JP2007009154A - Method for producing polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polyester, suppressing the change of the following polycondensation reaction by suppressing the change of the carboxy terminal group concentration of a polyester oligomer supplied into a polycondensation vessel in a simplified method and capable of producing a uniform polyester stably. <P>SOLUTION: This method for producing the polyester continuously by preparing slurry consisting of a dicarboxylic acid and a glycol in a slurry preparation vessel, feeding the slurry by a constant amount continuously into an esterification reaction vessel, performing the esterification reaction by using multiple esterification vessels and then performing the polycondensation is provided by controlling the slurry flow rate of the slurry fed to the esterification reaction vessel within a set value ±3%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a polyester capable of improving process stability and producing a stable polyester by controlling an esterification reaction.

  Polyester is used for various applications including films, fibers and bottles because of its excellent properties. Among these, polyethylene terephthalate is generally used because of its excellent mechanical strength, chemical resistance, and dimensional stability.

  In general, the production of a polyester by a direct esterification method is performed in two stages of an esterification reaction and a polycondensation reaction. In the production of polyethylene terephthalate, in order to stabilize the production process, the ratio of carboxyl end groups to hydroxyl end groups (hereinafter referred to as “end group ratio”) of the low polymer, which is an intermediate obtained by esterification reaction, is determined. It is important to adjust.

  For example, if the terminal group ratio fluctuates greatly, the progress rate of the polycondensation reaction fluctuates in the polycondensation step, resulting in problems such as fluctuations in the load of removing ethylene glycol and the polymer not reaching a predetermined degree of polymerization. . In terms of quality, a phenomenon occurs in which the hue of the polymer changes.

In general, in the polyester production method, when the carboxyl end group concentration of the obtained polyester is increased, the stability such as hydrolyzability of the polyester is deteriorated and the carboxyl end group concentration of the polyester is changed to a polycondensation reaction step in the production of the polyester. Since the final esterification reaction product to be supplied is greatly influenced by the carboxyl end group concentration of the oligomer, it is produced by supplying it to the polycondensation step in a state where the carboxyl end group concentration of the oligomer is lowered. For example, at least one reaction condition selected from the group consisting of temperature, pressure, residence time and ethylene glycol supply amount during the esterification reaction is adjusted so that the esterification reaction rate is 90 to 98%, and polycondensation is performed. A method of controlling the carboxyl end group concentration of the polyester after the reaction so as to become a certain amount within the range of 20 to 50 eq / ton (see Patent Document 1), the esterification reaction rate is in the range of 92 to 98%, and A method in which the proportion of carboxyl terminal groups in all terminal groups is an oligomer having a ratio of 35% or less, and this is subjected to a polycondensation reaction under reduced pressure so that the carboxyl terminal group concentration in the polyester is 35 eq / ton or less (see Patent Document 2). Adjusting at least one reaction condition selected from the group consisting of the temperature during the first stage polycondensation reaction, the residence time and the ethylene glycol supply amount, Alternatively, the first stage polycondensation reaction conditions are adjusted together with the esterification reaction rate of the esterification reaction product so that the carboxyl end group amount of the polyester after the polycondensation reaction becomes a constant value within the range of 15 to 50 eq / ton. A control method (see Patent Document 3) and a method (Patent Document 4) in which the carboxyl end group concentration of the polyester low polymer supplied to the final reaction vessel is 9 to 30 eq / ton are disclosed.
Japanese Patent Laid-Open No. 10-176043 Japanese Patent Laid-Open No. 10-251391 JP-A-11-106498 JP 2001-329058 A

  However, when the type of polycondensation catalyst system used for polyester production or polyester is used for limited applications, the above-described method is not necessarily optimal, and the polyester at the end of the final esterification reaction tank supplied to the polycondensation reaction step A method in which the carboxyl end group concentration of the oligomer is increased may have a high polycondensation activity or a high-quality polyester. In these cases, the variation of the carboxyl end group concentration of the oligomer greatly affects the reaction progress of the subsequent polycondensation reaction and the polyester quality compared to the above method. Must be suppressed with higher accuracy.

On the other hand, measuring the color tone of the product polymer and adjusting the esterification rate in the esterification process according to the deviation of the measured value from the target value, measuring the color tone of the product polymer, and the deviation of the measured value from the target value Of adjusting the residence time during the first polycondensation reaction according to the above, and measuring the color tone and intrinsic viscosity of the product polymer, and depending on the deviation of the measured value from the target value, ethylene glycol into the first stage polycondensation reaction can By adjusting the supply amount, the standard deviation of the color tone (b value) of the produced polyester is kept within 0.05 times the average value, and the standard deviation of the intrinsic viscosity is within 0.005 times the average value. The method of keeping is disclosed (see Patent Documents 5 to 7).
Japanese Patent No. 3375403 JP 2004-75955 A JP 2004-75957 A

  However, in the above method, since the polycondensation reaction has already progressed at the time when the color tone of the product polymer is measured, it cannot be said that the above problem has been solved because the adjustment of the esterification rate is delayed.

As a method for solving the above-described problem, a method is disclosed in which the electrical conductivity of an esterification reaction product is measured online and the esterification reaction is controlled based on the result (see, for example, Patent Documents 8 to 11). The method is a method for controlling the esterification reaction by utilizing the proportionality between the electrical conductivity of the esterification reaction product and the esterification reactivity, and the point that the esterification reactivity is directly measured. This is a control method that is one step ahead of the proposed method. However, this method has a problem that the influence of disturbance such as a change in the electric conductivity of the esterification reaction product due to the influence of water or unreacted ethylene glycol produced by the esterification reaction is large.
Japanese Patent Publication No.51-41679 JP-A-48-103537 JP 52-19634 A Japanese Patent Publication No. 5-32385

As a method for solving the above problems, the near-infrared characteristics of one or more of raw materials, reaction intermediate products or final products in the production process of polyester are continuously measured, and the obtained spectrum is used to measure A method for analyzing the physical properties of the resin and controlling the reaction conditions during the production process based on the analysis data is disclosed (see Patent Document 12). In the patent document, the method is provided at the bottom of the polycondensation tank in the polyester continuous production process. In addition, a near-infrared absorption spectrum detection terminal is installed at the outlet, and the carboxyl end group concentration of the polyester that always passes through the outlet is continuously measured, and the near-infrared absorption is also performed at the outlet of the second esterification reaction tank. A spectrum detection terminal is installed, and the esterification rate of the polyester oligomer passing through the detection terminal is continuously measured to obtain the target esterification rate. As described above, there is disclosed a method for feeding back to the second esterification reaction tank temperature controller and suppressing the change in the carboxyl end group concentration of the produced polyester, and a method for continuously measuring the infrared spectral absorption and controlling the reaction (see Patent Document 13). ing. These methods are effective as control methods for stabilizing the carboxyl end group concentration of polyester. However, in the case of continuous production over a long period of time, environmental changes such as detector contamination and temperature and pressure of the detector There is a problem that measurement fluctuations occur due to, for example, and there is a problem that reliability in long-term continuous operation may be inferior. Therefore, it is desired to construct a method that is more accurate and more reliable when operated for a long time with a simplified control method.
JP 11-315137 A JP-A-5-222178

As the simplified control method, the density and concentration of a slurry composed of terephthalic acid and ethylene glycol to be supplied to a polyester production process are continuously measured, and ethylene glycol with respect to terephthalic acid in the slurry obtained from the measured value is measured. A method for controlling the esterification reaction based on the molar ratio and a method for controlling the change in the ratio of terephthalic acid and ethylene glycol in the slurry according to the change in the slurry concentration are disclosed (see Patent Documents 14 and 15). . For example, in Patent Document 14, the fluctuation of the ethylene glycol / terephthalic acid molar ratio of the supply slurry when operated for 5 days is controlled to 1.51 ± 0.66%, resulting in the ester after the first stage esterification. It is disclosed that the esterification reaction rate is 85.0 ± 1.0% and the esterification reaction rate after the second stage esterification is 95.0 ± 0.5%.
JP-A-6-247899 JP 2004-75956 A

  These methods are effective methods for suppressing fluctuations in the esterification reaction, and the esterification reaction rate can be controlled with high accuracy. However, the esterification reaction rate depends on the carboxyl end group concentration and hydroxyl group of the polyester oligomer. In the esterification reaction, in general, the change in the carboxyl end group concentration and the hydroxyl end group concentration are linked, and the rate of change in the esterification reaction rate is the same as the carboxyl end group concentration alone. It becomes smaller than the fluctuation rate. Therefore, the slurry density control alone may not be sufficient for the requirement of stabilizing the carboxyl end group concentration of the polyester oligomer. In particular, in the above-described production method in which polycondensation is performed using an oligomer with an increased carboxyl end group concentration, it may be difficult to suppress fluctuations in the characteristics of the oligomer within a target range. Further, in this method, when a continuous operation is performed for a long time, the slurry concentration detector part may be clogged with dicarboxylic acid which is a solid content in the slurry, and the problem of the method is completely solved. It hasn't been done yet. For example, Patent Document 14 discloses a method in which two slurry densitometers are provided in parallel and can be switched to use any one of them, and used alternately at regular intervals.

  The object of the present invention is to suppress the fluctuation of the carboxyl end group concentration of the polyester oligomer supplied to the polycondensation reaction tank by a simplified method, thereby suppressing the fluctuation of the polycondensation reaction in the next step, and producing a homogeneous polyester. It is an object of the present invention to provide a method for producing a polyester which can be produced stably.

In order to solve the above problems, in order to suppress the fluctuation of the carboxyl end group concentration of the polyester oligomer at the outlet of the final esterification reactor, the fluctuation of the carboxyl end group concentration of the polyester oligomer at the outlet of the first esterification reactor is changed. It was important to suppress, and it was found that if the variation in the characteristics was suppressed, the variation in the carboxyl end group concentration of the polyester oligomer at the outlet of the final esterification reactor could be extremely small. Further, it was found that the fluctuation of the carboxyl terminal group concentration of the polyester oligomer at the outlet of the first esterification reaction tank was greatly influenced by the flow fluctuation of the polyester raw material slurry supplied to the first esterification reaction tank. completed.
That is, the present invention prepares a slurry composed of dicarboxylic acid and glycol in a slurry preparation tank, continuously supplies the slurry to an esterification reaction tank, and performs esterification reaction using a plurality of esterification reaction tanks. In the method for continuously producing polyester by performing polycondensation, and subsequently continuously producing the polyester, the slurry flow rate of the slurry supplied to the esterification reaction tank is controlled within a set value ± 3%. .
In this case, it is preferable to control the molar ratio of dicarboxylic acid / glycol of the slurry supplied to the esterification reaction tank to be within a set value ± 0.03%.
Moreover, in this case, it is preferable to control the slurry temperature supplied to the esterification reaction tank within a set value ± 4 ° C.
In this case, the first esterification reaction tank temperature is preferably controlled within a set value ± 3%.
Moreover, in this case, it is preferable to control the first esterification reaction tank pressure within a set value ± 2%.
In this case, it is preferable to control the liquid level of the first esterification reaction tank within a set value ± 0.2%.
In this case, it is preferable to control the carboxyl end group concentration of the polyester oligomer at the outlet of the first esterification reaction tank within ± 10% of the set value.
In this case, it is preferable that the variation of the carboxyl end group concentration of the oligomer at the outlet of the final esterification reaction tank is within a set value ± 6%.
In this case, the set value of the carboxyl terminal group concentration of the polyester oligomer at the outlet of the first esterification reaction tank is preferably 1900 to 3700 eq / ton.
In this case, the set value of the carboxyl end group concentration of the polyester oligomer at the outlet of the final esterification reaction tank is preferably 500 to 900 eq / ton.
In this case, the ratio of the carboxyl end group concentration to the total end group concentration of the polyester oligomer at the outlet of the final esterification reaction tank is preferably more than 35 to 48%.

