JP2007204743A - Polyester resin, polyester resin composition comprising the same and polyester molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin that can be used for solving problems, of conventional techniques, such as formation of aldehydes such as acetaldehyde or cyclic ester oligomers on molding, a polyester resin composition efficiently producing a hollow molded item or the like that is excellent in transparency and flavor retention, does not suffer from problems such as deterioration in transparency caused by mold stains on continuous molding and exhibits excellent dimensional stability under heat, and its use. <P>SOLUTION: The polyester resin is mainly constituted of an aromatic dicarboxylic acid component and a glycol component and contains phosphorous compounds in an amount of 100-10,000 ppm in terms of the phosphorus atom and water in an amount of 500-10,000 ppm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyester resin that can be used for deactivating the action of a polycondensation catalyst used in the production of polyester and suppressing the formation of aldehydes such as acetaldehyde and cyclic oligomers during molding, and a polyester resin comprising the same The present invention relates to a composition and its use.

  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 adopted as a material for containers such as juice and mineral water, and its spread is remarkable. Mass production by a continuous polymerization method is carried out in a factory. 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 is 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.

  In addition, a method of deactivating the polycondensation catalyst by kneading a thermoplastic resin containing a phosphorus compound into PET (for example, see Patent Document 15) or a method for reducing water to contain acetaldehyde (for example, Patent Document 16, 17). However, it has been found that not only the transparency of the molded article is lowered, but it cannot be said that oligomers and acetaldehyde can be reduced to a problem-free level, and the flavor may be affected. Thus, there is a problem that it is difficult to always obtain a molded article excellent in transparency and flavor retention, and a solution is desired.

  In addition, when PET is used as a container for filling beverages such as juice, oil, alcoholic beverages, etc., the UV-blocking property is insufficient, resulting in deterioration of the quality of the container contents, and small bottles have gas barrier properties. Because of the shortage, the quality of the contents deteriorates in the same way, causing problems, 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 JP 2004-359837 A JP-A-7-205257

  The present invention has a polyester resin that can be used to solve problems such as the formation of aldehydes such as acetaldehyde and cyclic oligomers during molding and deterioration of transparency, and the transparency and flavor of the conventional technology. Polyester resin composition with excellent retention, no problem such as deterioration of transparency due to mold fouling during continuous molding, and efficient production of hollow molded articles with excellent heat-resistant dimensional stability and uses thereof The purpose is to provide.

  In order to achieve the above object, the polyester resin of the present invention is mainly composed of an aromatic dicarboxylic acid component and a glycol component, and contains a phosphorus compound as a phosphorus atom in an amount of 100 to 10,000 ppm and water in an amount of 500 ppm to 10,000 ppm. Polyester resin.

  The polyester resin (1) of the present invention is a polyester resin (1) mainly comprising an aromatic dicarboxylic acid component and a glycol component, and containing a phosphorus compound as a phosphorus atom, preferably 200 to 8000 ppm, more preferably 300 to 6000 ppm. When the phosphorus atom in the polyester resin (1) is less than 100 ppm, the deactivation effect on the catalyst contained in the polyester resin (2) is reduced, and the cyclic oligomer such as a cyclic trimer in the obtained molded product is contained. The amount becomes very large and the mold becomes easily soiled. On the other hand, if it exceeds 10,000 ppm, the polymerization rate tends to be too high, the degree of polymerization becomes difficult to control and commercial production tends to be difficult.

  In addition, the water content of the polyester resin (1) of the present invention is preferably 800 ppm to 9000 ppm, more preferably 1000 ppm to 8000 ppm. If it is less than 500 ppm, the cyclic ester oligomer and acetaldehyde reducing effect is reduced, and the practicality is poor. On the other hand, if it exceeds 10,000 ppm, the molecular weight decreases due to hydrolysis due to excess water, and problems such as a decrease in bottle strength and a decrease in transparency due to the occurrence of silver are undesirable.

  In this case, the polycondensation catalyst is preferably at least one selected from the group consisting of Sb compounds and Ge compounds.

  In this case, the polyester resin (1) described above is composed of Al, Ti, V, Mn, Fe, Co, Ni, Zn, Nb, Mo, Cd, In, Sn, Ta, and Pb as a polycondensation catalyst. A polycondensation catalyst for the polyester resin (2) by mixing with a polyester resin (2) mainly composed of an aromatic dicarboxylic acid component and a glycol component and containing a compound containing at least one element selected from It can be used as a polyester resin that can deactivate the catalyst.

  In this case, the polyester resin (1) is composed of an acid component consisting of 20 mol% to 100 mol% of naphthalenedicarboxylic acid and 80 to 0 mol% of other carboxylic acid and a glycol component, The compound can be contained in an amount of 100 to 10,000 ppm as a phosphorus atom.

  In this case, the content of aldehydes in the polyester resin (1) is preferably 150 ppm or less.

  In this case, the phosphorus compound is at least 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. One type is preferred.

  In this case, at least selected from the group consisting of the polyester resin (1) described above and Al, Ti, V, Mn, Fe, Co, Ni, Zn, Nb, Mo, Cd, In, Sn, Ta, and Pb. A polyester resin composition comprising a polyester resin (2) mainly comprising an aromatic dicarboxylic acid component and a glycol component, containing a compound containing one kind of element and, if necessary, an antimony compound and / or a germanium compound. Can do.

  Further, the polyester resin composition has excellent flavor retention, low cyclic ester oligomer content, almost no occurrence of mold contamination during continuous molding, and thus excellent transparency and little variation in transparency. A molded article, for example, a hollow molded article, a sheet-like article, a stretched film, or the like, or a coating obtained by melt-extruding the polyester resin composition on a substrate can be provided.

  The polyester resin of the present invention is a polyester resin that can be used to deactivate the polycondensation catalyst used in the production of polyester and suppress the formation of aldehydes such as acetaldehyde and cyclic oligomers during molding. The polyester resin composition comprising the same is excellent in flavor retention, hardly generates mold stains during continuous molding, and therefore has little variation in transparency and transparency, particularly to hollow molded products and substrates. Give a coating or the like. Also, operability is improved.

Hereinafter, embodiments of the polyester resin and the polyester resin composition of the present invention and their uses will be specifically described.
(Polyester resin (1))
Examples of the phosphorus compound copolymerized or blended in the polyester resin (1) of the present invention include phosphoric acid compounds, phosphonic acid compounds, phosphinic acid compounds, phosphorous acid compounds, phosphonous acid compounds, and phosphinic acid. System compounds.
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 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 compound include methylphosphonous acid, dimethyl methylphosphonite, diphenyl methylphosphonite, phenylphosphonite, dimethyl phenylphosphonite, 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) of the present invention is a thermoplastic polyester mainly obtained from an aromatic dicarboxylic acid component and a glycol component, preferably a polyester containing an aromatic dicarboxylic acid unit of 50 mol% or more of the acid component, and more Preferably, the polyester contains 80 mol% or more of the aromatic dicarboxylic acid unit, more preferably polyester containing 85 mol% or more of the aromatic dicarboxylic acid unit of the acid component, and particularly preferably the aromatic dicarboxylic acid unit contains the aromatic dicarboxylic acid unit. A polyester containing 90 mol% or more of the acid component, most preferably an aromatic dicarboxylic acid unit containing 95 mol% or more of the acid component, which is obtained by copolymerizing or blending the above phosphorus compound.

  In addition, when the polyester resin composition of the present invention is used for a stretch molded article, the polyester resin (1) of the present invention is a thermoplastic polyester obtained mainly from an aromatic dicarboxylic acid component and a glycol component. The polyester preferably contains 85 mol% or more of the aromatic dicarboxylic acid unit, more preferably polyester containing 90 mol% or more of the aromatic dicarboxylic acid unit, and more preferably the aromatic dicarboxylic acid unit. Is a polyester containing 93 mol% or more of the acid component, and particularly preferably a polyester containing 95 mol% or more of the aromatic dicarboxylic acid unit of the acid component, which is obtained by copolymerizing or blending the above phosphorus compound.

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

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

  Examples of the dicarboxylic acid used as a copolymerization component when the polyester is a copolymer include isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, Aromatic dicarboxylic acids such as 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl ketone dicarboxylic acid and functional derivatives thereof, oxyacids such as p-oxybenzoic acid and oxycaproic acid and functional derivatives thereof, adipine Aliphatic dicarboxylic acids such as acid, sebacic acid, succinic acid, glutaric acid and dimer acid and their functional derivatives, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid and cyclohexanedicarboxylic acid and their functional derivatives Etc.

  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 the like alicyclic glycols, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-β-hydroxyeth Cyclophenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-β-hydroxyethoxyphenyl) sulfonic acid, aromatic glycols such as 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) of the present invention is a polyester whose main structural unit is composed of ethylene terephthalate, and more preferably contains 50 mol% or more of ethylene terephthalate units. A copolymer polyester containing naphthalenedicarboxylic acid, 1,4-cyclohexanedimethanol, succinic acid, and the like, more preferably 70 mol% or more of ethylene terephthalate units, particularly preferably polyester containing 90 mol% or more of ethylene terephthalate units, Most preferably, it is a polyester containing 95 mol% or more of ethylene terephthalate units, and is a copolymer or blend of the above phosphorus compounds.

  Further, another preferred example of the polyester resin (1) of the present invention is a polyester in which the main structural unit is composed of ethylene-2,6-naphthalate, preferably 50 mol% of ethylene-2,6-naphthalate units. More preferably 70% by mole or more of ethylene-2,6-naphthalate units, particularly preferably a polyester containing 90% by mole or more of ethylene-2,6-naphthalate units, most preferably ethylene-2. Polyester containing 95 mol% or more of 6-naphthalate unit, which is obtained by copolymerizing or blending the above phosphorus compound.

  In addition, other preferable examples of the polyester of the present invention are polyesters in which the main structural unit is composed of 1,3-propylene terephthalate, preferably a polyester containing 50 mol% or more of 1,3-propylene terephthalate units. More preferably, the polyester contains 70 mol% or more of 1,3-propylene terephthalate units, particularly preferably 90 mol% or more of 1,3-propylene terephthalate units, and most preferably 95 mol% or more of 1,3-propylene terephthalate units. The above phosphorus compound is copolymerized or blended.

  Further, other preferable examples of the polyester of the present invention are polyesters in which the main structural unit is composed of butylene terephthalate, preferably a copolymerized polyester containing 50 mol% or more of butylene terephthalate units, more preferably butylene terephthalate. A polyester containing 70 mol% or more, particularly preferably 90 mol% or more of a butylene terephthalate unit, most preferably a polyester containing 95 mol% or more of a butylene terephthalate unit, which is obtained by copolymerizing or blending the above phosphorus compound. is there.

  In addition, another preferable example of the polyester of the present invention is a polyester in which the main structural unit is composed of 1,4-cyclohexanedimethylene terephthalate, and more preferably 50 mol% or more of 1,4-cyclohexanedimethylene terephthalate units. More preferably 70 mol% or more of 1,4-cyclohexanedimethylene terephthalate units, particularly preferably polyester containing 90 mol% or more of 1,4-cyclohexanedimethylene terephthalate units, most preferably 1,4 cyclohexanedimethylene terephthalate units. A polyester containing 95 mol% or more of 4-cyclohexanedimethylene terephthalate unit, which is obtained by copolymerizing or blending 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. At this time, the transesterification reaction, esterification reaction, and melt polycondensation reaction may be performed in one step, or may be performed in multiple steps. Moreover, these may be implemented with a batch type reaction apparatus, and may be implemented with a continuous reaction apparatus.

  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 during the production of the polyester, and the addition time can be added at any stage from the early stage of the esterification process to the late stage of the initial condensation. It is preferable to add from the latter stage of the esterification step to the early stage of the initial condensation because of corrosion problems.

  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 90%, preferably 95% or more. Next, a phosphorus compound is added, and the first stage polycondensation is performed at 240 to 255 ° C., preferably 240 to 250 ° C., more preferably 240 to 248 ° C. at 300 to 0.1 Torr for 0.5 to 2 hours, Further, the polycondensation is carried out at 250 to 280 ° C., preferably 250 to 278 ° C., more preferably 250 to 275 ° C. at 10 to 0.1 Torr, preferably 5 to 0.1 Torr to the desired degree of polymerization. In particular, it is important to carry out the first stage polycondensation reaction at 250 ° C. or lower in order to achieve the object of the present invention.

  Further, for example, in the case of a copolyester of 2,6-naphthalenedicarboxylic acid, ethylene glycol and a phosphorus compound, it can be produced by the following method in substantially the same manner as described above. That is, any method employed when polyesterifying the esterification reaction product or transesterification product of 2,6-naphthalenedicarboxylic acid and / or its ester-forming derivative with ethylene glycol to form a polyester Can be synthesized.

  The addition time of the phosphorus compound is preferably added from the later stage of the transesterification process or the esterification process to the initial stage of the initial condensation because of the suppression of side reactions such as acetaldehyde formation and the problem of corrosion of the reactor stand as described above. .

  In the case of producing by an esterification reaction, a slurry containing 1.02 to 2.0 mol, preferably 1.03 to 1.4 mol of ethylene glycol is used per 1 mol of 2,6-naphthalenedicarboxylic acid. Adjusted and fed to the esterification reaction step.

  The preferable production conditions for the esterification reaction 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 90%, preferably 95% or more. Subsequently, a phosphorus compound is added, and the first stage polycondensation is performed at 240 to 285 ° C., preferably 240 to 275 ° C., more preferably 240 to 255 ° C. at 300 to 0.1 Torr for 0.5 to 2 hours, Furthermore, polycondensation is performed at 250 to 300 ° C., preferably 250 to 290 ° C., more preferably 250 to 285 ° C., and 10 to 0.1 Torr, preferably 5 to 0.1 Torr to the desired degree of polymerization. In particular, it is important to carry out the first stage polycondensation reaction at 285 ° C. or lower in order to achieve the object of the present invention.

  In the case of producing by transesterification, 1.1 to 2.0 mol, preferably 1.2 to 1.5 mol of ethylene glycol was contained with respect to 1 mol of dimethyl 2,6-naphthalenedicarboxylate. Prepare the solution and feed it to the transesterification step. The temperature of the transesterification reaction is 180 to 285 ° C, preferably 200 to 275 ° C. As the transesterification catalyst, fatty acid salts such as Zn, Cd, Mg, Mn, Co, Ca, Ba, carbonates, Pb, Zn, Sb, and Ge oxides are used. A low-order condensate having a molecular weight of about 200 to 500 is obtained by these transesterification reactions. Next, a polycondensation reaction is performed in the same manner as described above.

  The 2,6-naphthalenedicarboxylic acid, terephthalic acid or ethylene glycol which is the starting material is an ethylene glycol derived from virgin 2,6-naphthalenedicarboxylic acid, terephthalic acid or ethylene derived from paraxylene or naphthalene. Needless to say, 2,6-naphthalenedicarboxylic acid, terephthalic acid, bishydroxyethyl-2,6-naphthalate and bishydroxy recovered from used PEN bottles and PET bottles by chemical recycling methods such as methanol decomposition and ethylene glycol decomposition A recovered raw material such as ethyl terephthalate or ethylene glycol 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 and a germanium compound, in which the catalytic action is not deactivated by the phosphorus compound, are optimal.

  Specific examples of the Sb compound include antimony trioxide, antimony acetate, antimony tartrate, antimony tartrate, antimony oxychloride, antimony glycolate, antimony pentoxide, and triphenylantimony. The Sb compound is added so that the residual amount of Sb in the produced polymer is in the range of 50 to 300 ppm, preferably 55 to 200 ppm, more preferably 60 to 150 ppm.

  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. When a Ge compound is used, the amount used is 10 to 100 ppm, preferably 11 to 50 ppm, and more preferably 11 to 15 ppm as the residual amount of Ge in the polyester resin (1).

  The polyester resin polycondensed as described above is transported from the final melt polycondensation reactor to the nozzle in a molten state, for example, a method in which molten polyester is extruded into water through die pores and cut in water, or a die After being extruded in the form of strands from the pores into the air, the chips are formed into columns, spheres, squares or plates by a method of forming chips while cooling with cooling water. At this time, it is necessary to obtain the polyester resin (1) of the present invention by making the temperature in the molten state up to the nozzle as low as possible and making the residence time as short as possible. is there.

Moreover, as the cooling water at the time of chip formation of the melt polycondensed polyester, it is preferable to use cooling water satisfying at least one of the following (1) to (4), and more preferably (1) to (4 It is most preferable to use water that satisfies all of the above.
Na ≦ 1.0 (ppm) (1)
Mg ≦ 1.0 (ppm) (2)
Si ≦ 2.0 (ppm) (3)
Ca ≦ 1.0 (ppm) (4)

  The sodium content (Na) in the cooling water is preferably Na ≦ 0.5 ppm, more preferably Na ≦ 0.1 ppm. The magnesium content (Mg) in the cooling water is preferably Mg ≦ 0.5 ppm, more preferably Mg ≦ 0.1 ppm. Further, the content (Si) of silicon in the cooling water is preferably Si ≦ 0.5 ppm, more preferably Si ≦ 0.3 ppm. Furthermore, the calcium content (Ca) in the cooling water is preferably Ca ≦ 0.5 ppm, and more preferably Ca ≦ 0.1 ppm.

  In order to reduce sodium, magnesium, calcium, and silicon in the cooling water, an apparatus for removing sodium, magnesium, calcium, and silicon is installed in at least one place until the industrial water is sent to the chip cooling process. Also, a filter is installed to remove clay minerals such as silicon dioxide and aluminosilicate particles. Examples of the device for removing sodium, magnesium, calcium, and silicon include an ion exchange device, an ultrafiltration device, and a reverse osmosis membrane device.

