, oils, beverages, cosmetics and detergents, various resins have been adopted depending on the type of filling contents and the purpose of use thereof.

Of these, polyester is excellent in mechanical strength, heat resistance, transparency and gas barrier property, and is therefore most suitable as a material for a beverage filling container such as juice, soft drink, carbonated drink and the like.

Such polyester is supplied to a molding machine such as an injection molding machine to mold a preform for a hollow molded body, and the preform is inserted into a mold having a predetermined shape and stretch blow-molded, followed by a body portion of a bottle. Heat treatment (heat set)
It is then generally molded into a hollow molded container, and if necessary, the bottle cap is heat treated (crystallized in the cap).

However, conventional polyesters contain oligomers such as cyclic trimers, and these oligomers adhere to the inner surface of the mold, the gas exhaust port of the mold, and the exhaust pipe. Dirt was easy to occur.

Further, the polyester contains acetaldehyde which is a by-product. When the content of acetaldehyde in the polyester is high, the content of acetaldehyde in the material of the container or other packaging formed from this is also high, which affects the flavor and odor of the beverage or the like filled in the container or the like. Therefore, conventionally, various measures have been taken to reduce the acetaldehyde content in polyester.

In recent years, polyester containers centered on polyethylene terephthalate have been used in mineral water and water.
It has come to be used as a container for low flavor beverages such as ron tea. In the case of such a beverage, generally, these beverages are heat-filled or sterilized by heating after filling, but the flavor and odor of these contents cannot be improved only by reducing the acetaldehyde content of the beverage container. I understand.

For the metal can for beverages, a metal plate coated with a polyester film containing ethylene terephthalate as a main repeating unit on its inner surface is used for the purpose of process simplification, hygiene and pollution prevention. The method of making cans has come to be adopted. Also in this case, the contents are heat-sterilized at a high temperature after filling, but it has been found that the flavor and odor of the contents are not improved by using a film having a low acetaldehyde content.

In order to solve such a problem, a germanium compound is mainly used as a polycondensation catalyst, and the obtained PET is disclosed in JP-A-3-47830 (Patent Document 1).
Although the contact treatment with water is carried out by the method proposed in (2), there is a drawback that the germanium compound is expensive and the contact treatment with water further increases the cost.

[0011]

[Patent Document 1] Japanese Patent Laid-Open No. 3-47830

[0012]

DISCLOSURE OF THE INVENTION The present invention solves the problems of the above-mentioned conventional polyesters, and the crystallization of the plug portion occurs rapidly, and the shrinkage rate of the plug portion falls within an appropriate range. A polyester composition which gives a molded article having high speed, excellent transparency and residual off-taste, less offensive odor and excellent in aroma retention (flavorability) more economically, and a hollow molded article and a sheet-like article made of the same It is intended to be provided.

[0013]

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 of the same composition as the polyester chip. A polyester composition comprising fine 0.1 to 500 ppm, wherein the polyester is a germanium compound and a phosphorus compound, aluminum, silicon,
DSC containing a fine metal compound containing at least one element selected from the group consisting of manganese, iron, cobalt, zinc, gallium, strontium, zirconium, tin, tungsten and lead,
The polyester composition has a melting peak temperature on the highest temperature side of the melting peak temperature of 265 ° C. or less when measured by.

In this case, the content of germanium compound in the polyester, the content of phosphorus compound, and aluminum, silicon, manganese, iron, cobalt,
Zinc, gallium, strontium, zirconium, tin,
At least one selected from the group consisting of tungsten and lead
The content of the metal compound containing the element of the species is (1) to
Expression (4) can be satisfied. 0.1 ≤ Ge ≤ 0.9 (1) 0.15 ≤ P ≤ 3.3 (2) 0.05 ≤ M ≤ 3.0 (3) 0.1 ≤ M / P ≤ 3.0 (4) (In the above formula, Ge is the number of moles of germanium atom of the germanium compound per ton of polymer, P is the number of moles of phosphorus atom of the phosphorus compound per ton of polymer, and M is
Aluminum, silicon, manganese, iron, cobalt, zinc, gallium, strontium, per ton of polymer,
The number of moles of metal atoms of at least one metal compound selected from the group consisting of zirconium, tin, tungsten, and lead is shown. )

In this case, the content of the polyester film having the same composition as that of the polyester chip can 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.

Here, as described below, the melting point of fine is measured by a differential scanning calorimeter (DSC).
The melting peak temperature of DSC is called the melting point. The melting peak representing this melting point is composed of one or more melting peaks, and in the present invention, the melting peak is 1 or more.
In one case, the peak temperature, and in the case of a plurality of melting peaks, the highest melting peak temperature among the plurality of melting peaks is defined as "Fine melting peak". The peak temperature on the highest side of the peak temperature is referred to as "fine melting point" in Examples and the like.

In this case, the cyclic trimer content is
It can be up to 0.7% by weight. In this case, the cyclic trimer increase amount when melted at a temperature of 290 ° C. for 60 minutes can be 0.50 wt% 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 (5) to ( The polyester may be chipped with cooling water satisfying at least one of 8). N ≤ 1.0 (ppm) (5) M ≤ 0.5 (ppm) (6) S ≤ 2.0 (ppm) (7) C ≤ 1.0 (ppm) (8)

In this case, the polyester composition according to any one of claims 1 to 6 is further added with 0.1 ppb to 5 of at least one resin selected from the group consisting of a polyolefin resin, a polyamide resin and a polyacetal resin.
It can be made by blending 0000 ppm.

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 inexpensive, has excellent crystallization controllability of the spout, and has excellent transparency, heat resistance, mechanical properties, residual off-taste, and off-flavor. It gives a hollow molded article having excellent properties, a sheet-like material and a stretched film.

[0023]

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 a linear polyester containing 85 mol% or more of ethylene terephthalate units, and more preferably 90 mol% or more. ,
A linear polyester containing 95% by mole or more is particularly preferable.

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

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

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

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 decrease 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 cooling 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 is a polyester composition comprising a polyester chip whose main repeating unit is ethylene terephthalate, and 0.1 to 500 ppm of fine polyester having the same composition as the polyester chip. Yes, the polyester is
Germanium compounds and phosphorus compounds, aluminum,
DSC containing a fine metal compound containing at least one element selected from the group consisting of silicon, manganese, iron, cobalt, zinc, gallium, strontium, zirconium, tin, tungsten and lead, The polyester composition has a melting peak temperature on the highest temperature side of the melting peak temperature of 265 ° C. or less when measured by.