  The polyester production method of the present invention specifies the carboxyl end group concentration of the polyester oligomer at the outlet of the first esterification reaction tank by a very simple method of controlling the flow rate fluctuation of the raw material slurry supplied to the esterification reaction step within a specific range. As a result, the fluctuation of the carboxyl end group concentration of the polyester oligomer supplied to the polycondensation reaction tank is suppressed, so that the fluctuation of the polycondensation reaction in the next step is suppressed. Therefore, the quality variation of the obtained polyester is suppressed, and a very homogeneous polyester can be stably produced. In the polyester production method of the present invention, the esterification reaction is controlled with a slurry flow rate with high measurement accuracy and stable measurement value even when operated for a long period of time. It has the feature that the reliability of the system is stable. Therefore, it can be said that the control method has a balance between quality and economy, that is, cost performance. In addition, it has a feature that the above-mentioned effect can be stably expressed even in a production method in which a high degree of suppression is required for the variation of the carboxyl end group concentration of the polyester oligomer. Therefore, for example, the higher the carboxyl end group concentration of the polyester oligomer at the start of the polycondensation reaction, the higher the polycondensation activity and the higher the carboxyl end group concentration, such as titanium, tin and aluminum based polycondensation catalysts. Even if polycondensation is carried out in the polycondensation reaction, a polycondensation catalyst system is used in which the esterification reaction proceeds during the polycondensation reaction and the increase in the concentration of the final polyester is suppressed compared to the case of polycondensation with other polycondensation catalyst systems When applied to a conventional polyester manufacturing method, high productivity can be secured and high-quality polyester can be stably manufactured. Moreover, when the above method is applied to a composite polycondensation catalyst system composed of an aluminum compound and a phosphorus compound, in addition to the above-mentioned advantages, the transparency of the film is produced when a stretched film is produced using the obtained polyester resin. It has the advantage that it leads to the expression of a double effect that the effect of improving is also added.

  Hereinafter, an embodiment of a method for producing a polyester of the present invention will be described.

  The polyester referred to in the present invention is a polyester whose main repeating unit is ethylene terephthalate, preferably a linear polyester containing 70 mol% or more of ethylene terephthalate units, more preferably 80 mol% or more, particularly preferably 95 mol. It is a linear polyester containing at least%.

  Examples of the dicarboxylic acid used as a copolymerization component when the polyester is a copolymer include orthophthalic acid, isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 1,5-naphthalene. Dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl-4,4-dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, Aromatic dicarboxylic acids such as p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and functional derivatives thereof, lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid Or functional derivatives thereof, aliphatic dicarboxylic acids such as succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid And functional derivatives thereof, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and functional derivatives thereof.

  Examples of glycols used as a copolymerization component when the polyester is a copolymer include diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1 , 3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, poly Aliphatic glycols such as trimethylene glycol and polytetramethylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexane Cycloaliphatic glycols such as xanthanimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1, 4-bis (β-hydroxyethoxyphenyl) sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) Examples include aromatic glycols such as ethane, bisphenol A, and alkylene oxide adducts of bisphenol A.

Examples of the cyclic ester used for copolymerization of the polyester include ε-caprolactone, β-propionlactone, β-methyl-β-propionlactone, γ-valerolactone, glycolide, and lactide.

  Furthermore, examples of the polyfunctional compound as a copolymer component used when the polyester is a copolymer include trimellitic acid and pyromellitic acid as acid components, 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.

  The polyester of the present invention can contain a known phosphorus compound as a copolymerization component. As the phosphorus compound, a bifunctional phosphorus compound is preferable. For example, (2-carboxylethyl) methylphosphinic acid, (2-carboxyethyl) phenylphosphinic acid, 9,10-dihydro-10-oxa- (2,3- Carboxypropyl) -10-phosphaphenanthrene-10-oxide and the like. By including these phosphorus compounds as copolymerization components, it is possible to improve the flame retardancy of the resulting polyester.

  The polyester of the present invention can contain a known phosphorus compound as a copolymerization component. As the phosphorus compound, a bifunctional phosphorus compound is preferable. For example, (2-carboxylethyl) methylphosphinic acid, (2-carboxyethyl) phenylphosphinic acid, 9,10-dihydro-10-oxa- (2,3- Carboxypropyl) -10-phosphaphenanthrene-10-oxide and the like. By including these phosphorus compounds as copolymerization components, it is possible to improve the flame retardancy of the resulting polyester.

  In the present invention, it is preferable to carry out the polyester by a direct esterification method and a continuous method.

  The direct esterification method is advantageous in terms of economy as compared with the transesterification method. The continuous polycondensation method is advantageous in terms of quality uniformity and economy as compared to the batch polycondensation method.

  In the present invention, the number and size of the reactors in the esterification and polycondensation steps, the production conditions in each step, and the like can be appropriately selected without limitation.

  For example, a slurry containing 1.02 to 2.0 moles, preferably 1.03 to 1.95 moles of ethylene glycol per mole of terephthalic acid is prepared and used in the esterification reaction step. Supply continuously. The esterification reaction is preferably carried out using a multistage apparatus in which two or more esterification reaction tanks are connected in series while removing water generated by the reaction from the system with a rectification column. The temperature of the esterification reaction in the first stage is 240 to 270 ° C., preferably 245 to 265 ° C., and the pressure is normal pressure to 0.29 MPa, preferably 0.005 to 0.19 MPa. The temperature of the esterification reaction at the final stage is usually 250 to 290 ° C, preferably 255 to 275 ° C, and the pressure is usually 0 to 0.15 MPa, preferably 0 to 0.13 MPa. When carried out in three or more stages, the reaction conditions for the esterification reaction in the intermediate stage are conditions between the reaction conditions for the first stage and the reaction conditions for the final stage. The increase in the reaction rate of these esterification reactions is preferably distributed smoothly at each stage. Ultimately, it is desirable that the esterification reaction rate reaches 90% or more, preferably 93% or more. A low-order condensate having a molecular weight of about 500 to 2000 is obtained by these esterification reactions. Subsequently, it is transferred to a polycondensation reaction tank to carry out polycondensation. The number of reaction tanks in the polycondensation step is not limited. In general, a three-stage system of initial polycondensation, intermediate polycondensation and late polycondensation is employed. As for the polycondensation reaction conditions, the reaction temperature of the first stage polycondensation is 250 to 290 ° C., preferably 260 to 280 ° C., and the pressure is 0.065 to 0.0026 MPa, preferably 200 to 20 Torr. The temperature of the polycondensation reaction is 265 to 300 ° C., preferably 275 to 295 ° C., and the pressure is 0.0013 to 0.000013 MPa, preferably 0.00065 to 0.000065 MPa. When carried out in three or more stages, the reaction conditions for the intermediate stage polycondensation reaction are conditions between the reaction conditions for the first stage and the reaction conditions for the last stage. The degree of increase in intrinsic viscosity achieved in each of these polycondensation reaction steps is preferably distributed smoothly.

  In the present invention, a slurry comprising dicarboxylic acid and glycol is prepared in a slurry preparation tank, and the slurry is continuously supplied to the esterification reaction tank in a fixed amount, and an esterification reaction is performed using a plurality of esterification reaction tanks. In the method of continuously producing polyester by performing polycondensation, it is important to control the slurry flow rate of the slurry supplied to the esterification reaction tank within a set value ± 3%.

  In the techniques disclosed in the above-mentioned patent documents and the like, the carboxyl end group of the polyester oligomer is focused on and controlled by the value of the polyester oligomer supplied to the polycondensation step. It is a natural consequence that the carboxyl end group concentration of the polyester oligomer supplied to the polycondensation step has a great influence on the progress of the subsequent polycondensation reaction and the polyester quality.

  The present inventors diligently studied a method for suppressing the variation in the carboxyl end group concentration of the polyester oligomer at the final esterification reactor outlet, and the variation in the carboxyl end group concentration of the polyester oligomer at the final esterification reactor outlet is: The slurry which is almost governed by the carboxyl end group concentration of the polyester oligomer at the outlet of the first esterification reaction tank and the carboxyl end group concentration of the polyester oligomer at the outlet of the first esterification reaction tank is supplied to the esterification reaction system described above. By controlling the slurry flow rate, fluctuations in the carboxyl terminal group concentration of the polyester oligomer at the outlet of the first esterification reaction tank can be suppressed, resulting in a large increase in the subsequent polycondensation reaction and polyester quality. Influential final esterification reaction Carboxyl end group concentration variation of the polyester oligomer outlets and completed the present invention have found to be suppressed. Naturally, the carboxyl end group concentration of the polyester oligomer at the outlet of the final esterification reaction tank changes depending on the esterification reaction conditions after the first esterification reaction tank, so the reaction conditions must be controlled within a certain range. However, the control can be performed at a level at which a conventionally known method is applied, and a high level of carboxyl end group concentration obtained by the method of the present invention can be controlled.

  That is, it is important to control the supply amount of the slurry to the esterification reaction tank within a set value ± 3%. Within ± 2.5% is more preferred, and within ± 2.0% is even more preferred. The lower limit is most preferably ± 0% with no variation, but is preferably ± 0.3%, more preferably ± 0.5% from the viewpoint of cost performance. The method for controlling the supply amount of the slurry is not limited. For example, a method of changing the feed pump rotation speed so as to achieve a set flow rate using a flow meter, a bypass line returning to the slurry preparation tank is provided after the feed pump of the feed line, and the revolution speed of the feed pump is set. Method of adjusting the opening of the control valve provided in the bypass line so that the flow rate of the flow meter provided in the liquid feed line is constant, and the position of the slurry preparation tank and the first esterification reaction tank For example, and by feeding the slurry with the head pressure and adjusting the opening of a control valve provided in the liquid feed line so that the flow rate of the flow meter provided in the liquid feed line is constant. The type of flow meter is not limited. For example, a rotor flow meter, a rotor piston flow meter, an oval flow meter, a micro motion flow meter, and the like can be given. Moreover, you may adjust so that the liquid level of a 1st esterification reaction tank may become fixed.

  By controlling the slurry flow rate fluctuation, the carboxyl end group concentration fluctuation of the polyester oligomer at the outlet of the first esterification reaction tank is suppressed due to fluctuations in the amount of heat brought into the first esterification reaction tank caused by the flow fluctuation. It is inferred that this is caused because the excessive response of the temperature control of the first esterification reaction tank is suppressed.

  Moreover, since the molar ratio of dicarboxylic acid and glycol in the slurry also affects the esterification reaction, it is preferably controlled within a certain range. As the variation range, the range of the known technique described above is sufficient. A setting value within ± 0.3% is preferable. A set value within ± 0.25% is more preferable, and a set value within ± 0.2% is even more preferable. On the other hand, the lower limit is most preferably ± 0% which is unchanged, but from the viewpoint of cost performance, ± 0.01% is preferable, and ± 0.02% is more preferable.