  Although the polyester resin (1) of this invention is manufactured as mentioned above, in addition to these, the method shown below can be employ | adopted suitably. That is, a molten polycondensation polymer having an IV of 0.40 deciliter / gram or more, preferably 0.50 deciliter / gram or more, and more preferably 0.55 deciliter / gram or more is immediately converted into chips and immediately under reduced pressure or through an inert gas flow. In addition, a method of heat crystallization at a temperature of up to 150 ° C. and a method of solid-phase polymerization of a solution polycondensation prepolymer having an IV of 0.40 to 0.60 deciliter / gram can be used. Moreover, the method of melt-extruding polyester with a vent type extruder under pressure reduction or an inert gas distribution can be used. Moreover, the method of heat-processing a phosphorus containing polyester resin with organic solvents, such as water and chloroform, can also be used. Moreover, these methods can also be combined appropriately.

  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 intrinsic viscosity of the polyester resin (1) of the present invention is 0.40 to 1.20 deciliter / gram, preferably 0.50 to 1.00 deciliter / gram, more preferably 0.60 to 0.90 deciliter / gram. Most preferably, it is 0.65 to 0.85 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. In the case of solid phase polymerization, the density of the chip is 1.37 cm ³ / g or more.

  When the intrinsic viscosity is less than 0.40 deciliter / gram, the transparency of the obtained molded article is deteriorated, and the mechanical strength does not satisfy the practical range. On the other hand, if it exceeds 1.20 deciliters / gram, kneading is incomplete when a composition with the polyester resin (2) is molded, and a molded product of uniform quality cannot be obtained.

  The shape of the chip of the polyester resin (1) of 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 average weight of the chip is practically in the range of 2 to 40 mg / piece. In addition, when it is necessary to improve the solid-phase polymerization rate or to reduce the content of aldehydes more effectively, the average weight of the chips is preferably 1 to 5 mg / piece.

  The following method is illustrated as a specific method for adjusting the moisture of the polyester resin (1). First, in the drying step performed prior to melt molding, a method of concluding drying at a point of time when a predetermined moisture content is reached and subjecting to melt molding can be considered. Recently, there is an apparatus equipped with an on-line moisture meter in the drying process, and the use thereof is mentioned (moisture adjustment method 1). This method can be easily used by using a molding apparatus equipped with an online moisture meter such as a Karl Fischer online moisture analyzer Aqua Hunter manufactured by Matsui Seisakusho in the drying process.

  Further, as another method, there is a method in which the moisture content in the polymer is once reduced to the end of 500 ppm by drying and then the humidity is adjusted to adjust the moisture content to 500 to 10,000 ppm (moisture adjustment method 2). . In this case, the drying process includes a shelf-type hot air or a dryer with a flow of inert gas such as nitrogen, a shelf-type vacuum dryer, a continuous tank for supplying and discharging resin, and a double-cone heating dryer. A mold vacuum dryer, microwave dryer, or the like can be used. The drying conditions vary depending on the components and amount of copolymerization, but a temperature condition of 70 to 170 ° C. is usually used.

  The polyester resin having a moisture content of 500 to 10000 ppm can be obtained by absorbing moisture of the thus obtained dried polyester resin having a water content of less than 500 ppm. As a method of absorbing moisture, usually, a method of absorbing moisture in a constant temperature and humidity chamber or a constant temperature and humidity chamber adjusted to a constant temperature and a constant high humidity, or adding a certain amount of moisture to the resin with a blender or the like. The method of mixing and making it absorb in a chip | tip is mentioned. In particular, by using the moisture adjustment method 2, a polyester resin having a controlled and constant moisture content can be stably obtained even if the moisture content of the polyester resin used immediately before drying is variously different.

  Moreover, as another method, it can be set as the polyester resin of the moisture content of 500-10000 ppm by leaving the manufactured polyester resin (1) in the air | atmosphere and making it absorb moisture (moisture adjustment method 3).

  In addition, since the moisture content within the range of the present invention is larger than the moisture in the resin before normal molding, it is necessary to pay attention to the molding conditions in consideration of the balance between hydrolysis and thermal decomposition. Therefore, as a melt molding method of the polyester resin of the present invention, the ratio of the intrinsic viscosity X (dl / g) of the polyester resin composition before molding to the intrinsic viscosity (actual value) Y (dl / g) of the molded product ( It is preferable to perform melt molding under such a condition that Y / X) × 100 (%) (hereinafter referred to as IV retention) is 90% or more. By selecting a moisture content and melt molding conditions that maintain an IV retention of 90% or more, preferably 92% or more, the mechanical strength, transparency, etc. can be substantially reduced without reducing the acetaldehyde of the molded product. The aldehyde content can be kept low, and the object of the present invention can be achieved more preferably.

  The object of the present invention can be more preferably achieved by adjusting the water content and the melt molding conditions so that the IV retention is 90% or more, preferably 92% or more. If the IV retention is less than 90%, silver tends to be generated during molding, and the amount of acetaldehyde in the molded article increases with priority on the thermal decomposition reaction, or it is not suitable for melt molding due to excessive hydrolysis reaction. In some cases, the molecular weight is lowered and a satisfactory molded product cannot be obtained. The actual molding conditions vary depending on the molding machine or the extruder and cannot be defined unconditionally, and must be individually adjusted. For example, when the intrinsic viscosity Y of the molded product is low, the residence time of the polyester resin in the cylinder of the molding machine or extruder is shortened, or the melting temperature is lowered in consideration of transparency and mechanical properties. In addition to ensuring a good balance between the melt viscosity of the resin at each molding temperature and the pressure / speed of injection or extrusion, ensuring a sufficient melt state, suppressing the screw rotation speed and screw to avoid high shear It is possible to change the shape.

  Moreover, the aldehyde content of the polyester resin (1) of the present invention is preferably 100 ppm or less, and more preferably 50 ppm or less. When the aldehyde content is 150 ppm or less, there is no problem with the flavor retention of the contents filled in a molded body such as a hollow molded body obtained by molding a polyester resin composition with the polyester resin (2). When the content of aldehydes in the polyester resin (1) of the present invention exceeds 150 ppm, the flavor retention of the molded product content becomes very poor and causes a problem. The lower limit of the aldehyde content is 1 ppm, preferably 2 ppm, more preferably 3 ppm from the viewpoint of economical production.

  Here, the aldehydes are those in which the polyester resin (1) is ethylene glycol such as polyester having ethylene terephthalate as a main structural unit or polyester having ethylene-2,6-naphthalate as a main structural unit. In the case of polyester as the main component of the glycol component, it is acetaldehyde or formaldehyde, in the case of polyester having 1,3-propylene terephthalate as the main structural unit, it is allylaldehyde, and further, butylene terephthalate is the main structural unit. In the case of polyester, it is butanal. However, in the case of a polyester having butylene terephthalate as the main structural unit, the aldehyde is mostly detected as tetrahydrofuran.

  In addition, as a method for setting the content of aldehydes in the polyester resin (1) of the present invention to 150 ppm or less, a method of solid-phase polymerization of a solution-polymerized polyester prepolymer having an IV of 0.30 to 0.60, a predetermined IV A method of heat-treating polyester of the present invention under an inert gas atmosphere or under reduced pressure under conditions where IV does not substantially change or under a condition where the degree of increase in IV is small, polyester at a temperature of 50 to 180 ° C. under an inert stream or under reduced pressure From a method of heat-treating with polyester, a method of melt-extruding polyester with a vent-type extruder under reduced pressure or inert gas flow, a method of heat-treating a phosphorus-containing polyester resin with an organic solvent such as water or chloroform, or a solution dissolved in a solvent There are methods such as reprecipitation to precipitate polyester, and these are used alone or in appropriate combination. By using Te can be.

  Further, the dialkylene glycol content and the trialkylene glycol content copolymerized with the polyester resin (1) of the present invention are 10.0 mol% or less with respect to the glycol component constituting the polyester, respectively. 2.0 mol% or less, preferably 8.0 mol% or less and 1.5 mol% or less, respectively, more preferably 6.0 mol% or less and 1.0 mol% or less, respectively, more preferably, It is desirable that they are 5.0 mol% or less and 0.5 mol% or less, respectively. When the amount of dialkylene glycol exceeds 10 mol%, the thermal stability, thermal oxidation stability and color tone deteriorate, and the molecular weight decreases at the time of heat drying and molding of the polyester resin composition with the polyester resin (2). In addition, the content of aldehydes increases and coloring increases, which is not preferable.

  In addition, when the amount of trialkylene glycol exceeds 2 mol%, the thermal stability, thermal oxidation stability and color tone are deteriorated, and the molecular weight is obtained at the time of heat drying or molding of the polyester resin composition with the polyester resin (2). This is not preferable because the decrease is increased, and the content of aldehydes is increased and coloring is increased.

  Moreover, the lower limit values of the dialkylene glycol content and the trialkylene glycol content are 0.5 mol% and 0.1 mol%, respectively, and even if the content is reduced below these lower limits, the effect is not exhibited. However, in order to achieve this, a problem arises in terms of economy, such as a considerably low esterification reaction temperature and a long reaction time.

  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 by-produced during production from ethylene glycol, which is a 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) produced as a by-product during production from 1,3-propylene glycol, di (1,3) copolymerized with the polyester -Propylene glycol). Further, the trialkylene glycol copolymerized in the polyester is, for example, in the case of a polyester whose main structural unit is ethylene terephthalate, among the triethylene glycols by-produced in the same manner during production. In the case of a polyester having 1,3-propylene terephthalate as a main constituent unit, it is triethylene glycol (hereinafter abbreviated as TEG) copolymerized with the polyester. Of the tri (1,3-propylene glycol) (or tris (3-hydroxypropyl) ether) sometimes by-produced, the tri (1,3-propylene glycol) copolymerized with the polyester That is.

  In the production of the polyester resin (1) of the present invention, for example, a basic nitrogen compound can be used as a method for suppressing the dialkylene glycol content and the trialkylene glycol content within the scope of the present invention. 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. Also 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.

  It is also effective to maintain the reaction temperature around 230 ° C. until the esterification rate reaches 60% or more at the initial stage of the esterification reaction.

In addition, at least one metal atom selected from the group consisting of Zn atom, Fe atom, Ni atom, and Cr atom contained in the polyester resin (1) of the present invention is represented by the following formulas (5) to (8). It is preferable that the amount satisfies the above.
Cr ≦ 10ppm (5)
Fe ≦ 30ppm (6)
Ni ≤ 5ppm (7)
Zn ≦ 5ppm (8)

  The Cr atom content in the polyester resin (1) is preferably 8 ppm or less, more preferably 6 ppm or less, still more preferably 4 ppm or less, and most preferably 1 ppm or less as Cr atoms. The Fe atom content is 25 ppm or less, more preferably 20 ppm or less, further preferably 10 ppm or less, and most preferably 5 ppm or less as Fe atoms. The Ni atom content is preferably 3 ppm or less, more preferably 2 ppm or less, and most preferably 1 ppm or less as Ni atoms. The Zn atom content is preferably 4 ppm or less, more preferably 3 ppm or less, still more preferably 2 ppm or less, and most preferably 1 ppm or less. Furthermore, it is most preferable that all of the above formulas (5) to (8) are satisfied. The lower limit of the metal atom content is 0.01 ppm from the viewpoint of economy.

  When at least one of the metal atom contents exceeds the upper limit, the color tone of the polyester resin (1) is deteriorated, the aldehyde content is increased, and the polyester resin is composed of the polyester resin (2). Transparency of a molded article obtained from the composition is deteriorated, coloring of the molded article becomes intense, and flavor retention is also deteriorated, which is a problem.

  As a method for satisfying the above formulas (5) to (8), the content of Zn atom, Fe atom, Ni atom and Cr atom in the polyester resin (1) of the present invention may be an esterification reaction or heavy reaction. SUS316, SUS316L, SUS317, SUS317L, a high temperature corrosion resistant reactor made of Hastelloy, preferably SUS316L, SUS317, SUS317L, Hastelloy, or glass lining, most preferably SUS317. SUS317L, a Hastelloy reactor, a stirrer, or the like is used. In particular, it is necessary to use such a reactor as a reactor for reacting a phosphorus compound at 230 ° C. or higher. Usually, a metal-made reactor used for polycondensation of PET is not preferable because a large amount of Cr metal or Fe metal is eluted.

  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 A method such as a method of immersing in a solution of SUS316 or a method of attaching these solutions to the surface is adopted, but also in this case, SUS316 or higher corrosion resistance, preferably SUS316L, SUS317, SUS317L, Hastelloy screw or barrel It is necessary to use a twin-screw extruder composed of

  In addition, in the process of forming the polyester resin (1), the step of forming the melt polycondensation polymer into chips, the solid phase polymerization step, the step of transporting the melt polycondensation polymer chip or the solid phase polymerization polymer chip, etc. Particles and powders that are considerably smaller than the chips of a set size are sometimes generated. Here, such a fine granular material or powder is referred to as fine.

  Such fines have the property of promoting crystallization of the molded product from the polyester resin composition, and it is important to control the fine content of the polyester resin (1) to 1% by weight or less. When the fine content exceeds 1% by weight, the transparency of the molded article molded from the composition with the polyester resin (2) is deteriorated, the crystallization speed is high, and the fluctuation is very fast. These problems occur, and a polyester resin composition and a polyester molded body that achieve the object of the present invention cannot be obtained. The lower limit of the fine content of the polyester resin (1) is about 10 ppm or less, and making it lower is a problem in terms of economy.

  As a method of making the fine content of the polyester resin (1) 1% by weight or less, a molten polymer copolymerized with a phosphorus compound or a molten polymer kneaded with a phosphorus compound is discharged into water at about 5 to about 60 ° C. After cutting the chips with an underwater cutter and removing the water adhering to the chips, the chip is crystallized and dried with a tower crystallization apparatus where shear stress or impact force is not applied. Use a method of adding a fine removal step by air flow, a method of discharging molten polymer into water at about 10 to 60 ° C. and then converting it into a chip with a strand cutter, and carrying out high-density transportation after fine removal in the same way as before. Can do.

  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.

  In addition, the polyester resin (1) of the present invention is a polyester resin characterized in that the haze of a 4 mm-thick molded product obtained by injection molding is 40% or less. The haze of the molded body is preferably 20% or less, more preferably 10% or less, and particularly preferably 5% or less. 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 the crystallization speed occur. The lower limit of the haze is 1%, and even if it is reduced below this value, the effect hardly appears.

  In addition, as a method of obtaining the polyester resin (1) having a haze of the molded product of 40% or less, for example, a method using a Ge compound as a polycondensation catalyst, and when using a Sb compound, the Sb residual amount does not exceed 190 ppm. A method for controlling the amount to be added, a method for satisfying the above formulas (5) to (8) for the content of metal atoms such as Cr eluted from the reaction apparatus, and a temperature during polycondensation of 285 ° C. or less. In order to suppress thermal decomposition at the time of polycondensation as much as possible, crystallization or drying before molding or solid phase polymerization can be performed by a method using equipment in which the impact force is not applied to the chip as much as possible. These methods may be appropriately combined, but are not necessarily limited thereto.

  However, the cylinder temperature of the injection molding machine for molding the polyester resin (1) according to the present invention needs to be changed depending on the melting point of the polyester resin (1) to be used. Specifically, for a polyester resin (1) based on PET polyester, PBT polyester resin or PTT polyester resin, or polyester resin (1) based on PEN polyester resin, a measuring method is used. The other cylinder temperature set values described in (10) are 290 ° C. or 300 ° C., respectively.

  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 50 mol% or more of an aromatic dicarboxylic acid unit of the acid component, and more preferably aromatic polyester. A polyester containing 80 mol% or more of an aromatic dicarboxylic acid unit, more preferably a polyester containing 85 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 copolymer component when the polyester is a copolymer include isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, Aromatic dicarboxylic acids such as 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl ketone dicarboxylic acid and functional derivatives thereof, oxyacids such as p-oxybenzoic acid and oxycaproic acid and functional derivatives thereof, adipine Aliphatic dicarboxylic acids such as acid, sebacic acid, succinic acid, glutaric acid and dimer acid and their functional derivatives, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid and cyclohexanedicarboxylic acid and their functional derivatives Etc.

  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 the like alicyclic glycols, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-β-hydroxyeth Cyclophenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-β-hydroxyethoxyphenyl) sulfonic acid, aromatic glycols such as 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 80 mol% or more, and still more preferably ethylene terephthalate units. Copolyester containing 90 mol% or more and containing isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedimethanol, succinic acid, etc. as a copolymerization component, particularly preferably 95 mol% of ethylene terephthalate units. It is the polyester containing above.

  Examples of these polyesters include polyethylene terephthalate (hereinafter abbreviated as PET), poly (ethylene terephthalate-ethylene isophthalate) copolymer, poly (ethylene terephthalate-ethylene-2,6-naphthalate) copolymer, poly (ethylene). Terephthalate-1,4-cyclohexanedimethylene terephthalate) copolymer, poly (ethylene terephthalate-dioxyethylene terephthalate) copolymer, poly (ethylene terephthalate-1,3-propylene terephthalate) copolymer, poly (ethylene terephthalate-) Ethylene cyclohexylene dicarboxylate) copolymer, polyethylene terephthalate succinate copolymer, and the like.

  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. More preferably, it is a polyester containing 55 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably 95 mol% of ethylene-2,6-naphthalate units. It is the polyester containing above.

  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 55 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably a polyester containing 95 mol% or more of 1,3-propylene terephthalate units. It is.

