JP2006028302A - Polyester resin composition and polyester molding comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin composition excellent in transparency and flavor retention, capable of efficiently producing blow-molded article and the like excellent in heat resistant dimensional stability, by eliminating problems in conventional technology such as lowering of transparency due to mold staining at the consecutive molding, and to provide a molding comprising the composition. <P>SOLUTION: This polyester resin composition essentially comprises a polyester resin(1) mainly comprising an aromatic dicarboxylic acid component and an ethylene glycol component wherein 100-5,000 ppm, in terms of a phosphorus atom, of a phosphorus compound is copolymerized or blended, and a polyester resin(2) mainly comprising an aromatic dicarboxylic acid component and an ethylene glycol component. The molding obtained by molding the polyester composition has a haze value of 30% or lower. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention comprises a polyester resin composition in which the production of aldehydes such as acetaldehyde and the formation of cyclic ester oligomers are mainly suppressed by deactivating the action of a polycondensation catalyst used during the production of polyester, and a polyester resin composition comprising the same The present invention relates to a polyester molded article having excellent transparency and excellent flavor retention.

  Polyester whose main repeating unit is ethylene terephthalate (hereinafter sometimes abbreviated as PET or PET resin) is a carbonated beverage due to its excellent properties such as transparency, mechanical strength, heat resistance, and gas barrier properties. It is used as a material for containers such as juice and mineral water, and its spread is remarkable. In these applications, beverages that have been sterilized at high temperatures are hot-filled in polyester bottles, or sterilized at high temperatures after filling beverages. However, ordinary polyester bottles shrink during such hot-filling treatments. Deformation occurs and becomes a problem. As methods for improving the heat resistance of polyester bottles, methods have been proposed in which the bottle cap is heat treated to increase the degree of crystallinity and the stretched bottle is heat-set. In particular, when the crystallization of the plug portion is insufficient or the variation in crystallinity is large, the sealing performance with the cap is deteriorated, and the contents may leak.

  Specifically, in the case of beverages that require hot filling, such as fruit juice beverages, oolong tea, and mineral water, a method of crystallizing by heat treatment of the stopper portion of the preform or molded bottle (for example, Patent Documents 1 and 2) are common. Such a method, that is, a method of improving the heat resistance by heat-treating the plug portion and the shoulder portion, the time and temperature for the crystallization treatment greatly affect the productivity, and can be processed at a low temperature in a short time. It is preferable that the conversion rate is PET. On the other hand, the body portion is required to be transparent even if heat treatment is performed at the time of molding so as not to deteriorate the color tone of the contents of the bottle, and the mouthpiece portion and the body portion must have contradictory characteristics.

  Moreover, in order to improve the heat resistance of a bottle trunk | drum, the method of heat-processing by making the temperature of an extending | stretching blow metal mold high is taken, for example (for example, refer patent document 3). However, if a large number of bottles are continuously formed using the same mold by such a method, the bottle obtained with a long time operation is whitened, the transparency is lowered, and only a bottle having no commercial value can be obtained. . It has been found that this is due to adhesion of PET due to the PET surface on the mold surface, resulting in mold contamination, which is transferred to the bottle surface. In particular, in recent years, the molding speed has been increased along with the downsizing of the bottle. From the viewpoint of productivity, the melting time at the time of injection molding is shortened, the heating time for crystallization of the plug portion is shortened, or the mold. Contamination has become a greater problem and is not satisfactory with conventional PET, and a solution is desired.

  The polyester also contains acetaldehyde (hereinafter sometimes abbreviated as AA) as a by-product. When the content of acetaldehyde in the polyester is high, the content of acetaldehyde in the material such as a container molded from now on or other packaging also increases, which affects the flavor and odor of the beverage filled in the container. In recent years, polyester containers such as polyethylene terephthalate have come to be used as containers for low flavor beverages such as mineral water and oolong tea. In the case of such beverages, these beverages are generally heat-filled or sterilized by heating after filling, but it is becoming increasingly important to reduce the acetaldehyde content of the beverage container. In addition, for beverage metal cans, for the purposes of process simplification, hygiene, pollution prevention, etc., cans are made using a metal plate whose inner surface is coated with a polyester film whose main repeating unit is ethylene terephthalate. The method to do has come to be adopted. In this case as well, it is sterilized by heating at a high temperature after filling the contents. At this time, it has been found that the use of a film having a sufficiently low acetaldehyde content is an essential requirement for improving the flavor and odor of the contents. I came.

  For these reasons, various measures have been taken to reduce the acetaldehyde content in the polyester. As these measures, for example, a method of reducing oligomers and aldehydes by subjecting a polyester prepolymer obtained by melt polymerization to solid phase polymerization under reduced pressure or in the flow of an inert gas (for example, Patent Document 4, 5), a method in which the moisture content of the polyester prepolymer is adjusted to 2000 ppm or more, followed by crystallization and solid-phase polymerization (see, for example, Patent Document 6), the polyester particles with hot water at 50 to 200 ° C. After the treatment, a method of heat treatment under reduced pressure or inert gas flow (for example, see Patent Document 7), a method of extraction and washing with water or an organic solvent before and after solid-phase polymerization (for example, see Patent Document 8) ) Etc. have been proposed. However, even with a molded body using polyester obtained by these methods, it cannot be said that oligomers and acetaldehyde can be reduced to a satisfactory level, and the problem has not been solved.

  As a method for further solving such problems, a method of deactivating the catalyst by contacting polyethylene terephthalate with water (for example, see Patent Documents 9, 10, 11, and 12) and water treatment. PET (for example, see Patent Documents 13 and 14) in which the catalyst is deactivated by the above is disclosed. However, such a catalyst deactivation method by contact treatment with water is effective only for polyesters produced using a germanium compound as a polycondensation catalyst, and produced using an antimony compound, a titanium compound, an aluminum compound or the like as a catalyst. Since there is little effect on the deactivation of these catalysts in the polyester, the increase in the AA content during molding cannot be suppressed, and the properties such as the flavor and odor of the contents of the molded product are hardly improved. In addition, since an apparatus and a drying apparatus for the processing are necessary, there is a problem that the capital investment cost and the processing cost are excessive, leading to an increase in cost and poor profitability.

  Also disclosed is a polyester and a method thereof (see, for example, Patent Document 15) in which a polycondensation catalyst is deactivated by kneading a thermoplastic resin containing a phosphorus compound into PET to reduce the amount of cyclic oligomers generated upon melting. Has been. However, this technology reduces the amount of cyclic oligomers and aldehydes produced during melting, but the disclosed technology has a fluctuation in effects due to fluctuations in the amount of addition in the single addition method of phosphorus compounds. In addition, the crystallization characteristics and transparency of the obtained molded product and its fluctuations are a major problem. Also, in the phosphorus compound-containing thermoplastic resin kneading method, the thermal stability depending on the type of the thermoplastic resin, and the transparency of the molded product. It has been found that it is very difficult to obtain a molded article having an appropriate and stable crystallization rate and excellent in transparency, and a solution is desired.

JP 55-79237 A JP 58-110221 A Japanese Examined Patent Publication No.59-6216 JP 55-89330 A JP 55-89331 A JP 59-219328 A JP 56-55426 A Japanese Patent Laid-Open No. 55-13715 Japanese Patent Laid-Open No. 3-47830 Japanese Patent Laid-Open No. 3-174441 Japanese Patent Laid-Open No. 6-234834 JP-A-8-231689 Japanese Patent Laid-Open No. 3-72524 JP-A-4-21424 Japanese Patent Laid-Open No. 10-251393

  The present invention provides a polyester resin composition that can be used to solve the problems of the conventional techniques described above, such as formation of aldehydes such as acetaldehyde during molding and formation of cyclic ester oligomers, and transparency comprising the same. Another object of the present invention is to provide a polyester molded article excellent in odor and flavor retention and excellent in heat-resistant dimensional stability.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to achieve the above object. That is, the polyester resin composition of the present invention mainly comprises an aromatic dicarboxylic acid component and an ethylene glycol component, and a polyester resin (1) in which an amount of 100 to 5000 ppm is copolymerized or blended with a phosphorus compound as a phosphorus atom, A polyester resin composition comprising, as main components, a polyester resin (2) comprising an aromatic dicarboxylic acid component and an ethylene glycol component, and a haze of a molded product obtained by molding the polyester resin composition is 30. % Or less, preferably 20% or less, more preferably 10% or less.

  The polyester resin composition of the present invention mainly comprises a terephthalic acid component and an ethylene glycol component, and a polyester resin (1) copolymerized or blended in an amount of 100 to 5000 ppm with a phosphorus compound as a phosphorus atom, and mainly aromatic. A polyester resin composition comprising, as main components, a polyester resin (2) comprising a dicarboxylic acid component and an ethylene glycol component, and a haze of a molded product obtained by molding the polyester resin composition is 30% or less. The polyester resin composition is preferably 20% or less, more preferably 10% or less.

  When the haze of the molded product obtained by molding the polyester composition exceeds 30%, the transparency of the obtained molded product becomes worse and becomes a problem, and the commercial value is lost.

Here, the said molded object is a molded object of 5 mm thickness shape | molded by the method described in the term of the following measuring method.
In this case, the polyester resin composition of the present invention preferably has a fine content of 0.1 to 5000 ppm. Here, fine means a fine powder of polyester that has passed through a sieve having a nominal size of 1.7 mm according to JIS-Z8801, and the content thereof is measured by the following measuring method.

  Such fines have the property of promoting crystallization, and when they are present in large quantities, molded articles formed from such polyester compositions, for example, the transparency of the bottle becomes very poor, The amount of shrinkage at the time of crystallization of the plug portion does not fall within the range of the specified value, so that the cap cannot be sealed with a cap.

  In this case, the acetaldehyde content of the molded product obtained from the polyester resin composition is preferably 50 ppm or less.

  In this case, it is preferable that the crystallization temperature (Tc1) at the time of temperature rise of the molded body obtained from the polyester resin composition is 150 to 175 ° C.

  In this case, the phosphorus compound is composed of a phosphoric acid compound, a phosphonic acid compound, a phosphinic acid compound, a phosphorous acid compound, a phosphonous acid compound, and a phosphinic acid compound. It is preferably at least one selected from the group.

  In this case, the polycondensation catalyst of the polyester resin (2) is at least one selected from the group consisting of Al, Ti, Mn, Fe, Co, Zn, Nb, Mo, Cd, In, Sn, Ta, and Pb. A compound containing any of these elements, or an antimony compound and / or a germanium compound, if necessary, is preferable.

  The polyester resin composition has excellent transparency, little variation in transparency, low cyclic ester oligomer content, almost no occurrence of mold stains during continuous molding, and excellent flavor retention. A molded body, for example, a hollow molded body, a sheet-like material, a stretched film, and the like can be provided.

  The polyester resin composition of the present invention can be used to inactivate the action of a polycondensation catalyst used in the production of polyester and solve problems such as the formation of aldehydes and cyclic ester oligomers during molding. This is a polyester resin composition with little variation in transparency and crystallization speed, excellent flavor retention, no problems such as deterioration of transparency due to mold contamination during continuous molding, and hollow with excellent heat-resistant dimensional stability. Give shaped bodies and so on.

