JP5076437B2 - Polyester manufacturing method - Google Patents

Description

  The present invention relates to a method for continuously producing polyester. More specifically, the present invention relates to a method for producing a polyester that can be carried out economically and that can stably obtain a high-quality polyester.

  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.

  For example, in the case of PET, a polyester having aromatic dicarboxylic acid and alkylene glycol as main components as a typical polyester is bis ((ester) by esterification reaction or transesterification reaction between terephthalic acid or dimethyl terephthalate and ethylene glycol. An oligomer mixture such as 2-hydroxyethyl) terephthalate is produced, and this is produced by liquid phase polycondensation using a catalyst at high temperature under vacuum. In these production methods, a so-called direct polymerization method using terephthalic acid is widely practiced because it is advantageous in terms of raw material costs.

  In recent years, PET, which is the most representative polyester, has been faced with severe price competition for general-purpose products with the expansion of global production plants.

  In the direct polymerization method, the esterification reaction is generally carried out by a multi-stage esterification system having 2 to 3 reaction vessels. As one of the measures to meet the demand for the production cost reduction, the esterification reaction vessel Attention has been focused on a method in which singular is used as a single unit (hereinafter referred to as a single can esterification method).

  On the other hand, in the direct polymerization method described above, polyester is produced by mixing an aromatic dicarboxylic acid and glycol in a slurry preparation tank and supplying the slurry to an esterification reaction tank to carry out an esterification reaction. Since the aromatic dicarboxylic acid is solid and insoluble in glycol, these raw materials are supplied in a slurry form to the esterification reaction tank. In order to ensure the fluidity of this slurry, more than the theoretical amount of glycol is required. A method of supplying as a raw material and recovering an excess part is common. The esterified oligomer produces a polyester by deglycolization reaction in a polycondensation reaction tank. These excessively used glycols and glycols generated by the polycondensation reaction must be recovered and reused. Since methods for recovering and reusing these glycols greatly affect the production cost of polyester, various methods are disclosed.

A method of rectifying and removing the low boiling fraction of the distillate from the esterification reaction tank and recycling it to the slurry preparation tank (see Patent Document 1), and the low boiling fraction of ethylene glycol taken out from the esterification reaction tank Rectified and removed and supplied to the ethylene glycol storage tank, and a part of this is used as the circulating liquid of the wet condenser provided in the polycondensation reaction tank to supply the condensate to the ethylene glycol storage tank, and the ethylene glycol retained in the ethylene glycol storage tank. A method of reusing the mixture for slurry preparation (see Patent Document 2), condensing the distillate generated from the polycondensation reaction tank with a wet condenser, and sending it to a distillation column provided in the esterification reaction tank. After removing the water, the slurry is returned to the slurry preparation tank and reused (see Patent Document 3), and the distillate generated in the polycondensation reaction tank is continuously simply distilled, A method in which the bottom extraction liquid of the distillation can is sent to a batch-type single distillation can and subjected to simple distillation, and the distilled liquid excluding the first distillation portion is used as a part of the condensation liquid for the polycondensation reaction gas (Patent Document) 4), a part of the esterification reaction tank distillate and the polycondensation reaction tank distillate rectify and remove the low boiling fraction, and the remaining part of the polycondensation reaction tank distillate is the low boiling fraction. And the high boiling fraction is removed and recycled to the slurry preparation (see Patent Document 5). The distillate taken out from the reaction vessel in the second stage of the esterification reaction is directly purified without distillation purification. A method of reusing as a part or the whole amount (see Patent Document 6), a method of refining a distillate from a polycondensation reaction tank as a part of a raw material glycol by rectifying and removing a low boiling fraction by flash distillation. (See Patent Document 7).
Japanese Patent Laid-Open No. 53-126096 JP-A-55-56120 JP-A-60-163918 JP-A-8-325363 Japanese Patent No. 3424755 Japanese Patent Laid-Open No. 10-279777 WO01 / 088382

  Among the above techniques, the methods disclosed in Patent Documents 2 and 3 have a good balance between quality and economy, that is, cost performance is excellent. Is envied. In addition, there remains a problem with this method for stable operation over a long period of time, for example, a clogging of the recovered glycol transfer line may occur.