  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 55 mol% of butylene terephthalate units. More preferably, it is a polyester containing 80 mol% or more, more preferably 90 mol% or more, and particularly preferably a polyester containing 95 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 is directly reacted with ethylene glycol and, if necessary, other copolymerization components to distill off water and esterify, followed by 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, V, Mn, Fe, Co, Ni, Zn, Nb, Mo, Cd, In, Sn, Ta, and Pb; If necessary, it is preferable to use at least one selected from second metal compounds such as Ge compounds and Sb compounds. These compounds are added to the reaction system as powders, aqueous solutions, ethylene glycol solutions, ethylene glycol slurries and the like.

  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 A composite oxide, a reaction product of titanium alkoxide and a phosphorus compound, a reaction product obtained by reacting a phosphorus compound with a reaction product of titanium alkoxide and an aromatic polyvalent carboxylic acid or an anhydride thereof, and the like. Can be mentioned. The Ti compound is added so that the amount of Ti remaining in the produced polymer is in the range of 0.1 to 100 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 alkoxide such as xoxide, aluminum t-butoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate diiso-propoxide, etc., 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.

  Among these aluminum compounds, aluminum acetate, aluminum chloride, aluminum hydroxide, and aluminum hydroxide chloride having a high aluminum content are preferable, and aluminum acetate, aluminum chloride, and aluminum hydroxide chloride are more preferable from the viewpoint of solubility. Furthermore, the use of aluminum acetate is particularly preferred from the viewpoint of not corroding the device.

Here, aluminum hydroxide chloride is a general term for what is generally called polyaluminum chloride or basic aluminum chloride, and those used for water supply can be used. These are represented by, for example, the general structural formula [Al ₂ (OH) _n Cl _6-n ] _m (where 1 ≦ n ≦ 5). Among these, those having a low chlorine content are preferable from the viewpoint of not corroding the device.

  The above-mentioned aluminum acetate is a general term for those having a structure of an aluminum salt of acetic acid represented by basic aluminum acetate, aluminum triacetate, aluminum acetate solution, etc. Among these, from the viewpoint of solubility and solution stability The use of basic aluminum acetate is preferred. Of the basic aluminum acetates, aluminum monoacetate, aluminum diacetate, or those stabilized with boric acid are preferred. Examples of basic aluminum acetate stabilizers include urea and thiourea in addition to boric acid.

  The above aluminum compound is preferably solubilized in a solvent such as water or glycol. Solvents that can be used in the present invention are water and alkylene glycols. Examples of alkylene glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylene glycol, ditrimethylene glycol, tetramethylene glycol, ditetramethylene glycol, neopentyl glycol, and the like. . Preferably, they are ethylene glycol, trimethylene glycol, tetramethylene glycol, more preferably ethylene glycol. It is preferable to use those solubilized in water and / or ethylene glycol because the effects of the present invention can be remarkably exhibited.

  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.

  When an Al compound is used as a polycondensation catalyst, it is preferably used in combination with a phosphorus compound. Examples of such P compounds include phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, It is preferably at least one phosphorus compound selected from the group consisting of phosphinic acid compounds and phosphine compounds. By using these phosphorus compounds, an effect of improving the catalytic activity is seen, and an effect of improving physical properties such as thermal stability of the polyester is seen. Among these, use of a phosphonic acid compound is preferable because of its great effect of improving physical properties and improving catalytic activity. Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

  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 chemical formulas (Chemical Formula 1) to (Chemical Formula 6), respectively. It refers to a compound having the structure represented.

  Examples of the phosphonic acid compound used in the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl phosphophosphonate, diethyl benzylphosphonate, and the like. . Examples of the phosphinic acid 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, and triphenylphosphine oxide.

  Among the phosphinic acid-based compounds, phosphine oxide-based compounds, phosphonous acid-based compounds, phosphinic acid-based compounds, and phosphine-based compounds, the phosphorus compounds used in the present invention include the following chemical formulas (Chemical Formula 7) to (Chemical Formula 12). The compound represented by these is preferable.

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

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

(In the chemical formulas (Chemical Formula 13) to (Chemical Formula 15), R ¹ , R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, 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 a phosphorus compound used by this invention, the compound whose R < ¹ >, R < ⁴ >, R < ⁵ >, R < ⁶ > is group which has an aromatic ring structure among the said Chemical formula (Formula 13)-(Formula 15) is especially preferable.

  Examples of the phosphorus compound used in the present invention include, for example, 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, in the present invention, a phosphorus metal salt compound is particularly preferable 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, when a metal salt of a phosphonic acid compound is used, the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are 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 part 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 metal salt compound of phosphorus used in the present invention, it is preferable to use at least one selected from compounds represented by the following chemical formula (Chemical Formula 16) because the physical property improving effect and the catalytic activity improving effect are great.

(In the chemical formula (Chem. 16), 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 hydroxyl group or an alkoxyl 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. A hydrocarbon group having 1 to 50 carbon atoms including a group or 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 is a (l + m) -valent metal Represents a cation, n represents an integer of 1 or more, and 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 above chemical formula (Formula 16), it is preferable to use at least one selected from the compounds represented by the following chemical formula (Formula 17).

(In the chemical formula (Chemical Formula 17), 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, and 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.

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

  Among the above chemical formulas (Chemical Formula 17), 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 greatly preferred. 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, a phosphorus compound having at least one P—OH bond is particularly preferable as the phosphorus compound. In addition to particularly improving the physical properties improving effect of the polyester by containing these phosphorus compounds, the catalytic activity is improved by using these phosphorus compounds together with the aluminum compound used in the present invention during the polymerization of the polyester. The effect is seen greatly.
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, use of a phosphonic acid compound having at least one P-OH bond facilitates formation of a complex with an aluminum compound, and is highly preferable for improving the physical properties and improving the catalytic activity of the polyester.

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

  As the phosphorus compound having at least one P—OH bond used in the present invention, when at least one selected from the compounds represented by the following general formula (Formula 18) is used, the physical property improving effect and the catalytic activity improving effect are obtained. Largely preferred.

(In the chemical formula (Chemical Formula 18), 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. And may contain an aromatic ring structure such as a branched structure or 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 above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are 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.

  A preferable phosphorus compound used in the present invention includes a phosphorus compound represented by the chemical formula (Formula 19).

(In the chemical formula (Chemical Formula 19), 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 independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, which has an alicyclic structure, a branched structure or an aromatic ring structure. May be included.)

More preferably, at least one of R ¹ , R ² and R ^{3 in} the chemical formula (Chemical Formula 19) 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 hard to be distilled off at the time of superposition | polymerization, it is large and preferable.

  The phosphorus compound used in the present invention is preferably a phosphorus compound having a phenol moiety in the same molecule. In addition to enhancing the physical properties of polyester by containing a phosphorus compound having a phenol moiety in the same molecule, the effect of increasing catalytic activity by using a phosphorus compound having a phenol moiety in the same molecule during polymerization of the polyester Is larger, and therefore the productivity of polyester is excellent.

  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. When one or more compounds selected from the group consisting of a compound, a phosphonous acid compound, a phosphinic acid compound, and a phosphine compound are used, the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are greatly preferred. Among these, when a phosphonic acid compound having one or two or more phenol moieties in the same molecule is used, the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are particularly large and preferable.

  As the phosphorus compound having a phenol moiety used in the present invention in the same molecule, compounds represented by the following chemical formulas (Chemical Formula 26) to (Chemical Formula 28) are preferable.

(In the chemical formulas (Chemical Formula 26) to (Chemical Formula 28), R ¹ is a carbon 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 phenol part. Represents a hydrocarbon group having a number of 1 to 50. R ⁴ , R ⁵ , and R ⁶ each independently represent a substituent such as 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, R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group and the like. represents a hydrocarbon group. However, end each other hydrocarbon groups branched structure or cyclohexyl alicyclic structure or a phenyl or a good .R ² also contain an aromatic ring structure of naphthyl R ⁴ of Or may be combined.)

  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 chemical formula (Formula 29), and the like compounds represented by to (Formula 32). Among these, a compound represented by the following chemical formula (Chemical Formula 31) and dimethyl p-hydroxyphenylphosphonate are particularly preferable.

  As a compound represented by the above chemical formula (Chemical Formula 31), SANKO-220 (manufactured by Sanko Co., Ltd.) can be used.

  Among the phosphorus compounds having a phenol moiety used in the present invention in the same molecule, at least one selected from a metal salt compound of a specific phosphorus represented by the following chemical formula (Chemical Formula 33) is particularly preferable.

(In the chemical formula (Chemical Formula 33), 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. Represents a hydrocarbon group having 1 to 50 carbon atoms including a group, and 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 is 4 or less. M represents a (l + m) -valent metal cation, n represents an integer of 1 or more, and the hydrocarbon group includes an alicyclic structure such as cyclohexyl, a branched structure, and an aromatic ring structure such as phenyl and naphthyl. There may be.)

  Among these, at least one selected from compounds represented by the following chemical formula (Formula 34) is preferable.

(In the chemical formula (Chemical Formula 34), M ^{n +} represents an n-valent metal cation. N represents 1, 2, 3 or 4.)

  Among the chemical formulas (Chemical Formula 33) or (Chemical Formula 34), when M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn, catalytic activity is improved. The effect is large and preferable. Of these, Li, Na, and Mg are particularly preferable.

  Specific metal salt compounds of phosphorus used in the present invention include lithium [3,5-di-tert-butyl-4-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-hydroxybenzylphosphonic acid ethyl], nickel bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl], copper bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid] Ethyl], zinc bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl] and the like. 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 having a phenol moiety used in the present invention in the same molecule, at least one selected from specific phosphorus compounds having at least one P—OH bond represented by the following chemical formula (Formula 35) is particularly preferable. .

(In the chemical formula (Chemical Formula 35), 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. Represents a C1-C50 hydrocarbon group containing a group, n represents an integer of 1 or more, and 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, at least one selected from compounds represented by the following chemical formula (Formula 36) is preferable.

(In the chemical formula (Chemical Formula 36), 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. The hydrocarbon group is a fat such as cyclohexyl. (It may contain a ring 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 and 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.

  Among the phosphorus compounds having a phenol moiety used in the present invention in the same molecule, at least one phosphorus compound selected from specific phosphorus compounds represented by the following chemical formula (Chemical Formula 37) is preferable.

(In the above chemical formula (Chemical 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 each independently represent hydrogen and carbon atoms having 1 to 50 carbon atoms. Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrogen group, 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, a branched structure, or an aromatic such as phenyl or naphthyl. It may contain a ring structure.)

  Among the above chemical formulas (Chemical formula 37), it is preferable to use at least one selected from the compounds represented by the following chemical formula (Chemical formula 38) because the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are high.

(In the above chemical formula (Formula 38), R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. The 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 in} the above chemical formula 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, An aromatic group such as a naphthyl group, a group represented by —CH ₂ CH ₂ OH, and the like can be given.

  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 having a phenol moiety in the same molecule used in the present invention, a particularly desirable compound in the present invention is at least one phosphorus compound selected from compounds represented by chemical formulas (Chemical Formula 39) and (Chemical Formula 40). is there.

  As the compound represented by the above chemical formula (Chemical Formula 39), Irganox 1222 (manufactured by Ciba Specialty Chemicals) is commercially available, and as the compound represented by the chemical formula (Chemical Formula 40), Irganox 1425 (Ciba Specialty Chemical). Chemicals) is commercially available and can be used.

  Other phosphorus compounds that can be used in the present invention include a phosphonic acid group having a linking group (X) represented by the following chemical formulas (Chemical Formula 41) and (Chemical Formula 42) or a linking group represented by (Chemical Formula 43) ( Examples thereof include phosphonic acid-based compounds having no X).

The phosphorus compound represented by the formula (Formula 41), which is a phosphorus compound having a wide range of linking groups (X) that can be used in the present invention, is as follows.
[Chemical Formula 41] R ¹ —X— (P═O) (OR ² ) (OR ³ )
[In the chemical formula having a linking group (Chemical Formula 41), R ¹ represents an aromatic ring structure having 6 to 50 carbon atoms or a heterocyclic structure having 4 to 50 carbon atoms, and the aromatic ring structure or heterocyclic structure represents a substituent. You may have. X is a linking group, an aliphatic hydrocarbon having 1 to 10 carbon atoms (which may be linear, branched or alicyclic), or an aliphatic group having 1 to 10 carbon atoms containing a substituent. Hydrocarbon (which may be linear, branched or alicyclic), —O—, —OCH ₂ —, —SO ₂ —, —CO—, —COCH ₂ —, —CH ₂ OCO—, It is selected from —NHCO—, —NH—, —NHCONH—, —NHSO ₂ —, —NHC ₃ H ₆ OCH ₂ CH ₂ O—. R ² and R ³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. ]

  The substituent of the aromatic ring structure and the heterocyclic structure of the phosphorus compound represented by the chemical formula (Chemical Formula 41) is a hydrocarbon group having 1 to 50 carbon atoms (an alicyclic structure, a branched structure, an aromatic ring even if it is linear) Or a hydroxyl group, a halogen group, a C1-C10 alkoxyl group or an amino group (C1-C10 alkyl or alkanol-substituted). Or a nitro group, a carboxyl group, an aliphatic carboxylic acid ester group having 1 to 10 carbon atoms, a formyl group, an acyl group, a sulfonic acid group, a sulfonic acid amide group (an alkyl or alkanol substituent having 1 to 10 carbon atoms) One group selected from a phosphoryl-containing group, a nitrile group, and a cyanoalkyl group. Properly is two or more.

  Examples of the phosphorus compound represented by the chemical formula (Chemical Formula 41) include the following. Specifically, benzylphosphonic acid, benzylphosphonic acid monoethyl ester, 1-naphthylmethylphosphonic acid, 1-naphthylmethylphosphonic acid monoethyl ester, 2-naphthylmethylphosphonic acid, 2-naphthylmethylphosphonic acid monoethyl ester, 4-phenyl, Benzylphosphonic acid, 4-phenyl, benzylphosphonic acid monoethyl ester, 2-phenyl, benzylphosphonic acid, 2-phenyl, benzylphosphonic acid monoethyl ester, 4-chloro, benzylphosphonic acid, 4-chloro, benzylphosphonic acid mono Ethyl ester, 4-chloro, benzylphosphonic acid diethyl ester, 4-methoxy, benzylphosphonic acid, 4-methoxy, benzylphosphonic acid monoethyl ester, 4-methoxy, benzylphosphonic acid diethyl ester, 4 Methyl, benzylphosphonic acid, 4-methyl, benzylphosphonic acid monoethyl ester, 4-methyl, benzylphosphonic acid diethyl ester, 4-nitro, benzylphosphonic acid, 4-nitro, benzylphosphonic acid monoethyl ester, 4-nitro, Benzylphosphonic acid diethyl ester, 4-amino, benzylphosphonic acid, 4-amino, benzylphosphonic acid monoethyl ester, 4-amino, benzylphosphonic acid diethyl ester, 2-methyl, benzylphosphonic acid, 2-methyl, benzylphosphonic acid Monoethyl ester, 2-methyl, benzylphosphonic acid diethyl ester, 10-anthranylmethylphosphonic acid, 10-anthranylmethylphosphonic acid monoethyl ester, 10-anthranylmethylphosphonic acid diethyl ester, (4- Toxiphenyl-, ethoxy-) methylphosphonic acid, (4-methoxyphenyl-, ethoxy-) methylphosphonic acid monomethyl ester, (4-methoxyphenyl-, ethoxy-) methylphosphonic acid dimethyl ester, (phenyl-, hydroxy-) methylphosphonic acid, (Phenyl-, hydroxy-) methylphosphonic acid monoethyl ester, (phenyl-, hydroxy-) methylphosphonic acid diethyl ester, (phenyl-, chloro-) methylphosphonic acid, (phenyl-, chloro-) methylphosphonic acid monoethyl ester, (phenyl -, Chloro-) methylphosphonic acid diethyl ester, (4-chlorophenyl) -iminophosphonic acid, (4-chlorophenyl) -iminophosphonic acid monoethyl ester, (4-chlorophenyl) -iminophosphone Acid diethyl ester, (4-hydroxyphenyl-, diphenyl-) methylphosphonic acid, (4-hydroxyphenyl-, diphenyl-) methylphosphonic acid monoethyl ester, (4-hydroxyphenyl-, diphenyl-) methylphosphonic acid diethyl ester, (4 -Chlorophenyl-, hydroxy-) methylphosphonic acid, (4-chlorophenyl-, hydroxy-) methylphosphonic acid monomethyl ester, (4-chlorophenyl-, hydroxy-) methylphosphonic acid dimethyl ester, and other phosphorus compounds containing heterocycles As 2-benzofuranylmethylphosphonic acid diethyl ester, 2-benzofuranylmethylphosphonic acid monoethyl ester, 2-benzofuranylmethylphosphonic acid, 2- (5-methyl) benzofuranylmethylphospho Acid diethyl ester, 2- (5-methyl) benzo furanyl methyl phosphonic acid monoethyl ester, 2- (5-methyl) benzo furanyl methyl phosphonic acid. The phosphorus compound which has said coupling group is a preferable aspect at the point of polymerization activity.