  Hereinafter, embodiments of the polyester resin according to the present invention, the polyester resin composition of the present invention, and the polyester molded body comprising the same will be described in detail.

(Polyester resin (1))
Examples of the phosphorus compound copolymerized or blended in the polyester resin (1) according to the present invention include phosphoric acid compounds, phosphonic acid compounds, phosphinic acid compounds, phosphorous acid compounds, phosphonous acid compounds, and phosphine phosphines. An acid compound is mentioned.

  Specific examples of phosphoric acid compounds include, for example, phosphoric acid, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, diamyl phosphate, dihexyl phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triamyl phosphate Examples thereof include phosphate, trihexyl phosphate, ester of phosphoric acid and alkylene glycol, and the like.

  Specific examples of phosphonic acid compounds include, for example, methylphosphonic acid, dimethyl methylphosphonate, diphenyl methylphosphonate, phenylphosphonic acid, dimethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl phosphophosphonate, diethyl benzylphosphonate, triethylphosphono Examples include acetate, tributylphosphonoacetate, tri (hydroxyethyl) phosphonoacetate, tri (hydroxypropyl) phosphonoacetate, tri (hydroxybutyl) phosphonoacetate and the like.

  Specific examples of the phosphinic acid compounds include, for example, diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate, 2-carboxyethyl-methylphosphinic acid, 2 -Carboxyethyl-ethylphosphinic acid, 2-carboxyethyl-propylphosphinic acid, 2-carboxyethyl-phenylphosphinic acid, 2-carboxyethyl-m-toluylphosphinic acid, 2-carboxyethyl-p-toluylphosphinic acid, 2- Carboxyethyl-xylylphosphinic acid, 2-carboxyethyl-benzylphosphinic acid, 2-carboxyethyl-m-ethylbenzylphosphinic acid, 2-carboxymethyl-methylphosphinic acid, 2 Carboxymethyl-ethylphosphinic acid, 2-carboxyethyl-propylphosphinic acid, 2-carboxymethyl-phenylphosphinic acid, 2-carboxymethyl-m-toluylphosphinic acid, 2-carboxymethyl-p-toluylphosphinic acid, 2-carboxy Methyl-xylylphosphinic acid, 2-carboxymethyl-benzylphosphinic acid, 2-carboxymethyl-m-ethylbenzylphosphinic acid, and cyclic anhydrides thereof, or methyl ester, ethyl ester, propyl ester, butyl ester thereof , Ethylene glycol ester, propion glycol ester, ester with butanediol, and the like.

  Specific examples of phosphorous compounds include phosphorous acid and dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, diamyl phosphite, dihexyl phosphite, trimethyl phosphite, triethyl phosphite. , Triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylene diphosphite, phosphorous acid and alkylene Examples include esters with glycols.

Specific examples of the phosphonous acid compound include methylphosphonous acid, dimethyl methylphosphonite, diphenyl methylphosphonite, phenylphosphonous acid, phenyldimethylphosphonous acid, and phenyl phenylphosphonite. .
As other phosphorus compounds, phosphorus compounds other than those used in the following polyester resin (2) can also be used.

  The polyester resin (1) according to the present invention is a thermoplastic polyester mainly obtained from an aromatic dicarboxylic acid component and a glycol component, and preferably a polyester in which an aromatic dicarboxylic acid unit contains 70 mol% or more of the acid component. More preferably, it is a polyester in which the aromatic dicarboxylic acid unit contains 85 mol% or more of the acid component, and particularly preferably a polyester in which the aromatic dicarboxylic acid unit contains 95 mol% or more of the acid component, Are copolymerized or blended.

  Examples of the aromatic dicarboxylic acid component constituting the polyester resin (1) according to the present invention include aromatics such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, and diphenoxyethanedicarboxylic acid. Examples thereof include dicarboxylic acids and functional derivatives thereof.

  Examples of the glycol component constituting the polyester resin (1) according to the present invention include aliphatic glycols such as ethylene glycol, 1,3-trimethylene glycol and tetramethylene glycol, and alicyclic glycols such as cyclohexanedimethanol. It is done.

  Examples of the dicarboxylic acid used as a copolymerization component when the polyester is a copolymer include isophthalic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and 4,4′-diphenyl ether dicarboxylic acid. , Aromatic dicarboxylic acids such as 4,4′-diphenyl ketone dicarboxylic acid and functional derivatives thereof, oxyacids such as p-oxybenzoic acid and oxycaproic acid and functional derivatives thereof, adipic acid, sebacic acid, succinic acid, Examples thereof include aliphatic dicarboxylic acids such as glutaric acid and dimer acid and functional derivatives thereof, and alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid and cyclohexanedicarboxylic acid, and functional derivatives thereof.

  The glycol as a copolymerization component used when the polyester is a copolymer is diethylene glycol, 1,3-trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene. Glycols, 2-ethyl-2-butyl-1,3-propanediol, aliphatic glycols such as neopentyl glycol, dimer glycol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol 1,4-cyclohexane dimethylol, 2,5-norbornane dimethylol and other alicyclic glycols, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-β-hydroxyethoxy) Aromatic glycols such as phenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-β-hydroxyethoxyphenyl) sulfonic acid, and alkylene oxide adducts of bisphenol A, polyalkylene glycols such as polyethylene glycol and polybutylene glycol Etc.

Furthermore, examples of the polyfunctional compound as a copolymer component used when the polyester is a copolymer include trimellitic acid, pyromellitic acid, and the like as an acid component, and glycerin and pentane as glycol components. Mention may be made of erythritol. The amount of copolymerization component used should be such that the polyester remains substantially linear. Monofunctional compounds such as benzoic acid and naphthoic acid may be copolymerized.
A preferred example of the polyester resin (1) according to the present invention is a polyester in which the main structural unit is composed of ethylene terephthalate, and more preferably contains 70 mol% or more of ethylene terephthalate units. It is a copolyester containing 4-cyclohexanedimethanol and the like, particularly preferably a polyester containing 90 mol% or more of ethylene terephthalate units, which is obtained by copolymerizing the above phosphorus compound.

  The polyester resin (1) copolymerized or blended with the phosphorus compound of the present invention is a method in which the phosphorus compound is added and copolymerized during polycondensation, or at least one selected from the polyester resin and the phosphorus compound is used as an extruder, for example, Although it can be produced by a method of kneading with a twin screw extruder, it is not limited thereto.

  In the case of the copolymerization method, for example, in the case of a copolymerized polyester from terephthalic acid, ethylene glycol and a phosphorus compound, it can be produced by the following method.

  The esterification reaction product of terephthalic acid and / or an ester-forming derivative thereof and ethylene glycol can be polycondensed to be synthesized by any method employed for forming a polyester. The phosphorus compound is added at the time of production of the polyester, and the addition time can be added at any stage from the initial stage of the esterification process to the late stage of the initial condensation, but it improves the ability to deactivate the polycondensation catalyst and produces acetaldehyde. In view of the suppression of side reactions such as the above and the problem of corrosion of the reactor stand, it is preferable to add it after the end of the esterification step and later in the initial condensation.

  Preferred manufacturing conditions are as follows. That is, the esterification reaction is carried out at 230 to 250 ° C. under normal pressure to increased pressure for 0.5 to 5 hours so that the esterification reaction rate is at least 95%, preferably 98% or more. Subsequently, the first stage polycondensation is carried out at 240 to 255 ° C, preferably 240 to 250 ° C, more preferably 240 to 248 ° C and 300 to 0.1 Torr for 0.5 to 2 hours, and further 250 to 290 ° C. The polycondensation is preferably carried out at 250 to 280 ° C., more preferably at 250 to 275 ° C. to 10 to 0.1 Torr, preferably 5 to 0.1 Torr to the desired degree of polymerization. The phosphorus compound is added at any stage from the end of esterification to the end of the first stage polycondensation. It is also important to carry out the first stage polycondensation reaction at 250 ° C. or lower.

  Examples of the starting material terephthalic acid or ethylene glycol include virgin terephthalic acid derived from para-xylene or ethylene glycol derived from ethylene, as well as methanol decomposition and ethylene glycol decomposition from used PET bottles. A recovered raw material such as terephthalic acid, bishydroxyethyl terephthalate or ethylene glycol recovered by the chemical recycling method can also be used as at least a part of the starting raw material. Needless to say, the quality of the recovered raw material must be refined to a purity and quality suitable for the intended use.

  Polycondensation catalysts include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, indium, thallium, germanium, tin, lead, bismuth, scandium, yttrium, niobium, zirconium, hafnium, vanadium, chromium, One or more metal compounds selected from the group consisting of manganese, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, tellurium, tantalum, tungsten, gallium, aluminum, antimony, germanium, titanium, silicon, silver, etc. In particular, an antimony compound, a germanium compound, and a tungsten compound are most suitable because the catalytic action is hardly deactivated by the phosphorus compound.

  Specific examples of the Sb compound include antimony trioxide, antimony acetate, antimony tartrate, antimony tartrate, antimony oxychloride, antimony glycolate, antimony pentoxide, and triphenylantimony.

  Specific examples of the Ge compound include amorphous germanium dioxide, crystalline germanium dioxide, germanium tetroxide, germanium hydroxide, germanium oxalate, germanium chloride, germanium tetraethoxide, germanium tetra-n-butoxide, and germanium phosphite. And the like.

  W compounds include compounds such as tungstic acid, lithium tungstate, potassium tungstate, sodium tungstate, calcium tungstate, barium tungstate, cobalt tungstate, copper tungstate, manganese tungstate, tungsten ethoxide, ammonium tungstate, etc. Is mentioned.

  Moreover, in manufacture of the polyester resin (1) based on this invention, a basic nitrogen compound can be used for the production | generation suppression of diethylene glycol content. As the basic nitrogen compound, any of aliphatic, alicyclic, aromatic and heterocyclic nitrogen compounds may be used. 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 free form or as a salt of 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 initial polycondensation reaction is completed, and may be used alone or in combination of two or more. Good. The compounding amount of these basic nitrogen compounds is 0.01 to 1 mol%, preferably 0.05 to 0.7 mol%, more preferably 0.1 to 0.5 mol% per polyester.

  In addition, in the case of using a method of blending a phosphorus compound with a polyester resin, a method of melt-kneading the dried polyester resin and the phosphorus compound with a twin screw extruder into a chip, an aqueous solution of a phosphorus compound or an organic solvent This is possible by a method of immersing in the above solution or a method of attaching these solutions to the surface.

  The haze of a 4 mm-thick molded product obtained by injection molding the polyester resin (1) according to the present invention at 290 ° C. is 40% or less, preferably 20% or less, more preferably 10% or less, and most preferably 5% or less. Is desirable. When the haze exceeds 40%, various problems such as poor transparency of the molded article molded from the composition with the polyester resin (2) and an increase in crystallization speed occur. The polyester composition and the polyester molded product cannot be obtained. In particular, when the polyester molded body is used for an application requiring heat resistance, the haze of the molded body from the polyester resin composition is preferably 10% or less.