  The method for adjusting the molar ratio is not limited, but a method of continuously measuring online and adjusting the amount of dicarboxylic acid and / or glycol supplied to the slurry preparation tank is preferable. The measuring method is not limited. The method of measuring with a densitometer or a near-infrared spectrophotometer is mentioned.

  Moreover, since the temperature of the slurry also affects the esterification reaction in order to affect the amount of heat brought into the first esterification reaction tank, it is preferably controlled within a certain range. The slurry temperature is preferably controlled within ± 4 ° C. of the set value and supplied to the esterification reaction tank. The slurry temperature is more preferably controlled within ± 3 ° C. of the set value, and further preferably controlled within ± 2 ° C. It is particularly preferable to control within ± 1 ° C. When the temperature exceeds ± 4 ° C., even if the slurry supply amount is within the range of the present invention, the fluctuation in the progress of the esterification reaction becomes large and the carboxyl terminal group of the polyester oligomer (hereinafter sometimes simply referred to as oligomer) It is not preferable because the concentration fluctuation becomes large and it is difficult to ensure the above range, which leads to the progress of the subsequent polycondensation reaction and the quality fluctuation of the final product, such as color tone and transparency. On the other hand, the lower limit is most preferably ± 0 ° C., which is unchanged, but from the viewpoint of cost performance, ± 0.1 ° C. is preferable, and ± 0.3 ° C. is more preferable.

  The method for controlling the slurry temperature is not limited, but it is preferable to detect the temperature of the slurry preparation tank or the terephthalic acid temperature and feed back to the glycol temperature supplied to the preparation tank. The slurry temperature control may be controlled by installing a heat exchanger in the slurry preparation tank or slurry transfer line. In addition, a circulation line may be provided in the slurry preparation tank to circulate the slurry in the slurry preparation tank to improve the accuracy of temperature control. In the case of this method, it is preferable to add a temperature control function also to the circulation line. The above methods may be performed alone or a plurality of methods may be combined. Further, a slurry storage tank may be provided between the slurry preparation tank outlet and the esterification reaction tank supply to improve the accuracy of the slurry temperature control. In the case of this method, a temperature control mechanism may be added to the slurry storage tank. As a method of providing the slurry storage tank, the slurry adjustment in the slurry preparation tank may be carried out by a batch method. The batch type slurry preparation method facilitates the management of the composition ratio of the dicarboxylic acid and glycol of the slurry, which is an important process management item in slurry preparation, leading to the advantage that the control system for the management can be simplified. . In the case of this method, since the composition ratio of the dicarboxylic acid and the glycol can be adjusted in the slurry storage tank, there is an advantage that the composition ratio can be suppressed. In this method, slurry preparation may be carried out by a continuous method or a semibatch method. Moreover, you may implement combining this method and the former method.

  The set value of the slurry temperature is not limited, but is preferably from room temperature to 180 ° C. In general, in the polyester production process, the recovered glycol generated in the production process is often used as a part of the glycol prepared in the slurry. The recovered glycol may be recovered at the implant. In the method, the recovered glycol is in a warm state. Therefore, the set temperature is preferably a warmed state, and more preferably 70 to 150 ° C.

  Moreover, the fluctuation | variation of the carboxyl terminal group density | concentration of the polyester oligomer of the 1st esterification reaction tank exit is the temperature of the 1st esterification tank, pressure, and residence time (in the limited polyester production line, the liquid level of the reaction tank). Since it is influenced, it is preferable to control the factor within a set condition range. For example, the temperature is preferably within a set value ± 3%, and more preferably within ± 2%. On the other hand, the lower limit is most preferably ± 0% with no variation, but from the viewpoint of cost performance, ± 0.2% is preferable, and ± 0.5% is more preferable. Further, the pressure is preferably within a set value ± 4%, more preferably within ± 3%. Within ± 2.5% is more preferable. On the other hand, the lower limit is most preferably ± 0% with no variation, but from the viewpoint of cost performance, ± 0.2% is preferable, and ± 0.5% is more preferable. The liquid level is preferably within a set value ± 0.2%, and more preferably within ± 0.1%. On the other hand, the lower limit is most preferably ± 0%, which is unchanged, but from the viewpoint of cost performance, ± 0.02% is preferable, and ± 0.05% is more preferable. The liquid level can be controlled by setting the slurry flow rate control within the above range.

It is important to suppress the carboxyl end group concentration of the polyester oligomer at the outlet of the first esterification reaction tank within a set value ± 10%. Within ± 9% is preferable, within ± 8% is more preferable, and within ± 6% is more preferable. By making it within this range, it becomes possible to suppress the fluctuation of the carboxyl end group concentration of the oligomer at the outlet of the final esterification reaction tank to a preferable range, leading to the subsequent polycondensation reaction and stabilization of the quality of the obtained polyester. It is preferable because it is possible. On the other hand, the lower limit is most preferably ± 0%, which is unchanged, but from the viewpoint of cost performance, ± 0.5% is preferable, and ± 1.0% is more preferable.

  Although the set value of the carboxyl terminal group concentration of the polyester oligomer at the outlet of the first esterification reaction tank is not limited, the carboxyl terminal group concentration of the polyester oligomer at the outlet of the final esterification reaction tank or the ester after the second esterification reaction tank What is necessary is just to set suitably according to the reaction conditions of a chemical reaction tank. As will be described later, generally, the carboxyl end group concentration of the polyester oligomer at the outlet of the final esterification reaction tank is preferably set to a range of 250 to 900 eq / ton. In order to make this range, the set value of the carboxyl terminal group concentration of the polyester oligomer at the outlet of the first esterification reaction tank is preferably in the range of 800 to 3700 eq / ton. 1000 to 3400 eq / ton is more preferable, and 1200 to 3000 eq / ton is more preferable. When the set value of the carboxyl end group concentration of the polyester oligomer at the outlet of the first esterification reaction tank exceeds 3700 eq / ton, the clogging of the transfer line or the like by the oligomer may occur.

  The method for setting the polyester oligomer carboxyl end group concentration at the outlet of the first esterification reaction tank to the above range is not limited. For example, production equipment factors such as the structure of the esterification reactor, the composition ratio of dicarboxylic acid and glycol in the slurry supplied to the esterification reactor, esterification reaction temperature, esterification reaction pressure, esterification reaction time, etc. What is necessary is just to set reaction conditions etc. suitably. Moreover, you may adjust by adding water to an esterification reaction process.

  Moreover, the fluctuation | variation of the polyester oligomer carboxyl terminal group density | concentration of this 1st esterification reaction tank exit can be achieved by implementation of an above described method.

  Moreover, in this invention, it is preferable to make the carboxyl terminal group density | concentration of the oligomer of the final esterification reaction tank exit into the setting value +/- 6%. Within ± 5% is more preferable, within ± 4% is more preferable, and within ± 3% is particularly preferable. When the carboxyl end group concentration variation exceeds ± 5%, the variation in the above-mentioned problem is increased, and the uniformity of the quality of the obtained polyester is lowered, which is not preferable. On the other hand, the lower limit is most preferably ± 0% with no variation, but from the viewpoint of cost performance, ± 0.2% is preferable, and ± 0.5% is more preferable.

  The set value of the carboxyl end group concentration is not limited, but is preferably in the range of 150 to 900 eq / ton. The range of 170-800 eq / ton is more preferable, and the range of 190-700 eq / ton is more preferable. When the set value of the carboxyl end group concentration is less than 150 eq / ton, the polycondensation activity is lowered and the production of diethylene glycol in the polycondensation step is increased, which is not preferable. In particular, when a polycondensation catalyst system having a large influence of the carboxyl end group concentration of the polyester oligomer on the polycondensation reaction activity is used, the polycondensation catalyst activity is remarkably lowered, which is not preferable. On the other hand, when the set value of the carboxyl end group concentration exceeds 900 eq / ton, the subsequent polycondensation reaction proceeds unstably, and fluctuations in the degree of polymerization of the resulting polyester increase. Moreover, since the carboxyl terminal group density | concentration of polyester obtained becomes high and leads to stability reductions, such as a hydrolysis stability of polyester, it is unpreferable.

  In the present invention, the method for controlling the carboxyl end group concentration of the polyester oligomer at the final esterification reactor outlet to the above range is not limited, but the carboxyl end group concentration at the first esterification reactor outlet is within the above range. It is a preferred embodiment to control and stabilize the steps after the second esterification reaction tank and to control at the level that is practiced in normal polyester production.

  The method of the present invention described above is applicable to the production of polyester in a region where the concentration of carboxyl terminal groups of the polyester oligomer is higher than that used in the production of ordinary polyester. Since the fluctuation of the base concentration is suppressed, this method has a feature that a stable quality polyester can be obtained. Therefore, for example, a titanium, tin, and aluminum-based polycondensation catalyst has a higher polycondensation activity when the concentration of the carboxyl end group of the polyester oligomer at the start of the polycondensation reaction is higher, and the polycondensation catalyst with a higher concentration of the carboxyl end group. Polyester using a polycondensation catalyst system in which the esterification reaction proceeds even during the polycondensation reaction and the increase in the concentration of the final polyester is suppressed as compared with the case of polycondensation in other polycondensation catalyst systems It is one of the preferred embodiments that is applied to this manufacturing method. In the polycondensation catalyst system, performing the polycondensation reaction in a state where the carboxyl end groups of the oligomer at the start of the polycondensation reaction are increased can increase the productivity without deteriorating the polyester quality, so that it is cost effective. It is advantageous. However, in the polycondensation reaction in a state where the carboxyl end group concentration of the polyester oligomer is increased at the start of the polycondensation reaction, a method of starting the polycondensation reaction in a state where the carboxyl end group concentration is usually reduced is performed. Compared to the above, the fluctuation of the carboxyl end group concentration of the polyester oligomer greatly affects the subsequent polycondensation reaction and polyester quality. Production of polyesters under normal conditions with a reduced carboxyl end group concentration has been carried out. According to the method of the present invention, this problem can be improved, and when the above polycondensation catalyst is used, production with high cost performance becomes possible. Therefore, it is one of the preferred embodiments that the present invention is applied to the method for producing polyester using the polycondensation system and carried out under the above-mentioned conditions.

  In addition, when the polyester production method in the region where the carboxyl end group concentration of the polyester oligomer is increased is applied to a composite polycondensation catalyst system composed of an aluminum compound and a phosphorus compound described later, the obtained polyester resin is used. Thus, the use of the polycondensation catalyst system is one of the preferred embodiments because the effect of improving the transparency of the film is added when producing a stretched film.

  When the polyester oligomer production method is used in the region where the carboxyl end group concentration of the polyester oligomer is increased, the average value of the carboxyl end group concentration of the oligomer at the outlet of the final esterification reaction tank may be in the range of 500 to 900 eq / ton. preferable. In this case, the ratio of the carboxyl end group concentration to the total end group concentration of the oligomer at the outlet of the final esterification reaction tank is preferably more than 35 to 48%.