Further, the polyester composition of the present invention contains the content of germanium compound, the content of phosphorus compound, and aluminum, silicon, manganese, iron, cobalt, zinc, gallium, strontium,
A polyester composition characterized in that the content of a metal compound containing at least one element selected from the group consisting of zirconium, tin, tungsten and lead satisfies the following formulas (1) to (4): is there. 0.1 ≤ Ge ≤ 0.9 (1) 0.15 ≤ P ≤ 3.3 (2) 0.05 ≤ M ≤ 3.0 (3) 0.1 ≤ M / P ≤ 3.0 (4) (In the above formula, Ge is the number of moles of germanium atom of the germanium compound per ton of polymer, P is the number of moles of phosphorus atom of the phosphorus compound per ton of polymer, and M is
Aluminum, silicon, manganese, iron, cobalt, zinc, gallium, strontium, per ton of polymer,
The number of moles of metal atoms of at least one metal compound selected from the group consisting of zirconium, tin, tungsten, and lead is shown. )

The germanium compound used as a polycondensation catalyst during the production of the polyester according to the present invention is
Amorphous germanium dioxide, crystalline germanium dioxide, germanium tetroxide, germanium hydroxide, germanium oxalate, germanium chloride, germanium tetraethoxide, germanium tetra-n-butoxide, germanium phosphite and the like can be mentioned.

The above-mentioned germanium compound is a powder or a slurry of ethylene glycol, a solution dissolved in water by heating, a solution obtained by adding ethylene glycol to this solution and heat treatment, or dissolved in ethylene glycol together with a carboxylic acid. As a solution or the like, which is added during the production of the polyester according to the present invention, in particular, in order to produce the polyester according to the present invention, a solution obtained by heating and dissolving germanium dioxide in water, or by adding and heating ethylene glycol thereto,
It is preferably used as a solution in which water is distilled off. Also,
It can also be used as a solution obtained by heating and dissolving crystalline germanium dioxide together with polyphosphoric acid and pyrophosphoric acid in ethylene glycol, or a solution obtained by dissolving crystalline germanium dioxide in ethylene glycol under an ammonia gas atmosphere. These catalyst solutions can be added during the transesterification step or after the completion of the transesterification reaction and before the start of the polycondensation reaction, or during the esterification step or after the completion of the esterification reaction and before the start of the polycondensation reaction. .

The content of the germanium compound represented by the general formula (1) is in the range of 0.1 to 0.9 mol, preferably 0.15 to 0.9 mol, as the germanium atom of the germanium compound per ton of the polymer. 0.8 mol, more preferably 0.2 to 0.7 mol. If the amount is less than 0.1 mol per ton of polymer, the polycondensation reaction will be poor, and the transparency of the resulting hollow molded article of polyester, particularly stretch-heat-fixed hollow molded article, will be very poor, and fluctuations in crystallization rate will be extremely high. Grows to. On the other hand, if it exceeds 0.9 mol, the thermal oxidation stability of the polyester is poor, the hue is poor, and there is a problem in terms of economy.

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 in the range of 0.15 to 3.3 mol, preferably 0.2 to 2 as the phosphorus atom of the phosphorus compound per ton of the polymer. 0.5 mol, more preferably 0.3 to 2.0 mol. When the amount is less than 0.15 mol per ton of polymer, the transparency of the obtained hollow molded article, particularly the stretch-heat-fixed hollow molded article, becomes extremely poor. On the other hand, when it exceeds 3.3, 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 production of the polyester according to the present invention can be added at any stage of the above-mentioned polyester forming reaction step. When the transesterification reaction is used, it is preferably added after 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. In addition, a method of mixing a master-batch containing the phosphorus compound described above with a polyester blended with the following water-treated polyester or a polyolefin resin, or a method of contact-treated with an aqueous solution of the phosphorus compound or an organic solvent solution. Can be included.

At least one element selected from the group consisting of aluminum, silicon, manganese, iron, cobalt, zinc, gallium, strontium, zirconium, tin, tungsten, and lead used in the production of the polyester according to the present invention. Any metal compound can be used as long as it is a compound soluble in the reaction system.

Examples of these metal compounds include saturated aliphatic carboxylates such as acetates, unsaturated aliphatic carboxylates such as acrylates, aromatic carboxylates such as benzoic acid, trichloroacetic acid and the like. Halogen-containing carboxylate, hydroxycarboxylate such as lactate, inorganic acid such as carbonate, organic sulfonate such as 1-propanesulfonate, organic sulfate such as laurylsulfate, oxide, and hydroxyl Compounds, chlorides, alkoxides, acetylacetonates and the like chelate compounds, which are added to the reaction system as powders, aqueous solutions, ethylene glycol solutions, ethylene glycol slurries and the like.

Of these, the aluminum compound is specifically aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, Carboxylates such as aluminum trichloroacetate, aluminum lactate, aluminum citrate, aluminum salicylate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, polyaluminum chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate, phosphonic acid Inorganic acid salts such as aluminum, aluminum methoxide,
Aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum
Aluminum alkoxides such as n-butoxide and aluminum t-butoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate, aluminum chelate compounds such as di-isopropoxide, trimethylaluminum, triethylaluminum and other organic compounds. Aluminum compounds and their partial hydrolysates, aluminum oxide and the like can be 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 preferred.

As the manganese compound, fatty acid manganese salts such as manganese acetate, manganese carbonate, manganese nitrate,
It is preferable to use manganese chloride, manganese acetylacetonate, manganese naphthenate and hydrates thereof, and among them, manganese acetate tetrahydrate is particularly preferable.

As the cobalt compound, cobalt acetate,
Cobalt carbonate, cobalt nitrate, cobalt chloride, cobalt acetylacetonate, cobalt naphthenate and their hydrates are preferably used, and among them, cobalt acetate tetrahydrate is particularly preferable. As the zinc compound, it is preferable to use fatty acid zinc salts such as zinc acetate, zinc carbonate, zinc nitrate, zinc chloride, zinc acetylacetonate, zinc naphthenate and hydrates thereof, and among them, zinc acetate tetrahydrate. Is preferred.