  As a method for suppressing the haze characteristics of the polyester resin (1) according to the present invention within the above range, a method of controlling the residual amount of the polycondensation catalyst to the following range according to each polycondensation catalyst (polyester resin (1) Sb residual amount = 50 to 190 ppm, Ge residual amount = 10 to 50 ppm, W residual amount = 10 to 250 ppm), maintaining the temperature during polycondensation at 285 ° C. or less to suppress thermal decomposition during polycondensation as much as possible A method of using a polyester resin having an IV of 0.55 deciliter / gram or more as the polyester resin (1), a method of using equipment that does not impose as much impact force on the chip as possible before crystallization or drying before molding or solid phase polymerization, etc. These methods may be combined as appropriate, but are not necessarily limited thereto.

  The intrinsic viscosity of the polyester resin (1) according to the present invention is 0.45 to 1.00 deciliter / gram, preferably 0.48 to 0.90 deciliter / gram, more preferably 0.50 to 0.85 deciliter / gram. The most preferable range is 0.55 to 0.80 deciliter / gram. When the intrinsic viscosity is 0.60 deciliter / gram or more, it is preferable to use a method in which a polymer obtained by melt polycondensation is polymerized in a solid state.

  When the intrinsic viscosity is less than 0.45 deciliter / gram, the transparency of the obtained molded article is deteriorated, and the mechanical strength does not satisfy the practical range. Further, in order to produce a polyester resin exceeding 1.00 deciliter / gram, the polycondensation time becomes very long and the cost is increased, and it is not practical from the viewpoint of economy, and a composition of the polyester resin (2) is used. During molding, kneading is incomplete, and a molded product of uniform quality cannot be obtained.

The content of aldehydes such as acetaldehyde in the polyester resin (1) is 150 ppm or less, preferably 100 ppm or less, more preferably 70 ppm or less, still more preferably 60 ppm or less, and particularly preferably 50 ppm or less. desirable. When the content of aldehydes increases, the amount of aldehydes such as a molded product formed by mixing with the polyester resin (2) described later increases, and the effect of maintaining the flavor of the contents deteriorates. Further, the lower limit of the content of aldehydes is preferably 0.1 ppb from the viewpoint of production.
The content of aldehydes is known, such as performing solid phase polymerization, reducing the oxygen concentration during polycondensation and solid phase polymerization as much as possible, and reducing the resin temperature immediately after completion of polycondensation and solid phase polymerization. It can be lowered by means.
Moreover, when adding and mix | blending a phosphorus compound with an extruder after superposition | polymerization, the increase in aldehydes can be suppressed by using an extruder with a vent.

The shape of the polyester resin (1) chip according to the present invention may be any of a cylinder shape, a square shape, a spherical shape, a flat plate shape, and the like. The average particle diameter is usually 1.0 to 4 mm, preferably 1.0 to 3.5 mm, and more preferably 1.0 to 3.0 mm. For example, in the case of a cylinder type, it is practical that the length is about 1.0 to 4 mm and the diameter is about 1.0 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. The weight of the chip is practically in the range of 2 to 40 mg / piece.
Also, conventionally known UV absorbers, antioxidants, oxygen scavengers, lubricants added from the outside, lubricants that have been precipitated internally during the reaction, mold release agents, cores to the extent that physical properties such as polymer color and hydrolyzability are not impaired. Various additives such as an agent, a stabilizer, an antistatic agent, a bluing agent, a dye, and a pigment can be used in combination.

(Polyester resin (2))
The polyester resin (2) is a thermoplastic polyester mainly obtained from an aromatic dicarboxylic acid component and a glycol component, preferably a polyester containing 55 mol% or more of an aromatic dicarboxylic acid unit of the acid component, and more preferably aromatic polyester. A polyester containing 70 mol% or more of an aromatic dicarboxylic acid unit, more preferably a polyester containing 80 mol% or more of an aromatic dicarboxylic acid unit, and particularly preferably an aromatic dicarboxylic acid unit containing an acid component. Polyester containing 90 mol% or more.

  Examples of the aromatic dicarboxylic acid component constituting the polyester resin (2) according to the present invention include aromatics such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, and diphenoxyethanedicarboxylic acid. Examples thereof include dicarboxylic acids and functional derivatives thereof.

  Examples of the glycol component constituting the polyester resin (2) according to the present invention include aliphatic glycols such as ethylene glycol, 1,3-trimethylene glycol and tetramethylene glycol, and alicyclic glycols such as cyclohexanedimethanol. It is done.

  Examples of the dicarboxylic acid used as a copolymerization component when the polyester is a copolymer include isophthalic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and 4,4′-diphenyl ether dicarboxylic acid. , Aromatic dicarboxylic acids such as 4,4′-diphenyl ketone dicarboxylic acid and functional derivatives thereof, oxyacids such as p-oxybenzoic acid and oxycaproic acid and functional derivatives thereof, adipic acid, sebacic acid, succinic acid, Examples thereof include aliphatic dicarboxylic acids such as glutaric acid and dimer acid and functional derivatives thereof, and alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid and cyclohexanedicarboxylic acid, and functional derivatives thereof.

  The glycol as a copolymerization component used when the polyester is a copolymer is diethylene glycol, 1,3-trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene. Glycols, 2-ethyl-2-butyl-1,3-propanediol, aliphatic glycols such as neopentyl glycol, dimer glycol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol 1,4-cyclohexane dimethylol, 2,5-norbornane dimethylol and other alicyclic glycols, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-β-hydroxyethoxy) Aromatic glycols such as phenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-β-hydroxyethoxyphenyl) sulfonic acid, and alkylene oxide adducts of bisphenol A, polyalkylene glycols such as polyethylene glycol and polybutylene glycol Etc.

Furthermore, examples of the polyfunctional compound as a copolymer component used when the polyester is a copolymer include trimellitic acid, pyromellitic acid, and the like as an acid component, and glycerin and pentane as glycol components. Mention may be made of erythritol. The amount of copolymerization component used should be such that the polyester remains substantially linear. Monofunctional compounds such as benzoic acid and naphthoic acid may be copolymerized.
A preferred example of the polyester resin (2) according to the present invention is a polyester whose main structural unit is composed of ethylene terephthalate, preferably 55 mol% or more, more preferably 70 mol% or more of ethylene terephthalate units, and copolymerization. It is a copolyester containing isophthalic acid, 1,4-cyclohexanedimethanol or the like as a component, and particularly preferably a polyester containing 90 mol% or more of ethylene terephthalate units.

Examples of these polyesters include polyethylene terephthalate (hereinafter abbreviated as PET), poly (ethylene terephthalate-ethylene isophthalate) copolymer, poly (ethylene terephthalate-1,4-cyclohexanedimethylene terephthalate) copolymer, poly ( Examples thereof include an ethylene terephthalate-dioxyethylene terephthalate) copolymer, a poly (ethylene terephthalate-1,3-propylene terephthalate) copolymer, and a poly (ethylene terephthalate-ethylene cyclohexylene dicarboxylate) copolymer.
Another preferred example of the polyester resin (2) according to the present invention is a polyester in which the main structural unit is composed of ethylene-2,6-naphthalate, and preferably 55 mol% of ethylene-2,6-naphthalate units. Above, more preferably a polyester containing 70 mol% or more, particularly preferably a polyester containing 90 mol% or more of ethylene-2,6-naphthalate units.

  Examples of these thermoplastic polyesters include polyethylene-2,6-naphthalate (PEN), poly (ethylene-2,6-naphthalate-ethylene terephthalate) copolymer, poly (ethylene-2,6-naphthalate-ethylene isophthalate). ) Copolymer, poly (ethylene-2,6-naphthalate-dioxyethylene-2,6-naphthalate) copolymer, and the like.

  Further, another preferred example of the polyester resin (2) according to the present invention is a polyester in which the main structural unit is composed of 1,3-propylene terephthalate, and preferably 55 mol% or more of 1,3-propylene terephthalate units. More preferably, it is a polyester containing 70 mol% or more, and particularly preferably a polyester containing 90 mol% or more of 1,3-propylene terephthalate units.

  Examples of these polyesters include polypropylene terephthalate (PTT), poly (1,3-propylene terephthalate-1,3-propylene isophthalate) copolymer, poly (1,3-propylene terephthalate-1,4-cyclohexanedimethylene). Terephthalate) copolymer and the like.

  Furthermore, other preferable examples of the polyester resin (2) according to the present invention are polyesters in which the main structural unit is composed of butylene terephthalate, preferably 55 mol% or more, more preferably 70 mol% of butylene terephthalate units. The polyester containing the above, particularly preferably a polyester containing 90 mol% or more of butylene terephthalate units.

  Examples of these polyesters include polybutylene terephthalate (PBT), poly (butylene terephthalate-butylene isophthalate) copolymer, poly (butylene terephthalate-1,4-cyclohexanedimethylene terephthalate) copolymer, poly (butylene terephthalate- 1,3-propylene terephthalate) copolymer, poly (butylene terephthalate-butylene cyclohexylene dicarboxylate) copolymer, and the like.

  The polyester resin (2) according to the present invention can basically be produced by a conventionally known melt polycondensation method or a solid state polymerization method of a prepolymer produced by this method. The melt polycondensation reaction may be performed in one stage or may be performed in multiple stages. These may be comprised from a batch-type reaction apparatus, and may be comprised from the continuous-type reaction apparatus. The melt polycondensation step and the solid phase polymerization step may be operated continuously or may be operated separately.

  Hereinafter, an example of a preferable continuous production method of the polyester resin (2) according to the present invention will be described using polyethylene terephthalate (PET) as an example, but the present invention is not limited thereto. That is, a direct esterification method in which terephthalic acid, ethylene glycol and, if necessary, other copolymerization components are directly reacted to distill off water and esterify, and then polycondensation under reduced pressure in the presence of a polycondensation catalyst, or , Produced by a transesterification method in which dimethyl terephthalate, ethylene glycol, and other copolymerization components as required are reacted to distill off methyl alcohol and transesterify, followed by polycondensation under reduced pressure in the presence of a polycondensation catalyst. Is done. In addition, in order to increase the intrinsic viscosity, and to achieve a low acetaldehyde content and a low cyclic trimer content, such as a heat-resistant container for low flavor beverages and a film for the inner surface of a metal can for beverages, The resulting melt polycondensed polyester is subsequently subjected to solid state polymerization.

  Examples of the starting materials dimethyl terephthalate, terephthalic acid or ethylene glycol include virgin dimethyl terephthalate derived from paraxylene, ethylene glycol derived from terephthalic acid or ethylene, and methanol from used PET bottles. Recovered raw materials such as dimethyl terephthalate, terephthalic acid, bishydroxyethyl terephthalate or ethylene glycol recovered by chemical recycling methods such as decomposition and ethylene glycol decomposition can also be used as at least part of the starting material. Needless to say, the quality of the recovered raw material must be refined to a purity and quality suitable for the intended use.