  The average value of the carboxyl end group concentration is more preferably in the range of 520 to 800 eq / ton, and further preferably in the range of 540 to 700 eq / ton. When the average value of the carboxyl end group concentration is less than 500 eq / ton, the polycondensation catalyst activity decreases when, for example, a polycondensation catalyst system that has a large influence of the carboxyl end group concentration of the polyester oligomer on the polycondensation reaction activity is used This is not preferable. Moreover, when it applies to the composite type polycondensation catalyst system which consists of an aluminum compound and a phosphorus compound, since the transparency of the film at the time of manufacturing a stretched film using the obtained polyester resin falls, it is unpreferable. On the contrary, when the average value of the carboxyl end group concentration exceeds 900 eq / ton, the progress of the subsequent polycondensation reaction becomes unstable, and the fluctuation of the degree of polymerization of the resulting polyester becomes large. Moreover, since the carboxyl terminal group density | concentration of polyester obtained becomes high and leads to stability reductions, such as a hydrolysis stability of polyester, it is unpreferable. When carried out by this method, the average value of the carboxyl end group concentration of the polyester oligomer at the outlet of the first esterification reactor is preferably 1400 to 3700 eq / ton. 1600-3400eq / ton is more preferable, 1800-3000eq / ton is further more preferable.

  In the present invention, it is important to suppress the carboxyl end group concentration of the oligomer at the outlet of the final esterification reaction tank within the above average value range and the above-described fluctuation range. By suppressing the fluctuation range of the carboxyl end group concentration, high-quality polyester can be stably produced.

  When the polyester oligomer production method is used in the region where the carboxyl end group concentration of the polyester oligomer is increased, the carboxyl end group concentration is more affected by the carboxyl of the oligomer compared to the production method using the polyester oligomer having a low carboxyl end group concentration. In order to increase the influence of the end group concentration on the polycondensation catalyst activity and the polyester quality, the fluctuation range of the carboxyl end group concentration of the polyester oligomer at the outlet of the final esterification reactor is controlled within a set value ± 6.0%. It is preferable. Within ± 5.0% is more preferred, within ± 4.0% is more preferred, and within 3.0% is even more preferred. On the other hand, the lower limit is most preferably ± 0% with no variation, but from the viewpoint of cost performance, ± 0.2% is preferable, and ± 0.5% is more preferable.

  Moreover, when performing with the manufacturing method of the polyester in the area | region which raised the carboxyl terminal group density | concentration of the polyester oligomer, the ratio of the carboxyl terminal group density | concentration with respect to the total terminal group density | concentration of the oligomer of the final esterification reaction tank exit is more than 35 to 49%. Preferably, 37 to 48% is more preferable, and 39 to 47% is particularly preferable. When the carboxyl end group concentration ratio is 35% or less, for example, when a polycondensation catalyst system having a large influence of the carboxyl end group concentration of the polyester oligomer on the polycondensation reaction activity is used, the polycondensation catalyst activity decreases. It is not preferable. Moreover, when it applies to the composite type polycondensation catalyst system which consists of the below-mentioned aluminum compound and phosphorus compound, since the transparency of the film at the time of manufacturing a stretched film using the obtained polyester resin falls, it is unpreferable. On the contrary, when the ratio of the carboxyl end group concentration exceeds 49%, the progress of the subsequent polycondensation reaction becomes unstable, and the fluctuation of the degree of polymerization of the resulting polyester becomes large, which is not preferable. Moreover, since the carboxyl terminal group density | concentration of polyester obtained becomes high and leads to stability reductions, such as a hydrolysis stability of polyester, it is unpreferable.

  As described above, in the present invention, it is possible to suppress the characteristic fluctuation of the polyester oligomer by the above method, but in the esterification reaction step, the carboxyl end group concentration and the hydroxyl end group concentration of the polyester oligomer are further reduced. The control accuracy and stability may be improved by measuring online and feeding back to the slurry temperature control system.

  The method for measuring the oligomer property is not limited, but it is preferable to measure using a near-infrared spectrophotometer. It is preferable to continuously carry out using a near-infrared spectrophotometer in a portion where the oligomer is flowing, for example, a reaction can, a pipe or the like. There is no particular limitation as long as it is a near-infrared spectrophotometer that can be continuously measured online. For example, commercial products such as NIRS Systems (Nireco), BRAN LUEBBE, and near infrared on-line analyzers manufactured by Yokogawa Electric may be used, or a systemized device for this purpose can be manufactured. May correspond.

  In the method of the present invention, the detection cell of the near-infrared spectrophotometer needs to be installed in a high temperature region, and a design for the correspondence is necessary. Also, when installing between esterification reaction cans, it must be in a pressurized state, and when installing in the transfer line from the esterification reaction can to the initial polycondensation can, it must be structured to withstand both pressurization and decompression. There is. It is preferable to implement this measure as appropriate depending on the installation location.

  In the present invention, the installation location of the measurement cell of the near-infrared spectrophotometer may be set at any location from the start of the esterification reaction to just before the start of the polycondensation reaction. You may set to an esterification reaction can and you may install in the transfer line of each reaction can. You may install directly in each reaction can and a transfer line, and you may provide a bypass line and install in this bypass line. When detecting the inside of the reaction can when it is installed in the bypass line, it is preferable to provide a circulation line through which the reaction contents circulate in the target reaction can and install it in the circulation line. Since the installed measurement cell may require maintenance, it is preferably installed in the bypass line. In the present invention, as described above, the carboxyl end group concentration of the oligomer at the outlet of the first esterification reaction tank is important. For example, a bypass line is provided in the transfer line from the first esterification reaction tank to the second esterification reaction tank. It is preferable to install and measure by installing a detector in the bypass line. In addition, another detector may be installed in the transfer line from the final esterification reaction tank to the first polycondensation reaction tank to measure the characteristic values of both oligomers to increase the control accuracy. In the method of controlling the esterification reaction using a plurality of detectors, the measurement is performed by a detector installed in the transfer line at the outlet of the first esterification reaction tank, and the control by the measured value is sent to the first esterification reaction tank. It is preferable to feed back the slurry temperature to be supplied. Control by measurement values detected at other detection locations may be fed back to a control system that changes other esterification reactions, for example, the amount of glycol for adjusting the esterification reaction supplied to the second esterification reaction tank Good. What is necessary is just to select and implement the control system which can improve the accuracy most appropriately.

  For the above oligomer properties, only the carboxyl end group concentration may be measured, or both the carboxyl end group concentration and the hydroxyl end group concentration may be measured at the same time. When measuring at multiple locations, measure at each location. You may change the contents. For example, the control system by the detector installed in the transfer line at the first esterification reactor outlet is controlled by the carboxyl end group concentration, and the control system by the detector installed in the final esterification reactor outlet transfer line is the carboxyl end group. Preferably, both the concentration and the hydroxyl end group concentration are measured simultaneously and controlled so that both end group concentrations fall within a predetermined range. The near-infrared measurement wavelength is not limited. It is preferable to use a model oligomer corresponding to the measurement location and investigate and set the wavelength with high sensitivity and less disturbance. For example, it is preferable to use a wavelength of 1444 nm for the carboxyl end group concentration and 2030 nm for the hydroxyl end group concentration. Moreover, you may calculate from the analytical curve which combined the some wavelength.

  The calibration curve for the concentration of both end groups determined by the above method is preferably prepared using the above model oligomer. In this case, it is preferable to use values measured by the NMR method for the carboxyl end group concentration and the hydroxyl end group concentration of the model oligomer.

  In the case of carrying out by the above method, it is preferable to calculate from the characteristics of the oligomer based on a program incorporated in the computer in advance, and to reflect and control the slurry temperature and esterification reaction conditions.

  In the present invention, the polycondensation catalyst used for polyester production is not limited. For example, metals such as lithium, sodium, calcium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, and these metals The metal compound containing is mentioned. Among these, the use of antimony, germanium, titanium, tin and aluminum based polycondensation catalysts is preferred.

  Among the polycondensation catalysts, titanium, tin and aluminum-based polycondensation catalysts have a higher polycondensation activity and a higher carboxyl end group concentration when the polyester oligomer has a higher carboxyl end group concentration at the start of the polycondensation reaction. Even if the polycondensation is carried out in the state, the esterification reaction proceeds during the polycondensation reaction, and the increase in the concentration of the final polyester is suppressed compared to the case of polycondensation with other polycondensation catalyst systems. It is advantageous from the economical point of view to carry out the polycondensation reaction in a state where the carboxyl terminal group of the oligomer at the start of the step is increased. However, polycondensation with the carboxyl end group concentration of the oligomer increased increases the influence of the carboxyl end group concentration on the polycondensation catalytic activity, etc., so it is necessary to reduce the variation of the carboxyl end group concentration of the oligomer. There is. Conventionally known esterification reaction control methods have difficulty in answering this requirement, and thus polycondensation has been carried out with a low carboxyl end group concentration. As described above, since the carboxyl end group concentration of the polyester oligomer can be controlled with extremely high accuracy, the polyester production method of the present invention has increased the carboxyl end group concentration of the polyester oligomer when the polycondensation reaction is started. Even if polycondensation is carried out in the state, the polycondensation reaction is stabilized and the quality of the polyester can be stabilized. Therefore, the present invention can be applied to the production of polyester using a titanium, tin and aluminum-based polycondensation catalyst. This is a preferred embodiment because the effect can be further utilized. Of course, even in a method in which polycondensation is carried out in a state where the carboxyl end group concentration of the polyester oligomer is low, suppression of fluctuations in the carboxyl end group concentration of the polyester oligomer leads to stabilization of the polyester quality. Even in the general-purpose polyester method used, the technology for suppressing the fluctuation of the carboxyl end group concentration of the oligomer of the present invention can be effectively utilized.

  Among the titanium, tin, and aluminum polycondensation catalysts that are the polycondensation catalysts in which the effects of the above-described method of the present invention are more remarkably exhibited, the use of the aluminum-based polycondensation catalyst is effective for the color tone of the polyester obtained. In terms of stability, it is more preferable than other catalyst systems.

  In addition, when the aluminum-based polycondensation catalyst is used in the method of the present invention, the polyester resin obtained by starting polycondensation in a state where the carboxyl end group concentration of the polyester oligomer is increased is used. When the polyester film is manufactured, there is an advantage that a double effect that the effect of improving the transparency of the polyester film is exhibited can be exhibited.

Hereinafter, the aluminum-based polycondensation catalyst will be referred to.
The aluminum polycondensation is preferably a polycondensation catalyst system comprising at least one selected from the group consisting of aluminum compounds and at least one selected from the group consisting of phosphorus compounds.

The aluminum compound constituting the polycondensation catalyst of the present invention is not limited as long as it dissolves in a solvent, but aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, Carboxylates such as aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, aluminum tartrate, aluminum salicylate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate , Inorganic acid salts such as aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum Aluminum alkoxide such as muiso-propoxide, aluminum n-butoxide, aluminum t-butoxide, aluminum chelate compound such as aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate diiso-propoxide, trimethylaluminum Organic aluminum compounds such as triethylaluminum and partial hydrolysates thereof, reaction products composed of aluminum alkoxides and aluminum chelate compounds and hydroxycarboxylic acids, aluminum oxide, ultrafine aluminum oxide, aluminum silicate, aluminum and titanium or silicon, Composite with zirconium, alkali metal, alkaline earth metal, etc. Product and the like. Of these, carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

  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, for example, by the general structural formula [aluminum 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 amount of the aluminum compound used in producing the polyester according to the method of the present invention is 0 as an aluminum atom with respect to the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polyvalent carboxylic acid of the obtained polyester. 0.001 to 0.05 mol% is preferable, and 0.005 to 0.02 mol% is more preferable. If the amount used is less than 0.001 mol%, the catalytic activity may not be sufficiently exerted. If the amount used is more than 0.05 mol%, the thermal stability or thermal oxidation stability is lowered, resulting from aluminum. Occurrence of foreign matters or increase in coloring may be a problem. Thus, even if the addition amount of the aluminum component is small, the polycondensation catalyst of the present invention has a great feature in that it exhibits sufficient catalytic activity. As a result, the thermal stability and thermal oxidation stability are excellent, and foreign matters and coloring caused by aluminum are reduced.