  In addition, the glycol recovered by the above method includes, for example, a case where water generated by the reaction is reused without being completely removed. In the method, the use of the recovered glycol affects, for example, the progress of the esterification reaction, and consequently affects the quality and productivity of the polyester. However, the techniques disclosed in these patent documents are disclosures of techniques relating to a method for recovering and reusing raw glycol, and in a polyester production process for stabilizing the quality of polyester in a production method for reusing the recovered glycol. No mention is made regarding optimization of reaction conditions and the like.

  In addition, in the production of polyester, blockage of metal compounds used for esterification and transesterification reaction catalysts, so-called internal particle method in which fine particles are precipitated by reaction with metal compounds in the polyester production process, or electrostatic adhesion to polyester. In many cases, a phosphorus compound is added to block the metal compound to be added or to improve electrostatic adhesion characteristics. A part of these phosphorus compounds is mixed in the distilled glycol. Since the phosphorus compound mixed in the distillate glycol affects the reaction when reused, it is necessary to prevent or control the mixture. However, in the technique disclosed in the above-mentioned patent document, the glycol that is recycled and reused is used. No consideration is given to the inclusion of phosphorus compounds in the water.

In a method for producing polyethylene terephthalate by an internal particle method using a phosphorus compound having a specific structure, which is one of the methods for producing a polyester using a phosphorus compound, a part of the phosphorus compound is distilled out of the system together with ethylene glycol. When ethylene glycol is reused, there is a problem that a polyester giving desired surface properties cannot be obtained with good reproducibility when the film is formed by changing the particle size and the amount of precipitated particles and the amount of precipitated particles. As a method for solving this problem, a method of using ethylene glycol distilled after heat-treating ethylene glycol distilled from the production process of polyester in the presence of an alkali compound (Patent Document 8), distilling ethylene glycol in the same volume or more The method of using ethylene glycol obtained by adding and heating water and distilling off the mixed phosphorus compound together with water (see Patent Document 9) and 0.2 to 10 wt% of water with respect to distilled ethylene glycol A method of using ethylene glycol recovered by distillation after adding and heat-treating is disclosed (see Patent Document 10).
JP 57-14619 A JP 57-14620 A JP 59-96124 A

  Although the above method is an effective method for preventing the phosphorus compound from being mixed into the recovered ethylene glycol, it has a problem that it is disadvantageous in terms of economy. Therefore, in the manufacturing method of polyester using a phosphorus compound, establishment of a method in which glycol can be recycled and reused by removing the phosphorus compound mixed in the distillate glycol by a highly economical method is desired.

  As described above, each of the conventional methods has problems.

  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.

  The single-can esterification method has a problem that, for example, there is a phenomenon such as an increase in the short path of the reaction product, and the control accuracy of the esterification reaction is reduced, as compared with the multi-stage esterification method. Furthermore, in the method of recovering and distilling glycols distilled in the above-mentioned polyester production process, the quality variation of the polyester due to the response is taken into account, so in order to produce a homogeneous polyester, an esterification reaction is required. It is necessary to increase the control accuracy.

In the process of preparing a slurry consisting of terephthalic acid and ethylene glycol in the slurry preparation tank and continuously supplying it to the esterification reaction tank, the detector is directly connected to the pipe for transferring the slurry from the slurry preparation tank to the esterification reaction tank. Esterification reaction by installing a tube-type slurry concentration meter and increasing or decreasing the amount of terephthalic acid and / or ethylene glycol supplied to the slurry preparation tank according to the change in the slurry concentration detected by the slurry concentration meter A method of stabilizing the esterification reaction by controlling the ratio of terephthalic acid and ethylene glycol in the slurry supplied to the tank is disclosed (see Patent Document 11).
JP 2004-75956 A

  The technique disclosed in the above patent document is an effective method for stabilizing the esterification reaction in the single-can esterification method, and the esterification rate of the esterification reaction product is 94.4 to 95.7%. It is described that the range can be suppressed. The esterification reaction rate is determined from both the carboxyl end group concentration and the hydroxyl end group concentration of the polyester oligomer. In the esterification reaction, the change in the carboxyl end group concentration and the hydroxyl end group concentration are generally linked. The fluctuation rate of the esterification reaction rate is smaller than the fluctuation rate of the carboxyl end group concentration alone. 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 addition, the method has a problem in that when the continuous operation is performed for a long time, the slurry concentration detector may be clogged with dicarboxylic acid which is a solid content in the slurry. For example, a method is disclosed in which two sets of slurry densitometers are provided in parallel and can be switched to use any one of them, and used alternately at regular intervals. In such a background, it is desired to construct a control method that has higher accuracy than a conventionally known method and that does not decrease reliability even when operated for a long period of time.