Examples of the tin compound include dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin adeate, diphenyltin dilaurate, monobutyltin trichloride, Dibutyltin sulfide, dibutylhydroxytin oxide, methylstannonic acid, ethylstannonic acid and the like are preferable, and monobutylhydroxytin oxide is particularly preferable.

These metal compounds can be added to the reaction system at any stage of the polymerization reaction. For example, it can be added to the reaction system at any stage before and during the esterification reaction or transesterification reaction or immediately before the polycondensation reaction or at any stage during the polycondensation reaction. In particular, aluminum or its compound is preferably added immediately before the start of the polycondensation reaction.

The content of these metal compounds represented by the general formula (3) is in the range of 0.05 to 3.0 mol as the metal atom of the metal compound per ton of polymer,
Preferably 0.1 to 2.8 mol, more preferably 0.2
The range is up to 2.6 mol. 0./ton of polymer.
When the amount is less than 05 mol, the crystallization rate of the hollow molded article obtained from the obtained polyester, especially the plug portion of the stretch-heat-fixed hollow molded article, is greatly changed, and the flavor of the content is deteriorated. On the other hand, if it exceeds 3.0 mol, the thermal stability of the polyester is poor, the hue is poor, and the acetaldehyde content is high, which is a problem. Further, the crystallization speed fluctuation of the molded body also becomes large.

Further, the molar ratio M / P of the metal atom of the metal compound to the phosphorus atom of the phosphorus compound per ton of the polymer represented by the general formula (4) is in the range of 0.1 to 3.0. Yes, preferably 0.2 to 2.8, more preferably 0.
It is in the range of 3 to 2.6. If the M / P is less than 0.1, the transparency and the color tone of the obtained hollow molded article made of the polyester resin, particularly the stretch-heat-fixed hollow molded article, are extremely deteriorated. On the other hand, when it exceeds 3.0, the thermal stability of the polyester is poor and the content of acetaldehyde increases, which is a problem in terms of flavor.

The polyester composition of the present invention contains at least one metal compound selected from the group consisting of alkali metal compounds and alkaline earth metal compounds, and the metal atom of these metal compounds per ton of the polymer. As 0.001 to 2.0 mol, preferably 0.005 to
The content is preferably 1.5 mol, more preferably 0.01 to 1.0 mol. When the content of the alkali metal compound or the alkaline earth metal compound exceeds 2.0 mol%, problems such as a decrease in thermal stability, an increase in the generation of foreign matter or coloring, and a decrease in hydrolysis resistance occur. In addition, the content is 0.001
If it is less than the molar amount, the effect of suppressing the production of diethylene glycol and the catalytic activity are enhanced, and therefore the effect of further enhancing the reaction rate is not exhibited.

The alkali metal or alkaline earth metal is preferably at least one selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium. The compound is more preferred. When using an alkali metal or a compound thereof, it is particularly preferable to use lithium, sodium or potassium. Examples of compounds of alkali metals and alkaline earth metals include formic acid, acetic acid, and
Propionic acid, butyric acid, saturated aliphatic carboxylates such as oxalic acid, unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid, aromatic carboxylates such as benzoic acid, halogen-containing carboxylates such as trichloroacetic acid, Hydroxycarboxylic acid salts such as lactic acid, citric acid, salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, Inorganic acid salts such as bromic acid, 1-propanesulfonic acid, 1-pentanesulfonic acid, organic sulfonic acid salts such as naphthalenesulfonic acid, organic sulfates such as lauryl sulfuric acid, methoxy, ethoxy, n-propoxy, iso-
Examples thereof include alkoxides such as propoxy, n-butoxy and tert-butoxy, chelate compounds with acetylacetonate, hydrides, oxides and hydroxides.

These alkali metal compounds and alkaline earth metal compounds can be added to the reaction system at any stage of the polymerization reaction. For example, it can be added to the reaction system at any stage before and during the esterification reaction or transesterification reaction or immediately before the polycondensation reaction or at any stage during the polycondensation reaction. The above-mentioned alkali metal compound or alkaline earth metal compound is added to the reaction system as a powder, an aqueous solution, an ethylene glycol solution or the like.

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 copper, boron, indium, hafnium, niobium, tantalum, bismuth,
Examples thereof include oxides, halides, hydroxides, carbonates, sulfates, alkoxides and aliphatic or aromatic carboxylates of chromium, molybdenum, tellurium, nickel and the like.

Further, it is preferable to use a basic nitrogen compound in the production of the polyester according to the present invention. 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. The addition of these basic nitrogen compounds to the reaction system can be appropriately selected at any stage until the completion of the initial polycondensation reaction, and they may be used alone or in combination of two or more. Good.

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

In the polyester production process, in the step of forming the melt-polymerized polymer into chips, the solid-state 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, the molded article molded from such a polyester composition, especially the transparency of the bottle, is very high. 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 500 ppm, preferably 0.2 to 30.
It should be 0 ppm, more preferably 0.5 to 100 ppm. 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 is not possible, and the stretch-heat-fixing mold for molding the heat-resistant hollow molded container is heavily soiled, so that it is necessary to frequently clean the mold to obtain a transparent hollow molded container. Again 500
If it exceeds ppm, the crystallization speed will be high and the crystallization of the plug part of the hollow molding container will be excessive, so that the shrinkage amount of the plug part will not fall within the specified range and capping of the plug part will occur. It becomes defective, the contents leak, and the preform for hollow molding is whitened, which makes normal stretching impossible.

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

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 hollow-molding preform or sheet having good transparency and stretchability from a polyester composition containing fine particles having a melting peak temperature exceeding 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 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 a 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 taken out from the tank by a screw feeder and transported to the next process by a plug transport system or a bucket conveyor system, and fines are removed by an air flow classification process by an air flow immediately before or immediately after the next process. I do.

When solid-phase polymerization is carried out as required, the melt polycondensed polyester from which the fine or film-like substances have 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. 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 molten 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, and an air stream classification step using an air stream 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 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 0.5% by weight or less, still more preferably 0.40%.
It is less than or equal to wt. 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.

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 0.5% by weight or less. The amount of increase of the cyclic trimer is preferably 0.3% by weight or less, more preferably 0.1% by weight or less. The amount of increase of the cyclic trimer when melted at a temperature of 290 ° C. for 60 minutes is 0.
If it exceeds 5% by weight, the amount of cyclic trimer increases when the resin is melted during molding, and the amount of oligomer attached to the surface of the heating mold rapidly increases, resulting in a very poor transparency of the obtained hollow molded product. To do.