The phosphorus compound represented by the chemical formula (formula 41) having a linking group (X = — (CH ₂ ) _n —) that can be used in the present invention is as follows.
Formula _{^{42] (R 0) m -R1-}} (CH 2) n - (P = O) (OR 2) (OR 3)
[In the chemical formula (Chemical Formula 42), R ⁰ is a hydroxyl group, a C1-C10 alkyl group, —COOH group or —COOR ⁴ (R ⁴ represents a C1-C4 alkyl group), alkylene glycol group or monoalkoxyalkylene. Represents a glycol group (monoalkoxy represents C1-C4, alkylene glycol represents C1-C4 glycol). R ¹ represents an aromatic ring structure such as benzene, naphthalene, biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenylmethane, diphenyldimethylmethane, diphenyl ketone, anthracene, phenanthrene, and pyrene. R ² and R ³ each independently represent a hydrogen atom or a C1-C4 hydrocarbon group. m represents an integer of 1 to 5, and when R ⁰ is plural, it may be the same substituent or a combination of different substituents. n represents 0 or an integer of 1 to 5. ]

  Among the phosphorus compounds represented by the chemical formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure as benzene include the following. That is, 2-hydroxybenzylphosphonic acid diethyl ester, 2-hydroxybenzylphosphonic acid monoethyl ester, 2-hydroxybenzylphosphonic acid, 4-hydroxybenzylphosphonic acid diethyl ester, 4-hydroxybenzylphosphonic acid monoethyl ester, 4-hydroxy Benzylphosphonic acids, 6-hydroxybenzylphosphonic acid diethyl ester, 6-hydroxybenzylphosphonic acid monoethyl ester, 6-hydroxybenzylphosphonic acid, and the like include, but are not limited to, benzylphosphonic acids having a hydroxyl group introduced into the benzene ring. It is not a thing.

  2-n-butylbenzylphosphonic acid diethyl ester, 2-n-butylbenzylphosphonic acid monomethyl ester, 2-n-butylbenzylphosphonic acid, 3-n-butylbenzylphosphonic acid diethyl ester, 3-n-butylbenzylphosphonic acid Monoethyl ester, 3-n-butylbenzylphosphonic acid, 4-n-butylbenzylphosphonic acid diethyl ester, 4-n-butylbenzylphosphonic acid monoethyl ester, 4-n-butylbenzylphosphonic acid, 2,5-n -Dibutylbenzylphosphonic acid diethyl ester, 2,5-n-dibutylbenzylphosphonic acid monoethyl ester, 2,5-n-dibutylbenzylphosphonic acid, 3,5-n-dibutylbenzylphosphonic acid diethyl ester, 3,5- Monoethyl n-dibutylbenzylphosphonate Ester, 3, 5-n-butylbenzylphosphonic acid obtained by introducing an alkyl benzene rings, such as dibutyl benzyl phosphonic acid including but not limited to.

  Further, 2-carboxybenzylphosphonic acid diethyl ester, 2-carboxybenzylphosphonic acid monoethyl ester, 2-carboxybenzylphosphonic acid, 3-carboxybenzylphosphonic acid diethyl ester, 3-carboxybenzylphosphonic acid monoethyl ester, 3-carboxy Benzylphosphonic acid, 4-carboxybenzylphosphonic acid diethyl ester, 4-carboxybenzylphosphonic acid monoethyl ester, 4-carboxybenzylphosphonic acid, 2,5-dicarboxybenzylphosphonic acid diethyl ester, 2,5-dicarboxybenzylphosphone Acid monoethyl ester, 2,5-dicarboxybenzylphosphonic acid, 3,5-dicarboxybenzylphosphonic acid diethyl ester, 3,5-dicarboxybenzylphosphonic acid Ethyl ester, 3,5-dicarboxybenzylphosphonic acid, 2-methoxycarbonylbenzylphosphonic acid diethyl ester, 2-methoxycarbonylbenzylphosphonic acid monoethyl ester, 2-methoxycarbonylbenzylphosphonic acid, 3-methoxycarbonylbenzylphosphonic acid diethyl Ester, 3-methoxycarbonylbenzylphosphonic acid monoethyl ester, 3-methoxycarbonylbenzylphosphonic acid, 4-methoxycarbonylbenzylphosphonic acid diethyl ester, 4-methoxycarbonylbenzylphosphonic acid monoethyl ester, 4-methoxycarbonylbenzylphosphonic acid, 2,5-dimethoxycarbonylbenzylphosphonic acid diethyl ester, 2,5-dimethoxycarbonylbenzylphosphonic acid monoethyl ester Carboxyl on the benzene ring such as 2,5-dimethoxycarbonylbenzylphosphonic acid, 3,5-dimethoxycarbonylbenzylphosphonic acid diethyl ester, 3,5-dimethoxycarbonylbenzylphosphonic acid monoethyl ester, 3,5-dimethoxycarbonylbenzylphosphonic acid, etc. Benzylphosphonic acids into which a group or a carboxylic acid ester group has been introduced may be mentioned, but the invention is not limited thereto.

  Furthermore, 2- (2-hydroxyethoxy) benzylphosphonic acid diethyl ester, 2- (2-hydroxyethoxy) benzylphosphonic acid monoethyl ester, 2- (2-hydroxyethoxy) benzylphosphonic acid, 3- (2-hydroxyethoxy) ) Benzylphosphonic acid diethyl ester, 3- (2-hydroxyethoxy) benzylphosphonic acid monoethyl ester, 3- (2-hydroxyethoxy) benzylphosphonic acid, 4- (2-hydroxyethoxy) benzylphosphonic acid diethyl ester, 4- (2-hydroxyethoxy) benzylphosphonic acid monoethyl ester, 4- (2-hydroxyethoxy) benzylphosphonic acid, 2,5-di (2-hydroxyethoxy) benzylphosphonic acid diethyl ester, 2,5-di (2- Hydroxyethoxy Benzylphosphonic acid monoethyl ester, 2,5-di (2-hydroxyethoxy) benzylphosphonic acid, 3,5-di (2-hydroxyethoxy) benzylphosphonic acid diethyl ester, 3,5-di (2-hydroxyethoxy) Benzylphosphonic acid monoethyl ester, 3,5-di (2-hydroxyethoxy) benzylphosphonic acid, 2- (2-methoxyethoxy) benzylphosphonic acid diethyl ester, 2- (2-methoxyethoxy) benzylphosphonic acid monoethyl ester 1- (2-methoxyethoxy) benzylphosphonic acid, 3- (2-methoxyethoxy) benzylphosphonic acid monomethyl ester, 3- (2-methoxyethoxy) benzylphosphonic acid diethyl ester, 3- (2-methoxyethoxy) benzyl Phosphonic acid monoethyl ester 3- (2-methoxyethoxy) benzylphosphonic acid, 4- (2-methoxyethoxy) benzylphosphonic acid diethyl ester, 4- (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 4- (2-methoxyethoxy) ) Benzylphosphonic acid, 2,5-di (2-methoxyethoxy) benzylphosphonic acid diethyl ester, 2,5-di (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 2,5-di (2-methoxyethoxy) ) Benzylphosphonic acid, 3,5-di (2-methoxyethoxy) benzylphosphonic acid diethyl ester, 3,5-di (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 3,5-di (2-methoxyethoxy) ) Alkylene glycol group in benzene ring such as benzylphosphonic acid Include benzylphosphonic acids into which a monoalkoxylated alkylene glycol group has been introduced.

  The benzylic phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but the above-mentioned substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, 2 A mixture of -methoxyethoxy groups can also be used.

  Among the phosphorus compounds represented by the chemical formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure of naphthalene include the following. 1- (5-hydroxy) naphthylmethylphosphonic acid diethyl ester, 1- (5-hydroxy) naphthylmethylphosphonic acid monoethyl ester, 1- (5-hydroxy) naphthylmethylphosphonic acid, 1- (5-hydroxy) naphthylmethylphosphonic acid Diethyl ester, 1- (5-hydroxy) naphthylmethylphosphonic acid monoethyl ester, 1- (5-hydroxy) naphthylmethylphosphonic acid, 1- (5-n-butyl) naphthylmethylphosphonic acid diethyl ester, 1- (5-n- Butyl) naphthylmethylphosphonic acid monoethyl ester, 1- (5-n-butyl) naphthylmethylphosphonic acid, 1- (4-carboxy) naphthylmethylphosphonic acid diethyl ester, 1- (4-carboxy) naphthylmethylphosphonic acid monoethyl ester Ter, 1- (4-carboxy) naphthylmethylphosphonic acid, 1- (4-methoxycarbonyl) naphthylmethylphosphonic acid diethyl ester, 1- (4-methoxycarbonyl) naphthylmethylphosphonic acid monoethyl ester, 1- (4-methoxycarbonyl) Naphtylmethylphosphonic acid, 1- [4- (2-hydroxyethoxy)] naphthylmethylphosphonic acid diethyl ester, 1- [4- (2-hydroxyethoxy)] naphthylmethylphosphonic acid monoethyl ester, 1- [4- (2-hydroxy) Ethoxy)] naphthylmethylphosphonic acid, 1- (4-methoxyethoxy) naphthylmethylphosphonic acid diethyl ester, 1- (4-methoxyethoxy) naphthylmethylphosphonic acid monoethyl ester, 1- (4-methoxyethoxy) naphthylmethyl Phosphonic acid, 1- (5-hydroxy) naphthylmethylphosphonic acid diethyl ester, 2- (6-hydroxy) naphthylmethylphosphonic acid diethyl ester, 2- (6-hydroxy) naphthyl monoethylphosphonic acid, 2- (6-hydroxy) naphthyl Methylphosphonic acid, 2- (6-n-butyl) naphthylmethylphosphonic acid diethyl ester, 2- (6-n-butyl) naphthylmethylphosphonic acid monoethyl ester, 2- (6-n-butyl) naphthylmethylphosphonic acid, 2- ( 6-carboxy) naphthylmethylphosphonic acid diethyl ester, 2- (6-carboxy) naphthylmethylphosphonic acid monoethyl ester, 2- (6-carboxy) naphthylmethylphosphonic acid, 2- (6-methoxycarbonyl) naphthylmethylphosphonic acid diethyl ester 2- (6-methoxycarbonyl) naphthylmethylphosphonic acid monoethyl ester, 2- (6-methoxycarbonyl) naphthylmethylphosphonic acid, 2- [6- (2-hydroxyethoxy)] naphthylmethylphosphonic acid diethyl ester, 2- [6 -(2-hydroxyethoxy)] naphthylmethylphosphonic acid monoethyl ester, 2- [6- (2-hydroxyethoxy)] naphthylmethylphosphonic acid, 2- (6-methoxyethoxy) naphthylmethylphosphonic acid diethyl ester, 2- (6- Methoxyethoxy) naphthylmethylphosphonic acid monoethyl ester, 2- (6-methoxyethoxy) naphthylmethylphosphonic acid and the like on the naphthalene ring, alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monoalkoxyal Although such phosphonic acids such as glycol group is introduced are exemplified but not limited thereto.

  The naphthalene phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but includes the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, 2 A mixture of methoxyethoxy groups can also be used.

  Among the phosphorus compounds represented by the chemical formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure of biphenyl include the following. That is, 4- (4-hydroxyphenyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenyl) benzylphosphonic acid, 4- (4-n- Butylphenyl) benzylphosphonic acid diethyl ester, 4- (4-n-butylphenyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenyl) benzylphosphonic acid, 4- (4-carboxyphenyl) benzylphosphone Acid diethyl ester, 4- (4-carboxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyl) benzylphosphonic acid, 4- (4-methoxycarbonylphenyl) benzylphosphonic acid diethyl ester, 4- (4 -Methoxycarbonylph Nyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyl) benzylphosphonic acid, 4- (4-hydroxyethoxyphenyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxyethoxyphenyl) benzylphosphonic acid mono Ethyl ester, 4- (4-hydroxyethoxyphenyl) benzylphosphonic acid, 4- (4-methoxyethoxyphenyl) benzylphosphonic acid diethyl ester, 4- (4-methoxyethoxyphenyl) benzylphosphonic acid monoethyl ester, 4- ( 4-methoxyethoxyphenyl) phosphones in which an alkyl group, a carboxyl group, a carboxylic ester group, an alkylene glycol group, a monomethoxyalkylene glycol group or the like is introduced into a biphenyl ring such as benzylphosphonic acid Although s and the like are not limited thereto.

  The biphenyl phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but includes the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, 2 A mixture of methoxyethoxy groups can also be used.

  Among the phosphorus compounds represented by the chemical formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure as diphenyl ether include the following. That is, 4- (4-hydroxyphenyloxy) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenyloxy) benzylphosphonic acid, 4- (4 -N-butylphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-butylphenyloxy) benzylphosphonic acid, 4- (4- Carboxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyloxy) benzylphosphonic acid, 4- (4-methoxycarbonylphenyloxy) Benji Phosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyloxy) benzylphosphonic acid, 4- (4-hydroxyethoxyphenyloxy) benzylphosphonic acid Monoethyl ester, 4- (4-hydroxymethoxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenyloxy) benzylphosphonic acid, 4- (4-methoxyethoxyphenyloxy) benzylphosphonic acid monoethyl An alkyl group on a diphenyl ether ring such as ester, 4- (4-methoxyethoxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenyloxy) benzylphosphonic acid, Rubokikishiru group, a carboxylic acid ester group, an alkylene glycol group, and a phosphonic acids like are introduced monomethoxy polyalkylene glycol groups are not limited thereto.

  The diphenyl ether phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but includes the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, 2 A mixture of -methoxyethoxy groups can also be used.

  Among the phosphorus compounds represented by the chemical formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure as diphenithioether include the following. That is, 4- (4-hydroxyphenylthio) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenylthio) benzylphosphonic acid, 4- (4 -N-butylphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-butylphenylthio) benzylphosphonic acid, 4- (4- Carboxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenylthio) benzylphosphonic acid, 4- (4-methoxycarbonylphenylthio) Benzylphosphonic acid monoethyl Ester, 4- (4-methoxycarbonylphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenylthio) benzylphosphonic acid, 4- (4-hydroxyethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenylthio) benzylphosphonic acid, 4- (4-methoxyethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenylthio) benzylphosphonic acid and other diphenylthioether rings have an alkyl group, a carboxyl group, a carboxylic acid ester Group, alkylene glycol group, and a phosphonic acids like are introduced monomethoxy polyalkylene glycol groups are not limited thereto.

  The diphenylthioether-based phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but includes the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, A mixture of 2-methoxyethoxy groups can also be used.

  Among the phosphorus compounds represented by the chemical formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure of diphenyl sulfone include the following. 4- (4-hydroxyphenylsulfonyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenylsulfonyl) benzylphosphonic acid, 4- (4-n -Butylphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-butylphenylsulfonyl) benzylphosphonic acid, 4- (4-carboxyphenyl) Sulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenylsulfonyl) benzylphosphonic acid, 4- (4-methoxycarbo) Ruphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenylsulfonyl) benzylphosphonic acid, 4- (4-hydroxyethoxyphenyl) Sulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenylsulfonyl) benzylphosphonic acid, 4- (4-methoxyethoxyphenylsulfonyl) Benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenylsulfonyl) ) Examples include, but are not limited to, phosphonic acids in which an alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monomethoxyalkylene glycol group or the like is introduced into a diphenylsulfone ring such as benzylphosphonic acid. .

  The diphenylsulfone-based phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but includes the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, A mixture of 2-methoxyethoxy groups can also be used.

  Among the phosphorus compounds represented by the chemical formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure of diphenylmethane include the following. That is, 4- (4-hydroxybenzyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxybenzyl) benzylphosphonic acid, 4- (4-n- Butylbenzyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylbenzyl) benzylphosphonic acid monoethyl ester, 4- (4-butylbenzyl) benzylphosphonic acid, 4- (4-carboxybenzyl) benzylphosphonic acid Monoethyl ester, 4- (4-carboxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxybenzyl) benzylphosphonic acid, 4- (4-methoxycarbonylbenzyl) benzylphosphonic acid monoethyl ester, 4- ( 4-methoxycarbonyl Benzyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylbenzyl) benzylphosphonic acid, 4- (4-hydroxyethoxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxybenzyl) benzylphosphonic acid Monoethyl ester, 4- (4-hydroxymethoxybenzyl) benzylphosphonic acid, 4- (4-methoxyethoxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxybenzyl) benzylphosphonic acid monoethyl ester, 4 An alkyl group, a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group or the like is introduced into a diphenylmethane ring such as-(4-methoxyethoxybenzyl) benzylphosphonic acid. And the like phosphonic acids include but are not limited thereto.

  The diphenylmethane phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but includes the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, 2 A mixture of methoxyethoxy groups can also be used.

  Among the phosphorus compounds represented by the chemical formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure of diphenyldimethylmethane include the following. That is, 4- (4-hydroxyphenyldimethylmethyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenyldimethylmethyl) benzylphosphonic acid, 4 -(4-n-butylphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-butylphenyldimethylmethyl) benzylphosphonic acid 4- (4-carboxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyldimethylmethyl) Benzylphosphonic acid, 4- (4-methoxycarbonylphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyldimethylmethyl) ) Benzylphosphonic acid, 4- (4-hydroxyethoxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenyldimethyl) Methyl) benzylphosphonic acid, 4- (4-methoxyethoxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenyldimethylmethyl) benzene Alkyl groups, carboxyxyl groups, carboxylic acid ester groups, alkylene glycol groups, monomethoxyalkylene glycol groups, etc. were introduced into diphenylmethane rings such as diphosphonic acid monoethyl ester and 4- (4-methoxyethoxyphenyldimethylmethyl) benzylphosphonic acid. Examples thereof include, but are not limited to, phosphonic acids.

  The diphenyldimethylmethane-based phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group Also, a mixture of 2-methoxyethoxy groups can be used.

  Among the phosphorus compounds represented by the chemical formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds whose aromatic ring structure having a substituent is diphenyl ketone include the following. That is, 4- (4-hydroxybenzoyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxybenzoyl) benzylphosphonic acid, 4- (4-n- Butylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-butylbenzoyl) benzylphosphonic acid, 4- (4-carboxybenzoyl) benzylphosphonic acid Monoethyl ester, 4- (4-carboxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxybenzoyl) benzylphosphonic acid, 4- (4-methoxycarbonylbenzoyl) benzylphosphonic acid monoethyl ester, 4- ( 4 Methoxycarbonylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylbenzoyl) benzylphosphonic acid, 4- (4-hydroxyethoxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxybenzoyl) benzyl Phosphonic acid monoethyl ester, 4- (4-hydroxymethoxybenzoyl) benzylphosphonic acid, 4- (4-methoxyethoxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxybenzoyl) benzylphosphonic acid monoethyl ester , 4- (4-methoxyethoxybenzoyl) benzylphosphonic acid and the like on an alkyl group, a carboxy group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxy group Although such phosphonic acids such as alkylene glycol group is introduced are exemplified but not limited thereto.