  The polycondensation reaction is performed using a polycondensation catalyst. As the polycondensation catalyst, a compound containing at least one element selected from the group consisting mainly of Al, Ti, Mn, Fe, Co, Zn, Nb, Mo, Cd, In, Sn, Ta, and Pb, and as required It is preferable to use at least one selected from second metal compounds such as Ge compounds, Sb compounds, and W compounds. These compounds are added to the reaction system as powders, aqueous solutions, ethylene glycol solutions, ethylene glycol slurries and the like. Al, Ti, Mn, Fe, Co, Zn, Nb, Mo, Cd, In, Sn, Ta, and Pb are preferable because they are easily deactivated by the phosphorus compound contained in the polyester resin (1). Of these, Al and Ti are particularly preferably used. The term “mainly” is mainly responsible for the polymerization activity, and means a higher polymerization rate when the same amount is polymerized alone.

  Specific examples of the Ti compound include tetraalkyl titanates such as tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, tetra-n-butyl titanate and partial hydrolysates thereof, titanium acetate, titanyl oxalate. , Titanyl ammonium oxalate, titanyl sodium oxalate, potassium titanyl oxalate, calcium titanyl oxalate, titanium strontium oxalate, etc. Titanium fluoride, potassium hexafluorotitanate, ammonium hexafluorotitanate, cobalt hexafluorotitanate, manganese hexafluorotitanate, titanium acetylacetonate, titanium and silicon or zirconium Ranaru composite oxide, a reaction product of titanium alkoxide and the phosphorus compound. The Ti compound is added so that the remaining amount of Ti in the produced polymer is in the range of 0.1 to 50 ppm.

  Specific examples of the Al compound include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, and aluminum lactate. , Carboxylates such as aluminum citrate and aluminum salicylate, inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, polyaluminum chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate and aluminum phosphonate Aluminum methoxide, Aluminum ethoxide, Aluminum n-propoxide, Aluminum iso-propoxide, Aluminum n-bub Aluminum alkoxides such as oxide and aluminum t-butoxide, aluminum chelate compounds such as aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate diiso-propoxide, and organoaluminum compounds such as trimethylaluminum and triethylaluminum And a partial hydrolyzate thereof, aluminum oxide and the like. Of these, carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred. The Al compound is added so that the remaining amount of Al in the produced polymer is in the range of 5 to 200 ppm.

  Moreover, in the manufacturing method of the polyester resin (2) based on this invention, you may use together an alkali metal compound or an alkaline-earth metal compound. The alkali metal or alkaline earth metal is preferably at least one selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba, and the use of an alkali metal or a compound thereof is preferable. More preferred. When using an alkali metal or a compound thereof, use of Li, Na, K is particularly preferable. Examples of the alkali metal and alkaline earth metal compounds include saturated aliphatic carboxylates such as formic acid, acetic acid, propionic acid, butyric acid, and succinic acid, and unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid. , Aromatic carboxylates such as benzoic acid, halogen-containing carboxylates such as trichloroacetic acid, hydroxycarboxylates such as lactic acid, citric acid and salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphorus Inorganic acid salts such as acid hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid and bromic acid, and organic sulfonates such as 1-propanesulfonic acid, 1-pentanesulfonic acid and naphthalenesulfonic acid , Organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butyl Alkoxides such as alkoxy, chelate compounds and the like acetylacetonate, hydrides, oxides, and hydroxides and the like.

The 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. The alkali metal compound or alkaline earth metal compound is added so that the residual amount of these elements in the produced polymer is in the range of 1 to 100 ppm.
The polycondensation catalyst used in the present invention is preferably used in combination with a phosphorus compound.

  The P compound used in the present invention is at least one selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. It is preferably a phosphorus compound. By using these phosphorus compounds during the polymerization of the polyester, an effect of improving the catalytic activity and an effect of improving the thermal stability of the polyester can be seen. Among these, use of a phosphonic acid-based compound is preferable because of its large catalytic activity improvement effect and polyester thermal stability improvement effect. Among the above-described phosphorus compounds, use of a compound having an aromatic ring structure is preferable because it has a large catalytic activity improvement effect and a polyester thermal stability improvement effect.

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

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

  Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds, compounds represented by the following formulas (7) to (12) are preferably used.

  Among the phosphorus compounds described above, the use of a compound having an aromatic ring structure is preferable because the effect of improving the catalytic activity is great.

  Moreover, as a phosphorus compound used by this invention, when the compound represented by following General formula (13)-(15) is used, especially the improvement effect of a catalyst activity is large and preferable.

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

As the phosphorus compound used in the present invention, in the above formula (13) ~ (15), R 1, R 4, R 5, R ⁶ is a group having an aromatic ring structure is particularly preferable.

  Examples of the phosphorus compound used in the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl phosphophosphonate, diethyl benzylphosphonate, diphenylphosphinic acid, diphenyl. Examples thereof include methyl phosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate, diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide. Of these, dimethyl phenylphosphonate and diethyl benzylphosphonate are particularly preferred.

  Among the phosphorus compounds described above, it is particularly preferable to use a phosphorus compound having a phenol moiety in the same molecule as the phosphorus compound used in the present invention. The phosphorus compound having a phenol moiety in the same molecule is not particularly limited as long as it is a phosphorus compound having a phenol structure, but a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound having a phenol moiety in the same molecule. Use of one or more compounds selected from the group consisting of a compound, a phosphonous acid compound, a phosphinic acid compound, and a phosphine compound is preferable because the effect of improving the catalytic activity is great. Among these, the use of a phosphonic acid compound having one or two or more phenol moieties in the same molecule is particularly preferable because the effect of improving catalytic activity is particularly large.

  Moreover, as a phosphorus compound which has the phenol part used by this invention in the same molecule, since catalyst activity improves especially, it is preferable to use the compound represented by the following general formula (16)-(18).

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

  Examples of the phosphorus compound having a phenol moiety used in the present invention in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, and diphenyl p-hydroxyphenylphosphonate. Bis (p-hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, phenyl bis (p-hydroxyphenyl) phosphinate, p-hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, p-hydroxyphenylphenylphosphinic acid phenyl, p-hydroxyphenylphosphinic acid, p-hydroxyphenylphosphinic acid methyl, p-hydroxyphenylphosphinic acid phenyl, bis (p- Rokishifeniru) phosphine oxide, tris (p- hydroxyphenyl) phosphine oxide, bis (p- hydroxyphenyl) methyl phosphine oxide, and the following equation (19), and the like compounds represented by - (22). Among these, a compound represented by the following formula (21) and dimethyl p-hydroxyphenylphosphonate are particularly preferable.

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

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

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

Further, among the above-described phosphorus compounds, when the metal portion of the metal salt is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn, the catalytic activity is improved. Is preferable. Of these, Li, Na, and Mg are particularly preferable.

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

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

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

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

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

Examples of R ¹ include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R ³ O ⁻ include hydroxide ions, alcoholate ions, acetate ions, and acetylacetone ions.

  Among the phosphorus compounds described above, the use of a compound having an aromatic ring structure is preferable because the effect of improving the catalytic activity is great.

  Among the above formulas (24), it is preferable that M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, and Mg are particularly preferable.

  Examples of the metal salt compound of phosphorus used in the present invention include lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [ethyl (1-naphthyl) methylphosphonate], Potassium [(2-naphthyl) methylphosphonate ethyl], magnesium bis [(2-naphthyl) methylphosphonate ethyl], lithium [benzylphosphonate ethyl], sodium [benzylphosphonate ethyl], magnesium bis [benzylphosphonate ethyl], Beryllium bis [benzyl phosphonate], strontium bis [benzyl phosphonate], manganese bis [ethyl benzyl phosphonate], sodium benzyl phosphonate, magnesium bis [benzyl phosphonate], sodium [( -Anthryl) methylphosphonate ethyl], magnesium bis [(9-anthryl) methylphosphonate ethyl], sodium [ethyl 4-hydroxybenzylphosphonate], magnesium bis [4-hydroxybenzylphosphonate ethyl], sodium [4-chlorobenzyl] Phenyl phosphonate], magnesium bis [4-chlorobenzylphosphonate ethyl], sodium [methyl 4-aminobenzylphosphonate], magnesium bis [4-aminobenzylphosphonate methyl], sodium phenylphosphonate, magnesium bis [phenylphosphone] Acid ethyl], zinc bis [ethyl phenylphosphonate] and the like. Among these, lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [ethyl (1-naphthyl) methylphosphonate], lithium [ethyl benzylphosphonate], Sodium [ethyl benzylphosphonate], magnesium bis [ethyl benzylphosphonate], sodium benzylphosphonate and magnesium bis [benzylphosphonic acid] are particularly preferred.

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

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

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

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

  Among the above formulas (25) or (26), when M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu and Zn, the effect of improving the catalytic activity is obtained. Largely preferred. Of these, Li, Na, and Mg are particularly preferable.

  Specific phosphorus metal salt compounds used in the present invention include lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-]. Ethyl hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], potassium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di- tert-butyl-4-hydroxybenzylphosphonate methyl], strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], barium bis [3,5-di -Tert-butyl-4-hydroxybenzylphosphonate phenyl], manganese bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], nickel bis [3,5-di-tert-butyl-4] -Ethyl ethyl hydroxybenzylphosphonate], copper bis [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], zinc bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate] ] Etc. are mentioned. Among these, lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [ Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

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

  Among the phosphorus compounds described above, the use of a compound having an aromatic ring structure is preferable because the effect of improving the catalytic activity is great.

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

(In Formula (27), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a hydrocarbon group having 1 to 50 carbon atoms. R ² represents Hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, n represents an integer of 1 or more, and the hydrocarbon group is an alicyclic structure such as cyclohexyl, It may contain a branched structure or an aromatic ring structure such as phenyl or naphthyl.)

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

  Among the phosphorus compounds described above, the use of a compound having an aromatic ring structure is preferable because the effect of improving the catalytic activity is great.

  Examples of the phosphorus compound having at least one P-OH bond used in the present invention include (1-naphthyl) methylphosphonic acid ethyl, (1-naphthyl) methylphosphonic acid, (2-naphthyl) methylphosphonic acid ethyl, benzylphosphonic acid ethyl, Benzylphosphonic acid, ethyl (9-anthryl) methylphosphonate, ethyl 4-hydroxybenzylphosphonate, ethyl 2-methylbenzylphosphonate, phenyl 4-chlorobenzylphosphonate, methyl 4-aminobenzylphosphonate, 4-methoxybenzylphosphone Examples include ethyl acid. Of these, ethyl (1-naphthyl) methylphosphonate and ethyl benzylphosphonate are particularly preferred.

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

(In the formula (28), R ¹ and R ² each independently represent hydrogen, a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl. Represents a hydrocarbon group containing 1 to 50 carbon atoms, and n represents an integer equal to or greater than 1. The hydrocarbon group includes an alicyclic structure such as cyclohexyl, a branched structure, and an aromatic ring structure such as phenyl or naphthyl. May be good.)

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

(In Formula (29), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group containing 1 to 50 carbon atoms. The hydrocarbon group is an alicyclic ring such as cyclohexyl. It may contain a structure, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

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

  Specific phosphorus compounds having at least one P—OH bond used in the present invention include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4. -Methyl hydroxybenzylphosphonate, isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, phenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert -Octadecyl butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid and the like. Of these, ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

  As a preferable phosphorus compound used by this invention, the phosphorus compound represented by Chemical formula (30) is mentioned.