The polyester composition of the present invention, in which the amount of cyclic trimer increased by 0.5% by weight 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 to achieve the above object will be described below. Examples of the hot water treatment method include a method of immersing in hot water and a method of spraying water on the chips with a shower. The treatment time is 5 minutes to 2 days, preferably 10 minutes to 1 day, more preferably 30 minutes to 10 hours, and the water temperature is 20 to 180 ° C., preferably 40.
To 150 ° C, more preferably 50 to 120 ° C.

The method of industrially performing water treatment will be illustrated below, but the method is not limited thereto. 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 diameter 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 (9) to (13) are satisfied, and the water treatment is performed. 1 ≤ X ≤ 50,000 (pieces / 10 ml) (9) 0.001 ≤ N ≤ 1.0 (ppm) (10) 0.001 ≤ M ≤ 0.5 (ppm) (11) 0.001 ≤ C ≤ 1 0.0 (ppm) (12) 0.01 ≤ S ≤ 2.0 (ppm) (13)

By setting any of the number of particles in 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.

The number of particles in water introduced into the water treatment tank is 500
At least one of the steps up to the supply of natural water such as industrial water to the treatment tank is carried out as a method of reducing the number to 100 pieces / 10 ml or less.
Install devices to remove particles at more than one place.

In order to reduce sodium, magnesium, calcium and silicon in the water introduced into the water treatment tank, at least one or more of sodium and magnesium are supplied in the process until natural water such as industrial water is supplied to the treatment tank.
Install a device to remove calcium and silicon. Examples of these devices include the same devices as those used for the treatment of chip cooling water.

When the polyester chips and steam or steam-containing gas are brought into contact with each other for treatment, 50 to 50
Steam or steam-containing gas or steam-containing air at a temperature of 150 ° C., preferably 50 to 110 ° C. is preferably supplied or present 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
It will be held for 10 hours.

The method for industrially carrying out the contact treatment between the granular polyethylene terephthalate and steam or a steam-containing gas is 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 the polyester chips are continuously contacted with steam, granular tower terephthalate is continuously received from the upper part in a tower type processing apparatus, and steam is continuously supplied in cocurrent or countercurrent to contact with steam. Can be processed.

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

For drying the polyester chips which have been subjected to the contact treatment with water or steam, a commonly used polyester drying treatment 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 aeration of 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 the molecular weight from being lowered by hydrolysis or thermal oxidative decomposition of the polyester.

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

The solid compound polyester may be blended with the phosphorus compound by dry blending the solid compound polyester with the phosphorus compound, or the polyester master-batch chip and the solid polymer polyester chip obtained by melt-kneading the phosphorus compound. 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.

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. , (5) ~ below
It is preferable that the polyester is formed into chips after melt polycondensation so as to satisfy at least one and preferably all of (8). N ≤ 1.0 (ppm) (5) M ≤ 0.5 (ppm) (6) S ≤ 2.0 (ppm) (7) C ≤ 1.0 (ppm) (8)

The sodium content (N) in the 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), the magnesium content (M), the silicon content (S) and the 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 the solidified polycondensation of the melted polycondensed polyester which was made into chips while being cooled with cooling water that deviates from the above conditions, it was attached to the chip surface in the chipping step and brought into the solid phase 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 the sheet is manufactured, the scale is clogged in the molten polymer filtration filter at the time of film formation, the filtration pressure of the filter increases sharply, and the operability and the productivity are deteriorated. 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 least at one or more places 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.

In addition, 50,000 particles having a particle size of 1 to 25 μm existing in the introduced water introduced from outside the system / 10 m
It is preferable to use water adjusted to 1 or less. The number of particles having a particle size of 1 to 25 μm in the introduced water is preferably 1,000.
0 pieces / 10 ml or less, more preferably 1000 pieces / 1
It is 0 ml or less, particularly preferably 100 pieces / 10 ml or less.

The polyester composition of the present invention is obtained by adding at least one resin selected from the group consisting of a polyolefin resin, a polyamide resin and a polyacetal resin to the above polyester composition in an amount of 0.1 ppb to 50,000 ppm.
Is a polyester composition. The blending ratio of the above-mentioned polyolefin resin and the like in the polyester composition of the present invention is 0.1 ppb to 5000.
0 ppm, preferably 0.3 ppb to 10,000 pp
m, more preferably 0.5 ppb to 100 ppm, further preferably 1.0 ppb to 1 ppm, particularly preferably 1.0 ppb to 45 ppb. Compounding amount is 0.1pp
When it is less than b, the crystallization rate becomes very slow and the crystallization of the plug part of the hollow molded article becomes insufficient. Therefore, if the cycle time is shortened, the shrinkage amount of the plug part falls within the specified range. Since there is no capping, the stretch heat-fixing mold for molding the heat-resistant hollow molded body is heavily contaminated, and the mold must be frequently cleaned to obtain a transparent hollow molded body. If it exceeds 50,000 ppm, the crystallization rate will be high and the crystallization of the plug part of the hollow molded article will be excessive, and the amount of shrinkage and shrinkage of the plug part will not fall within the specified range, resulting in poor capping. Leakage of the product occurs and the preform for the hollow molded body is whitened, which makes normal stretching impossible. Also,
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 can be obtained. . Further, when the above-mentioned polyolefin resin or the like is used alone, it is hardly effective in preventing stains on the heating die, but it has been found that coexistence with a specific amount of fine is very effective on stains on the die.

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

Examples of the polyethylene resin blended in the polyester composition of the present invention include ethylene homopolymer, ethylene, and propylene, butene-1,3-methylbutene-1, pentene-1,4-methylpentene. −
1, hexene-1, octene-1, decene-1, and other α-olefins having about 2 to 20 carbon atoms, vinyl acetate,
Examples thereof include copolymers with vinyl compounds such as vinyl chloride, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, and styrene. Specifically, for example, low / medium / high density polyethylene etc. (branched or linear) ethylene homopolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-4-
Methylpentene-1 copolymer, ethylene-hexene-1
Ethylene resins such as copolymers, ethylene-octene-1 copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-ethyl acrylate copolymers Is mentioned.