  The diphenyl ketone phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but the above-mentioned substituent, hydroxyl group, alkyl group, carboxyl group, carboxy ester group, 2-hydroxyethoxy group, A mixture of 2-methoxyethoxy groups can also be used.

  Among the phosphorus compounds represented by the chemical formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds having an anthracene substituted aromatic ring structure include the following. That is, 9- (10-hydroxy) anthrylmethylphosphonic acid diethyl ester, 9- (10-hydroxy) anthrylmethylphosphonic acid monoethyl ester, 9- (10-hydroxy) anthrylmethylphosphonic acid, 9- (10-n- Butyl) anthrylmethylphosphonic acid diethyl ester, 9- (10-n-butyl) anthrylmethylphosphonic acid monoethyl ester, 9- (10-n-butyl) anthrylylmethylphosphonic acid, 9- (10-carboxy) anthryl Methylphosphonic acid diethyl ester, 9- (10-carboxy) anthrylmethylphosphonic acid monoethyl ester, 9- (10-carboxy) anthrylmethylphosphonic acid, 9- (10-carboxy) 9- (2-hydroxyethoxy) anthrylmethylphosphone Acid di Chill ester, 9- (2-hydroxyethoxy) anthrylmethylphosphonic acid monoethyl ester, 9- (2-hydroxyethoxy) anthrylmethylphosphonic acid, 9- (2-methoxyethoxy) anthrylmethylphosphonic acid diethyl ester, 9- (2 -Methoxyethoxy) anthrylmethylphosphonic acid monoethyl ester, 9- (2-methoxyethoxy) anthrylmethylphosphonic acid, 9- (2-methoxycarbonyl) anthrylmethylphosphonic acid diethyl ester, 9- (2-methoxycarbonyl) anthryl Anthracene rings such as methylphosphonic acid monoethyl ester and 9- (2-methoxycarbonyl) anthrylmethylphosphonic acid have alkyl groups, carboxyxyl groups, carboxylic acid ester groups, alkylene glycol groups, monomethoxy groups. Although such phosphonic acids such as alkylene glycol group is introduced are exemplified but not limited thereto.

  The anthracene phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but includes the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, 2 A mixture of -methoxyethoxy groups can also be used.

  Among the phosphorus compounds represented by the chemical formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure as phenanthrene include the following. 1- (7-n-butyl) phenanthrylmethylphosphonic acid diethyl ester, 1- (7-n-butyl) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-n-butyl) phenanthrylmethylphosphone Acid, 1- (7-carboxy) phenanthrylmethylphosphonic acid diethyl ester, 1- (7-carboxy) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-carboxy) phenanthrylmethylphosphonic acid, 1- (7 -Hydroxyethoxy) phenanthrylmethylphosphonic acid diethyl ester, 1- (7-hydroxyethoxy) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-hydroxyethoxy) phenanthrylmethylphosphonic acid, 1- (7-methoxyethoxy) ) Phenanthryl 1- (7-methoxyethoxy) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-methoxyethoxy) phenanthrylmethylphosphonic acid, 1- (7-methoxycarbonyl) phenanthrylmethylphosphonic acid diethyl ester Ester, 1- (7-methoxycarbonyl) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-methoxycarbonyl) phenanthrylmethylphosphonic acid, etc., phenanthrene ring, alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol Examples thereof include, but are not limited to, phosphonic acids into which a group or a monomethoxyalkylene glycol group has been introduced.

  The phenanthrene-based phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but includes the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, 2 A mixture of methoxyethoxy groups can also be used.

  Among the phosphorus compounds represented by the chemical formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds in which the aromatic ring structure having a substituent is pyrene include the following. 1- (5-hydroxy) pyrenylmethylphosphonic acid diethyl ester, 1- (5-hydroxy) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-hydroxy) pyrenylmethylphosphonic acid, 1- (5-n- Butyl) pyrenylylmethylphosphonic acid diethyl ester, 1- (5-n-butyl) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-n-butyl) pyrenylmethylphosphonic acid, 1- (5-carboxy) pyrenyl Methylphosphonic acid diethyl ester, 1- (5-carboxy) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-carboxy) pyrenylmethylphosphonic acid, 1- (5-hydroxyethoxy) pyrenylmethylphosphonic acid diethyl ester, 1- ( 5-hydroxyethoxy) pyrenylmethylphos Acid monoethyl ester, 1- (5-hydroxyethoxy) pyrenylmethylphosphonic acid, 1- (5-methoxyethoxy) pyrenylmethylphosphonic acid diethyl ester, 1- (5-methoxyethoxy) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-methoxyethoxy) pyrenylmethylphosphonic acid, 1- (5-methoxycarbonyl) pyrenylmethylphosphonic acid diethyl ester, 1- (5-methoxycarbonyl) pyrenylmethylphosphonic acid monoethyl ester, 1- (5- Examples include, but are not limited to, phosphonic acids in which an alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monomethoxyalkylene glycol group or the like is introduced into a pyrene ring such as (methoxycarbonyl) pyrenylmethylphosphonic acid. Not shall.

  The pyrene phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but includes the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, 2 A mixture of methoxyethoxy groups can also be used.

  Substituents such as hydroxyl groups, alkyl groups, carboxyl groups, carboxyester groups, 2-hydroxyethoxy groups, 2-methoxyethoxy groups introduced into the series of aromatic rings are complexed with aluminum atoms during polymerization of the polyester. It is estimated to be deeply related to In addition, a carboxyl group or a hydroxyl group that is a functional group at the time of polyester formation is also included, and since it is easily dissolved or taken into the polyester matrix, it is considered to be particularly effective for polymerization activity and foreign matter reduction.

Compared to an unsubstituted group in which R ⁰ is a hydrogen atom bonded to an aromatic ring structure (R ¹ ), a C1-C10 alkyl group, —COOH group or —COOR ⁴ (R ⁴ is C1-C4) used in the present invention. A phosphorus compound substituted with an alkylene glycol group or a monoalkoxyalkylene glycol group (monoalkoxy represents C1-C4, alkylene glycol represents a C1-C4 glycol) only improves the catalytic activity. However, it is preferable in terms of the effect of reducing foreign matter.
Examples of the substituent bonded to the aromatic ring structure include C1-C10 alkyl groups, carboxyl and carboxyl ester groups, alkylene glycols and monoalkoxy alkylene glycols. From the viewpoint of the effect of reducing foreign matter, carboxyl and carboxyl ester groups, alkylene glycols and monoalkoxy alkylene glycols are more preferable. The reason for this is unknown, but it is assumed that the compatibility with the alkylene glycol, which is a medium for the polyester and the catalyst, is improved.

The phosphorus compound represented by the chemical formula (Formula 43) which is a phosphorus compound having no linking group (X) that can be used in the present invention is as follows.
[Chemical Formula 43] R ¹ — (P═O) (OR ² ) (OR ³ )
[On the other hand, in the phosphorus compound represented by the above chemical formula (Formula 43) having no linking group (X), R ¹ represents an aromatic ring structure having 6 to 50 carbon atoms or a heterocyclic structure having 4 to 50 carbon atoms, The aromatic ring structure or the heterocyclic structure may have a substituent. R ² and R ³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure.
The substituent of the aromatic ring structure and the heterocyclic structure of the phosphorus compound represented by the chemical formula (Chemical Formula 43) is a hydrocarbon group having 1 to 50 carbon atoms (even if it is a straight chain, an alicyclic structure, a branched structure, an aromatic ring Or a hydroxyl group, a halogen group, a C1-C10 alkoxyl group or an amino group (C1-C10 alkyl or alkanol-substituted). Or a nitro group, a carboxyl group, an aliphatic carboxylic acid ester group having 1 to 10 carbon atoms, a formyl group, an acyl group, a sulfonic acid group, a sulfonic acid amide group (an alkyl or alkanol substituent having 1 to 10 carbon atoms) 1 type selected from phosphoryl-containing groups, nitrile groups, and cyanoalkyl groups. Ku is 2 or more. The aromatic ring structure represented by the chemical formula (Chemical Formula 43) is selected from benzene, naphthalene, biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenylmethane, diphenyldimethylmethane, anthracene, phenanthrene and pyrene. And the heterocyclic structure is selected from furan, benzofuran, isobenzofuran, dibenzofuran, naphthalane and phthalide. Moreover, it is preferable that at least one of R ² and R ^{3 in} the above formula (Formula 43) is a hydrogen atom. ]

Examples of the phosphorus compound represented by the chemical formula (Formula 43) that can be used in the present invention include the following phosphorus compounds. That is, (3-nitro, 5-methyl) -phenylphosphonic acid diethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid monoethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid, ( 3-nitro, 5-methoxy) -phenylphosphonic acid diethyl ester, (3-nitro, 5-methoxy) -phenylphosphonic acid monoethyl ester, (3-nitro, 5-methoxy) -phenylphosphonic acid, (4-chloro ) -Phenylphosphonic acid diethyl ester, (4-chloro,)-phenylphosphonic acid monoethyl ester, (4-chloro) -phenylphosphonic acid, (5-chloro,)-phenylphosphonic acid diethyl ester, (5-chloro, ) -Phenylphosphonic acid monoethyl ester, (5-chloro,)-phenylphosphonic acid, ( -Nitro, 5-methyl) -phenylphosphonic acid diethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid monoethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid, (4-nitro) -Phenylphosphonic acid diethyl ester, (4-nitro) -phenylphosphonic acid monoethyl ester, (4-nitro) -phenylphosphonic acid, (5-nitro) -phenylphosphonic acid diethyl ester, (5-nitro) -phenylphosphone Acid monoethyl ester, (5-nitro) -phenylphosphonic acid, (6-nitro) -phenylphosphonic acid diethyl ester, (6-nitro) -phenylphosphonic acid monoethyl ester, (6-nitro) -phenylphosphonic acid, (4-nitro, 6-methyl) -phenylphosphonic acid diethyl ester, 4-nitro, 6-methyl) -phenylphosphonic acid monoethyl ester, (4-nitro, 6-methyl) -phenylphosphonic acid, and other phosphorus compounds represented by the formula (Chemical Formula 42): , biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenylmethane, diphenyldimethylmethane, diphenyl ketone, anthracene, i.e. a methylene chain is a linking group from the respective structural formulas having an aromatic ring structure such as phenanthrene and pyrene, -CH 2 _- and The removed phosphorus compound group and the heterocyclic ring-containing phosphorus compound include 5-benzofuranylphosphonic acid diethyl ester, 5-benzofuranylphosphonic acid monoethyl ester, 5-benzofuranylphosphonic acid, 5- (2-methyl) Benzov Niruhosuhon acid diethyl ester, 5- (2-methyl) benzo furanyl phosphonic acid monoethyl ester, 5- (2-methyl) benzo furanyl phosphonic acid. The phosphorus compound having no linking group described above has a slightly lower polymerization activity than the phosphorus compound having the linking group described above, but can be used as a polyester polymerization catalyst when the catalyst preparation method described in the present invention is used. It is.

  In the present invention, it is a preferred embodiment that the phosphorus compound is preheated in at least one solvent selected from the group consisting of water and alkylene glycol. The treatment improves the polycondensation catalyst activity by using the above phosphorus compound in combination with the above-mentioned aluminum or aluminum compound, and decreases the foreign matter forming property due to the polycondensation catalyst.

  The solvent used when heat-treating the phosphorus compound in advance is not limited as long as it is at least one selected from the group consisting of water and alkylene glycol, but it is preferable to use a solvent that dissolves the phosphorus compound. As the alkylene glycol, it is preferable to use glycol which is a constituent component of the target polyester such as ethylene glycol. The heat treatment in the solvent is preferably performed after dissolving the phosphorus compound, but may not be completely dissolved. Further, it is not necessary that the compound retains the original structure after the heat treatment, and the solubility in the solvent may be improved by the modification by the heat treatment.

  Although the temperature of heat processing is not specifically limited, It is preferable that it is the range of 20-250 degreeC. More preferably, it is the range of 100-200 degreeC. The upper limit of the temperature is preferably around the boiling point of the solvent used. Although the heating time varies depending on conditions such as temperature, the heating temperature is preferably in the range of 1 minute to 50 hours, more preferably 30 minutes to 10 hours, and even more preferably 1 to 5 hours. Range. The pressure of the heat treatment system may be normal pressure, higher or lower, and is not particularly limited. The concentration of the solution is preferably 1 to 500 g / l as a phosphorus compound, more preferably 5 to 300 g / l, and still more preferably 10 to 100 g / l. The heat treatment is preferably performed in an atmosphere of an inert gas such as nitrogen. The storage temperature of the solution or slurry after heating is not particularly limited, but is preferably in the range of 0 ° C to 100 ° C, and more preferably in the range of 20 ° C to 60 ° C. It is preferable to store the solution in an atmosphere of an inert gas such as nitrogen.

  When the phosphorus compound is previously heat-treated in a solvent, aluminum used in the present invention or a compound thereof may coexist. Alternatively, the aluminum used in the present invention or a compound thereof may be added as a powder, solution, or slurry to a phosphorus compound that has been previously heat-treated in a solvent. Furthermore, you may heat-process the solution or slurry after addition. The solution or slurry obtained by these operations can be used as the polycondensation catalyst according to the present invention. It is preferable to add 95% by mass or more dissolved or dispersed in a solvent comprising a glycol component.

  As the usage-amount of the phosphorus compound in this invention, 0.0001-0.1 mol% is preferable with respect to the number-of-moles of all the structural units of the carboxylic acid component of the polyester obtained, 0.005-0.05 mol% More preferably it is.

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

  Examples of the Fe compound include ferrous chloride, ferric chloride, ferrous sulfate, ferrous oxide, ferric oxide, ferrous acetate, ferric acetate, and the like.

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

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

  Examples of the Sn compound include stannous chloride, stannic chloride, stannous sulfate, stannous oxide, stannic oxide, tetraphenyltin, stannous octoate, stannous acetate, stannic acetate, Dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin sulfide, dibutylhydroxytin oxide, methyl Stannic acid, ethylstannic acid and the like can be mentioned.

  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.

  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 antimony compound is preferably added in an amount of 50 ppm or less as an antimony atom to the polyester obtained by polymerization. A more preferable addition amount is 30 ppm or less. When the amount of antimony added exceeds 50 ppm, metal antimony is precipitated, and darkening and foreign matter are generated in the polyester.

  The germanium compound is preferably added in an amount of 20 ppm or less as germanium atoms to the polyester obtained by polymerization. A more preferable addition amount is 10 ppm or less. If the amount of germanium added exceeds 20 ppm, it is not preferable because it is disadvantageous in terms of cost.

  Although it does not specifically limit as an antimony compound which can be used in this invention, An antimony trioxide, an antimony pentoxide, an antimony acetate, an antimony glycoxide etc. are mentioned as a suitable compound, Especially use of antimony trioxide is preferable. Further, the germanium compound is not particularly limited, and examples thereof include germanium dioxide and germanium tetrachloride. Germanium dioxide is particularly preferable. As germanium dioxide, both crystalline and amorphous materials can be used.

  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 melt polycondensation polyester obtained as described above is, for example, a method in which the melt polyester is extruded into water from the die pores after completion of the melt polycondensation and cut in water, or after the melt polycondensation is finished in the air from the die pores. After being extruded into strands, the chips are formed into columns, spheres, squares or plates by a method of forming chips while cooling with cooling water.

  Moreover, as the cooling water at the time of chip formation of the melt polycondensed polyester, it is preferable to use cooling water that satisfies at least one of the above (1) to (4), and more preferably (1) to (4 It is most preferable to use water that satisfies all of the above.

  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. When the intrinsic viscosity is less than 0.50 deciliter / gram, there is a problem that the elastic recovery and durability of the obtained molded article are deteriorated. 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 a molded article, the thermal decomposition becomes severe, the molecular weight decreases drastically, 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 during molding is increased, and the increase in the content of aldehydes is increased. 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. 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 by-produced during production from ethylene glycol, which is a 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, 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 mean that ethylene glycol is a major component of glycol component, such as polyester whose main constituent unit is ethylene terephthalate and polyester whose main constituent unit is ethylene-2,6-naphthalate. In the case of polyester as a component, it is acetaldehyde or formaldehyde, in the case of polyester having 1,3-propylene terephthalate as a main constituent unit, allyl aldehyde, and in the case of polyester having butylene terephthalate as a main constituent unit. Butanal. However, in the case of polyester having butylene terephthalate as the main structural unit, the aldehyde is mostly detected as tetrahydrofuran.

  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.

  In addition, for the flavor retention of the molded article comprising the polyester resin composition of the present invention, the polyester resin (2) according to the present invention has a free aromatic dicarboxylic acid content derived from the polyester of 20 ppm or less, It is preferable that the polyester resin has a free glycol content of 70 ppm or less, a free aromatic dicarboxylic acid monoglycol ester content of 100 ppm or less, and a free aromatic dicarboxylic acid diglycol ester content of 150 ppm or less.

  As a method for producing such a polyester resin (2), for example, the following method can be employed. That is, a method of solid-phase polymerization of a solution-polymerized polyester prepolymer having IV of 0.40 to 0.60 can be used. Also, a method in which a predetermined IV polyester is heat-treated under an inert gas atmosphere or under reduced pressure under conditions where IV does not substantially change can be used. Moreover, the method of drying polyester at the temperature of 70-180 degreeC under pressure reduction or an inert airflow can be used. Moreover, the method of heat-processing a polyester resin with organic solvents, such as chloroform, can also be used.