(In the formula (30), R ¹ represents a hydrocarbon group having ¹ to 49 carbon atoms, or a hydrocarbon group having ¹ to 49 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and R ² , R ³ Each independently represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and the hydrocarbon group includes an alicyclic structure, a branched structure or an aromatic ring structure. You may go out.)

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

  Specific examples of these phosphorus compounds are shown below.

  Moreover, since the phosphorus compound used by this invention has a large molecular weight, since an effect is difficult to distill off at the time of superposition | polymerization, an effect is large and preferable.

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

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

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

(In said formula (38), R < ³ >, R < ⁴ > represents a C1-C50 hydrocarbon group containing hydrogen, a C1-C50 hydrocarbon group, a hydroxyl group, or an alkoxyl group each independently. Hydrocarbon group. May contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

Examples of R ³ and R ⁴ include short chain aliphatic groups such as hydrogen, methyl and butyl groups, long chain aliphatic groups such as octadecyl, phenyl groups, naphthyl groups, substituted phenyl groups and naphthyl groups. An aromatic group such as a group, a group represented by —CH ₂ CH ₂ OH, and the like.

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

  Among the phosphorus compounds described above, a phosphorus compound particularly preferable to be used in the present invention is at least one phosphorus compound selected from compounds represented by the chemical formulas (39) and (40).

  As the compound represented by the chemical formula (39), Irganox 1222 (manufactured by Ciba Specialty Chemicals) is commercially available, and as the compound represented by the chemical formula (40), Irganox 1425 (Ciba Specialty Chemicals) Are available on the market.

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

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

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

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

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

  Examples of the aluminum salt of the phosphorus compound used in the present invention include an aluminum salt of ethyl (1-naphthyl) methylphosphonate, an aluminum salt of (1-naphthyl) methylphosphonic acid, an aluminum salt of ethyl (2-naphthyl) methylphosphonate, and benzylphosphone. Aluminum salt of ethyl acid, aluminum salt of benzylphosphonic acid, aluminum salt of ethyl (9-anthryl) methylphosphonate, aluminum salt of ethyl 4-hydroxybenzylphosphonate, aluminum salt of ethyl 2-methylbenzylphosphonate, 4-chloro Aluminum salt of phenyl benzylphosphonate, aluminum salt of methyl 4-aminobenzylphosphonate, aluminum salt of ethyl 4-methoxybenzylphosphonate, aluminum salt of ethyl phenylphosphonate It is below. Among these, an aluminum salt of ethyl (1-naphthyl) methylphosphonate and an aluminum salt of ethyl benzylphosphonate are particularly preferable.

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

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

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

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

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

  Examples of the aluminum salt of the specific phosphorus compound used in the present invention include aluminum salt of ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzyl. Aluminum salt of methyl phosphonate, aluminum salt of isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, aluminum salt of phenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3 , 5-di-tert-butyl-4-hydroxybenzylphosphonic acid aluminum salt and the like. Of these, the aluminum salt of ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and the aluminum salt of methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

  Examples of the second metal compound that can be used for producing the polyester resin (2) according to the present invention include lithium, sodium, magnesium, calcium, antimony, germanium, tantalum, tungsten, zirconium, hafnium, silicon, iron, nickel, and gallium. And their compounds.

  The use of these compounds in combination within the range of addition amounts that do not cause problems in the product, such as the characteristics, processability, and color tone of the polyester resin (2) as described above, leads to productivity by shortening the polycondensation time. It is effective and preferable in improving.

  The intrinsic viscosity of the polyester resin (2) according to the present invention, particularly the polyester resin (2) in which the main repeating unit is composed of ethylene terephthalate, is 0.55 to 1.50 deciliter / gram, preferably 0.60 to 1. .30 deciliter / gram, more preferably 0.65 to 1.00 deciliter / gram, most preferably 0.70 to 0.85 deciliter / gram. When the intrinsic viscosity of the polyester resin is less than 0.55 deciliter / gram, the mechanical properties of the obtained molded article and the like are poor. In addition, when the intrinsic viscosity of the polyester resin exceeds 1.50 deciliters / gram, a free low molecular weight compound that affects the fragrance retention is caused by the resin temperature becoming high at the time of melting by a molding machine or the like, resulting in severe thermal decomposition. Problems such as an increase and the molded body are colored yellow occur.

  The intrinsic viscosity of the polyester resin (2) according to the present invention, particularly the polyester resin (2) in which the main repeating unit is composed of 1,3-propylene terephthalate is 0.50 to 1.30 deciliter / gram. , Preferably 0.55 to 1.20 deciliter / gram, more preferably 0.60 to 1.00 deciliter / gram. If the intrinsic viscosity is less than 0.50 deciliter / gram, the elastic recovery and durability of the obtained molded article are deteriorated, which is a problem. The upper limit of the intrinsic viscosity is 1.30 deciliters / gram. If the upper limit is exceeded, the resin temperature becomes high at the time of molding of the molded article, the thermal decomposition becomes severe, the molecular weight is drastically lowered, and it is colored yellow. Such problems occur.

  The intrinsic viscosity of the polyester resin (2) according to the present invention, particularly the polyester resin (2) in which the main repeating unit is composed of ethylene-2,6-naphthalate, is preferably 0.40 to 1.00 deciliter / gram, Is in the range of 0.42 to 0.90 deciliter / gram, more preferably 0.45 to 0.80 deciliter / gram. When the IV is less than 0.40 deciliter / gram, the mechanical properties of the obtained molded article are poor. In addition, when it exceeds 1.00 deciliter / gram, it becomes necessary to increase the resin temperature at the time of melting by a molding machine or the like, so that thermal decomposition is accompanied, and free low molecular weight compounds that affect the fragrance retention Problems such as an increase and the molded body are colored yellow occur.

  The content of dialkylene glycol copolymerized with the polyester resin (2) according to the present invention is preferably 0.5 to 7.0 mol%, more preferably 1.0, of the glycol component constituting the polyester. It is desirable to be -6.0 mol%, more preferably 1.0-5.0 mol%. When the amount of dialkylene glycol exceeds 7.0 mol%, the thermal stability is deteriorated, the decrease in molecular weight becomes large during molding, and the increase in the content of aldehydes is unfavorable. Further, in order to produce a polyester having a dialkylene glycol content of less than 0.5 mol%, it is necessary to select uneconomical production conditions as transesterification conditions, esterification conditions or polymerization conditions, which is costly. Do not fit. Here, the dialkylene glycol copolymerized in the polyester, for example, in the case of a polyester whose main structural unit is ethylene terephthalate, is a diethylene glycol produced as a by-product during production from ethylene glycol, which is glycol. Among them, diethylene glycol (hereinafter abbreviated as DEG) copolymerized with the polyester, and in the case of a polyester having 1,3-propylene terephthalate as a main constituent unit, is glycol 1 Of di (1,3-propylene glycol) (or bis (3-hydroxypropyl) ether) by-produced from 1,3-propylene glycol during production, di (1,3-propylene) copolymerized with the polyester Glycol (hereinafter referred to as DPG).

  The diethylene glycol content copolymerized with the polyester resin (2) according to the present invention, in particular, the polyester whose main repeating unit is composed of ethylene terephthalate is 1.0% of the glycol component constituting the polyester resin. It is desirable that the amount is ˜5.0 mol%, preferably 1.3 to 4.5 mol%, more preferably 1.5 to 4.0 mol%. When the diethylene glycol content exceeds 5.0 mol%, the thermal stability is deteriorated, the decrease in molecular weight during molding is increased, and the increase in the acetaldehyde content is increased. Moreover, when diethylene glycol content is less than 1.0 mol%, the transparency of the obtained molded object worsens.

  In addition, it is desirable that the 5 mm-thick molded article obtained by injection molding the polyester resin (2) according to the present invention has a haze of 30% or less, preferably 20% or less, and more preferably 10% or less. When the haze of the molded body exceeds 30%, the transparency of the molded body from the polyester resin composition with the polyester resin (1) is deteriorated, which becomes a problem.

  Moreover, the crystallization temperature (Tc1) at the time of temperature rising of the molded body obtained by injection molding the polyester resin (2) according to the present invention is 150 to 180 ° C, preferably 152 to 175 ° C, more preferably 155 to 170. It is preferably in the range of ° C.

  In addition, the content of aldehydes such as acetaldehyde in the polyester resin (2) according to the present invention is 50 ppm or less, preferably 30 ppm or less, more preferably 10 ppm or less. When the aldehyde content exceeds 50 ppm, the effect of flavor retention of the contents such as a molded article molded from the polyester resin composition is deteriorated. Further, these lower limits are preferably 0.1 ppb from the viewpoint of production.

  Here, the aldehydes are acetaldehyde when the polyester is a polyester having ethylene terephthalate as a main constituent unit, and allylaldehyde in the case of a polyester having 1,3-propylene terephthalate as a main constituent unit. It is.

  Further, when the polyester resin (2) according to the present invention is a polyester resin having ethylene terephthalate as a main repeating unit, and the polyester resin composition comprising this is used as a material for a container for low flavor beverages such as mineral water. The acetaldehyde content is desirably 10 ppm or less, preferably 6 ppm or less, and more preferably 4 ppm or less.

  The content of the cyclic ester oligomer of the polyester resin (2) according to the present invention is 70% or less, preferably 60% or less, more preferably 50% of the content of the cyclic ester oligomer contained in the polyester melt polycondensate. Hereinafter, it is particularly preferably 35% or less. The lower limit of the cyclic ester oligomer content is 20% or more, preferably 22% or more, more preferably 25% or more of the cyclic ester oligomer content contained in the melt polycondensate from the viewpoint of economical production. In addition, the content of the cyclic ester oligomer contained in the melt polycondensate of the polyester resin (2) is a free polycondensate present in the polyester resin (2) having a melt polycondensation number average molecular weight of about 5000 or more. The content of the cyclic n-mer having the highest content among several cyclic ester oligomers. In the case where the polyester resin (2) according to the present invention is PET, which is a representative polyester having ethylene terephthalate as a main structural unit, the cyclic n-mer is a cyclic trimer, and melt polycondensation. Since the content of the cyclic trimer of the polyester is about 1.0% by weight, the content of the cyclic trimer is preferably 0.70% by weight or less, more preferably 0.50% by weight or less, and still more preferably Is preferably 0.40% by weight or less. When a heat-resistant hollow molded article or the like is molded from the polyester resin composition of the present invention, heat treatment is performed in a heating mold, but when the cyclic trimer content is 0.70% by weight or more, heating is performed. The adhesion of the oligomer to the mold surface increases rapidly, and the transparency of the obtained hollow molded article is very deteriorated.

  The shape of the polyester resin (2) chip according to the present invention may be any of a cylinder shape, a square shape, a spherical shape or a flat plate shape. The average particle diameter is usually 1.0 to 4 mm, preferably 1.0 to 3.5 mm, and more preferably 1.0 to 3.0 mm. For example, in the case of a cylinder type, it is practical that the length is about 1.0 to 4 mm and the diameter is about 1.0 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. The weight of the chip is practically in the range of 2 to 40 mg / piece.