  The phosphorus compound constituting the polycondensation catalyst of the present invention is not particularly limited, but phosphoric acid and phosphoric acid esters such as trimethyl phosphoric acid, triethyl phosphoric acid, phenyl phosphoric acid and triphenyl phosphoric acid, phosphorous acid and trimethyl. Phosphite, triethyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylene diphosphite And the like.

  The phosphorus compound constituting the polymerization catalyst of the present invention is not particularly limited, but phosphoric acid and phosphoric acid esters such as trimethyl phosphoric acid, triethyl phosphoric acid, phenyl phosphoric acid and triphenyl phosphoric acid, phosphorous acid and trimethyl phosphine. Phyto, triethyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylene diphosphite, etc. And phosphite esters.

  More preferable phosphorus compound of the present invention is at least one phosphorus compound selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. It is. 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 formulas (Formula 1) to (Formula 6), respectively. It refers to a compound having the structure represented.

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

  Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds, the phosphorus compounds of the present invention are represented by the following formulas (Chemical Formula 7) to (Chemical Formula 12). Are preferred.

  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.

  In addition, when the compounds represented by the following general formulas (Chemical Formula 13) to (Chemical Formula 15) are used as the phosphorus compound of the present invention, the physical property improving effect and the catalytic activity improving effect are particularly large and preferable.

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

  Examples of the phosphorus compound of the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, diphenylphosphinic acid, diphenylphosphinic acid. Examples include methyl, 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 phosphorus metal salt compound 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 physical properties improving effect and catalytic activity improving effect of the polyester, which are the problems of the present invention, are improved. Largely preferred. 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 phosphorus metal salt compound of the present invention, it is preferable to use at least one selected from the compounds represented by the following general formula (Chemical Formula 16) because the effect of improving the physical properties and the effect of improving the catalytic activity are large.

(In the 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 general formula (Chemical Formula 16), it is preferable to use at least one selected from the compounds represented by the following General Formula (Chemical Formula 17).

(In the 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 formulas (Chemical Formula 17), it is preferable that M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, and Mg are particularly preferable.

  Examples of the metal salt compound of phosphorus according to 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 [Ethyl benzylphosphonate], strontium bis [ethyl benzylphosphonate], manganese bis [ethyl benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonic acid], sodium [(9-anths L) ethyl methylphosphonate], magnesium bis [(9-anthryl) methylphosphonate ethyl], sodium [ethyl 4-hydroxybenzylphosphonate], magnesium bis [4-hydroxybenzylphosphonate ethyl], sodium [4-chlorobenzylphosphone] Acid phenyl], magnesium bis [4-chlorobenzylphosphonate ethyl], sodium [methyl 4-aminobenzylphosphonate], magnesium bis [4-aminobenzylphosphonate methyl], sodium phenylphosphonate, magnesium bis [phenylphosphonic 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 enhancing the physical properties improving effect of the polyester by containing these phosphorus compounds, the catalytic activity is improved by using these phosphorus compounds in combination with the aluminum compound of the present invention at the time of polymerization of the polyester. Seen large.
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 of the present invention, it is preferable to use at least one selected from the compounds represented by the following general formula (Chemical Formula 18) because the physical property improving effect and the catalytic activity improving effect are large. .

(In the 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 of the present invention include (1-naphthyl) methylphosphonic acid ethyl, (1-naphthyl) methylphosphonic acid, (2-naphthyl) methylphosphonic acid ethyl, benzylphosphonic acid ethyl, benzylphosphonic acid. Acid, ethyl (9-anthryl) methylphosphonate, ethyl 4-hydroxybenzylphosphonate, ethyl 2-methylbenzylphosphonate, phenyl 4-chlorobenzylphosphonate, methyl 4-aminobenzylphosphonate, ethyl 4-methoxybenzylphosphonate Etc. Of these, ethyl (1-naphthyl) methylphosphonate and ethyl benzylphosphonate are particularly preferred.

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

(In the 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 of the present invention has a large molecular weight, it is more effective because it is less likely to be distilled off during polymerization.

The phosphorus compound of 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 polyester productivity 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 a phosphorus compound which has the phenol part of this invention in the same molecule | numerator, the compound represented by the following general formula (Formula 26)-(Formula 28) is preferable.

(In the formulas (Chemical Formula 26) to (Chemical Formula 28), R ¹ is a carbon having 1 to 50 carbon atoms including a phenol moiety, a substituent such as a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a phenol moiety. Represents a hydrocarbon group having 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. It represents a hydrocarbon group. However, end each other hydrocarbon groups branched structure or cyclohexyl alicyclic structure or a phenyl or naphthyl aromatic ring structure that may contain .R ² and R ⁴ of the coupling Even if it is.)

  Examples of the phosphorus compound having the phenol moiety of the present invention in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, 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- Phenyl hydroxyphenylphenylphosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, bis (p-hydroxyphenyl Yl) phosphine oxide, tris (p- hydroxyphenyl) phosphine oxide, bis (p- hydroxyphenyl) methyl phosphine oxide, and the following formula (Formula 29), and the like compounds represented by to (Formula 32). Among these, a compound represented by the following formula (Formula 31) and dimethyl p-hydroxyphenylphosphonate are particularly preferable.

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

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

(In 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 R ⁴ represents a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl 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 or naphthyl. And it may be.)

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

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

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

Specific phosphorus metal salt compounds of the present invention include lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzyl] Ethyl phosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], potassium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [3 , 5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di-tert- Methyl butyl-4-hydroxybenzylphosphonate], strontium bis [3,5-di-te t-butyl-4-hydroxybenzylphosphonate ethyl], barium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate phenyl], manganese bis [3,5-di-tert-butyl-4- Ethyl hydroxybenzylphosphonate], nickel bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], copper bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate] And zinc bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate]. 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 the phenol moiety of 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 general formula (Formula 35) is particularly preferable.

(In 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 Represents a C1-C50 hydrocarbon group containing an alkoxyl 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.)

  Among these, at least one selected from compounds represented by the following general formula (Formula 36) is preferable.

(In the formula (Chemical Formula 36), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group containing 1 to 50 carbon atoms. The hydrocarbon group is a fatty acid 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 of the present invention include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxy Methyl benzylphosphonate, isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, phenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl Examples include octadecyl-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 the phenol moiety of the present invention in the same molecule, at least one phosphorus compound selected from specific phosphorus compounds represented by the following general formula (Formula 37) is preferable.

(In the above 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 are each independently 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 general formulas (Chemical Formula 37), it is preferable to use at least one selected from the compounds represented by the following General 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 formula (Chemical 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 including 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 include short chain aliphatic groups such as hydrogen, methyl and butyl groups, long chain aliphatic groups such as octadecyl, phenyl groups, naphthyl groups, substituted phenyl groups and naphthyl groups. An aromatic group such as a group, a group represented by —CH ₂ CH ₂ OH, and the like.

  Specific phosphorus compounds of the present invention include diisopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di-n-butyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, Examples include 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 the phenol moiety of the present invention in the same molecule, 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).

  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 Formula 41) and (Chemical Formula 42) or a linking group represented by (Chemical Formula 43) (X And phosphonic acid-based compounds not having).

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.
(Formula 41)
R ¹ —X— (P═O) (OR ² ) (OR ³ )
[In the above formula (Formula 41) having a linking group, 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 the heterocyclic structure is 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 heterocyclic structure of the phosphorus compound represented by the 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) 1 type selected from a phosphoryl-containing group, a nitrile group, and a cyanoalkyl group. It is 2 or more.

  Examples of the phosphorus compound represented by the 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, ( -Methoxyphenyl-, 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) -iminophos Phosphonic 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 containing heterocyclic rings Compounds include 2-benzofuranylmethylphosphonic acid diethyl ester, 2-benzofuranylmethylphosphonic acid monoethyl ester, 2-benzofuranylmethylphosphonic acid, 2- (5-methyl) benzofuranylmethylphosphoric acid. Acid diethyl ester, 2 - (5-methyl) benzo furanyl methyl phosphonic acid monoethyl ester, 2 - (5-methyl) such as 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 formula (Formula 41) having a linking group (X = — (CH ₂ ) _n —) that can be used in the present invention is as follows.
(Chemical Formula 42)
^{_{(R 0) m -R1- (CH}} 2) n - (P = O) (OR 2) (OR 3)
[In the formula (Chemical Formula 42), R ⁰ is a hydroxyl group, a C1-C10 alkyl group, a —COOH group or —COOR ⁴ (R ⁴ represents a C1-C4 alkyl group), an alkylene glycol group or a 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 formula (Formula 42) of 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 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 -N-dibutylbenzylphosphonic acid monoethyl 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 formula (Formula 42) of the present invention, examples of the phosphorus compound 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 formula (Formula 42) of the present invention, examples of the phosphorus compound 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,
Alkyl groups on the biphenyl ring such as 4- (4-methoxyethoxyphenyl) benzylphosphonic acid diethyl ester, 4- (4-methoxyethoxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenyl) benzylphosphonic acid And phosphonic acids into which a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group and the like are introduced, 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 formula (Formula 42) of the present invention, examples of the phosphorus compounds having an aromatic ring structure having a substituent 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 formula (Formula 42) of the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure as diphenthioether 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 formula (Formula 42) of the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure of diphenylsulfone 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 formula (Formula 42) of 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 formula (Formula 42) of 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 An alkyl group, a carboxy group, a carboxylate group, an alkylene glycol group, a monomethoxyalkylene glycol group, etc. were introduced into a diphenylmethane ring such as diethylphosphonic 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 formula (Formula 42) of the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure as 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, carboxy group, carboxylic acid ester group, alkylene glycol group, 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 formula (Formula 42) of 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, carboxyl 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 formula (Formula 42) of the present invention, examples of the phosphorus compounds having an aromatic ring structure having a substituent 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. 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 formula (Formula 42) of the present invention, examples of the phosphorus compounds having an aromatic ring structure having a substituent as 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 the aromatic ring structure (R ¹ ), the C ¹ -C 10 alkyl group, —COOH group or —COOR ⁴ (R ⁴ is a C 1 -C ⁴ alkyl group) of the present invention. A phosphorus compound substituted with an alkylene glycol group or a monoalkoxyalkylene glycol group (monoalkoxy represents C1 to C4, alkylene glycol represents a C1 to C4 glycol) not only improves the catalytic activity, From the viewpoint 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 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 43)
R ¹ − (P═O) (OR ² ) (OR ³ )
On the other hand, in the phosphorus compound represented by the above 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 ring structure or 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 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 a phosphoryl-containing group, a nitrile group, and a cyanoalkyl group. It is 2 or more. The aromatic ring structure of (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 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, ( 3-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) -phenyl Phosphonic 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), A methylene chain that is a linking group from each structural formula having an aromatic ring structure such as naphthalene, biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenyl methane, diphenyl dimethyl methane, diphenyl ketone, anthracene, phenanthrene, and pyrene, that is, —CH ₂ — As a phosphorus compound group from which benzene is removed, and as a heterocyclic ring-containing phosphorus compound, 5-benzofuranylphosphonic acid diethyl ester, 5-benzofuranylphosphonic acid monoethyl ester, 5-benzofuranylphosphonic acid, 5- (2-methyl) ) Benzo Raniruhosuhon 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. However, when the catalyst preparation method of the present invention is used, it can be used as a polyester polymerization catalyst. .