  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 content of the fine in the polyester resin (2) according to the present invention 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, most preferably Preferably it is 0.1-100 ppm. When the blending amount is less than 0.1 ppm, the crystallization rate becomes very slow, and the crystallization of the plug portion of the hollow molded container becomes insufficient, and therefore the shrinkage amount of the plug portion falls within the specified range. It does not fit, and capping is impossible. On the other hand, when it exceeds 5000 ppm, the crystallization speed becomes faster than necessary and the fluctuation of the speed becomes large. Therefore, the degree of crystallinity of the plug portion of the hollow molded body becomes excessive and fluctuated, and therefore the amount of shrinkage of the plug portion does not fall within the specified value range, resulting in poor capping of the plug portion and leakage of contents. Occurs, and the preform for the hollow molded body is whitened, so that normal stretching is impossible. In particular, when the polyester resin (2) is used as a polyester resin for a hollow molded article, the fine content is preferably 0.1 to 500 ppm.

  Further, when the polyester resin (2) according to the present invention is a polyester resin having ethylene terephthalate as a main repeating unit, the haze of a molded product obtained by injection molding thereof is 30% or less, preferably 20% or less. More preferably, it is 10% or less, and the crystallization temperature (Tc1) at the time of temperature rise is 140 to 180 ° C., preferably 145 to 175 ° C., more preferably 150 to 170 ° C.

  The shape of the chip of the polyester resin (2) 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.

  In addition, when it is necessary to improve the solid-phase polymerization rate or to reduce the content of aldehydes more effectively, the average weight (W) of the chips is also preferably 1 to 5 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 aldehydes of the obtained molded product As a result, the content of is extremely increased, 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. Further, when the blending amount of the polyester resin (1) exceeds 10 parts by weight, the molecular weight of the obtained molded product is lowered, the bottle strength is lowered, the heat resistance is deteriorated, or the color is yellow. As a result, there is a problem that the commercial value is reduced.

A preferred catalyst combination mainly used in the polyester resin composition of the present invention is:
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 50 ppm or less, preferably 30 ppm or less, more preferably 10 ppm or less, and further preferably 5 ppm or less. When the content of aldehydes is 50 ppm or more, the flavor and odor of contents such as containers molded from this polyester resin composition are deteriorated. In particular, the polyester resin (2) according to the present invention is a polyester resin whose main repeating unit is composed of ethylene terephthalate, and the polyester resin composition comprising this is used as a material for containers for low flavor beverages such as mineral water. In such a case, the content of aldehydes in the polyester resin composition is desirably 10 ppm or less, preferably 8 ppm or less, more preferably 6 ppm or less, and most preferably 5 ppm or less.

  Examples of a method for obtaining a polyester resin composition having an aldehyde content of 50 ppm or less include a method using a polyester resin (1) and a polyester resin (2) having an aldehyde content of 50 ppm or less, and aldehydes of both polyester resins. The method of calculating from content and the mixing ratio of both resin and making it 50 ppm or less etc. are mentioned.

  The content of the cyclic ester oligomer in the polyester resin composition of 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 melt polycondensate of the polyester resin. % Or less, 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.

  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.

Further, the content of aldehydes in the molded product obtained by injection molding of the polyester resin composition was B _t ppm, and the content of aldehydes in the polyester resin composition before injection molding was B ₀ ppm. In this case, it is preferred that B _t -B ₀ is 30 ppm or less, preferably 20 ppm or less, more preferably 10 ppm or less, and most preferably 5 ppm or less. When B _t -B ₀ exceeds 30 ppm, the content of aldehydes such as the obtained molded article cannot be reduced to 50 ppm or less, which is a problem.

Further, the values of B _t -B ₀ of the polyester resin composition of the present invention, that no molded article properties such as flavor and aroma of the contents is changed by using the following polyester resin composition 30ppm Obtainable. When the value of B _t -B ₀ exceeds 30 ppm, the bad odor is too tight and the flavor retention is poor, and the contents such as flavor and aroma are deteriorated, which causes a problem. In addition, the lower limit value of B _t -B ₀ is 1 ppm, and it has been found that even if it is reduced to less than this value, the flavor retention does not change and is ineffective.

Further, the content of cyclic ester oligomers of polyester resin composition content of the cyclic ester oligomer of the molded body obtained by injection molding and A _t ppm, the polyester resin composition before injection molding of the present invention A in case of the _{0 ppm,} preferably a t -A ₀ is less than 300 ppm, more preferably less than 200 ppm, it is preferred particularly preferably 100ppm or less. _The lower limit of A t -A ₀ is 5ppm in terms of economic productivity. If A _t -A ₀ of the is 500ppm or less, the exhaust port of the molding machine, is capable of long-time molding free from problems such as contamination and clogging of such molten resin discharge port and the molding die, the transparency A good polyester molded body is obtained, and there is no problem in operability. However, if the the A _t -A ₀ exceeds 500ppm, the outlet of the molding machine, etc. is vigorously dirt and clogging of such molten resin discharge port and the molding die, a long time molding becomes difficult. At the time of molding a hollow molded body, the transparency becomes very bad, which is a problem.

  The polyester resin composition of the present invention comprises: a content of phosphorus atom contained in the polyester resin (1); a type of polycondensation catalyst metal atom contained in the polyester resin (2); a content of polycondensation catalyst metal atom; It can be obtained by appropriately adjusting the blending ratio of the resin (1) and the polyester resin (2). For example, the molar ratio of the phosphorus atom residual amount (P) to the residual amount of metal atoms (Me) derived from the polycondensation catalyst excluding the residual amount of Ge metal atoms and the residual amount of Sb metal atoms remaining in the polyester resin composition ( P / Me) is 0.3-20, preferably 0.5-15, more preferably 1.0-10, and the phosphorus atom residual amount is 0.5-200 ppm, preferably 1-150 ppm, more preferably Is a method of blending the polyester resin (1) and the polyester resin (2) so as to be 5 to 100 ppm, or using a Ge compound as a polycondensation catalyst of the polyester resin (1), and polycondensation of the polyester resin (2) A method using at least one selected from the group consisting of an aluminum compound or a titanium compound as a catalyst, or a method combining these methods. However, it is not limited to these.

  It is desirable that the 5 mm-thick molded product obtained by injection molding the polyester resin composition of the present invention has a haze of 30% or less, preferably 25% or less, more preferably 20% or less. In particular, when the polyester resin composition of the present invention is used for a hollow molded article, the haze is preferably 15% or less, and when used for a heat-resistant hollow molded article, the haze is preferably 10% or less. When the haze of the molded body exceeds 30%, the transparency of the obtained molded body is deteriorated, which causes a problem and the commercial value is lost.

  In addition, the measurement of the cyclic ester oligomer content of the polyester resin (1), the molding method of the molded body (stepped molding plate) from the polyester resin (1), and the measurement of the cyclic ester oligomer content of the molded body are as follows. Explain in the Law section. However, the cylinder temperature of the injection molding machine for molding the molded body must be changed depending on the melting point of the polyester resin (2) to be used. The PET polyester, PBT polyester resin, PTT polyester resin and fat For the polyester resin composition comprising the polyester resin (2) such as a group polyester resin or the polyester resin composition comprising the polyester resin (2) which is the PEN-based polyester resin, the measurement method (10) is used. The other set values of the cylinder temperature are set to 290 ° C. or 300 ° C., respectively.

  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 140 to 180 ° C., preferably in the range of 145 to 175 ° C., and more preferably in the range of 150 to 170 ° C. When Tc1 exceeds 180 ° 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 140 ° C., the transparency of the hollow molded article is lowered, which causes a problem.

  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.

  In order to prevent the mixing ratio from fluctuating at the time of mixing or molding, the chip shape and grain weight of the polyester resin (1) and the polyester resin (2) must be substantially the same.

  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 value range, capping defects occur, and the heat-fixed mold for forming heat-resistant hollow molded products is heavily soiled. When trying to obtain a transparent hollow molded product, the mold is frequently cleaned. There must be. On the other hand, 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 shrinkage amount of the plug part will not fall within the specified value range, resulting in capping failure and contents. Leakage, and the preform for the hollow molded body is whitened, which makes normal stretching impossible. Also, in the case of a sheet-like material, if it exceeds 1000 ppm, the transparency is very poor, the stretchability is also impaired, and normal stretching is impossible, and only a stretched film with large thickness spots 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, 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.

  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 intrinsic viscosity of the molded body composed of the polyester resin composition of the present invention is 0.55 to 1.50. It is preferably deciliter / gram, more preferably 0.58 to 1.20 deciliter / gram.

  In the case where 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 acetaldehyde content of the molded body composed of the polyester resin composition of the present invention is preferably 50 ppm or less, preferably Is 30 ppm or less, more preferably 25 ppm or less, and still more preferably 18 ppm or less.

  The polyester resin composition of the present invention includes other thermoplastic resins such as gas barrier polyesters, ultraviolet absorbing polyesters, gas barrier polyamide resins, etc. in addition to the above-mentioned added amounts of thermoplastic resins and aldehyde reducing agents. As appropriate, an appropriate amount of can be blended within a range that does not impair the effects of the present invention.

  In addition, the polyester resin composition of the present invention may include a known ultraviolet absorber, antioxidant, oxygen scavenger, lubricant added from the outside, lubricant precipitated inside the reaction, mold release agent, core as necessary. Various additives such as an agent, a stabilizer, an antistatic agent, a bluing agent, a dye, and a pigment 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 slipping property, winding property 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 terephthalate such as calcium oxalate, calcium, barium, zinc, manganese, magnesium, 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 can be contained.

(Uses such as polyester moldings)
The aldehyde content in applications such as molded articles comprising the polyester resin composition of the present invention (hereinafter simply referred to as molded articles) is 70 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less, even more preferably 15 ppm or less, most preferably. Is 10 ppm or less. When the aldehyde content exceeds 70 ppm, the flavor retention of the molded product content is deteriorated, which is a problem.

  In the case where 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 acetaldehyde content of the molded body composed of the polyester resin composition of the present invention is preferably 30 ppm or less, preferably Is 25 ppm or less, more preferably 20 ppm or less, still more preferably 15 ppm or less, and most preferably 10 ppm or less. In particular, in the case of a low flavor beverage container such as mineral water, it is desirable that it is 20 ppm or less, preferably 15 ppm or less, more preferably 10 ppm or less.

  The cyclic ester oligomer content of the molded article comprising the polyester resin composition of the present invention is 70% or less, preferably 60% or less, more preferably 70% or less of the cyclic ester oligomer content of the melt polycondensation polyester prepolymer of the polyester resin (2). Is 50% or less, most preferably 40% or less.

  In the case where 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 cyclic trimer content of the molded body composed of the polyester resin composition of the present invention is 0. .5% by weight or less, preferably 0.4% by weight or less, preferably 0.35% by weight or less. If it exceeds 0.5% by weight, mold contamination during molding becomes severe, which is a problem.

  Further, the amount of increase in the cyclic ester oligomer when the molded article comprising the polyester resin composition of the present invention is melted at a temperature of X ° C. for 60 minutes is 0.40% by weight or less, preferably 0.30% by weight or less, more preferably Is 0.20% by weight or less, most preferably 0.10% by weight or less. The temperature X ° C. is 290 ° C. in the case of a polyester resin composition comprising the polyester resin (2) such as the PET polyester, PBT polyester resin, and PTT polyester resin, and the PEN polyester resin In the case of the polyester resin composition which consists of a certain polyester resin (2), it is 300 degreeC.

  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 molded body made of the polyester resin composition of the present invention is melted at a temperature of 290 ° C. for 60 minutes. The increase amount of the cyclic trimer is 0.40% by weight or less, preferably 0.30% by weight or less, more preferably 0.20% by weight or less, and most preferably 0.10% by weight or less. The increase in the amount of the cyclic trimer when melted for 60 minutes at a temperature of 290 ° C. exceeds 0.40% by weight means that the catalytic action of the polycondensation catalyst of the polyester resin (2) has been completely deactivated. The cyclic trimer regenerates during molding and melting, and oligomer adhesion to the surface of the heating mold increases rapidly during continuous molding, and the transparency of the resulting molded body such as a hollow molded body is increased. There arises a problem that it is very deteriorated and a great amount of labor and time are required for cleaning the mold. Further, the lower limit value of the cyclic trimer increase amount is about 0.01% by weight, and even if the lower limit value is decreased below this, the economic effect on the above problems is very small. Here, the amount of increase in the cyclic trimer when melted at a temperature of 290 ° C. for 60 minutes is from a 3 mm thick plate of a stepped molded plate obtained by the molding method described in the “Measurement Method” section below. This is the value obtained for the sample.

  The polyester resin composition of the present invention is formed by molding a hollow molded body, a tray, a biaxially stretched film or other packaging material, a metal can coating film, a fiber including a monofilament, and the like using a commonly used melt molding method. Alternatively, a coating coated on another substrate can be formed by a melt extrusion method. 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 sheet-like material comprising the polyester resin composition of the present invention can be produced by a means known per se. For example, it can be manufactured using a general sheet forming machine equipped with an extruder and a die or a sheet forming machine by calendering.

  Further, the sheet-like material can be formed into a cup shape or a tray shape by pressure forming or vacuum forming. Moreover, the polyester molding from the polyester resin composition of this invention can be used also for the use of the tray-shaped container for cooking food with a microwave oven and / or an oven range, or heating frozen food. it can. In this case, after the sheet-like material is formed into a tray shape, it is thermally crystallized to improve heat resistance.

Moreover, the polyester resin composition of this invention can be used also as one structural layer which took the form of a film form or a coating film form in composite molded objects, such as a laminated molded object and a laminated film. In particular, it is used for manufacturing containers and the like in the form of a laminate with PET. Examples of the laminated molded body include a two-layer structure composed of two layers of an outer layer made of the polyester resin composition of the present invention and a PET inner layer, or two layers of an inner layer made of the polyester resin composition of the present invention and a PET outer layer. A three-layer structure comprising a polyester resin composition of the present invention, a three-layer structure comprising an outer layer and an innermost layer of PET, or an outer layer and an innermost layer comprising a polyester resin composition of the present invention And a three-layer structure formed of an intermediate layer of PET, an intermediate layer including the polyester resin composition of the present invention, and a five-layer structure formed of an innermost layer, a central layer, and an innermost layer of PET. Can be mentioned. In the PET layer, other gas barrier resins, ultraviolet blocking resins, heat resistant resins, recovered products from used polyethylene terephthalate bottles, and the like can be mixed and used at an appropriate ratio.
Other examples of the laminated molded body include a laminated molded body with a resin other than polyester such as polyolefin, and a laminated molded body with a different type of substrate such as paper or a metal plate.

There is no restriction | limiting in particular in the thickness of the said laminated molded object, and the thickness of each layer. The laminated molded body can be used in various shapes such as a sheet-like material, a film-like material, a plate-like material, a hollow body, and a container.
The laminate can be produced by co-extrusion using a number of extruders corresponding to the type of the resin layer and a multi-layered multi-die, or with a number of injection machines corresponding to the type of the resin layer. It can also be done by co-injection using an injection runner and injection mold.

Another application of the polyester resin composition of the present invention is a film laminated on one or both sides of a laminated metal plate. Examples of the metal plate used include tinplate, tin-free steel, and aluminum.
As a laminating method, a conventionally known method can be applied, and it is not particularly limited, but it is preferable to carry out by a thermal laminating method that can achieve organic solvent-free and can avoid adverse effects on the taste and odor of food products due to the residual solvent. In particular, the thermal laminating method by energization processing of a metal plate is particularly recommended. In the case of double-sided lamination, lamination may be performed simultaneously or sequentially.
Needless to say, a film can be laminated to a metal plate using an adhesive.

  Moreover, a metal container is obtained by shape | molding using the said laminated metal plate. The method for forming the metal container is not particularly limited. Further, the shape of the metal container is not particularly limited, but is preferably applied to a so-called two-piece can produced by a molding process such as drawing, drawing and ironing, and stretch draw molding. The present invention can also be applied to a so-called three-piece can in which a top cover suitable for filling a food product such as a coffee drink is wrapped to fill the contents.

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, it is generally heat-set in a blow mold and heat resistant. 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 is also used for the production of a stretched hollow molded body by a so-called compression molding method in which a preform obtained by compression molding a melted mass cut after melt extrusion is stretch blow molded. be able to.

  The polyester resin composition of the present invention can produce fibers by a conventional melt spinning method, and a method of spinning and stretching in two steps and a method of performing in one step can be adopted. Furthermore, all known fiber manufacturing methods such as staple manufacturing methods and monofilaments with crimping, heat setting and cutting steps can be applied.

  Further, the obtained fiber can have various fiber structures such as an irregular cross-section yarn, a hollow cross-section yarn, a composite fiber, and an original yarn, and a known means such as blending or blending is also used in yarn processing. be able to.

  Furthermore, the polyester fiber can be made into a fiber structure such as a woven or knitted fabric or a non-woven fabric.

  The above polyester fibers are used for interior and bedding fibers such as clothing fibers, curtains, carpets, futons, fiber fills, tensile cords such as tire cords and ropes, civil engineering and building materials, and vehicles such as airbags. It can be used for various fiber applications such as fibers for industrial materials represented by materials, various fabrics, various knitted fabrics, nets, short fiber nonwoven fabrics, and long fiber nonwoven fabrics.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
The main characteristic value measurement methods will be described below.

(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.
The IV retention is a value obtained by dividing the IV of the molded product by the IV of the polyester resin composition and multiplying this by 100.