(Polyester resin composition)
The polyester resin composition of the present invention is a polyester resin composition containing the polyester resin (1) and the polyester resin (2) as main components. The mixing ratio of the polyester resin (1) and the polyester resin (2) constituting the polyester resin composition of the present invention is 0.01 weight of the polyester resin (1) with respect to 100 parts by weight of the polyester resin (2). Parts to 10 parts by weight are preferred. When the blending amount of the polyester resin (1) is less than 0.01 parts by weight, the polycondensation catalyst contained in the polyester resin (2) cannot be sufficiently deactivated, and the resulting molded article contains acetaldehyde. The amount becomes very large, which affects the flavor retention and becomes a problem. In addition, the cyclic ester oligomer content of the molded body is extremely increased, and the mold contamination during continuous molding becomes severe. For this reason, the problem that the molded object excellent in transparency cannot be obtained arises. Moreover, when the compounding quantity of the said polyester resin (1) exceeds 10 weight part, the problem that the heat resistance of the obtained molded object worsens or it is colored yellow and the commercial value falls arises.

Preferred catalyst combinations used primarily in the polyester compositions of the present invention are:
Polyester resin (1) Polyester resin (2)
Ge Al
Ge Ti
Sb Al
Sb Ti
Is preferred.

  The polyester resin (1) and the polyester resin (2) preferably have substantially the same resin composition. Here, “substantially the same” means that the difference in composition is 10 mol% or less, preferably 8 mol% or less, more preferably 6 mol% or less, still more preferably 4 mol% or less, particularly preferably 3 mol% or less. Preferably it is 2 mol% or less. In the case of dialkylene glycol derived from alkylene glycol used in polyester resin (1) and polyester resin (2), the difference in composition is 15 mol% or less, preferably 12 mol% or less, more preferably 10 mol% or less, More preferably, it may be 8 mol% or less, particularly preferably 6 mol% or less, and most preferably 5 mol% or less.

  The content of aldehydes in the polyester resin composition of the present invention is 30 ppm or less, preferably 20 ppm or less, more preferably 10 ppm or less, and further preferably 5 ppm or less. When the content of aldehydes is 30 ppm or more, the flavor and odor of contents such as containers molded from this polyester resin composition are deteriorated. In particular, when the polyester resin according to the present invention is a polyester resin in which the main repeating unit is composed of ethylene terephthalate, the polyester resin composition comprising this is used as a material for a container for low flavor beverages such as mineral water. The content of aldehydes in the polyester resin composition is 10 ppm or less, preferably 8 ppm or less, more preferably 6 ppm or less, and most preferably 5 ppm or less.

  In general, a polyester resin contains a copolymer component and a fine powder having the same copolymer component content as that of a polyester chip, that is, a fine or film-like material in an amount of several hundred ppm to about several weight%. It is out. As described above, such fines have the property of promoting crystallization of polyester, and when present in a large amount, the transparency of the polyester molded body molded from the polyester resin composition containing the fines is low. Various problems as described above occur, such as being very bad.

  In the present invention, the fine content of the polyester resin composition is 0.1 to 5000 ppm, preferably 0.1 to 3000 ppm, more preferably 0.1 to 1000 ppm, still more preferably 0.1 to 500 ppm, and most preferably 0. .1 to 100 ppm. In order to reduce the fine content in the polyester resin composition of the present invention to less than 0.1 ppm, it is necessary to spend considerable equipment costs such as installing a number of fine removal devices in the production equipment, which is economical. It is a problem in terms of sex. In addition, for example, in the case of PET, when the content of fine in the polyester resin composition of the present invention is less than 0.1 ppm, the crystallization rate becomes very slow. As a result, the amount of shrinkage of the plug portion does not fall within the specified range, and capping becomes impossible, and the stretched heat-fixing mold for molding the heat-resistant hollow molded container is contaminated. In order to obtain a violent and transparent hollow molded container, the mold must be frequently cleaned. Moreover, when it exceeds 5000 ppm in the polyester resin composition of this invention, while the crystallization speed | rate becomes quicker than necessary, the fluctuation | variation of the speed | rate will also become large. Therefore, in the case of a sheet-like material, the transparency and the surface state are deteriorated, and when this is stretched, the thickness unevenness is deteriorated. Further, in the case of a molded body, the transparency becomes worse, and transparent spots and crystallization speed spots are generated, which is a problem. For example, in the case of a hollow molded body of PET, the degree of crystallinity of the plug part is excessive and fluctuated, and therefore the amount of shrinkage of the plug part does not fall within the specified value range, resulting in poor capping of the plug part. Leakage of the contents occurs, and the preform for the hollow molded body is whitened, so that normal stretching is impossible. In particular, when the polyester resin composition is used as a heat resistant hollow molded article, the fine content is preferably 0.1 to 500 ppm.

  As a method of reducing the fine content to the above range, for example, it can be reduced by changing the opening of the decoration in the fine removal process, or by controlling the processing time in the fine removal process, Further, any method such as by changing the sieving speed can be used.

  Such fine and film-like materials may include those having a melting point higher by about 5 to 20 ° C. than the normal melting point. When using a feeding device that applies impact force or shear force to a melt polycondensation polyester chip or a solid-state polymerization polyester chip, or a stirrer that applies shear force to the chip, a melting point that is about 5 to 20 ° C. higher than the normal melting point Very fine and film-like materials are generated. This is presumably because the chip generates heat due to a large force such as impact force applied to the chip surface, and at the same time, oriented crystallization of polyester occurs on the chip surface, resulting in a dense crystal structure. When such a polyester containing a high melting point fine or the like is further subjected to solid phase polymerization or contact treatment with water, the melting point of the fine or the like may be further increased. When the polyester resin (2) of the present invention is PET, fine and film-like materials having a melting point exceeding 260 ° C. are problematic.

  Therefore, a specific example of a method for preventing the polyester resin composition of the present invention from containing such fines will be described below. In the case of a melt polycondensed polyester resin, as described above, a method of extruding the molten polyester from the die after the melt polycondensation into the water and cutting it in the water, or a method of extruding it in the air and immediately cooling it with cooling water After draining the polyester chip formed into a chip shape, and then removing the chip, fine and film-like shapes other than the predetermined size by the vibration sieving process and the airflow classification process by the gas flow, or the water washing process process, Examples thereof include a method of sending to a storage tank by a plug transport system or a bucket type transport system. It is preferable that the chip is extracted from the tank by a device such as a screw feeder that does not apply a shearing force to the chip, and transported to the next process by a plug transport system or a bucket conveyor transport system. In the case of subsequent solid-phase polymerization, it is desirable to perform a fine removal process by providing an airflow classifier using an air flow or a vibration sieving apparatus immediately before the solid-phase polymerization step.

  For solid-phase polymerization, do not use a solid-phase polymerization apparatus that applies a large shearing force or impact force to the chip, such as a rotary heating blender or a solid-phase polymerization apparatus with a stirrer for stirring the chip. It is desirable to make it.

  Most of the transportation of melt-polycondensed prepolymer chips and polyester chips after solid-phase polymerization adopts the plug transport system and bucket-type conveyor transport system, and the chip extraction from the crystallizer and solid-state polymerization reactor It is desirable to use an apparatus that can suppress the impact between the chip and process equipment, transportation piping, and the like as much as possible by using a screw feeder. In particular, when the polyester resin (2), which is the main component of the polyester resin composition, is produced, it is necessary to take the various measures described above.

  When the polyester resin (2) according to the present invention is a polyester resin in which the main repeating unit is composed of ethylene terephthalate, the content of the cyclic trimer of the polyester resin composition of the present invention is 0.70 weight. % Or less, preferably 0.60% by weight or less, more preferably 0.50% by weight or less. When molding a heat-resistant molded article or the like from the polyester resin composition of the present invention, heat treatment is performed in a heating mold or the like. If the content of the cyclic trimer exceeds 0.70% by weight, heating is performed. The adhesion of the oligomer to the mold surface increases rapidly, and the transparency of the resulting molded product is very deteriorated. In particular, in the case of a heat-resistant hollow molded article, the content of the cyclic trimer is desirably 0.40% by weight or less.

  When the polyester is a polyester mainly composed of ethylene terephthalate, the acetaldehyde content of the molded product obtained by injection molding the polyester resin composition of the present invention is 50 ppm or less, preferably 30 ppm or less, more preferably 10 ppm. The following is desirable. When the acetaldehyde content exceeds 50 ppm, the effect of flavor retention of contents such as a molded article molded from this polyester resin composition is deteriorated. Further, these lower limits are preferably 0.1 ppb from the viewpoint of production. In particular, when used as a material for containers for low flavor beverages such as mineral water, the acetaldehyde content is desirably 13 ppm or less, preferably 10 ppm or less, and more preferably 8 ppm or less.

  When the polyester is a polyester having ethylene terephthalate as a main structural unit, the crystallization temperature at the time of temperature rise of a test piece from a molded product having a thickness of 2 mm obtained by injection molding the polyester resin composition of the present invention. (Hereinafter referred to as “Tc1”) is in the range of 150 to 175 ° C., preferably in the range of 152 to 172 ° C., more preferably in the range of 155 to 170 ° C. When Tc1 exceeds 175 ° C., the heating crystallization rate becomes very slow, the crystallization of the hollow molded body plug portion becomes insufficient, and the problem of leakage of contents occurs. On the other hand, when Tc1 is less than 150 ° C., the transparency of the hollow molded body is lowered, which causes a problem.

  The polyester resin composition of the present invention comprises, for example, a method using a polyester resin (1) having a haze of 40% or less by the following measurement method, and a polyester resin (2) having a haze of 30% or less. A method using a polyester resin composition, a method in which a polyester resin (1) and a polyester resin (2) are melt-mixed by a twin screw extruder, and a polyester having a fine content in the range of 0.1 to 5000 ppm as described below. Although it can obtain by the method of using a resin composition, the method of combining these methods, etc., it is not limited to these.

  The polyester resin composition of the present invention can be obtained by mixing the polyester resin (1) and the polyester resin (2) by a conventionally known method. For example, the polyester resin (1) and the polyester resin (2) are dry blended with a tumbler, V-type blender, Henschel mixer, etc., and the dry blended mixture is a single screw extruder, twin screw extruder, kneader For example, a method of melt-mixing at least once, and a method of solid-phase polymerization of the melted mixture under a high vacuum or an inert gas atmosphere as necessary may be mentioned.

  The polyester resin composition of the present invention may be blended with at least one resin selected from the group consisting of polyolefin resin, polyamide resin, polyacetal resin, and polybutylene terephthalate resin in an amount of 0.1 ppb to 1000 ppm. Good. The blending ratio of the thermoplastic resin such as the polyolefin resin in the polyester resin composition of the present invention is 0.1 ppb to 1000 ppm, preferably 0.3 ppb to 100 ppm, more preferably 0.5 ppb to 1 ppm, and still more preferably 0. .5 ppb to 45 pbb. When the blending amount is less than 0.1 ppb, the crystallization speed becomes very slow and the crystallization of the plug part of the hollow molded body becomes insufficient. Therefore, if the cycle time is shortened, the shrinkage amount of the plug part is specified. Since it does not fall within the range of values, capping defects occur, and the stretched heat-fixed mold that forms a heat-resistant hollow molded body is heavily soiled, and when trying to obtain a transparent hollow molded body, the mold is frequently cleaned. There must be. If it exceeds 1000 ppm, the crystallization speed will be high, and the crystallization of the plug part of the hollow molded body will be excessive, and the amount of shrinkage and shrinkage of the plug part will not fall within the specified range, resulting in capping failure. Leakage occurs, and the preform for the hollow molded body is whitened, so that normal stretching is impossible. Also, in the case of a sheet-like material, if it exceeds 1000 ppm, the transparency becomes very poor, the stretchability is also impaired and normal stretching is impossible, and only a stretched film with large thickness unevenness and poor transparency is obtained. I can't.