  On the other hand, regarding the production method of the multistage esterification method using a plurality of esterification reaction tanks, the following techniques are disclosed regarding the method for controlling the carboxyl end group concentration of the polyester oligomer.

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 be a certain amount within the range of 20 to 50 eq / ton (see Patent Document 12), the esterification reaction rate is in the range of 92 to 98%, and A method in which the proportion of carboxyl end groups in all end groups is 35% or less and a polycondensation reaction is performed under reduced pressure so that the carboxyl end group concentration in the polyester is 35 eq / ton or less (see Patent Document 13), Adjust at least one reaction condition selected from the group consisting of temperature, residence time, and ethylene glycol supply amount during the first stage polycondensation reaction. 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 14) and a method (Patent Document 15) 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, in order to satisfy the above requirements, the above-described method is not necessarily optimal, and it is preferable to increase the carboxyl end group concentration of the polyester oligomer at the outlet of the final esterification reaction tank supplied to the polycondensation reaction step. In this method, since the variation in the carboxyl end group concentration of the oligomer significantly affects the reaction progress of the subsequent polycondensation reaction and the polyester quality compared to the above method, the variation in the carboxyl end group concentration of the oligomer is It is necessary to suppress with higher accuracy.

For example, as a method for suppressing fluctuations in the carboxyl end group concentration of the polyester oligomer at the outlet of the final esterification reactor, the color tone of the product polymer is measured, and the ester in the esterification step is determined according to the deviation of the measured value from the target value. A method for adjusting the conversion rate, a method for measuring the color tone of the product polymer, a method for adjusting the residence time during the first polycondensation reaction according to the deviation of the measured value from the target value, and a method for measuring the color tone and intrinsic viscosity of the product polymer By adjusting the amount of ethylene glycol supplied to the first stage polycondensation reactor according to the deviation of the measured value from the target value, the standard deviation of the color tone (b value) of the produced polyester is 0 of the average value. A method is disclosed in which the value is maintained within 0.05 times and the standard deviation of the intrinsic viscosity is maintained within 0.005 times the average value (see Patent Documents 16 to 18).
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 on-line and the esterification reaction is controlled based on the result (see, for example, Patent Documents 19 to 22). 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 measured spectrum is used to measure Has been disclosed (see Patent Document 23), which is provided at the bottom of a polycondensation tank in a continuous polyester 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 of feeding back to the second esterification reaction tank temperature controller and suppressing the carboxyl end group concentration change of the produced polyester, and a method of continuously measuring infrared spectral absorption to control the reaction (see Patent Document 24). 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 the above, and the 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 described above, each of the conventional methods has problems.

  In view of the above-described conventional problems, the present invention is a method that is highly economical in a method for continuously producing a polyester by performing an esterification reaction in the presence of a phosphorus compound and using a single esterification reaction tank. And it aims at providing the method of collect | recovering and recycle | reusing the glycol distilled in the manufacturing process of this polyester, without reducing the quality of the polyester obtained.

In order to solve the above-mentioned problems, the present invention was completed by intensive studies. That is, the present invention is a method for producing a polyester carried out in the presence of a phosphorus compound. A slurry comprising a dicarboxylic acid and a glycol prepared in a slurry preparation tank is continuously supplied to an esterification reaction tank, and a single ester is produced. The esterification reaction is carried out using an oxidization reaction tank, and the resulting esterification reaction product is continuously supplied to the polycondensation reaction tank for polycondensation, and the glycol distilled from this production process is distilled. In the manufacturing method of the polyester which carries out fractional distillation and recycle | circulating and reuses, the following requirements are satisfy | filled simultaneously.
(1) Adding a phosphorus compound to the transfer line of the esterification reaction product from the esterification reaction tank to the polycondensation reaction tank. (2) Distillation with the distillate from the esterification reaction tank and polycondensation. Divide and process the distillate from the reaction tank

  In this case, it is preferable to recycle and reuse the residual glycol obtained by distilling off the low-boiling fraction mainly composed of water from the distillate (A) distilled from the esterification reaction tank.