(2) Acetaldehyde content of polyester (hereinafter referred to as “AA”)
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. The said operation is repeated 5 times and let the average value be AA content.

(3) Diethylene glycol content of polyester (hereinafter referred to as “DEG”), triethylene glycol content (hereinafter referred to as “TEG”)
Polyester was dissolved in deuterated trifluoroacetic acid / chloroform under deuterium (volume ratio 1/9), and ¹ H-NMR was measured with an AVANCE-500 type NMR apparatus manufactured by Bruca Biospin. It calculated | required from the integral intensity | strength of the peak of the proton of each copolymerization component.

(4) Polyester cyclic trimer content (hereinafter referred to as “CT content”)
300 mg of a sample is dissolved in 3 ml of a hexafluoroisopropanol / chloroform mixed solution (volume ratio = 2/3), and further diluted with 30 ml of chloroform. To this is added 15 ml of methanol to precipitate the polymer, followed by filtration. The filtrate was evaporated to dryness, brought to a constant volume with 10 ml of dimethylformamide, and the cyclic trimer was quantified by high performance liquid chromatography.

(5) Color b value of polyester chip and molded body The crystallized polyester chip and the molded body (thickness 4 mm) of the following (10) were used as a color difference meter TC-1500MC-88 JIS-Z8722 manufactured by Tokyo Denshoku (Hunter color difference) It measured according to.

(6) Moisture content measurement in polyester (wt%)
(Measured with the Karl Fischer trace moisture measuring device CA-100 manufactured by Mitsubishi Chemical and the moisture vaporizer VA-100)
A moisture vaporizer VA-100 manufactured by Mitsubishi Chemical was previously dried in two drying cylinders (filled with silica gel and phosphorus pentoxide), and the heating furnace was heated to 230 ° C. while flowing nitrogen gas at a flow rate of 250 ml / min. The sample board was put into a heating furnace, and after confirming that the dry nitrogen obtained from the heating furnace and the sample board was anhydrous with a trace moisture measuring device CA-100, 3 g of the sample was previously dried. Weigh accurately in a sample container and immediately place the sample in the sample board. The water vaporized from the sample is transported to a trace moisture measuring device CA-100 by dry nitrogen and subjected to Karl Fischer titration to determine the moisture content.

(7) Measurement of Fine Content About 0.5 kg of resin, a sieve (A) with a wire mesh with a nominal size of 5.6 mm according to JIS-Z8801, and a sieve with a wire mesh with a nominal size 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 then filtered through a G1 glass filter manufactured by Iwaki Glass Co., Ltd. collected. These were dried together with a glass filter in a dryer at 100 ° C. for 2 hours, then cooled and weighed. Again, the same operation of washing and drying with ion-exchanged water was 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.
(8) Haze (Fraction%)
A sample was cut from the molded article (wall thickness 4 mm) of the following (10), and measured with a Nippon Denshoku Co., Ltd. haze meter, model NDH2000.

(9) Increase amount of cyclic trimer by molding (A _t -A ₀ ) and increase amount of acetaldehyde content by molding (B _t -B ₀ )
From a polyester resin composition, the CT content of A _t and injection molding prior to the polyester resin composition of the samples from the central portion of the method the plate of 3mm thickness stepped molded plate according to (10) (n = 5) CT was determined and calculated from the amount _{A 0} by the following formula (n = 5).
Cyclic trimer increase by molding = A _t - A ₀
Further, AA content of the polyester resin composition before AA content B _t and injection molding of samples taken from the central portion of the plate of 2mm thickness stepped molded plate obtained by the method (10) from the polyester resin composition was determined and calculated from B ₀ by the following formula (n = 5).
Amount of increase in AA content due to molding = B _t -B ₀
In addition, _A0 and _B0 are calculated | required by calculation from CT content of each polyester resin to comprise, AA content, and a structure ratio.

(10) Molding of a stepped molded plate 1) Molding of a stepped molded plate In molding of a stepped molded plate according to the description of this patent, a famous machine is used by using the samples described in 2), 3) and 4) below. 2 mm to 11 mm (part A thickness = 2 mm, part B thickness = 3 mm) having a gate part (G) as shown in FIG. 1 and FIG. A stepped molding plate having a thickness of C part = 4 mm, D part thickness = 5 mm, E part thickness = 10 mm, and F part thickness = 11 mm) was injection molded.
In order to prevent moisture absorption of the chips during molding, a dry inert gas (nitrogen gas) purge was performed in the molding material hopper.
The plasticizing conditions of the M-150C-DM injection molding machine are as follows: feed screw rotation speed = 70%, screw rotation speed = 120 rpm, back pressure 0.5 MPa, cylinder temperature 45 ° C., 250 ° C. from the bottom of the hopper in order, nozzle The temperature was set at 290 ° C. 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 characteristics of the molded product 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.
In the case of a polyester resin composition from PEN-based polyester, the cylinder temperature of the injection molding machine is set to 45 ° C. and 250 ° C. in order from directly below the hopper, and other cylinder temperatures including nozzles are set to 300 ° C. The cooling water of 30 degreeC was poured into.
A 2 mm thick plate (part A in FIG. 1) measures the crystallization temperature (Tc1) and acetaldehyde content at elevated temperature, and a 3 mm thick plate (part B in FIG. 1) has a cyclic trimer content (CT Content), a 4 mm-thick plate of polyester resin (1) (part C in FIG. 1) and a 5 mm-thick plate of polyester resin composition (part D in FIG. 1) were measured for haze (degree%). A 4 mm thick plate (C portion in FIG. 1) of the polyester resin composition is used for color measurement.

2) Polyester resin (1)
Molding is performed by the method of 1) above using a polyester resin (1) chip dried under reduced pressure to a moisture content of about 50 ppm or less using a Yamato Scientific vacuum dryer type DP61. It is necessary to dry before molding the moisture-absorbed polyester resins (A) to (J).

3) Polyester resin (2)
The polyester resin (1) is molded by the method of 1) above using a polyester resin (2) chip dried under reduced pressure to a moisture content of about 50 ppm or less using a vacuum dryer.

4) Polyester resin composition In Examples 1-8 and Comparative Examples 1-5, the polyester resin composition that was quickly mixed so as not to change the moisture content of the polyester resin of Table 1 was subjected to molding as it was.

(11) Molding of hollow molded body (in the case of PET polyester)
In Examples 1 to 8 and Comparative Examples 1 to 5, the polyester resin composition quickly mixed without changing the moisture content in Table 1 was used as it was with a M-150C-DM injection molding machine manufactured by Meiki Seisakusho. A preform was molded at a resin temperature of 290 ° C. 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 with a LB-01E molding machine manufactured by CORPOPLAST, and then heat-set in a mold set at about 150 ° C., and a container having a capacity of 2000 cc (body thickness 0. 45 mm). The stretching temperature was controlled at 100 ° C.
However, in the continuous molding acceleration test, 1000 pieces were continuously formed in the same manner as described above except that the mold setting temperature was about 160 ° C. and the heat setting time was about 2 minutes. The appearance of the 10th and 1000th bottles was observed. Further, before starting the acceleration test, the blow mold was cleaned of all dirt on the mold surface with gauze previously containing a mixed solvent of hexafluoroisopropanol / chloroform.
(Bottle appearance evaluation)
◎: Very good transparency ○: Good transparency △: Slightly poor transparency ×: Poor transparency

(12) Sensory test Boiled distilled water was put into the hollow container obtained in (11) above, kept for 30 minutes after sealing, and allowed to stand at 55 ° C. for 1 week. After opening, the flavor and smell were tested. Use distilled water as a blank for comparison. The sensory test was carried out by 10 panelists according to the following criteria, and the average values were compared.
(Evaluation criteria)
◎: Feel no strange taste or smell ○: Feel a slight difference from the blank △: Feel a difference from the blank ×: Feel a considerable difference from the blank XX: Feel a very large difference from the blank

(13) Appearance of stepped molded body The appearance of the stepped molded body of (10) was visually determined.
×: Appearance is poor due to silver
△: Silver is not generated, but hue and transparency are poor ○: Appearance is good

(14) UV blocking property (%)
A sample was cut from the molded article (thickness 2 mm) of the above (10), and the ultraviolet blocking property at 380 nm was measured with an absorbance measuring device U-2900 manufactured by Hitachi, Ltd. Good UV blocking properties are exhibited at 90% or more.

(Polyester resin (1) -TA)
1162 kg of high-purity terephthalic acid and 2 times its molar amount of ethylene glycol were charged into a heat-medium circulating esterification reactor, and 0.3 mol% of triethylamine was added to the acid component at 245 ° C. under a pressure of 0.25 MPa. While distilling water out of the system, the esterification reaction was carried out for 2 hours 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 as a polycondensation catalyst, a crystalline germanium dioxide / ethylene glycol solution and a polyester obtained from a heat-treated solution of phosphoric acid and ethylene glycol were each about 20 ppm in terms of residual Ge. And P was added so that the residual amount was about 2000 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 0.65 deciliter / gram. Following release of pressure, the resin under slight pressure was led to an underwater cutter to form a chip to obtain a cylindrical chip. At the time of chip formation, the resin temperature from the polycondenser outlet to the nozzle pores was about 270 ° C., and the entire amount was chipped within about 30 minutes.
Then, it was immediately heat-treated at about 50 to about 150 ° C. in a vacuum dryer and processed by a vibration sieving step and an airflow classification step to obtain a crystallized polymer. The IV was 0.65 deciliter / gram, the acetaldehyde content was 43 ppm, the DEG content was 4.7 mol%, and the CT content was 0.83 wt%. The moisture content was adjusted to 3500 ppm by adjusting the drying conditions. The characteristics are shown in Table 1.

(Polyester resin (1) -TB)
Except for shortening the polycondensation time, the melt polycondensation reaction was carried out under the same conditions as for obtaining the polyester resin (1) -TA until the IV was about 0.56 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 state polymerization was performed at 205 ° C., and the IV was 0.72 deciliter / gram, the acetaldehyde content was 25 ppm, the DEG content was 5.0 mol%, and the CT content was 0.46 wt%. The water content was set to 700 ppm. The characteristics are shown in Table 1.

(Polyester resin (1) -TC)
As a polycondensation catalyst, polycondensation is carried out in the same manner as the polyester resin (1) -TA except that antimony trioxide is added instead of crystalline germanium dioxide so that the residual amount of Sb is 180 ppm and the residual amount of P is about 500 ppm. And a polyester resin with IV = 0.68 deciliter / gram was obtained. Dry crystallization was performed in the same manner as described above except that the final treatment temperature was 180 ° C. The moisture condition was adjusted to 3500 ppm by adjusting the drying conditions. The characteristics are shown in Table 1.

(Polyester resin (1) -TD)
As a polycondensation catalyst, polycondensation is carried out in the same manner as in the polyester resin (1) -TA except that antimony trioxide is added instead of crystalline germanium dioxide so that the residual amount of Sb is 170 ppm and the residual amount of P is about 9000 ppm. And a polyester resin with IV = 0.55 deciliter / gram was obtained. This was subjected to solid phase polymerization in the same manner as polyester resin (1) -TB. IV is 0.72 deciliter / gram, acetaldehyde content is 23 ppm, DEG content is 4.7 mol%, CT content is 0.43 wt%. The moisture condition was adjusted to 3500 ppm by adjusting the drying conditions. The characteristics are shown in Table 1.

(Polyester resin (1) -TE) (Production method of polyester of comparative example)
The polyester resin (1) -TE having a moisture content of 46 ppm was obtained by adjusting the drying conditions of the polyester resin (1) -TB. The characteristics are shown in Table 1.

(Polyester resin (1) -TF) (Production method of polyester of comparative example)
The polyester resin (1) -TB was absorbed to obtain a polyester resin (1) -TF having a moisture content of 12000 ppm. The characteristics are shown in Table 1.

(Polyester resin (1) -TG)) (Manufacturing method of polyester of comparative example)
Polycondensation is performed in the same manner as the polyester resin (1) -TA except that antimony trioxide is added as a polycondensation catalyst instead of crystalline germanium dioxide so that the residual amount of Sb is 380 ppm and the residual amount of P is 40 ppm. IV = 0.55 deciliter / gram of polyester resin was obtained. This was subjected to solid phase polymerization in the same manner as polyester resin (1) -TB. The moisture condition was adjusted to 3500 ppm by adjusting the drying conditions. The characteristics are shown in Table 1.

(Polyester resin (1) -TH)) (Production method of comparative polyester)
Into a heat transfer circulating esterification reactor, 1512 kg of high-purity terephthalic acid and 2 times its molar amount of ethylene glycol were charged, 0.3 mol% of triethylamine was added to the acid component, and the pressure was increased to 255 ° 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%. This BHET mixture was transported to a polycondensator with a stirrer, and as a polycondensation catalyst, a crystalline germanium dioxide / ethylene glycol solution and a polyester obtained by heating a solution of phosphoric acid and ethylene glycol were used. About 20 ppm and triethyl phosphoric acid were added so that the residual amount of P was 16000 ppm. Next, the mixture was stirred at 255 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Thereafter, while raising the temperature to 260 ° C., the pressure of the reaction system was gradually lowered to 13.3 Pa (0.1 Torr) for 50 minutes for the first stage of initial polycondensation, and further polymerization was carried out at 285 ° C. and 13.3 Pa. However, it gelled and could not be polymerized. The characteristics are shown in Table 1.

(Polyester resin (2) -a) (base resin production method)
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 polycondensed at about 275 ° C. and 0.3 to 1 torr with stirring in the final polycondensation reactor. The obtained melt polycondensed PET had an intrinsic viscosity of 0.55 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 207 ° 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 had an intrinsic viscosity of 0.74 deciliter / gram, an acetaldehyde content of 3.2 ppm, a DEG content of 2.6 mol%, a cyclic trimer content of 0.32 wt%, and a density of 1 400 g / cm ³ . Al residual amount was 20 ppm, and P residual amount was 35 ppm. The characteristics are shown in Table 1.

(Polyester resin (2) -b)
The same method as in the case of the polyester resin (2) -a except that an ethylene glycol solution of titanium tetrabutoxide, an ethylene glycol solution of magnesium acetate tetrahydrate as a polycondensation catalyst, and an ethylene glycol solution of phosphoric acid as a stabilizer are used. A melt polycondensed PET was obtained. The obtained melt polycondensed PET had an intrinsic viscosity of 0.58 deciliter / gram.
Next, solid phase polymerization was performed in the same manner as in the case of the polyester resin (2) -a.
The obtained PET has an intrinsic viscosity of 0.75 deciliter / gram, an acetaldehyde content of 5 ppm, a DEG content of 2.6 mol%, a cyclic trimer content of 3800 ppm, and a density of 1.399 g / cm ³ . there were. Ti residual amount was 3.5 ppm, Mg residual amount was 2 ppm, P residual amount was 7 ppm, and fine content was about 50 ppm. The characteristics are shown in Table 1.

(Polyester resin (2) -c)
A melt polycondensed PET was obtained in the same manner as in the case of the polyester resin (2) -a except that an ethylene glycol solution of antimony trioxide was used as the polycondensation catalyst and an ethylene glycol solution of phosphoric acid was used as the stabilizer. The obtained melt polycondensed PET had an intrinsic viscosity of 0.57 deciliter / gram. Next, solid phase polymerization was performed in the same manner as in the case of the polyester resin (2) -a.
The obtained PET has an intrinsic viscosity of 0.75 deciliter / gram, an acetaldehyde content of 5.1 ppm, a DEG content of 2.6 mol%, a cyclic trimer content of 3400 ppm, and a density of 1.402 g / cm. ³ . The residual amount of Sb was 290 ppm and the residual amount of P was 12 ppm. The characteristics are shown in Table 1.

Example 1
The above-mentioned polyester resin (2) -a, 98 parts by weight, and catalyst deutilized moisture-containing polyester resin (1) -TA, 2 parts by weight were mixed in a blender. Thereafter, a stepped molded plate was formed by the method (10), and a bottle was formed by the method (11).
The CT content of the polyester resin composition is 3300 ppm, the CT content of the molded plate is 3200 ppm, the increase amount of the cyclic trimer by molding is −100 ppm, and the increase amount B _t -B ₀ of the acetaldehyde content by molding is 9.0 ppm The IV retention rate was 95%, the appearance of the molded product was good with good, the sensory test was good, and the bottle appearance evaluation by the continuous molding acceleration test was good. Table 2 shows the results.

(Examples 2 to 7)
Although the test of Example 2-7 was implemented similarly to Example 1, all the evaluation items did not have a problem. Table 2 shows the results.

(Comparative Example 1)
The polyester resin (2) -a, 98 parts by weight and polyester resin (1) -TE, 2 parts by weight were mixed in a blender. Thereafter, a stepped molded plate was formed by the method (10), and a bottle was formed by the method (11).
The CT content of the polyester resin composition is 3230 ppm, the CT content of the molding plate is 3340 ppm, the increase amount ΔCT of the cyclic trimer by molding is 110 ppm, B _t -B ₀ is 11.6 ppm, the IV retention is 98%, molding The appearance of the product was good with ○, and the sensory test was ○, but the bottle appearance evaluation by the continuous molding acceleration test was poor with x. Table 2 shows the results.

(Comparative Examples 2 and 3)
Evaluation of Comparative Examples 2 and 3 was carried out in the same manner as Example 1. None of them had satisfactory characteristics, and the evaluation results were not satisfactory. It is shown in Table 2.

(Comparative Example 4)
The polyester resin (2) -a, 100 parts by weight, was formed into a stepped plate by the method (10), and a bottle was formed by the method (11).
The CT content of the polyester resin composition is 3200 ppm, the CT content of the molded plate is 4000 ppm, the amount of the cyclic trimer increased by molding is 800 ppm, B _t -B ₀ is 20.0 ppm, the IV retention rate is 98%, and the molded product The appearance was good with ○, but the sensory test was Δ, and the bottle appearance evaluation by the continuous molding acceleration test was bad with ×. Table 2 shows the results.