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

  As the polyamide resin blended in the polyester resin composition of the present invention, 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 MXD6, nylon 6 / MXD6, nylon MXD6 / MXDI, nylon 6/66, nylon 6/610, nylon 6/12, nylon 6 / 6T, nylon 6I / 6T, and the like. These resins may be crystalline or amorphous.

  In addition, the production of a polyester resin composition containing a thermoplastic resin such as the polyolefin resin can be carried out by directly adding the thermoplastic resin to the polyester resin (2) so that its content falls within the above range. In addition to the method of adding a conventional method such as a method of adding and melting and kneading as a master batch, the thermoplastic resin is used in the production stage of the polyester resin (2), for example, at the time of melt polycondensation, immediately after melt polycondensation, Immediately after pre-crystallization, at the time of solid-phase polymerization, immediately after solid-phase polymerization, or until it reaches the molding stage after finishing the production stage, etc. Or after mixing by the method of making it contact with the said thermoplastic resin member under the flow conditions of the chip | tip of a polyester resin (2), the method of melt-kneading etc. can also be used.

  The polyester resin composition of the present invention can be preferably used as a hollow molded article, a tray, a packaging material such as a biaxially stretched film, a film for covering a metal can, a fiber containing a monofilament, and the like. Moreover, the polyester resin composition of this invention can be used also as 1 component layers, such as a multilayer molded object and a multilayer film.

  The polyester resin composition of the present invention can be used to mold films, sheets, containers, and other packaging materials using commonly used melt molding methods. Moreover, it is possible to improve mechanical strength by extending | stretching the sheet-like material which consists of a polyester resin composition of this invention at least to a uniaxial direction. The stretched film comprising the polyester resin composition of the present invention is a sheet-like material obtained by injection molding or extrusion molding, and is usually selected from uniaxial stretching, sequential biaxial stretching, and simultaneous biaxial stretching used for PET stretching. The stretching method is used. It can also be formed into a cup shape or a tray shape by pressure forming or vacuum forming.

Below, the concrete manufacturing method about the various uses in the case of PET is demonstrated easily.
In producing a stretched film, the stretching temperature is usually 80 to 130 ° C. Stretching may be uniaxial or biaxial, but biaxial stretching is preferred from the viewpoint of film physical properties. In the case of uniaxial stretching, the stretching ratio is usually 1.1 to 10 times, preferably 1.5 to 8 times. In the case of biaxial stretching, the longitudinal and transverse directions are usually 1.1 to 8 times, respectively. Preferably, it may be performed in a range of 1.5 to 5 times. The vertical / horizontal magnification is usually 0.5 to 2, preferably 0.7 to 1.3. The obtained stretched film can be further heat-set to improve heat resistance and mechanical strength. The heat setting is usually performed under tension at 120 to 240 ° C., preferably 150 to 230 ° C., usually for several seconds to several hours, preferably several tens of seconds to several minutes.

  In producing the hollow molded body, the blow molded from the polyester resin composition of the present invention is stretch blow molded, and an apparatus conventionally used in blow molding of PET can be used. Specifically, for example, once a preform is formed by injection molding or extrusion molding, the plug part and the bottom part are processed as it is, and then reheated, and then 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 of the molding machine and the nozzle is usually in the range of 260 to 300 ° C. The stretching temperature is usually 70 to 120 ° C., preferably 90 to 110 ° C., and the stretching ratio is usually 1.5 to 3.5 times in the longitudinal direction and 2 to 5 times in the circumferential direction. The obtained hollow molded body can be used as it is, but in particular in the case of beverages that require hot filling, such as fruit juice beverages and oolong teas, in general, heat-setting treatment is performed in a blow mold, Used to impart sex. The heat setting is usually performed at 100 to 200 ° C., preferably 120 to 180 ° C. for several seconds to several hours, preferably several seconds to several minutes, under tension by compressed air or the like.

  In addition, in order to impart heat resistance to the plug part, the plug part of the preform obtained by injection molding or extrusion molding is crystallized in a far-infrared or near-infrared heater installation oven, or after the bottle is molded The stopper is crystallized with the heater.

  The polyester resin composition of the present invention includes, in addition to the above-mentioned added amount of thermoplastic resin, other thermoplastic resins such as gas barrier polyamides such as gas barrier polyesters, ultraviolet absorbing polyesters, and xylylene group-containing polyamides. An appropriate amount of a resin or the like can be blended as necessary within a range that does not impair the effects of the present invention.

  In addition, the polyester resin composition of the present invention includes a known ultraviolet absorber, antioxidant, oxygen scavenger, lubricant added from the outside, lubricant precipitated inside the reaction, mold release agent, nucleating agent as necessary. Various additives such as stabilizers, antistatic agents, bluing agents, dyes and pigments may be blended.

  In addition, when the polyester resin composition of the present invention is used for a film application, in order to improve handling properties such as slipperiness, rollability, and blocking resistance, calcium carbonate, magnesium carbonate, barium carbonate, Inorganic particles such as calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, and magnesium phosphate, organic salt particles such as calcium oxalate, calcium, barium, zinc, manganese, magnesium, terephthalate, divinylbenzene, styrene, acrylic acid Inactive particles such as cross-linked polymer particles such as methacrylic acid, acrylic acid, or vinyl monomers of methacrylic acid alone or as a copolymer may be contained.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. (1) Intrinsic viscosity of polyester (hereinafter referred to as “IV”)
It calculated | required from the solution viscosity at 30 degreeC in a 1,1,2,2-tetrachloroethane / phenol (2: 3 weight ratio) mixed solvent.
As a sample for measuring the intrinsic viscosity of the polyester chip, the polyester is frozen and ground for measurement.

(2) Acetaldehyde content of polyester (hereinafter referred to as “AA content”)
Sample / distilled water = 0.2 to 1 g / 2 cc of glass ampoule substituted with nitrogen was sealed and subjected to extraction treatment at 160 ° C for 2 hours. After cooling, acetaldehyde in the extract was subjected to high-sensitivity gas chromatography. The concentration was measured by chromatography and the concentration was expressed in ppm.

(3) Diethylene glycol content of polyester (hereinafter referred to as [DEG content])
It decomposed | disassembled with methanol and quantified DEG content by gas chromatography, and represented with the ratio (mol%) with respect to all the glycol components.

(4) Polyester cyclic trimer content (hereinafter referred to as “CT content”)
The sample is frozen and crushed or chopped, dissolved in a hexafluoroisopropanol / chloroform mixture, and further diluted with chloroform. Methanol is added to this to precipitate the polymer and then filtered. The filtrate was evaporated to dryness, made constant with dimethylformamide, and a cyclic trimer composed of ethylene terephthalate units was quantified by liquid chromatography. The said operation is repeated 5 times and let the average value be CT content.

(5) Measurement of Fine Content About 0.5 kg of resin is sieved with a wire mesh having a nominal size of 5.6 mm according to JIS-Z8801 (A) and a screen having a diameter of 1.7 mm (diameter) 20 cm) (B) was placed on a sieve combined in two stages, and sieved at 1800 rpm for 1 minute with a swing type sieve shaker SNF-7 manufactured by Terraoka. This operation was repeated and a total of 20 kg of resin was sieved. However, when the fine content is small, the amount of the sample is appropriately changed.

    The fine sieved under the sieve (B) is washed with a 0.1% aqueous cationic surfactant solution, then washed with ion-exchanged water, and filtered through a G1 glass filter manufactured by Iwaki Glass Co., Ltd. It was. These were dried together with a glass filter in a dryer at 100 ° C. for 2 hours, then cooled and weighed. Again, the same operations of washing and drying with ion-exchanged water were repeated to confirm that the weight became constant, and the weight of the glass filter was subtracted from this weight to obtain the fine weight. The fine content is the fine weight / the total resin weight that has been sieved.

(6) Average density of polyester chip and density of preform plug part It measured at 30 degreeC with the density gradient tube of the calcium nitrate / water mixed solution.

(7) Haze (Fraction%)
Samples were cut from the body (wall thickness: about 0.40 mm) of the molded body (wall thickness 5 mm) and (11) below, and measured with a Nippon Denshoku Co., Ltd. haze meter, model NDH2000.

(8) Crystallization temperature (Tc1) when the molded body is heated
Measured with a differential thermal analyzer (DSC) manufactured by Seiko Denshi Kogyo Co., Ltd., RDC-220. Use 10 mg of the sample from the center of the 2 mm thick plate of the molded plate (10) below. The temperature is raised at a rate of temperature rise of 20 ° C./minute, and the temperature at the top of the crystallization peak observed in the middle is measured to obtain the crystallization temperature at the time of temperature rise (Tc1).

(9) Density increase due to heating of preform plug portion The preform plug portion was heat-treated for 60 seconds with a homemade infrared heater, a sample was taken from the top surface, and the density was measured.

(10) Molding of Stepped Molded Plate of Polyester Resin (1), Polyester Resin (2) and Polyester Resin Composition In molding of a stepped molded plate according to the present patent description, the moisture content is reduced by using a vacuum dryer. Polyester chips dried under reduced pressure to 50 ppm or less have a gate part (G) as shown in FIGS. 1 and 2 by an injection molding machine M-150C (DM) type injection molding machine manufactured by Meiki Seisakusho. 2 mm, B part thickness = 3 mm, C part thickness = 4 mm, D part thickness = 5 mm, E part thickness = 10 mm, F part thickness = 11 mm) Molded.

A polyester chip previously dried under reduced pressure using a vacuum dryer DP61 manufactured by Yamato Scientific was used, and a dry inert gas (nitrogen gas) purge was performed in the molding material hopper in order to prevent moisture absorption of the chip during molding.
The plasticizing conditions of the M-150C (DM) injection molding machine are: feed screw rotation speed = 70%, screw rotation speed = 120 rpm, back pressure 0.5 MPa, cylinder temperature 45 ° C., 250 ° C. in order from directly below the hopper The temperature was set at 290 ° C. including the nozzle. The injection conditions are 20% for injection speed and holding pressure, and the injection pressure and holding pressure are adjusted so that the weight of the molded product is 146 ± 0.2g. In this case, the holding pressure is 0.5MPa lower than the injection pressure. It was adjusted.
The upper limit of the injection time and pressure holding time is set to 10 seconds and 7 seconds, respectively, and the cooling time is set to 50 seconds. The total cycle time including the time for taking out the molded product is about 75 seconds.

Although the temperature of the mold is always controlled by introducing cooling water having a water temperature of 10 ° C., the mold surface temperature at the time of stable molding is around 22 ° C.
The test plate for evaluating the molded product characteristics was arbitrarily selected from the 11th to 18th shots of the stable molded product after the molding material was introduced and the resin was replaced.