  Further, in this case, from the distillate (B) distilled from the polycondensation reaction tank, the low-boiling fraction mainly composed of water and the high-boiling fraction containing polyester oligomer, phosphorus compound, etc. are fractionally removed. It is preferable to recycle the glycol of the fraction.

  In this case, by controlling the water content of the fractionated and recovered glycol, the water content in the slurry is adjusted to X ± 1.1% by mass (where X represents a number of 1 or more and 2 or less). It is preferable to control so that it becomes.

  Further, in this case, it is preferable to control the amount of heat per unit time of the reactant staying in the esterification reaction tank to be within ± 1.5% of the set value.

  The method for producing a polyester according to the present invention is a method for continuously producing a polyester in the presence of a phosphorus compound and using a single esterification reaction tank. The compound is removed by a highly economical method, and it is possible to avoid the adverse effect on the polycondensation catalytic activity and quality of the polyester due to the phosphorus compound, and to recycle it, so that the operating cost of the recovery can be achieved without reducing the quality of the polyester. Reduction and simplification of equipment can be achieved. The recycling cost of the recovered glycol can greatly reduce the production cost of the polyester. Furthermore, in this production method, there is an extremely remarkable effect that high-quality polyester can be stably and continuously produced over a long period of time without reducing polycondensation productivity. Therefore, this is a cost-effective polyester production method.

  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 their functional derivatives, 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 alcohol 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 this invention, it is preferable to implement the said polyester by the direct esterification method and a continuous method using a single esterification reaction tank.

  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 addition, it is economically advantageous to perform the esterification reaction in a single esterification reaction tank. That is, a slurry composed of dicarboxylic acid and glycol is prepared in a slurry preparation tank, the slurry is continuously supplied to the esterification reaction tank, and the esterification reaction is performed using a single esterification reaction tank. It is preferable to continuously supply the esterification reaction product to the polycondensation reaction tank to carry out polycondensation to continuously produce polyester.

  In the present invention, the polyester is preferably produced in the presence of a phosphorus compound. The addition of the phosphorus compound may stabilize the polycondensation catalyst, improve electrostatic adhesion, or give an effect such as an increase in polycondensation catalyst activity in a polycondensation catalyst mainly composed of an aluminum compound. it can.

  In the present invention, it is preferable to distill the glycol distilled from the production process of the polyester by distillation and recycle it. This measure can greatly reduce the production cost of the polyester.

In the present invention, it is preferable that the following requirements are simultaneously satisfied in the polyester production method.
(1) Adding a phosphorus compound to the transfer line of the esterification reaction product from the esterification reaction tank to the polycondensation reaction tank.
(2) The distillate from the esterification reaction tank and the distillate from the polycondensation reaction tank are treated separately.

  Furthermore, in the present invention, it is possible to circulate and reuse the residual glycol obtained by distilling off the low-boiling fraction mainly composed of water from the distillate (A) distilled from the esterification reaction tank, From the distillate (B) distilled from the polycondensation reaction tank, the low boiling fraction mainly composed of water and the middle distillate glycol obtained by fractionating and removing the high boiling fraction containing polyester oligomer, phosphorus compound, etc. By recirculating and reusing, by controlling the water content of the glycol collected by fractional distillation, the water content in the slurry is X ± 1.1% by mass (where X is a number of 1 or more and 2 or less. It is a more preferable embodiment that control is performed.

  In this invention, if the said requirements are satisfy | filled, the reaction tank size of esterification and a polycondensation process, the manufacturing conditions of each process, etc. can be selected suitably without limitation. For example, a slurry containing 1.2 to 2.5 moles, preferably 1.3 to 2.2 moles of ethylene glycol with respect to 1 mole of terephthalic acid is prepared and used in the esterification reaction step. Supply continuously. The esterification reaction is preferably carried out using one esterification reaction tank while removing water produced by the reaction from the system with a rectification column. The temperature of the esterification reaction is 240 to 270 ° C., preferably 245 to 265 ° C., the pressure is preferably normal pressure to 300 KPa, more preferably 20 to 280 kPa, and further preferably 40 to 260 kPa. 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, middle-stage polycondensation, and late-stage polycondensation is taken, but a one-stage or two-stage system is preferred in view of cost reduction. Regarding the polycondensation reaction conditions, for example, the reaction temperature of the first stage polycondensation in a two-stage system is 250 to 290 ° C., preferably 260 to 280 ° C., and the pressure is 10 to 2.7 KPa, preferably 2.7. The temperature of the second stage polycondensation reaction is 265 to 300 ° C, preferably 275 to 295 ° C, and the pressure is 1.3 to 0.13 KPa, preferably 0.65 to 0.065 KPa. is there.