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-
Other α-olefins having about 2 to 20 carbon atoms such as 1 and copolymers with vinyl compounds such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester and styrene. To be Specific examples thereof include propylene-based resins such as propylene homopolymer, propylene-ethylene copolymer, and propylene-ethylene-butene-1 copolymer. Further, as the α-olefin resin blended in the polyester composition of the present invention, homopolymers of α-olefins such as 4-methylpentene-1 having about 2 to 8 carbon atoms, those α-olefins, and ethylene , Propylene, butene-1, 3-methylbutene-1, pentene-1, hexene-1, octene-1, decene-1 and the like, and copolymers with other α-olefins having about 2 to 20 carbon atoms. To be Specifically, for example, butene-1 homopolymer, 4-methylpentene-1
Homopolymer, butene-1-ethylene copolymer, butene-
Examples thereof include butene-1 type resins such as 1-propylene copolymers and copolymers of 4-methylpentene-1 and C _{2 to} C ₁₈ α-olefins.

Examples of the polyamide resin blended in the polyester composition of the present invention include butyrolactam, δ-valerolactam, ε-caprolactam, enantolactam, ω-laurolactam, and other lactam polymers, 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 containing the above-mentioned polyolefin resin or the like in the present invention, a resin such as the above-mentioned polyolefin resin or the like is directly added to the polyester so that the content thereof is in the above range, and the mixture is melt-kneaded. Or, by a conventional method such as a method of adding as a master-batch and melt-kneading, or the like, the resin is used in the production step of the polyester, for example, during melt polycondensation, immediately after melt polycondensation, immediately after pre-crystallization, and solid phase. At the time of polymerization, immediately after solid phase polymerization, etc., or in the process from the end of the production stage to the molding stage, etc., it is added directly as powder or granules, or the polyester chips are flowed. It is also possible to use a method of mixing the resin member under the conditions, for example, a method of mixing the resin member, or a method of melting and kneading after the contact treatment.

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.

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

Therefore, in the method for producing a 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 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 size 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.

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

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

In addition, JIS B 9908 (1991)
Examples of the material of 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 deciliters / gram, and more preferably 0.58 to 1.20 deciliters / 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.
It is 0 ppm or less, more preferably 10 ppm or less, and further preferably 5 ppm or less. When the acetaldehyde content is 50 ppm or more, the flavor and odor of the contents such as containers molded from this polyester are deteriorated.

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

In the present invention, the shape of the polyester chip 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.

Further, 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 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 168 ° C
When it exceeds, 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 the saturated fatty acid monoamide include lauric acid amide, palmitic acid amide, stearic acid amide and behenic acid amide. Examples of unsaturated fatty acid monoamides include oleic acid amide, erucic acid amide ricino-acid amide, and the like. Examples of the saturated fatty acid bisamide include methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebisbehenic acid amide, hexamethylenebisstearic acid amide, and hexamethylenebisbehenic acid. Examples include amides. Examples of unsaturated fatty acid bisamides include ethylenebisoleic acid amide and hexamethylenebisoleic acid amide. Preferable amide compounds are saturated fatty acid bisamide, unsaturated fatty acid bisamide and the like. The compounding amount of such an amide compound is 1
It is in the range of 0 ppb to 1 × 10 ⁵ ppm.

Further, a metal salt compound of an aliphatic monocarboxylic acid having 8 to 33 carbon atoms such as naphthenic acid, caprylic acid, capric acid, lauric acid, 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 product, a packaging material such as a tray, a biaxially stretched film, a film for coating a metal can and the like. Further, the polyester composition of the present invention can 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 generally used melt molding method. Also,
It is possible to improve the mechanical strength by stretching the sheet-like material comprising the polyester composition of the present invention 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. It is also possible to form into a recup shape or a tray shape by pressure forming or 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 a hollow molded article, a briform molded from the polyester 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 120 ° C.
At 110 ° C, the draw ratio is usually 1.5-3.5 in the machine direction.
It may be performed in the range of 2 to 5 times in the circumferential direction. The obtained hollow molded article can be used as it is, but in particular, a fruit juice beverage,
In the case of beverages such as oolong tea that require hot filling, they are generally used after being subjected to heat setting treatment in a blow mold to impart heat resistance. The heat setting is usually 100 to 200 ° C., preferably 12 under tension such as compressed air.
It is carried out at 0 to 180 ° C. for several seconds to several hours, preferably several seconds to several minutes. Also, 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, a dye, and a pigment.

When the polyester composition of the present invention is used for a film, in order to improve handling properties such as slipperiness, winding property and blocking resistance, calcium carbonate and magnesium carbonate are added to the polyester composition. Inorganic particles such as barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, and magnesium phosphate, organic salt particles such as terephthalate salts such as calcium and calcium oxalate, barium, zinc, manganese, and magnesium, and divinylbenzene, Inert particles such as cross-linked polymer particles such as styrene, acrylic acid, methacrylic acid, vinyl monomers of acrylic acid or methacrylic acid, homopolymers or copolymers, can be contained.

[0132]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. In addition, the measuring method of the main characteristic value in this specification is demonstrated below.

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

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

(3) Content of cyclic trimer of polyester (hereinafter referred to as "CT content") 300 mg of a sample was dissolved in 3 ml of a hexafluoroisopropanol / chloroform mixture (volume ratio = 2/3), Dilute by adding 30 ml of chloroform.
15 ml of methanol was added to this to precipitate the polymer, and the polymer was filtered. The filtrate was evaporated to dryness, the volume was adjusted to 10 ml with dimethylformamide, and the cyclic trimer was quantified by high performance liquid chromatography.

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

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

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

(7) Measurement of melting peak temperature of fine (hereinafter referred to as "melting point of fine") Differential scanning calorimeter (DS) manufactured by Seiko Instruments Inc.
C), measured using RDC-220. In (6),
Fines collected from 20 kg of polyester were dried under reduced pressure at 25 ° C for 3 days, and a sample of 4 m was used for each measurement.
DSC measurement at a temperature rising rate of 20 ° C./min using g,
Obtain the melting peak temperature on the highest side of the melting peak temperature. The measurement is performed on a maximum of 10 samples, and the average value of the melting peak temperatures on the highest temperature side is obtained. Melting peak is 1
In the case of two, the temperature is calculated.