  A 2 mm thick plate (part A in FIG. 1) measures the crystallization temperature (Tc1) at elevated temperature and acetaldehyde content (AA content), and a 3 mm thick plate (part B in FIG. 1) has an annular 3 quantity. The body content (CT content) is measured, and the 5 mm-thick plate (D portion in FIG. 1) is used for haze (degree of craze) measurement.

(11) Molding of Hollow Molded Body A preform was molded at a resin temperature of 290 ° C. using an M-150C (DM) injection molding machine manufactured by Koki Seisakusho using the dried polyester resin and polyester resin composition. The plug portion of this preform was heated and crystallized with a home-made plug portion crystallizer. Next, this preformed body was biaxially stretched and blown at a magnification of about 2.5 times in the longitudinal direction and about 3.8 times in the circumferential direction on an LB-01E molding machine manufactured by CORPOPLAST, and subsequently set at about 150 ° C. The container was heat-set in a mold to form a 1000 cc container (trunk thickness 0.40 mm). The stretching temperature was controlled at 100 ° C.

(12) Evaluation of leakage of contents from hollow molded body Filled hollow molded body molded in (11) above with 90 ° C hot water, capped with a capping machine, and then left the container down, leaving the contents leaked. Examined. The deformation state of the plug after capping was also examined.

(Polyester resin (1) -A)
1162 kg of high-purity terephthalic acid and its 2-fold molar amount of ethylene glycol are charged into a heat-medium circulating esterification reactor equipped with a stirrer, 0.3 mol% of triethylamine is added to the acid component, and 245 ° C. under a pressure of 0.25 MPa. Then, the esterification reaction was carried out for 2 hours while distilling water out of the system to obtain a mixture of bis (2-hydroxyethyl) terephthalate and oligomer (hereinafter referred to as BHET mixture) having an esterification rate of 95%. The BHET mixture was transported to a polycondensator, and for this, a polyester residual amount of about 2000 ppm and a residual Ge amount were obtained for an ethylene glycol solution of phosphoric acid and a polyester capable of obtaining a crystalline germanium dioxide / ethylene glycol solution as a polycondensation catalyst. So as to be about 20 ppm. Subsequently, it stirred at 245 degreeC for 10 minutes by the normal pressure in nitrogen atmosphere. Thereafter, the pressure of the reaction system is gradually lowered while raising the temperature to 250 ° C., and the initial polycondensation of the first stage is performed at 13.3 Pa (0.1 Torr) for 50 minutes. Further, the IV is increased at 275 ° C. and 13.3 Pa. The polycondensation reaction was carried out to about 0.66 deciliter / gram. Subsequent to releasing the pressure, the resin under slight pressure was discharged into cold water in the form of a strand, quenched, and converted into a chip with a strand cutter to obtain a cylindrical chip.

  Then, it was immediately heat-treated at about 50 to about 170 ° C. under a nitrogen flow in a stationary drier, and processed by a vibration sieving step and an air flow classification step to obtain a crystallized polymer. The IV was 0.66 deciliter / gram, the acetaldehyde content was 40 ppm, the DEG content was 5.0 mol%, the fine content was about 60 ppm, and the haze of the 4 mm molded body was 16.0%.

(Polyester resin (1) -B)
Except for shortening the polycondensation time, the melt polycondensation reaction was carried out under the same conditions as in obtaining the polyester resin (1) -A until the IV was about 0.55 deciliter / gram.
After the polyester chip obtained by the melt polycondensation reaction is heat-treated to crystallize the polyester, it is dried at about 100 ° C. to 130 ° C. and then at 150 ° C. in a stationary solid phase polycondensation tower under a nitrogen stream, Solid phase polymerization was carried out at 200 ° C. to obtain a solid phase polycondensation polyester resin having an IV of 0.70 deciliter / gram, an acetaldehyde content (A ₀ ) of 30 ppm and a DEG content of 5.1 mol%. Further, the solid-phase polymerization PET chip was treated by a vibration sieving step and an airflow classification step to make the fine content about 50 ppm. The haze of the 4 mm mm molded body was 6.2%.

(Polyester resin (1) -C)
Antimony trioxide is added as a polycondensation catalyst so that the residual amount is about 300 ppm, and the polycondensation temperature is set to 295 ° C. Under the same conditions as for obtaining the polyester resin (1) -A, the IV is about 0.1. The melt polycondensation reaction was carried out to 50 deciliters / gram.
The polyester chip obtained by the melt polycondensation reaction was heat-treated with a rotary blender and finely removed by a vibration sieving step and an airflow classification step to obtain a crystallized polymer. The residual amount of P was 1890 ppm, the acetaldehyde content was 75 ppm, the DEG content was 5.1 mol%, the fine content was about 70 ppm, and the haze of the 4 mm molded body was 53.5%.

(Polyester resin (2) -A)
A slurry of high-purity terephthalic acid and ethyl glycol is continuously supplied to the first esterification reactor containing the reactants in advance, and the average residence is maintained at about 250 ° C. and 0.5 kg / cm ² G under stirring. The reaction was carried out for 3 hours. This reaction product was sent to the second esterification reactor, and the reaction was carried out with stirring at about 260 ° C. and 0.05 kg / cm ² G to a predetermined reactivity. In addition, an ethylene glycol solution of basic aluminum acetate, Irganox 1222 (manufactured by Ciba Specialty Chemicals), and an ethylene glycol solution in which ethylene glycol was previously heated were continuously supplied to the second esterification reactor. The esterification reaction product is continuously fed to the first polycondensation reactor, and is stirred for about 1 hour at about 265 ° C. and 25 torr, and then stirred for about 2 hours at about 265 ° C. and 3 torr. The mixture was further subjected to polycondensation at about 275 ° C. and 0.3 to 1 torr with stirring in the final polycondensation reactor for a period of time. The obtained melt polycondensed PET had an intrinsic viscosity of 0.57 deciliter / gram. The polycondensation reaction product is chipped into a cylinder-shaped chip, followed by crystallization 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 under a nitrogen atmosphere. Solid state polymerization was carried out at about 206 ° C. After the solid-phase polymerization, the fine particles were removed by continuous treatment in the sieving step and the fine removal step.

The obtained PET has an intrinsic viscosity of 0.75 deciliter / gram, an acetaldehyde content of 3.0 ppm, a DEG content of 2.6 mol%, a cyclic trimer content of 3500 ppm, and a density of 1.398 g / cm. ^3. The haze of the molded product by the method (9) was 6.3%, and Tc1 was 164 ° C. Al residual amount was 21 ppm, P residual amount was 30 ppm, and fine content was about 50 pm.

  The cyclic trimer content was determined by dissolving the polymer in a hexafluoroisopropanol / chloroform mixture, adding methanol to the diluted solution and precipitating the polymer, filtering, and evaporating the filtrate to dryness. Solidified, made up to volume with dimethylformamide, and quantified by liquid chromatography.

Example 1
The polyester resin (2) -A, 98 parts by weight, and the catalyst-reused polyester resin (1) -A, 2 parts by weight were mixed in a blender. Thereafter, a stepped formed plate was formed by the method (9), and a bottle that was a hollow formed body was formed by the method (10).
The haze of the stepped molded plate (5 mm thick) is 9.8%, Tc1 of the polyester resin composition is 169 ° C., and the density of the plug portion is 1.380 g / cm 3, which is a problem-free value, and is transparent in the bottle The property (haze) was also good at 1.3%. In addition, there was no problem in the contents leakage test, and there was no deformation of the plug part. There was no problem with the AA content of the bottle being 13.0 pm.

(Example 2)
The polyester resin (2) -A, 98 parts by weight, and the catalyst-reused polyester resin (1) -B, 2 parts by weight are mixed, and the stepped molding plate is formed by the method of molding evaluation (9) in the same manner as in Example 1. The bottle which is a hollow molded object was shape | molded by the method of (11).
The haze of the stepped molded plate (5 mm thick) is 7.0%, the Tc1 of the polyester resin composition is 169 ° C., and the density of the plug portion is 1.380 g / cm 3, which is a value that is not a problem, and is transparent in the bottle The property (haze) was also good at 1.2%. In addition, there was no problem in the contents leakage test, and there was no deformation of the plug part. There was no problem with the AA content of the bottle being 12.7 pm.

(Comparative Example 1)
The polyester resin (2) -A, 98 parts by weight, and the catalyst depleted polyester resin (1) -C, 2 parts by weight are mixed, and in the same manner as in Example 1, a stepped molded plate is formed by the method of molding evaluation (9). The bottle which is a hollow molded object was shape | molded by the method of (11).
The haze of the stepped plate (5 mm thickness) was as high as 42.1%, Tc1 was as low as 141 ° C., the haze of the bottle was as high as 7.2%, and the transparency was very poor. The density of the hollow molded body plug portion was as high as 1.395 g / cm 3, and leakage was confirmed in the content leakage test.

  The polyester resin of the present invention is suitably used as a polyester resin that can be used to deactivate the polycondensation catalyst used during the production of polyester and suppress the formation of cyclic ester oligomers and aldehydes during molding. be able to. In particular, the polyester resin composition of the present invention has an appropriate crystallization rate, is excellent in transparency and flavor retention, has no problems such as deterioration of transparency due to mold contamination during continuous molding, and has a heat resistant dimensional stability. Is a polyester resin composition capable of efficiently producing excellent hollow molded articles and the like. From this, a molded article having the above-mentioned characteristics can be obtained, which contributes greatly to the industry.

Plan view of the stepped molded plate used in the examples Side view of the stepped molded plate of FIG.

Claims (8)

  A polyester resin (1) mainly composed of an aromatic dicarboxylic acid component and an ethylene glycol component, copolymerized or blended in an amount of 100 to 5000 ppm with a phosphorus compound as a phosphorus atom, and mainly composed of an aromatic dicarboxylic acid component and an ethylene glycol component A polyester resin composition comprising a polyester resin (2) as a main component, wherein the haze of a molded product obtained by molding the polyester resin composition is 30% or less Composition.   The polyester resin composition according to claim 1, wherein the aromatic dicarboxylic acid component of the polyester resin (1) is a terephthalic acid component.   The polyester resin composition according to claim 1, wherein the fine content is 0.1 to 5000 ppm.   The polyester resin composition according to claim 2, wherein the molded body has an acetaldehyde content of 50 ppm or less.   The polyester resin composition according to any one of claims 2 to 4, wherein a crystallization temperature (Tc1) at the time of temperature rise of the molded body is 150 to 175 ° C.   The phosphorus compound is at least one selected from the group consisting of a phosphoric acid compound, a phosphonic acid compound, a phosphinic acid compound, a phosphorous acid compound, a phosphonous acid compound, and a phosphinic acid compound. The polyester resin composition according to any one of claims 1 to 5.   A compound in which the polycondensation catalyst of the polyester resin (2) contains at least one element selected from the group consisting of Al, Ti, Mn, Fe, Co, Zn, Nb, Mo, Cd, In, Sn, Ta, and Pb; Or these are the antimony compound and / or a germanium compound as needed, The polyester resin composition in any one of Claims 1-6 characterized by the above-mentioned.   A polyester molded article obtained by molding the polyester resin composition according to claim 1.

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