  Hereinafter, the detail of the said manufacturing method is mentioned.

  When polycondensation of polyester is carried out in the presence of a phosphorus compound, a part of the phosphorus compound added to the polycondensation reaction system is distilled together with a distillate such as glycol. When the phosphorus compound contained in the distillate is returned to the polyester production process, it may adversely affect the polycondensation catalytic activity of the polyester and the polyester quality. Therefore, when the distillate glycol is reused, it is necessary to prevent or control the mixing of the phosphorus compound into the recovered glycol. For example, when an aluminum compound is used in the polycondensation catalyst system, the amount of the phosphorus compound greatly affects the polycondensation catalyst activity. In addition, when a compound containing a hindered phenol residue is used as the phosphorus compound, the structural change of the distilling phosphorus compound occurs, and when the modified phosphorus compound is mixed in the polyester, the polyester is crystallized at a temperature rise. The temperature (Tc1) decreases.

  For example, PET has been adopted as a material for containers such as carbonated drinks, juices, and mineral water because of its excellent transparency, mechanical strength, heat resistance, gas barrier properties, and the like. In these applications, beverages that have been sterilized at high temperatures are hot-filled in polyester bottles, or sterilized at high temperatures after filling beverages. However, ordinary polyester bottles shrink during such hot-filling treatments. Deformation occurs and becomes a problem. As methods for improving the heat resistance of polyester bottles, methods have been proposed in which the bottle cap is heat treated to increase the degree of crystallinity and the stretched bottle is heat-set. In particular, when the crystallization of the plug portion is insufficient or the variation in crystallinity is large, the sealing performance with the cap is deteriorated, and the contents may leak.

  In addition, in the case of beverages that require hot filling, such as fruit juice beverages, oolong tea, and mineral water, a method of crystallizing by heat-treating the plug portion of the preform or molded bottle is common. Such a method, that is, a method of improving the heat resistance by heat-treating the plug portion and the shoulder portion, the time and temperature for the crystallization treatment greatly affect the productivity, and can be processed at a low temperature in a short time. It is preferable that the conversion rate is PET. On the other hand, the body portion is required to be transparent even if heat treatment is performed at the time of molding so as not to deteriorate the color tone of the contents of the bottle, and the mouthpiece portion and the body portion must have contradictory characteristics. On the other hand, if the crystallization speed is too high, the crystallization becomes non-uniform and distortion occurs in the plug portion, leading to leakage of the filling liquid.

  As a solution to such a problem, there is a method of optimizing the crystallization rate of PET, and it is known that Tc1, which is a measure of the crystallization rate, is in the optimum range. Although the appropriate crystallization speed slightly changes depending on the bottle production process equipment, a Tc1 product at 150 to 170 ° C. is desired from the market. The polycondensation catalyst system composed of the above aluminum compound and phosphorus compound has a characteristic that PET of 150 to 170 ° C., which is the optimum Tc1, can be obtained, unlike the antimony polycondensation catalyst that has been widely used conventionally, for example. However, when a phosphorus compound is mixed in the recovered glycol, it leads to a decrease in Tc1 of the polyester obtained, leading to deterioration of the excellent properties of the polycondensation catalyst system of the present invention.

  Further, in a polycondensation catalyst that is blocked by a phosphorus compound such as a titanium compound or a tin compound, variations in the amount or quality of the phosphorus compound greatly affect the polycondensation catalyst activity.

  In the present invention, as described above, it is preferable to add the phosphorus compound to the transfer line of the esterification reaction product from the esterification reaction tank to the polycondensation reaction tank. As a result, the distillate distilled from the esterification reaction tank does not contain phosphorus compounds, and the incorporation of the phosphorus compound distilled from the polyester production process is limited to the distillate distilled from the polycondensation reaction tank. Is done. Therefore, in the present invention, it is preferable to carry out the fractionation separately from the distillate distilled from the esterification reaction tank and the distillate distilled from the polycondensation reaction tank. Processing the two separately has a great impact on the economic efficiency, that is, the reduction of operating expenses and the simplification of equipment as described later.