  Phosphorus compounds have been known as heat stabilizers for polyesters, but it has not been known so far that even when these compounds are used in combination with conventional metal-containing polyester polymerization catalysts, melt polymerization is greatly promoted. It was. Actually, even if the phosphorus compound of the present invention is added when the polyester is melt-polymerized using the antimony compound, titanium compound, tin compound or germanium compound which is a typical catalyst for polyester polymerization as a polymerization catalyst, it is substantially useful. It is not observed that the polymerization is accelerated to a certain level.

  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-mentioned 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 heat-treating a phosphorus compound in a solvent in advance, the aluminum of the present invention or a compound thereof may coexist. Alternatively, the aluminum of the present invention or a compound thereof may be added in a powder form, a solution form, or a slurry form 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 of 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.

  In the present invention, a polycondensation catalytic activity having high practicality can be expressed by using the above-mentioned aluminum or its compound in combination with a phosphorus compound, but it can be selected from a smaller amount of alkali metal, alkaline earth metal and compound thereof. It is a preferred embodiment that at least one of these is coexistent as the second metal-containing component. The coexistence of such a second metal-containing component in the catalyst system is effective in improving productivity by obtaining a catalyst component having an increased reaction rate in addition to an effect of suppressing the formation of diethylene glycol, and thus a higher reaction rate. .

  A technique of adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound to obtain a catalyst having sufficient catalytic activity is known. When such a known catalyst is used, a polyester having excellent thermal stability can be obtained. However, a known catalyst used in combination with an alkali metal compound or an alkaline earth metal compound is added in an amount to obtain practical catalytic activity. However, when an alkali metal compound is used, the hydrolysis resistance of the resulting polyester is reduced and the amount of foreign matter resulting from the alkali metal compound is increased. Moreover, when used for a film, the film properties and the like deteriorate. In addition, when an alkaline earth metal compound is used in combination, the thermal stability of the obtained polyester is lowered when it is attempted to obtain practical activity, coloring due to heating is large, the amount of foreign matter generated is increased, and water resistance is increased. Degradability also decreases.

When adding an alkali metal, an alkaline earth metal and a compound thereof, the amount M (mol%) used is 1 × 10 ⁻⁶ or more and 0.1 or more relative to the number of moles of all polycarboxylic acid units constituting the polyester. It is preferably less than mol%, more preferably 5 × 10 ^{−6 to} 0.05 mol%, still more preferably 1 × 10 ^{−5 to} 0.03 mol%, and particularly preferably 1 × 10 10. ^{-5 to} 0.01 mol%. Since the addition amount of alkali metal and alkaline earth metal is small, it is possible to increase the reaction rate without causing problems such as deterioration of thermal stability, generation of foreign substances, coloring, deterioration of hydrolysis resistance, etc. is there. When the amount M of the alkali metal, alkaline earth metal, or compound thereof is 0.1 mol% or more, the thermal stability decreases, the generation of foreign matter and coloring, and the hydrolysis resistance become problems in product processing. A case occurs. When M is less than 1 × 10 ⁻⁶ , the effect is not clear even when added.

  In the present invention, the alkali metal or alkaline earth metal constituting the second metal-containing component preferably used in addition to aluminum or a compound thereof includes Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr. , Ba is preferable, and among these, at least one selected from Li, Na, Mg or a compound thereof is more 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.

  Among these alkali metals, alkaline earth metals or their compounds, when using strongly alkaline ones such as hydroxides, these tend to be difficult to dissolve in diols such as ethylene glycol or organic solvents such as alcohols. The solution must be added to the polymerization system in an aqueous solution, which may cause a problem in the polymerization process. Furthermore, when a strongly alkaline material such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during the polymerization, and the polymerized polyester tends to be colored, and the hydrolysis resistance also decreases. Tend to. Accordingly, the alkali metal or their compounds or alkaline earth metals or their compounds suitable for the present invention are preferably saturated aliphatic carboxylates, unsaturated aliphatic carboxylates, aromatics of alkali metals or alkaline earth metals. Aromatic carboxylates, halogen-containing carboxylates, hydroxycarboxylates, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromic acid Selected inorganic acid salts, organic sulfonates, organic sulfates, chelate compounds, and oxides. Among these, from the viewpoints of ease of handling and availability, use of saturated aliphatic carboxylates of alkali metals or alkaline earth metals, particularly acetates is preferred.

  In the present invention, in the polyester produced in the presence of the above polycondensation catalyst, it is preferable that the aluminum-based foreign matter insoluble in the polyester determined by the following evaluation method is 3500 ppm or less.

Aluminum-based foreign matter insoluble in polyester is evaluated by the following method.
[Aluminum-based foreign substance evaluation method insoluble in polyester]
30 g of polyester pellets after melt polycondensation and 300 ml of parachlorophenol / tetrachloroethane (3/1: weight ratio) mixed solution are put into a round bottom flask with a stirrer, and the pellets are added to the mixed solution at 100 to 105 ° C. for 2 hours. Stir and dissolve. The solution was allowed to cool to room temperature, and a polytetrafluoroethylene membrane filter (Advantec PTFE membrane filter, product name: T100A047A) having a diameter of 47 mm / pore size of 1.0 μm was used, and the total amount was under a pressure of 0.15 MPa. Use to filter out foreign objects. The effective filtration diameter was 37.5 mm. After completion of the filtration, the product is subsequently washed with 300 ml of chloroform, and then dried under reduced pressure at 30 ° C. for a whole day and night. The amount of aluminum element was quantified on the filtration surface of the membrane filter using a scanning X-ray fluorescence analyzer (manufactured by RIGAKU, ZSX100e, Rh tube 4.0 kW). The quantification is performed on a portion having a diameter of 30 mm at the center of the membrane filter. The calibration curve of the fluorescent X-ray analysis is obtained using a polyethylene terephthalate resin having a known aluminum element content, and the apparent aluminum element amount is expressed in ppm. The measurement is carried out by measuring the intensity of aluminum-Kα radiation under the conditions of PHA (wave height analyzer) 100-300 using X-ray output 50 kV-70 mA, pentaerythritol as a spectral crystal, PC (proportional counter) as a detector. . The amount of aluminum element in the polyethylene terephthalate resin for the calibration curve is quantified by high frequency inductively coupled plasma emission spectrometry.

  In the present invention, the amount of aluminum-based foreign matter insoluble in polyester measured by the above evaluation method is preferably 2500 ppm or less. 1500 ppm or less is more preferable. 1000 ppm or less is particularly preferable. When the amount of aluminum-based foreign matters insoluble in polyester exceeds 3500 ppm, fine foreign matters insoluble in the polyester cause the haze of the molded product to deteriorate when molded as a molded product such as a film or a bottle. Therefore, it is not preferable. Moreover, it leads to the subject that the filter clogging at the time of filtration of polyester in a polycondensation process or a molding process increases.

The amount of the aluminum-based foreign substance insoluble in the polyester measured by the above evaluation method is a converted value to the last, and the content relative to the total amount of the polyester used for the above evaluation becomes a very small amount of ppb level. The transparency of the molded product deteriorates due to the amount of this very small amount of foreign matter. The aluminum-based foreign matter that is insoluble in polyester measured by the above evaluation method has low affinity for polyester. It is presumed that a void is formed at the interface between the aluminum-based foreign material and light is scattered by the void and the transparency of the molded body is lowered.

In the present invention, the method of setting the amount of aluminum-based foreign matter insoluble in the above polyester to 3500 ppm or less is not limited, and examples thereof include the following methods.
(1) The quality of the aluminum compound constituting the polycondensation catalyst of the present invention is optimized.
For example, methods such as specifying the insoluble content when the aluminum compound is dissolved in water, specifying the crystallinity of the aluminum compound, and specifying the amount of water of crystallization of the aluminum compound are included. It is also a preferred embodiment to use an additive that improves the solubility of the aluminum compound in a solvent such as water and a compound that improves the stability of the aluminum compound against hydrolysis and the like.
For example, regarding the method for specifying the insoluble content when an aluminum compound is dissolved in water, the amount of insoluble content in the water of the aluminum compound measured by the method shown below is the scale.
[Measurement method of insoluble content of aluminum compound in water]
30 g of an aluminum compound is added to 1500 ml of pure water at room temperature stirred at 200 rpm, and stirring is continued for 6 hours at room temperature. Subsequently, the liquid temperature is raised to 95 ° C., and stirring is further continued at the same temperature for 3 hours to dissolve the aluminum compound. The obtained solution is allowed to cool to room temperature, filtered through a cellulose acetate membrane filter having a pore size of 0.2 μm (Avantec cellulose acetate type membrane filter, product name: C020A047A), and washed with 50 ml of pure water. The filter obtained by filtering the insoluble matter is dried in a vacuum dryer at 60 ° C. for 12 hours to determine the weight (W) of the insoluble matter. The insoluble content of the aluminum compound in water is calculated by the following formula. When the aluminum compound is an aqueous solution, a part of the aqueous solution is collected, the solid content in the aqueous solution is measured by evaporating the aqueous solution to dryness, and the concentration of the aluminum compound in the aqueous solution is obtained using the solid content as the weight of the aluminum compound. The amount of the aluminum compound in the aqueous solution is determined by filtering the aqueous solution in an amount of 30 g. In the case of the aqueous solution, when the concentration of the aluminum compound in the aqueous solution was higher than 2% by mass, pure water was added to dilute the aluminum so as to be 2% by mass, followed by filtration. The dilution is performed under the same conditions as the dissolution of the solid aluminum compound. The above operation is performed in a clean bench.
Insoluble content in water (ppm) = [W (mg) / 30000 (mg)] × 10 ⁶
It is a preferred embodiment to use one having an insoluble content in water measured by the above method of 700 ppm or less. However, by optimizing the embodiment shown below, it is possible to reduce the amount of aluminum-based foreign matter insoluble in polyester to 3500 ppm or less even when an aluminum compound having an insoluble content in water of more than 700 ppm is used. Therefore, this range is not limited.
(2) The structure of the phosphorus compound, which is another component constituting the polycondensation catalyst of the present invention, is optimized, or the aluminum compound and the phosphorus compound are reacted in advance.
(3) Optimize the addition time and addition method in the production process of the polyester of the above aluminum compound or phosphorus compound.