(Comparative Example 5)
Although the composition of Comparative Example 5 in Table 2 was evaluated in the same manner as described above, the CT content of the molded plate was 4200 ppm, the amount of increase in the cyclic trimer due to molding was 1000 ppm, and B _t -B ₀ was 35.4 ppm. Although the IV retention was 98%, the appearance of the molded product was Δ, the hue and transparency were poor, the sensory test was XX, and the bottle appearance evaluation by the continuous molding acceleration test was XX. Table 2 shows the results.

(Polyester resin (1) -NA)
A heat medium circulating esterification reactor with a stirrer made of Hastelloy was charged with 1512 kg of naphthalenedicarboxylic acid and twice its amount of ethylene glycol, 0.3 mol% of triethylamine was added to the acid component, and 255 under a pressure of 0.25 MPa. The esterification reaction was carried out for 2 hours while distilling water out of the system at 0 ° C. to obtain a mixture of bis (2-hydroxyethyl) naphthalate and oligomer (hereinafter referred to as BHEN mixture) having an esterification rate of 95%. This BHEN mixture was transported to a Hastelloy-made polycondensator with a stirrer, and a crystalline germanium dioxide / ethylene glycol solution and a polyester obtained by heating phosphoric acid and ethylene glycol as a polycondensation catalyst to the polyester were obtained respectively. An amount of about 20 ppm and a P residual amount of about 2000 ppm were added. Next, the mixture was stirred at 255 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Thereafter, while raising the temperature to 280 ° C., the pressure in the reaction system is gradually reduced to 13.3 Pa (0.1 Torr) for 50 minutes to perform the first stage initial polycondensation, and then the IV is increased at 295 ° C. and 13.3 Pa. The polycondensation reaction was carried out to about 0.65 deciliter / gram. Subsequent to releasing the pressure, the resin under slight pressure was discharged into cold water in the form of a strand and rapidly cooled, and was converted into a chip with a strand cutter to obtain a cylindrical chip. At the time of chip formation, the resin temperature from the polycondenser outlet to the nozzle pores was about 295 ° C., and the entire amount was chipped within about 30 minutes.

  Then, it was immediately heat-treated at about 50 to about 150 ° C. in a vacuum dryer, and processed by a vibration sieving step and an airflow classification step to obtain a crystallized polymer. IV is 0.65 deciliter / gram, acetaldehyde content is 43 ppm, DEG content is 5.0 mol%, Fe atom content, Cr atom content, Ni atom content and Zn atom content are all 0.1 ppm Met. The characteristics are shown in Table 3. The fine content was about 500 ppm.

(Polyester resin (1) -NB, (1) -NC, (1) -ND, (1) -NE)
The moisture content was adjusted to the value shown in Table 3 by adjusting the drying conditions of the resin obtained by polycondensation reaction in the same manner as for the polyester resin (1) -NA. The characteristics are shown in Table 3.

(Polyester resin (1) -NF)
Polyester resin (1) -NF was obtained by performing polycondensation in the same manner as the polyester resin (1) -NA except that the residual amount of P was about 9000 ppm. The moisture condition was adjusted to 3500 ppm by adjusting the drying conditions. The characteristics are shown in Table 3.

(Polyester resin (1) -NG)
The esterification reactor was charged with 756 kg of naphthalenedicarboxylic acid, 983 kg of high-purity terephthalic acid and 2 times its molar amount of ethylene glycol, 0.3 mol% of triethylamine was added to the acid component, and 245 MPa under pressure of 0.25 MPa. A mixture of bis (2-hydroxyethyl) naphthalate, bis (2-hydroxyethyl) terephthalate and oligomer (hereinafter referred to as BHEN) having an esterification rate of 95% while distilling water out of the system at 2 ° C. for 2 hours. A mixture). This BHEN mixture is transported to the polycondensator with a stirrer, and as a polycondensation catalyst, a crystalline germanium dioxide / ethylene glycol solution and a polyester obtained by heating phosphoric acid and ethylene glycol are obtained. An amount of about 20 ppm and a P residual amount of about 2000 ppm were added. 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 0.65 deciliter / gram. Subsequent to releasing the pressure, the resin under slight pressure was discharged into cold water in the form of a strand and rapidly cooled, and was converted into a chip with a strand cutter to obtain a cylindrical chip. At the time of chip formation, the resin temperature from the polycondenser outlet to the nozzle pores was about 270 ° C., and the entire amount was chipped within about 30 minutes.

  Then, it was immediately heat-treated at about 50 to about 150 ° C. in a vacuum dryer, and processed by a vibration sieving step and an airflow classification step to obtain a crystallized polymer. As the resin composition, naphthalenedicarboxylic acid 50 mol%, terephthalic acid 50 mol%, IV was 0.65 deciliter / gram, acetaldehyde content was 43 ppm, and DEG content was 4.5 mol%. The characteristics are shown in Table 3. The fine content was comparable to that of the polyester resin (1) -NA.

(Polyester resin (1) -NH)
The esterification reactor was charged with 295 kg of naphthalenedicarboxylic acid, 1285 kg of high-purity terephthalic acid, and twice its amount of ethylene glycol, 0.3 mol% of triethylamine was added to the acid component, and 245 ° C. under a pressure of 0.25 MPa. A mixture of bis (2-hydroxyethyl) naphthalate, bis (2-hydroxyethyl) terephthalate and oligomer having an esterification rate of 95% (hereinafter referred to as a BHEN mixture) I got). The BHEN mixture was transported to the polycondensator with a stirrer, and the residual germanium was obtained for each of the polyesters obtained from the crystalline germanium dioxide / ethylene glycol solution and the heat-treated solution of phosphoric acid and ethylene glycol as the polycondensation catalyst. To about 20 ppm and the residual amount of P was about 2000 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 0.65 deciliter / gram. Subsequent to releasing the pressure, the resin under slight pressure was discharged into cold water in the form of a strand and rapidly cooled, and was converted into a chip with a strand cutter to obtain a cylindrical chip. At the time of chip formation, the resin temperature from the polycondenser outlet to the nozzle pores was about 270 ° C., and the entire amount was chipped within about 30 minutes.

  Then, it was immediately heat-treated at about 50 to about 150 ° C. in a vacuum dryer, and processed by a vibration sieving step and an airflow classification step to obtain a crystallized polymer. As the resin composition, naphthalenedicarboxylic acid was 15 mol%, terephthalic acid was 85 mol%, IV was 0.65 deciliter / gram, acetaldehyde content was 45 ppm, and DEG content was 4.7 mol%. The characteristics are shown in Table 3. The fine content was comparable to that of the polyester resin (1) -NA.

(Polyester resin (1) -NI)
The esterification reactor was charged with 1512 kg of naphthalenedicarboxylic acid and 2 times its molar amount of ethylene glycol, 0.3 mol% of triethylamine was added to the acid component, and water was added outside the system at 255 ° C. under a pressure of 0.25 MPa. An esterification reaction was carried out for 2 hours while distilling off to obtain a mixture of bis (2-hydroxyethyl) naphthalate and oligomer (hereinafter referred to as BHEN mixture) having an esterification rate of 95%. The BHEN mixture was transported to the polycondensator with a stirrer, and the residual germanium was obtained for each of the polyesters obtained from the crystalline germanium dioxide / ethylene glycol solution and the heat-treated solution of phosphoric acid and ethylene glycol. And about 20 ppm and the residual amount of P was 60 ppm. Next, the mixture was stirred at 255 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Thereafter, while raising the temperature to 280 ° C., the pressure in the reaction system is gradually reduced to 13.3 Pa (0.1 Torr) for 50 minutes to perform the first stage initial polycondensation, and then the IV is increased at 295 ° C. and 13.3 Pa. The polycondensation reaction was carried out to about 0.65 deciliter / gram. Subsequent to releasing the pressure, the resin under slight pressure was discharged into cold water in the form of a strand and rapidly cooled, and was converted into a chip with a strand cutter to obtain a cylindrical chip. At the time of chip formation, the resin temperature from the polycondenser outlet to the nozzle pores was about 295 ° C., and the entire amount was chipped within about 30 minutes.
Then, it was immediately heat-treated at about 50 to about 150 ° C. in a vacuum dryer and treated by a vibration sieving step to obtain a crystallized polymer. The IV was 0.65 deciliter / gram, the acetaldehyde content was 30 ppm, and the DEG content was 2.3 mol%. The characteristics are shown in Table 3. The fine content was 2.3% by weight.

(Polyester resin (1) -NJ)
The esterification reactor was charged with 1512 kg of naphthalenedicarboxylic acid and 2 times its molar amount of ethylene glycol, 0.3 mol% of triethylamine was added to the acid component, and water was added outside the system at 255 ° C. under a pressure of 0.25 MPa. An esterification reaction was carried out for 2 hours while distilling off to obtain a mixture of bis (2-hydroxyethyl) naphthalate and oligomer (hereinafter referred to as BHEN mixture) having an esterification rate of 95%. The BHEN mixture was transported to the polycondensator with a stirrer, and the residual germanium was obtained for each of the polyesters obtained from the crystalline germanium dioxide / ethylene glycol solution and the heat-treated solution of phosphoric acid and ethylene glycol as the polycondensation catalyst. The total amount of P was about 20 ppm and the remaining amount of P was 16000 ppm. Next, the mixture was stirred at 255 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Thereafter, while the temperature was raised to 280 ° C., the pressure of the reaction system was gradually lowered to 13.3 Pa (0.1 Torr) for 50 minutes for the first stage initial polycondensation, and further polymerization was carried out at 295 ° C. and 13.3 Pa. However, it gelled and could not be polymerized. The characteristics are shown in Table 3.

(Polyester resin (2) -d)
A slurry of high-purity terephthalic acid and ethyl glycol is continuously supplied to a first esterification reactor containing a reaction product in advance in a heat-medium circulation type ester polymerization apparatus, and is stirred at about 250 ° C., 0. The reaction was carried out at 5 kg / cm ² G for an average residence time of 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 polycondensed at about 275 ° C. and 0.3 to 1 torr with stirring in the final polycondensation reactor. The obtained melt polycondensed PET had an intrinsic viscosity of 0.55 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 207 ° 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 had an intrinsic viscosity of 0.74 deciliter / gram, an acetaldehyde content of 3.2 ppm, a DEG content of 2.6 mol%, and a cyclic trimer content of 0.32 wt%. Al residual amount was 20 ppm, and P residual amount was 35 ppm. The moisture content was 35 ppm by vacuum drying. The characteristics are shown in Table 4. The fine content was about 50 ppm.

(Polyester resin (2) -e)
The same method as in the case of the polyester resin (2) -d except that an ethylene glycol solution of titanium tetrabutoxide, an ethylene glycol solution of magnesium acetate tetrahydrate as a polycondensation catalyst, and an ethylene glycol solution of phosphoric acid as a stabilizer are used. A melt polycondensed PET was obtained. The obtained melt polycondensed PET had an intrinsic viscosity of 0.58 deciliter / gram.
Next, solid phase polymerization was performed in the same manner as in the case of the polyester resin (2) -d.
The obtained PET had an intrinsic viscosity of 0.73 deciliter / gram, an acetaldehyde content of 5 ppm, a DEG content of 2.6 mol%, and a cyclic trimer content of 3300 ppm. The residual amount of Ti was 3.5 ppm, the residual amount of Mg was 2 ppm, the residual amount of P was 7 ppm, the fine content was about 50 ppm, and the moisture content was 35 ppm.
The characteristics are shown in Table 4.

(Polyester resin (2) -f)
A melt polycondensed PET was obtained in the same manner as in the case of the polyester resin (2) -d except that an ethylene glycol solution of antimony trioxide as a polycondensation catalyst and an ethylene glycol solution of phosphoric acid as a stabilizer were used. The obtained melt polycondensed PET had an intrinsic viscosity of 0.57 deciliter / gram. Next, solid phase polymerization was performed in the same manner as in the case of the polyester resin (2) -d.
The obtained PET had an intrinsic viscosity of 0.75 deciliter / gram, an acetaldehyde content of 5.1 ppm, a DEG content of 2.6 mol%, and a cyclic trimer content of 3100 ppm. The residual amount of Sb was 290 ppm, the residual amount of P was 12 ppm, and the moisture content was 30 ppm. The characteristics are shown in Table 4. The fine content was about 50 ppm.

(Example 8)
The polyester resin (2) -d, 98 parts by weight, and the catalyst-reused moisture-containing polyester resin (1) -NA, 2 parts by weight were mixed in a blender. Thereafter, a stepped molded plate was formed by the method (7), and a bottle was formed by the method (8).
The CT content of the polyester resin composition is 3140 ppm, the CT content of the molded plate is 3150 ppm, the increase amount of the cyclic trimer by molding is 10 ppm, the increase amount B _t -B ₀ of the acetaldehyde content by molding is 9.1 ppm, The IV retention rate was 95%, the appearance of the molded product was good with ○, and the bottle appearance evaluation by the continuous molding acceleration test was also good with ○. Table 5 shows the results.

(Examples 9 to 13)
Although the test of Examples 9-13 was implemented similarly to Example 8, all the evaluation items did not have a problem. Table 5 shows the results.

(Example 14)
Although the test of Example 14 was implemented similarly to Example 8, there was no problem in evaluation items other than the ultraviolet shielding property. Table 5 shows the results.

(Comparative Example 6)
The polyester resin (2) -d, 98 parts by weight and polyester resin (1) -NE, 2 parts by weight were mixed in a blender. Thereafter, a stepped molded plate was formed by the method (7), and a bottle was formed by the method (8).
The polyester resin composition has a CT content of 3140 ppm, the molded plate has a CT content of 3140 ppm, the cyclic trimer increase ΔCT by molding is 0 ppm, and B _t -B ₀ is 10.6 ppm. %, The appearance of the molded product was x, and the bottle appearance evaluation by the continuous molding acceleration test was x. Table 5 shows the results.

(Comparative Examples 7 and 8)
Evaluation of Comparative Examples 7 and 8 was carried out in the same manner as in Example 8. None of them had satisfactory characteristics, and the evaluation results were not satisfactory. Table 5 shows.

(Comparative Example 9)
The polyester resin (2) -d, 100 parts by weight, was formed into a stepped molded plate by the method (7), and a bottle was molded by the method (8).
The CT content of the polyester resin composition is 3200 ppm, the CT content of the molded plate is 4200 ppm, the increase amount of the cyclic trimer by molding is 1010 ppm, B _t -B ₀ is 20.5 ppm, the IV retention rate is 98%, the molded product The appearance was good with ○, but the bottle appearance evaluation by the continuous molding acceleration test was poor with x.
Table 5 shows the results.

(Comparative Example 10)
The composition of Comparative Example 10 in Table 5 was evaluated in the same manner as described above, but the CT content of the molded plate was 4040 ppm, the amount of cyclic trimer increased by molding was 1000 ppm, B _t -B ₀ was 29.0 ppm, and IV The retention rate was 99%, the appearance of the molded product was Δ, the hue and transparency were poor, and the bottle appearance evaluation by the continuous molding acceleration test was xx.
Table 5 shows the results.

  The polyester resin of the present invention is a polyester resin that can be used to deactivate the polycondensation catalyst used in the production of polyester and suppress the formation of aldehydes such as acetaldehyde and cyclic ester oligomers during molding. It can be used suitably. In particular, the polyester resin composition of the present invention 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 hollow molded body excellent in heat-resistant dimensional stability. It is a polyester resin composition that can be produced efficiently, and from this, it is possible to obtain a molded product having the above-mentioned characteristics, and it is important to contribute 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 comprising an aromatic dicarboxylic acid component and a glycol component mainly, containing a phosphorus compound as a phosphorus atom in an amount of 100 to 10,000 ppm and water in an amount of 500 ppm to 10,000 ppm. The polyester resin according to claim 1, wherein the polycondensation catalyst is at least one selected from the group consisting of Sb compounds and Ge compounds. The polyester resin (1) is at least one selected from the group consisting of Al, Ti, V, Mn, Fe, Co, Ni, Zn, Nb, Mo, Cd, In, Sn, Ta, and Pb as a polycondensation catalyst. Deactivating the polycondensation catalyst of the polyester resin (2) by mixing with a polyester resin (2) mainly containing an aromatic dicarboxylic acid component and a glycol component, which contains a compound containing an element, and then melt-treating the polyester resin (2). The polyester resin according to claim 1, wherein the polyester resin can be used. The polyester resin (1) is composed of an acid component consisting of 20 to 100 mol% of naphthalenedicarboxylic acid and 80 to 0 mol% of other carboxylic acid, and a glycol component, and the phosphorus compound is used as a phosphorus atom and is 100 to 10,000 ppm It contains, The polyester resin in any one of Claims 1-3 characterized by the above-mentioned. The group consisting of the polyester resin (1) according to any one of claims 1 to 4 and Al, Ti, V, Mn, Fe, Co, Ni, Zn, Nb, Mo, Cd, In, Sn, Ta, and Pb. A polyester resin composition comprising a polyester resin (2) mainly comprising an aromatic dicarboxylic acid component and a glycol component, containing a compound containing at least one element selected from the group consisting of an antimony compound and / or a germanium compound as required. object. A polyester molded article obtained by melt-molding the polyester resin composition according to claim 5. A polyester molded body according to claim 6, wherein the polyester molded body is any one of a hollow molded body, a sheet-like material, and a stretched film obtained by stretching the sheet-like material in at least one direction. A coated product obtained by melt-extruding the polyester resin composition according to claim 5 onto a substrate.

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