  In the distillate (A) distilled from the esterification reaction tank, since no phosphorus compound is mixed, the low-boiling fraction mainly composed of water is removed by distillation, and the residue is reused as glycol for producing polyester. It is preferable.

  On the other hand, since the distillate (B) distilled from the polycondensation reaction tank is mixed with a phosphorus compound, and the mixed phosphorus compound has a higher boiling point than glycol, it has a low boiling point like the distillate (A). The phosphorus compound cannot be removed simply by removing the fraction, and it is contained in the residue. Therefore, when the residue is recycled and reused, the mixed phosphorus compound is circulated in the polyester production process, causing polycondensation catalyst activity and a decrease in Tc1 of the resulting polyester. Therefore, the distillate (B) is recycled as a low-boiling distillate mainly composed of water and a middle distillate obtained by distilling off a high-boiling distillate containing a polyester oligomer, a phosphorus compound, etc. as glycol for polyester production. It is preferable to use it.

  When distillate (A) is reused as part or all of the glycol for esterification reaction, the distillate (A) is the same as distillate (B). Is not preferable because the distillate (A) is excessively processed, resulting in an increase in equipment and operating costs, which is economically disadvantageous.

  In the direct esterification method, 90 to 95% of the amount of distillate distilled in the polyester production process is generated in the esterification process, although there are some variations depending on the production conditions of the polyester. Therefore, the amount of the distillate (A) is overwhelmingly larger than that of the distillate (B), and for the distillate occupying the overwhelming majority, only the low boiling point cut may be performed, And as will be described later, since this distillation can be distilled by the amount of heat of the distillate itself, the effects of reducing operating costs and simplifying equipment are greatly expressed. Therefore, it can be said that the economic effect of carrying out the distillation treatment by dividing the distillate (A) and the distillate (B) as described above is great.

  In the present invention, the fractionation method is not limited, but the fraction removal of the low-boiling fraction of the distillate (A) from the esterification reaction tank can be continuously performed by the heat of the distillate itself. preferable. Therefore, it is preferable to carry out in-line. This can further reduce operating costs and simplify equipment. If necessary, auxiliary heating by heating or exchanging piping is not excluded.

In the above-described method for recovering glycol in-line, it is preferable to distill off a low-boiling fraction containing water as a main component, and to recycle and reuse the residue taken out from the bottom of the distillation column. In this case, it is preferable to circulate and reuse without completely removing water from the viewpoint of economy.
However, the amount of water in the recovered glycol must be controlled because it leads to fluctuations in the esterification reaction. The optimization of the amount of water in the recovered glycol will be described later.

  In the above-mentioned method for recovering glycol in-line, it is preferable to circulate a part of the residue extracted from the bottom of the distillation column used in the recovery to the distillation column (hereinafter referred to as distillation column liquid circulation method). This is an embodiment. By carrying out the method, occurrence of clogging of the liquid feed line corresponding to the residue is suppressed, and long-term stable production becomes possible. The glycol distilled in the polyester production process contains solids that are hardly soluble or insoluble in glycols made of polyester oligomers and the like due to entrainment of droplets. As a matter of course, the solid content is contained in the distillation column residue and recycled to the polyester production process in the distillation. Therefore, when polyester is continuously produced over a long period of time, in the liquid feed line for the residue, the solid content in the residue or the solid content precipitated in the liquid feed line There has been a problem that stable operation may be difficult due to a decrease in liquid feeding property and clogging of the line, and improvement has been desired. The present invention solves this problem by the above-mentioned extremely simple method. The reason why the above-mentioned problem is solved by the implementation of the distillation column liquid circulation method is not clear, but increases the liquid flow rate and flow rate of the residual liquid, maintains the liquid temperature, suppresses the temperature fluctuation, and extends the residence of the residual liquid in the distillation column. It is inferred that this is caused by the suppression of precipitation of solids due to the sum of a plurality of factors such as the structural change of solids due to. Here, it is speculated that the structural change takes into account the effects of both chemical change and physical change. That is, as a chemical change, an improvement in solubility in glycol and a decrease in crystallinity due to a reduction in molecular weight due to glycolysis of oligomers in a solid content, and a change in crystallinity, etc. of solid content can be considered as a physical change. . Moreover, the implementation of the distillation column liquid circulation method leads to improvement of fractionation accuracy in addition to suppression of line clogging.