In the present invention, when the polycondensation catalyst system is used, the haze value of the uniaxially stretched film evaluated by the following evaluation method is preferably 0.6% or less.
[Haze value of uniaxially stretched film]
The polyester resin was dried under vacuum at 130 ° C. for 12 hours and 1000 ±±
Create a 100 μm sheet. The heat press temperature, pressure and time are 320 ° C., 100 kg / cm ² G and 3 seconds, respectively. After pressing, the sheet is put into water and rapidly cooled. The obtained sheet is uniaxially stretched 3.5 times by a batch type stretching machine (manufactured by TM LONGCO., INC, FILM STRETCHER) to obtain a uniaxially stretched film of 300 ± 20 μm. The stretching temperature is blow temperature 95 ° C / plate temperature 100 ° C. The stretching speed is 15,000% / min. The haze of the obtained uniaxially stretched film is measured according to JIS-K7136 using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., 300A). The measurement is performed 5 times and the average value is obtained. The haze value is displayed as a converted value of a film thickness of 300 μm.
0.5% or less is more preferable. When the haze value exceeds 0.6%, it is not preferable because a highly transparent molded body cannot be obtained with respect to a molded body molded by molding with stretching of a film or a bottle. In particular, when a biaxially stretched film is used, a large number of films are overlapped so as to have a thickness of about 9.4 mm (50 in the case of a film thickness of 188 μm), and 45 degrees with respect to vertical under a fluorescent lamp. The effect that the very subtle white turbidity evaluated when observing with the naked eye is not seen is exhibited. The cloudiness is a very slight difference in optical characteristics and cannot be differentiated by a conventionally known haze value. Therefore, although it is a characteristic that does not pose a problem for the use of general-purpose optical applications, it is noted as a characteristic value that may cause a problem in applications that require high optical characteristics. Hereinafter, this characteristic value is referred to as weak cloudiness.

  The method for bringing the haze value of the uniaxially stretched film and the weak cloudiness of the biaxially stretched film into the range of the present invention is not limited. For example, the above-described polyester-insoluble aluminum-based foreign matter is 1000 ppm or less, and In the polyester production method, it can be achieved by simultaneously satisfying that the average value of the carboxyl end group concentration of the polyester oligomer supplied to the polycondensation reaction step and the fluctuation range thereof are within the above-mentioned preferable ranges.

  The reason why the above-mentioned optical characteristics are improved by the above-mentioned characteristics is unclear, but it is possible to suppress the formation of aluminum-based foreign particles or aggregates that reduce the light transmittance due to the carboxyl end groups of polyester oligomers and polyesters, It is presumed that it is expressed by the promotion of solubilization.

  The present invention will be specifically described with reference to the following examples. In addition, these Examples illustrate this invention and are not limited. Further, the intrinsic viscosity, oligomer carboxyl end group concentration and polymer carboxyl end group concentration in the following examples were measured by the following methods.

1. Intrinsic viscosity The sample is dissolved in 50 ml of phenol / tetrachloroethane (weight ratio 6/4). This solution was taken in a 40 ml Ubbelohde viscosity tube, and the intrinsic viscosity (IV) was calculated by measuring the number of seconds dropped in a constant temperature bath at 30 ° C.

2. Oligomer carboxyl end group concentration The oligomer was pulverized with a handy mill (pulverizer) without exhibiting drying. A sample of 1.00 g was precisely weighed and 20 ml of pyridine was added. Several grains of zeolite were added and dissolved by boiling for 15 minutes. Immediately after boiling and refluxing, 10 ml of pure water was added and allowed to cool to room temperature. Titration with N / 10-NaOH was performed using phenolphthalein as an indicator. Do the same for the blank without the sample. When the oligomer did not dissolve in pyridine, the reaction was carried out in benzyl alcohol. AVo (eq / ton) is calculated according to the following equation.
AVo = (A−B) × 0.1 × f × 1000 / W
(A = drop constant (ml), B = blank drop constant (ml), f = factor N / 10-NaOH, W = weight of sample (g))
The quantitative value was measured three times and the average value was used.

3. Oligomer hydroxyl end group concentration 9 mg sample was placed in a sample tube and dissolved by adding 0.3 ml of CDCl ₃ + HFIP-d2 (1 + 1). CDCl ₃ 0.3 ml wokuwae, saranipirizin-d5 30 Maikrol was added, mixed well, centrifuged, and the H-NMR spectrum of the soluble matter was measured using a 500 MHz apparatus.

4. Polymer acid value 15 mg of a sample was dissolved in 0.13 ml of hexafluoroisopropanol (HFIP) / CDCl ₃ = 1/1 mixed solvent, diluted with 0.52 ml of CDCl ₃ , and further 0.2 M triethylamine solution (HFIP / CDCl ₃ Using a solution to which 22 μl of 1/9) was added, H-NMR measurement at 500 MHz was performed for quantification. The measurement was performed three times and the average value was used.

5. Evaluation method for aluminum-based foreign substances insoluble in polyester 30 g of polyester pellets after melt polycondensation and 300 ml of parachlorophenol / tetrachloroethane (3/1: weight ratio) mixed solution are put into a round bottom flask equipped with a stirrer. It stirred and melt | dissolved in the mixed solution at 100-105 degreeC for 2 hours. The solution was allowed to cool to room temperature, and a polytetrafluoroethylene membrane filter (Advantec PTFE membrane filter, product name: T100A047A) having a diameter of 47 mm / pore size of 1.0 μm was used, and the total amount was under a pressure of 0.15 MPa. The foreign matter was filtered off with The effective filtration diameter was 37.5 mm. After completion of the filtration, the product was subsequently washed with 300 ml of chloroform, and then dried under reduced pressure at 30 ° C. overnight. The amount of aluminum element was quantified on the filtration surface of the membrane filter with a scanning fluorescent X-ray analyzer (manufactured by RIGAKU, ZSX100e, Rh line sphere 4.0 kW). The quantification was performed on a portion having a diameter of 30 mm at the center of the membrane filter. The calibration curve of the X-ray fluorescence analysis was determined using a polyethylene terephthalate resin having a known aluminum element content, and the apparent aluminum element amount was expressed in ppm. The measurement was carried out by measuring the intensity of Al-Kα rays under the conditions of PHA (wave height analyzer) 100-300 using X-ray output 50 kV-70 mA and using pentaerythritol as a spectroscopic crystal and PC (proportional counter) as a detector. . The amount of aluminum element in the PET resin for the calibration curve was quantified by high frequency inductively coupled plasma emission spectrometry.

6. Haze value of uniaxially stretched film The polyester resin was dried at 130 ° C. for 12 hours under vacuum and 1000 ±±
Create a 100μm sheet. The heat press temperature, pressure and time were 320 ° C., 100 kg / cm ² G and 3 seconds, respectively. After pressing, the sheet was put into water and rapidly cooled. The obtained sheet was uniaxially stretched 3.5 times by a batch type stretching machine (manufactured by TM LONG CO., INC, FILM STRETCHER) to obtain a uniaxially stretched film of 300 ± 20 μm. The stretching temperature was blow temperature 95 ° C./plate temperature 100 ° C. The stretching speed was 15,000% / min. The haze of the obtained uniaxially stretched film was measured according to JIS-K7136 using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., 300A). In addition, the measurement was performed 5 times and the average value was calculated | required. The haze value was displayed as a converted value of a film thickness of 300 μm.

7. Slightly cloudy sensation 50 biaxially stretched polyester films with a thickness of 188 μm were superposed, and the cloudiness sensation when observed with the naked eye at an angle of 45 degrees with respect to the vertical under a fluorescent lamp was determined based on the following criteria. .
○: No white turbidity ・; Very slight white turbidity ×: White turbidity ××: Strong white turbidity

Example 1
(1) Preparation of polycondensation catalyst solution (Preparation of ethylene glycol solution of phosphorus compound)
After adding 2.0 liters of ethylene glycol to a flask equipped with a nitrogen introduction tube and a cooling tube at room temperature and normal pressure, while stirring at 200 rpm in a nitrogen atmosphere, Irganox 1222 (Ciba 39) represented by -200 g of Specialty Chemicals) was added. Further, 2.0 liters of ethylene glycol was added, the temperature was raised by changing the jacket temperature setting to 196 ° C., and the mixture was stirred under reflux for 60 minutes from the time when the internal temperature reached 185 ° C. or higher. Thereafter, the heating was stopped, the solution was immediately removed from the heat source, and the solution was cooled to 120 ° C. or less within 30 minutes while maintaining the nitrogen atmosphere. The mole fraction of Irganox 1222 in the obtained solution was 40%, and the mole fraction of the compound whose structure changed from Irganox 1222 was 60%.
(Preparation of aqueous solution of aluminum compound)
After adding 5.0 liters of pure water to a flask equipped with a cooling tube at room temperature and normal pressure, 200 g of basic aluminum acetate was added as a slurry with pure water while stirring at 200 rpm. Further, pure water was added so as to be 10.0 liters as a whole, and the mixture was stirred at normal temperature and pressure for 12 hours. Thereafter, the jacket temperature was changed to 100.5 ° C., the temperature was raised, and the mixture was stirred under reflux for 3 hours from the time when the internal temperature reached 95 ° C. or higher. Stirring was stopped and the mixture was allowed to cool to room temperature to obtain an aqueous solution.
(Preparation of ethylene glycol mixed solution of aluminum compound)
After adding an equal volume of ethylene glycol to the aqueous aluminum compound solution obtained by the above method and stirring for 30 minutes at room temperature, the internal temperature is controlled to 80 to 90 ° C., and the pressure is gradually reduced to reach 27 hPa while stirring for several hours. Water was distilled off from the system to obtain an ethylene glycol solution of an aluminum compound at 20 g / l. The peak integrated value ratio of ²⁷ Al-NMR spectrum of the obtained aluminum solution was 2.2.