(8) Crystallization temperature (Tc
1) Differential thermal analyzer (DS) manufactured by Seiko Electronics Co., Ltd.
C), measured with RDC-220. Using 10 mg of a sample from the center of a 2 mm-thick plate of the following (13) shaped plate. The temperature is raised at a temperature rising rate of 20 ° C./minute, and the peak temperature of the crystallization peak observed during the heating is measured and used as the crystallization temperature during heating (Tc1).

(9) Average Density of Polyester Chip, Density of Preform Plug Portion and Density Deviation of Plug Portion Measurement was carried out at 30 ° C. with a density gradient tube of a calcium nitrate / water mixed solution. Further, the density of the plug portion was calculated as an average value of 10 samples crystallized by the method (11), and the density deviation of the plug portion was calculated from the value of 10 samples.

(10) Haze (% haze) and haze unevenness Samples were cut from the body (wall thickness 5 mm) of the following (13) and the body (wall thickness approximately 0.4 mm) of the hollow molded body of (14). , Nippon Denshoku Co., Ltd. haze meter, model NDH2
Measured at 000. In addition, a forming plate formed 10 times in succession
The haze (wall thickness: 5 mm) was measured, and the haze unevenness was determined by the following. Haze spot = maximum haze value / minimum haze value

(11) Density increase due to heating of preform 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.

(12) Molding of Stepped Molded Plate In the molding of the stepped molded plate described in 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).

(13) 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.

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

(15) Sensory test Distilled water at 95 ° C. was put into the hollow molded article molded in the above (13), and the bottle was sealed and held for 30 minutes, cooled to room temperature and left at room temperature for 1 month. The odor and other tests were conducted. Distilled water is used as a blank for comparison. The sensory test was carried out by 10 panelists according to the following criteria, and the average values were compared. (Evaluation criteria) ◎: No off-taste or smell is felt ○: A slight difference from the blank is felt △: A difference from the blank is felt ×: A considerable difference from the blank is felt × ×: Very large difference from the blank Feel

(16) Cooling water in the chipping step and sodium content, calcium content, magnesium content and silicon content in the introduced water of the water treatment step The particle-removed and ion-exchanged cooling water or the introduced water was collected. After filtering with a 1G1 glass filter manufactured by Iwaki Glass Co., Ltd., the filtrate was measured by an atomic absorption method, an ICP method, or an ICP-MS method.

(17) Measurement of the Number of Particles in Cooling Water in the Chip Making Step, and Introduced Water and Recycled Water in the Water Treatment Step Cooling water in the chip making step, introduced water after particle removal and ion exchange, or a filtration device (5 ) And the recycled water treated in the adsorption tower (8) were measured using PAC 150 manufactured by Seishin Enterprise Co., Ltd., which is a particle measuring device by the light blocking method, and the number of particles was expressed as 10/10 ml.

(18) Measurement of 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 A slurry of high-purity terephthalic acid and ethyl glycol was continuously supplied to a first esterification reactor containing a reactant in advance, and the mixture was stirred to about 2
The reaction was carried out at 50 ° C. and 0.5 kg / cm ² G. The reaction mass is sent to the second esterification reactor and stirred for about 26
The reaction was carried out at 0 ° C. and 0.05 kg / cm ² G to a predetermined degree of reactivity. Further, crystalline germanium dioxide is dissolved in water by heating, and ethylene glycol is added to the solution, and a catalyst solution obtained by heat treatment, a water / ethylene glycol solution of basic aluminum acetate and an ethylene glycol solution of phosphoric acid are separately prepared. The second esterification reactor was continuously fed. The esterification reaction product is continuously fed to the first polycondensation reactor, and is stirred at about 265 ° C. at 25 torr for 1 hour, and then is stirred at the second polycondensation reactor at about 265 ° C. for 3 torr.
r for 1 hour and with stirring in the final polycondensation reactor, about 27
Polycondensation was performed at 5 ° C. and 0.5 to 1 torr, and an intrinsic viscosity of 0.
56 deciliter / gram of melt polycondensed polyester was obtained. This polyester is used for industrial water (derived from underground river water)
Was treated with a filter filtration device and an ion exchange device, and the number of particles having a particle size of 1 to 25 μm was about 1000 particles / 10 m.
1, sodium content 0.02ppm, magnesium content 0.02ppm, calcium content 0.01
The content of fine and film was reduced to 50 ppm or less by chipping while cooling with cooling water having a ppm and silicon content of 0.10 ppm, and then removing fine and film-like substances by a vibrating sieving step and an air stream classification step. .

Then, it was sent to a crystallization apparatus, and continuously crystallized at about 155 ° C. in a nitrogen atmosphere, further preheated to about 200 ° C. in a nitrogen atmosphere, and then sent to a continuous solid-state polymerization reactor at about 207 ° C. in a nitrogen atmosphere. Solid-state polymerized. After the solid phase polymerization, the fine particles were removed by continuously treating them in the sieving step and the fine particles removing step, and the fine content was adjusted to about 50 ppm. The obtained PET had an intrinsic viscosity of 0.74 deciliter / gram, a cyclic trimer content of 0.30% by weight, and a density of 1.4031 g / cm ³ .

The raw material chip supply port (1) at the upper part of the treatment tank, the overflow discharge port (2) located at the upper limit level of the treated water in the treatment tank, and the discharge of the mixture of polyester chips and treated water at the lower part of the treatment tank. The treated water discharged from the outlet (3) and the overflow flow outlet and the treated water that passed through the polyester chip drainer (4) discharged from the outlet at the lower part of the treatment tank have a filter medium of paper. Piping (6) sent again to the water treatment tank via the fine filtration removal device (5) which is a continuous filter and the adsorption tower (8), GAF filter bag PE-1P2S (polyester felt, manufactured by ISP) Introducing water obtained by introducing new ion-exchanged water from outside the system into the inlet (9) in the middle of this pipe (6) via a device for removing particles in water and an ion-exchanger with a filtration accuracy of 1 μm) With mouth (7) Tower type capacitive 50 m ^3, a polyethylene terephthalate using a processing tank shown in FIG. 3 - DOO (hereinafter,
Abbreviated as PET) Chips were continuously treated with water.