  Therefore, the setting of the liquid temperature of the residual part and the temperature range, the storage capacity of the residual part at the bottom of the distillation column, the return position of the circulating liquid, the circulation amount, etc. are important. The conditions are not limited, but the following method is preferred. For example, the return position of the circulating liquid is preferably the uppermost portion of the storage portion of the residue from the middle stage of the distillation column to the bottom of the distillation column. Although it is preferable to return to the middle stage of the distillation column in terms of improving the distillation accuracy, it is disadvantageous in terms of temperature control. It is determined as appropriate in the balance between the two. The pump used for circulation may be either a reverse type or a non-reverse type, but the reverse type is preferred. The storage amount is preferably maintained at 25 to 70% by mass with respect to the circulation amount. The circulation amount is preferably 30 to 75% by mass of the residual amount.

  In addition, regarding the control of the liquid level of the distillation column, for example, it is conceivable to control the flow rate of glycol added to the distillation column in addition to glycol distilled from the esterification reaction tank. As the glycol to be added to the distillation column, any of a novel glycol, a glycol generated and recovered in the polymerization step, a glycol distilled from another distillation column, and a glycol recovered from another system may be used. It is not necessary to directly control the flow rate of glycol added to the distillation column, even if the flow rate is indirectly regulated within a certain range by controlling the glycol storage tank and the liquid level and temperature of the previous process. Good. It is also conceivable to control the liquid level by the amount extracted from the distillation column. In this case, the extraction amount is preferably within a range in which the storage amount is kept at 25 to 70% by mass with respect to the circulation amount and the circulation amount is kept at 30 to 75% by mass as described above. It is not necessary to directly control the flow rate of the extraction amount, and the flow rate may be indirectly regulated within a certain range depending on the process into which the extracted liquid flows or the liquid level and temperature in the subsequent process.

  The circulating fluid temperature is more preferably 160 to 180 ° C. 164-173 degreeC is more preferable, and 168-175 degreeC is further more preferable. It is preferable to add a temperature adjusting function to the circulation line for maintaining the temperature and controlling the temperature. When the temperature is lower than 160 ° C., the line clogging frequency increases. On the contrary, when it exceeds 180 degreeC, it leads to the increase in energy loss and becomes economically disadvantageous. Moreover, it leads to the fall of distillation accuracy.

  The performance of the distillation column used in the above method is not limited, but 8 to 18 stages are preferable. 9 to 15 stages are more preferable. Either a bubble column or a packed column may be used.

  In the case of glycol distilled from the above esterification reaction tank, the solid content contained in the glycol has a low melting point, and it is dissolved in the reaction system in the esterification reaction step, reacts and is taken into the polyester, so there is no need to remove it. . However, it is preferable to prevent clogging of the liquid feed line of the distillation residue due to the solid analysis by the distillation column liquid circulation method described above.

  On the other hand, since the distillate (B) from the polycondensation reaction tank is a decompression system, it is recovered by cooling and condensing with a wet condenser. Therefore, it is necessary to heat and supply to the distillation column. Therefore, the distillation process of the distillate (B) may be performed by an off-line process instead of an in-line process. Alternatively, batch processing may be used.

  In addition, the solid content contained in the fraction distilled from the polycondensation reaction tank has a high melting point, and if it is contained in recovered glycol and circulated in the polyester production process, it does not react with the polyester in the polyester production process, and foreign matter is generated. It is not preferable because it may lead to. Therefore, it is preferable to take measures to prevent the solid content from being mixed into the recovered glycol. Although this method is not limited, it is preferable to remove the solid content in the condensate recovered by cooling and condensing with a wet condenser and supplying it to the distillation column. The method for removing the solid content is not limited. For example, it is preferable to carry out by filtration, centrifugal separation, natural sedimentation or the like and a combination thereof.

  The distillate fraction (B) may be fractionated at the same time by distilling the low-boiling fraction and the high-boiling fraction with one distillation column, or the distillation column is divided into two groups, with water as the main component. After removing the low-boiling fraction, the high-boiling fraction containing a polyester oligomer or a phosphorus compound may be removed by distillation. The latter is preferred because it allows efficient distillation. The fractional distillation may be carried out batchwise. The performance of the distillation column in the fractional distillation is not limited, but a total of 20 to 50 stages is preferable.