(2) Esterification reaction and polycondensation A high-speed stirrer is provided in the transfer line from the third esterification reaction tank to the first polycondensation reaction tank, comprising three continuous esterification reaction tanks and three polycondensation reaction tanks. 0.75 parts by mass of ethylene glycol with respect to 1 part by mass of high-purity terephthalic acid was continuously supplied to a slurry preparation tank. The glycol temperature of the slurry was controlled so that the slurry temperature in the slurry adjusting tank was 95 ± 2 ° C. The temperature control of the slurry preparation tank continuously monitors the slurry preparation tank temperature and the glycol temperature supplied to the preparation tank, while continuously changing the glycol addition temperature using a heat exchanger by a feedback circuit, and preparing the slurry The tank was also provided with a temperature adjustment function, and the slurry temperature in the slurry preparation tank was controlled to be constant. The prepared slurry is continuously supplied, the first esterification tank has a reaction temperature of 250 ° C. and 110 kPa, the second esterification reaction tank has 260 ° C. and 105 kPa, the third esterification reaction tank has 260 ° C. and 105 kPa, and the second ester A polyester oligomer was obtained by continuously adding 0.025 parts by mass of ethylene glycol to the chemical reaction tank. The variation rate of the slurry flow rate was controlled within ± 1.5% of the set value. The slurry flow rate was adjusted by changing the rotation speed of the liquid feed pump using a rotary piston flow meter. The molar ratio of ethylene glycol and terephthalic acid was controlled within ± 0.25%. The molar ratio was adjusted by measuring the amount of terephthalic acid in the slurry using a near-infrared spectrophotometer and adjusting the amount of ethylene glycol supplied to the slurry preparation tank. Moreover, the temperature and pressure fluctuations of the first esterification reaction tank were controlled within ± 1.3%. Moreover, the fluctuation | variation of the liquid level of the 1st esterification reaction tank was less than +/- 0.2%. The average AVO of the oligomer at the outlet of the first esterification reaction tank was 2200 eq / ton. In addition, AVo and OHVo of the oligomers at the outlet of the third esterification reaction tank were 800 eq / ton and 985 eq / ton on average, respectively, and AV% was 44.8 mol%. The oligomer is continuously transferred to a continuous polycondensation apparatus comprising three reaction tanks, and the ethylene glycol solution of the aluminum compound and the ethylene glycol solution of the phosphorus compound prepared by the above method in an in-line mixer installed in the transfer line. Are continuously added while stirring with an agitating mixer so as to be 0.015 mol% and 0.036 mol% as aluminum atoms and phosphorus atoms with respect to the acid component in the polyester, respectively. Was 265 [deg.] C., 9 kPa, the medium polycondensation reaction tank was 265-268 [deg.] C., 0.7 kPa, and the final polycondensation reaction tank was 273 [deg.] C., 13.3 Pa to obtain PET with IV 0.620. Table 1 shows the characteristic values of the obtained PET. The NMR spectrum of the mixed solution of the aluminum compound solution and the phosphorus compound solution at the outlet of the stirring mixer does not exist in the spectrum of the ethylene glycol solution of the phosphorus compound before mixing with the ethylene glycol solution of the aluminum compound. A broad peak (referred to as coordination peak) was observed in the range of. The integral value of the coordination peak is the value of the NMR spectrum peak of the phosphorus atom bonded with the hydroxyl group observed in the vicinity of 25 to 27 ppm present in the NMR spectrum of the ethylene glycol solution of the phosphorus compound before mixing with the ethylene glycol solution of the aluminum compound. It was 45% with respect to the integrated value.
AVp of the obtained polyester is 22.5 eq / ton on average, and the amount of aluminum-based foreign matter insoluble in polyester is 400 ppm on average. Moreover, the haze value of the uniaxially stretched film was 0.2 to 0.6% and was excellent in transparency.
(3) Film formation The polyester resin obtained by the above method was dried under reduced pressure at 135 ° C. and 133 Pa for 6 hours, supplied to an extruder, melt extruded into a sheet at about 280 ° C., and a metal roll maintained at a surface temperature of 20 ° C. The film was rapidly cooled and solidified to obtain a cast film having a thickness of 1400 μm. At this time, microfiltration was performed using a sintered filter material made of stainless steel having a filterable particle size of 10 μm (initial filtration efficiency of 95%) as a filter material for removing foreign substances from molten PET. This cast film was heated to 100 ° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a difference in peripheral speed to obtain a uniaxially oriented PET film.
Thereafter, the coating solution prepared by the following method was finely filtered with a felt type polypropylene filter medium having a filterable particle size of 10 μm (initial filtration efficiency of 95%), applied to one side of the PET film by a reverse roll method, and dried. . The coating amount at this time was 0.5 g / m ² . Subsequently, after the coating, the edge of the film was held with a clip, guided to a hot air zone heated to 130 ° C. and dried, and then stretched 4.0 times in the width direction. Subsequently, with the film width fixed, the film was heated by an infrared heater at 250 ° C. for 0.6 seconds to obtain a biaxially oriented PET film having a thickness of 188 μm on which an adhesion modified layer was formed.
The coating solution was prepared by the following method.
In a stainless steel autoclave equipped with a stirrer, thermometer, and partial reflux condenser, 345 parts of dimethyl terephthalate, 211 parts of 1,4 butanediol, 270 parts of ethylene glycol, and 0.5 parts of tetra-n-butyl titanate Was transesterified from 160 ° C. to 220 ° C. over 4 hours. Next, 14 parts of fumaric acid and 160 parts of sebacic acid were added, and the temperature was raised from 200 ° C. to 220 ° C. over 1 hour to carry out an esterification reaction. Next, the temperature was raised to 255 ° C., and the reaction system was gradually reduced in pressure, and then reacted for 1.5 hours under reduced pressure of 29.3 Pa to obtain a pale yellow transparent polyester resin A-1. 75 parts of copolymer polyester resin, 56 parts of methyl ethyl ketone and 19 parts of isopropyl alcohol were charged into a reactor equipped with a stirrer, thermometer, refluxing device and quantitative dropping device, and heated and stirred at 65 ° C. to obtain the copolymer polyester resin. Dissolved. After the resin was completely dissolved, 15 parts of maleic anhydride was added. Next, a solution obtained by dissolving 10 parts of styrene and 1.5 parts of azobisdimethylvaleronitrile in 12 parts of methyl ethyl ketone was dropped into the polyester solution at 0.1 ml / min, and stirring was further continued for 2 hours. After sampling for analysis from the reaction solution, 5 parts of methanol was added. Next, 300 parts of water and 15 parts of triethylamine were added to the reaction solution and stirred for 1 hour. Thereafter, the temperature in the reactor was raised to 100 ° C., and methyl ethyl ketone, isopropyl alcohol and excess triethylamine were distilled off to obtain a light yellow transparent water-dispersed graft copolymer resin. 40 parts of a 25% aqueous dispersion of this water-dispersed graft copolymer resin, 24 parts of water and 36 parts of isopropyl alcohol were mixed, and 1% by weight of an anionic surfactant and a lubricant (manufactured by Nissan Chemical Industries, Ltd., Snowtex OL) was added in an amount of 5% by mass to obtain a coating solution.
The transparency of the obtained biaxially stretched PET film was good and stable. The occurrence of a weak cloudiness was observed only in a few lots. These results are shown in Table 1.
The values shown in Table 1 are the evaluation results of 50 samples (for 25 days) sampled every 12 hours. Moreover, the fluctuation | variation range of the carboxyl terminal group of the polyester oligomer was calculated | required by following formula (1) from the maximum value, minimum value, and average value of 50 samples.
[{(Maximum value−minimum value) × 1/2} / average value] × 100 (%) (1)
Further, the standard deviation (s) was obtained by the following equation (2).
Standard deviation (s) = {(measured value−average value) ² sum / number of samples (50)} ^1/2 ... (2)

(Comparative Example 1)
In Example 1, polyester was obtained in the same manner as in Example 1 except that the fluctuation range of the slurry flow rate supplied to the first esterification reaction tank was set to ± 5%. The fluctuation of the liquid level in the first esterification reactor exceeded ± 0.2%. The results are shown in Table 1.
The variation of the carboxyl end group concentration of the polyester oligomer in this comparative example was large. Therefore, the transparency of the obtained polyester resin and film was inferior. For example, in the biaxially stretched PET film, a weak cloudiness was frequently generated.

(Examples 2 and 3)
In Example 1, polyester was obtained in the same manner as in Example 1 except that the fluctuation range of the slurry flow rate supplied to the first esterification reaction tank was changed to set values ± 1.0% and 0.5%, respectively. .
The fluctuation | variation of the carboxyl terminal group density | concentration of the polyester oligomer in a present Example was further suppressed rather than the method of Example 1, and the transparency of the obtained polyester resin and film was further stabilized.

Example 4
In Example 3, polyester was obtained in the same manner as in Example 3 except that the control of the slurry temperature supplied to the first esterification reaction tank was stopped. The fluctuation range of slurry temperature is 90 ± 5%
Met. The results are shown in Table 1. Although the fluctuation | variation of the carboxyl terminal group density | concentration of the polyester oligomer worsened from Example 3, and the fluctuation | variation of the transparency of the polyester resin and film which were obtained increased a little, it was a practical level.

(Comparative Example 2)
In Example 4, polyester was obtained in the same manner as in Example 4 except that the fluctuation range of the slurry flow rate supplied to the first esterification reaction tank was set to ± 5%. The fluctuation of the liquid level in the first esterification reactor exceeded ± 0.2%. The results are shown in Table 1.
The variation in the carboxyl end group concentration of the polyester oligomer in this comparative example was worse than that in Comparative Example 1. Therefore, the transparency of the obtained polyester resin and film was further deteriorated.

  The polyester production method of the present invention specifies the carboxyl end group concentration of the polyester oligomer at the outlet of the first esterification reaction tank by a very simple method of controlling the supply amount of the raw slurry supplied to the esterification reaction step to a specific range. By a very simple method of controlling the range, fluctuations in the carboxyl end group concentration of the polyester oligomer supplied to the polycondensation reaction tank are suppressed, so fluctuations in the polycondensation reaction in the next step are suppressed. Therefore, the quality variation of the obtained polyester is suppressed, and a very homogeneous polyester can be stably produced. In the polyester production method of the present invention, the esterification reaction is controlled with a slurry flow rate with high measurement accuracy and stable measurement value even when operated for a long period of time. It has the feature that the reliability of the system is stable. Therefore, it can be said that the control method has a balance between quality and economy, that is, cost performance. In addition, it has a feature that the above-mentioned effect can be stably expressed even in a production method in which a high degree of suppression is required for the variation of the carboxyl end group concentration of the polyester oligomer. Therefore, for example, the higher the carboxyl end group concentration of the polyester oligomer at the start of the polycondensation reaction, the higher the polycondensation activity and the higher the carboxyl end group concentration, such as titanium, tin and aluminum based polycondensation catalysts. Even if polycondensation is carried out in the polycondensation reaction, a polycondensation catalyst system is used in which the esterification reaction proceeds during the polycondensation reaction and the increase in the concentration of the final polyester is suppressed compared to the case of polycondensation with other polycondensation catalyst systems When applied to a conventional polyester manufacturing method, high productivity can be secured and high-quality polyester can be stably manufactured. Moreover, when the above method is applied to a composite polycondensation catalyst system composed of an aluminum compound and a phosphorus compound, in addition to the above-mentioned advantages, the transparency of the film is produced when a stretched film is produced using the obtained polyester resin. It has the advantage that it leads to the expression of a double effect that the effect of improving is also added. Therefore, it is important to contribute to the industry.

Claims (11)

  A slurry composed of dicarboxylic acid and glycol is prepared in a slurry preparation tank, and the slurry is continuously supplied in a fixed amount to the esterification reaction tank, followed by esterification reaction using a plurality of esterification reaction tanks and subsequent polycondensation. In the method for continuously producing polyester, a method for producing polyester, characterized in that the slurry flow rate of the slurry supplied to the esterification reaction tank is controlled within a set value ± 3%.   2. The method for producing a polyester according to claim 1, wherein the molar ratio of dicarboxylic acid / glycol in the slurry supplied to the esterification reaction tank is controlled within a set value ± 0.3%.   The method for producing a polyester according to claim 1 or 2, wherein the slurry temperature supplied to the esterification reaction tank is controlled within a set value ± 4 ° C.   The method for producing a polyester according to any one of claims 1 to 3, wherein the temperature of the first esterification reaction tank is controlled within a set value ± 3%.   The method for producing a polyester according to any one of claims 1 to 4, wherein the first esterification reaction tank pressure is controlled within a set value ± 2%.   The method for producing a polyester according to any one of claims 1 to 5, wherein the liquid level of the first esterification reaction tank is controlled within a set value ± 0.2%.   The method for producing a polyester according to any one of claims 1 to 6, wherein the carboxyl end group concentration of the polyester oligomer at the outlet of the first esterification reaction tank is controlled within ± 10% of the set value.   The method for producing a polyester according to any one of claims 1 to 7, wherein the variation of the carboxyl end group concentration of the oligomer at the outlet of the final esterification reactor is within a set value ± 6%.   9. The method for producing a polyester according to claim 1, wherein the set value of the carboxyl end group concentration of the polyester oligomer at the outlet of the first esterification reaction tank is 1900 to 3700 eq / ton.   10. The method for producing a polyester according to claim 1, wherein the set value of the carboxyl end group concentration of the polyester oligomer at the outlet of the final esterification reaction tank is 500 to 900 eq / ton.   The method for producing a polyester according to any one of claims 1 to 10, wherein the ratio of the carboxyl end group concentration to the total end group concentration of the polyester oligomer at the outlet of the final esterification reactor is more than 35 to 49%.