The above-mentioned solid-state polymerization PET chip was treated by a vibrating sieving step and an air stream classifying step, and the fine content was about 50 ppm (the peak temperature on the highest side of the fine melting peak temperature was 248). C.), and then continuously charged from the upper supply port (1) of the treatment tank controlled to a treated water temperature of 95 ° C., and the water treatment tank lower discharge port (3) at a water treatment time of 3 hours. The water treatment was performed while continuously extracting the PET chip together with the treated water from). The content of particles having a particle size of 1 to 25 μm in the introduced water collected before the ion-exchanged water inlet (9) of the above-mentioned treatment device is about 1000 particles / 10 m.
1, sodium content 0.02ppm, magnesium content 0.02ppm, calcium content 0.01
ppm and silicon content is 0.10 ppm, and the number of particles of recycled water having a particle size of 1 to 40 μm after treatment in the filtration device (5) and the adsorption tower (8) is about 18,000 particles / 1
It was 0 ml.

After the water treatment, the product was continuously dried with heated dry air, and subsequently treated in a vibrating sieving process and an airflow classifying process to remove fines and film-like substances, and the fines content was adjusted to about 50 ppm. The peak temperature on the highest side of the melting peak temperature of this fine was 248 ° C.
The water-treated PET composition had an intrinsic viscosity of 0.74 deciliter / gram, a DEG content of 2.7 mol%, an AA content of 2.9 ppm, a cyclic trimer content of 0.30 wt%, and a cyclic structure. The amount of trimer increased was 0.07% by weight, the fine content was about 50 ppm, the melting point of fine was 248 ° C., and there was no film. The germanium content measured by atomic absorption spectrometry is 0.33 mol per ton of PET, the aluminum content is 0.37 mol per ton of PET, and the phosphorus content is 0.90 per ton of PET.
It was a mole.

The PET composition obtained was evaluated using a molded plate and a biaxially stretched molded bottle. The results are shown in Table 1.
Shown in. The haze of the molded plate was 3.9%, the haze unevenness of the molded plate was 0.2%, and the Tc1 of the molded plate was 166 ° C. Bottle mouth density of the plug portion is 1.377g / cm ^3, the spout unit density deviation of no value problem and 0.001 g / cm ^3, the body portion haze of the bottle was good and 0.9%. 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 16.3 ppm, and the result of the sensory test was “⊚”, which was a value with no problem. Further, continuous stretching blow molding of 5000 or more lines was carried out, but no mold stain was observed, and there was no problem. In the manufacturing process, all of the melt-polymerized prepolymer chips and solid-phase polymerized chips are transported by a bucket type conveyor transportation system, and all chips are extracted from the reactor or storage layer by a screw feeder.
Was used. The same method was used in Examples 2 to 5.

Example 2 A PET composition was prepared in the same manner as in Example 1 except that the amounts and ratios of basic aluminum acetate and phosphoric acid added were changed as shown in Table 1 and the water treatment was omitted. Obtained. The results are shown in Table 1. Obtained P
The properties of the ET composition and the properties of the bottle were good and there was no problem.

(Example 3) The solid-state polymerized PET obtained in Example 2 was treated with the same water treatment apparatus and method as in Example 1. A linear low-density polyethylene (MI = about 0.9 g / 10 min, density = about 0.923 g / cm ³ ) was kneaded with the obtained water-treated PET by a twin-screw extruder to finely disperse the polyethylene. The prepared PET master (fine content is about 50 ppm, peak temperature on the highest side of the fine melting peak temperature is 248 ° C.) is prepared, and this master is added to the water-treated PET described above. The PET composition obtained by mixing so that polyethylene was about 10 ppb was evaluated using a molded plate and a biaxially stretched molded bottle. 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 4) Toyobo nylon resin, T60
0 (polyamide resin obtained from metaxylylenediamine and adipic acid, Ny-MXD6) and PET before water treatment in Example 1 were kneaded in the same manner as in Example 1 to produce a PET master. PET before water treatment
A PET composition (IV is 0.74 deciliters / gram, DEG content is 2.8 mol%, A
A content is 3.5 ppm, cyclic trimer content is 0.3
3% by weight, increase of cyclic trimer is 0.46% by weight, fine content is about 50 ppm, film-like material is not contained,
Further, the melting point of fine was 246 ° C.) and the evaluation was performed 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 0.7%, and the Tc1 of the molded plate was 156 ° C. Bottle mouth density of the plug portion is 1.382 g / cm ^3, the spout unit density deviation of no value problem and 0.003 g / cm ^3, the body portion haze of the bottle was 2.0% and good.

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 8.9 ppm, and the result of the sensory test was “⊚”, which was a problem-free value.

Example 5 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.

The slurry of terephthalic acid and ethylene glycol (virgin product) (ethylene glycol / terephthalic acid molar ratio = 1.6) was charged with bis (hydroxyethyl) terephthalate, and the temperature was kept at 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 has been transferred, from a plurality of polycondensation catalyst supply pipes, 0.97 as phosphorus atoms per ton of produced polyester resin.
An ethylene glycol solution of phosphoric acid in an amount such that the content is about 30 mol (about 30 ppm with respect to the produced polyester resin), 0.56 mol as aluminum atom per ton of the produced polyester resin (about 15 ppm with respect to the produced polyester resin) Content of acetylacetonate in ethylene glycol, and 0.3 g of germanium atom per ton of produced polyester resin.
3 mol (approx. 24 ppm based on polyester resin produced)
After adding an amount of crystalline germanium dioxide ethylene glycol solution such that the content becomes, the system temperature is raised from 250 ° C. to 275 ° C. over 1 hour, and the atmospheric pressure is changed from 350 Pa to 1 hour, Then, under a reduced pressure of 150 Pa and at 278 ° C., the obtained resin has an intrinsic viscosity of 0.56.
Melt polycondensation was performed for a time of 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 chips obtained above were 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 flow of 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
4 deciliters / gram, DEG content 3.1 mol%, AA content 3.3 ppm, cyclic trimer content 0.32% by weight, cyclic trimer increase 0.42% by weight The fine content was about 50 ppm, the film-like material was not contained, and the fine melting point was 246 ° C.) was evaluated using a molded plate and a biaxially stretched molded bottle.

The haze of the molded plate was 7.5%, the haze unevenness of the molded plate was 0.3%, and the Tc1 of the molded plate was 161 ° C. Bottle mouth density of the plug portion is 1.378g / cm ^3, the spout unit density deviation of no value problem and 0.003 g / cm ^3, the body portion haze of the bottle was good and 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 20.5 ppm, and the result of the sensory test was “⊚”, which was a value with no problem.

(Comparative Example 1) The addition amounts and ratios of basic aluminum acetate and phosphoric acid were changed as shown in Table 1, and the prepolymer melt-polycondensed in the same manner as in Example 1 was used without removing fines and the like. Then, it was transported to a temporary storage silo by a low-density transportation method, then put into a rotary tumbler, crystallized at 140 ° C. under reduced pressure while rotating, and then solid-state polymerized at 217 ° C. The transportation to the solid-state polymerization apparatus and the transportation after the solid-state polymerization were all performed by the low-density transportation method.

The PET thus obtained was treated with water under the same conditions as in Example 1. In all steps from melt polycondensation to after water treatment, no treatment was performed with a fine removing device. Table 1 shows the characteristics of the obtained PET composition, the molded plate molded from the PET composition, and the biaxially stretch-molded bottle. The transparency of the obtained bottle was poor, and the deformation of the spout and the leakage of the contents were examined, but the leakage of the contents was severe, which was a problem.

Comparative Example 2 PE was prepared in the same manner as in Comparative Example 1 except that the addition amount and ratio of basic aluminum acetate and phosphoric acid were changed as shown in Table 1 and the water treatment was omitted.
A T composition was obtained. The results are shown in Table 1. 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. When visually observed from the side of the bottle mouth part, it was found to be considerably yellow and there was a problem in the appearance of the bottle. The sensory test is also
X was very bad.

[0170]

[Table 1]

[0171]

According to the polyester composition of the present invention,
It is excellent in economy, crystallization controllability during melt molding, and long-term continuous moldability.
The sheet-like material and the stretched film are excellent in transparency and heat-resistant dimensional stability, and in particular, the shrinkage rate of the plug portion of the hollow molded body is in an appropriate range, and residual off-flavor and off-flavor are generated when the liquid container is used. Hard to do.

[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.

FIG. 3 is a schematic view of a water treatment device used in an example.

[Explanation of symbols]

1 Raw Material Chip Supply Port 2 Overflow Discharge Port 3 Polyester Chip and Treated Water Discharge Port 4 Drainer 5 Fine Removal Device 6 Piping 7 Recycled Water or / and Ion Exchange Water Inlet 8 Adsorption Tower 9 Ions Exchange water inlet

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // B29K 67:00 B29K 67:00 B29L 22:00 B29L 22:00 (72) Inventor Yoshitaka Eto Shiga Prefecture 20F Term, No. 248, Takagi, Shiga-machi, Shiga-gun (Reference) 3E086 AD04 BA02 BA15 BA35 BB15 BB90 CA11 4F208 AA24C AA24K AB19 AG07 AH55 LA02 LA04 LB01 LG01 4F210 AA03 AA23 AA24 AA29 AB16 AG01 4J002 BB022 CF2 CL020102021BB01 BB022041BB01 AB01 AC01 AD07 AD10 AE01 AE03 AE18 BA03 BA04 BA05 BB13A BD07A BF25 BF26 CA04 CA05 CA06 CB05A CB06A CB10A CB12A CC06A EA02 EB05A FC03 FC08 FC36 FC38 HA01 HB01 JA041 JA091 JA111 JA121 JA161 JA201 JA231 JA251 JB131 JB171 JC031 JC221 JC261 JC371 JC461 JC471 JC481 JC551 JC561 JC571 JC581 JC751 JF011 JF111 JF151 JF153 JF181 JF183 JF221 JF223 JF231 JF233 JF331 JF333 JF351 JF353 JF 361 JF363 JF371 JF373 JF381 JF383 JF511 JF513 JF541 JF561 JF563 JF571 JF573 KD02 KD07 KE02 KE05 KH08 LA01 LB08 LB10

Claims (10)

[Claims] 1. A polyester chip whose main repeating unit is ethylene terephthalate, and a polyester fine 0.1 having the same composition as the polyester chip.
From about 500 ppm, wherein the polyester is a germanium compound and a phosphorus compound, and a group consisting of aluminum, silicon, manganese, iron, cobalt, zinc, gallium, strontium, zirconium, tin, tungsten, and lead. A metal compound containing at least one selected element, and
When the fineness of the polyester is measured by DSC,
The melting peak temperature on the highest side of the melting peak temperature is 265.
A polyester composition having a temperature of not higher than ° C. 2. The content of a germanium compound in the polyester, the content of a phosphorus compound, and selected from the group consisting of aluminum, silicon, manganese, iron, cobalt, zinc, gallium, strontium, zirconium, tin, tungsten, and lead. The polyester composition according to claim 1, wherein the content of the metal compound containing at least one element satisfies the following formulas (1) to (4). 0.1 ≤ Ge ≤ 0.9 (1) 0.15 ≤ P ≤ 3.3 (2) 0.05 ≤ M ≤ 3.0 (3) 0.1 ≤ M / P ≤ 3.0 (4) (In the above formula, Ge is the number of moles of germanium atom of the germanium compound per ton of polymer, P is the number of moles of phosphorus atom of the phosphorus compound per ton of polymer, and M is
Aluminum, silicon, manganese, iron, cobalt, zinc, gallium, strontium, per ton of polymer,
The number of moles of metal atoms of at least one metal compound selected from the group consisting of zirconium, tin, tungsten, and lead is shown. ) 3. The polyester composition according to claim 1, wherein the content of the polyester film material having the same composition as that of the polyester chips is 10 ppm or less. 4. The polyester composition according to claim 1, wherein the content of the cyclic trimer is 0.7% by weight or less. 5. The polyester composition according to claim 1, wherein the amount of cyclic trimer increase when melted at a temperature of 290 ° C. for 60 minutes is 0.50% by weight or less. object. 6. The chip content of the polyester after melt polycondensation, sodium content (N), magnesium content (M), silicon content (S) and calcium content (C). Is a polyester chipped with cooling water that satisfies at least one of the following (5) to (8), and the polyester composition according to any one of claims 1 to 5. N ≤ 1.0 (ppm) (5) M ≤ 0.5 (ppm) (6) S ≤ 2.0 (ppm) (7) C ≤ 1.0 (ppm) (8) 7. The polyester composition according to claim 1, further comprising 0.1 ppb to 50,000 ppm of at least one resin selected from the group consisting of a polyolefin resin, a polyamide resin, and a polyacetal resin. A polyester composition comprising: 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 9 in at least one direction.