  The method for reusing the recovered glycol recovered by the above method is not limited. It is preferably stored in a recovered glycol storage tank and reused. In this case, the volume of the lower part of the distillation column may be increased, and the amount supplied to the recovered glycol storage tank may be adjusted by storing in this part. Moreover, you may supply to a slurry preparation tank directly, without collect | recovering collection | recovery glycol. In addition, the recovered glycol from each of the distillate from the esterification reaction tank and the distillate from the polycondensation reaction tank may be handled separately or may be handled collectively.

  In the present invention, the ratio of the recovered glycol used for slurry preparation is not limited, but the total amount of glycol generated in the polyester production process is used, and the self-balance method is used to supply the shortage with new glycol. preferable.

  In the present invention, when the recovered glycol is ethylene glycol, the low boiling point impurities are mainly those having a boiling point of 165 ° C. or less other than water, acetaldehyde, 2-methyl-1,3-dioxolane, methyl cellosolve or these compounds. It becomes a target.

  In the glycol recovery method, the control of the amount of water in the recovered glycol is an important factor because it affects the quality and production cost of the polyester. That is, if the amount of water is large, the recovery cost is reduced, but this leads to fluctuations in the esterification reaction, resulting in fluctuations in the quality of the polyester. Conversely, if the water content is reduced, it is preferable for the quality fluctuation of the polyester, but it is disadvantageous in terms of the recovery cost.

  In the prior art, it was recovered in an almost anhydrous state from the viewpoint of quality. Therefore, the present inventors diligently studied the optimum value of the amount of water in the slurry supplied to the esterification reaction tank, and set the amount of water in the slurry to X ± 1.1% by mass (where X is 1 or more and 2 or more). It has been found that it is preferable to control within the following number). The fluctuation range is more preferably controlled within ± 0.9% by mass, and further preferably controlled within ± 0.7% by mass. On the other hand, the lower limit of the fluctuation range is most preferably ± 0%, which is unchanged, but is preferably ± 0.01% by mass and more preferably ± 0.03% by mass from the viewpoint of cost performance.

  By controlling the water content within this range, the effect of the water content on the esterification reaction can be balanced with the recovery cost. If X is less than 1% by mass, it is necessary to reduce the amount of water in the recovered glycol, which increases the recovery cost. Furthermore, when moisture is contained in the slurry, the fluidity of the slurry composed of carboxylic acid and glycol is improved by the moisture, leading to stabilization of the esterification reaction, and as a result, stabilizing the quality of the polyester. Is added. That is, when the polyester is produced only with a new glycol, or when the water content of the recovered glycol is recovered and produced in a substantially anhydrous state, that is, the method in which the water content in the slurry is in a substantially anhydrous state. In comparison, the fluidity of the slurry is improved by the moisture contained in the slurry, the supply accuracy of the slurry to the esterification reaction tank is improved, and the process and quality can be stabilized. Further, since the supply stability of the slurry can be ensured even if the amount of glycol used during slurry preparation is reduced, stable production is possible even if the ratio of the amount of glycol in the slurry is lowered, which is economically advantageous. On the other hand, when X exceeds 2% by mass, the effect of improving the fluidity of the slurry is saturated and the esterification reaction becomes unstable, resulting in large fluctuations in the characteristics of the esterification reaction product. This is not preferable because the quality variation such as the carboxyl end group concentration and color tone of the polyester becomes large. Further, when the fluctuation range exceeds ± 1.1% by mass, the esterification reaction becomes unstable, and the characteristic fluctuation of the esterification reaction product increases, resulting in the carboxyl end group concentration and color tone of the final polyester as a result. This is not preferable because quality fluctuations increase.

  In the present invention, it is a preferred embodiment to control the water content in the slurry within the above range by controlling the water content in the recovered glycol.

  In the present invention, the method for measuring and controlling the amount of water in the slurry is not limited. For example, the method for measuring the amount of water includes a method of measuring online using a near-infrared spectrophotometer or a gas chromatograph, a method of sampling periodically and performing an offline analysis using the Karl Fischer method. A method of measuring online using a near-infrared spectrophotometer is preferred.

  The measurement device, the installation location of the measurement detector, and the measurement wavelength in the case of online measurement by quantifying using a near-infrared spectrophotometer are not limited.

  A measuring instrument will not be specifically limited if it is a near-infrared spectrophotometer which can measure continuously on-line. 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.

  There is no limitation on the measurement wavelength of near-infrared light for determining the amount of water. It is preferable to measure and measure a wavelength with high sensitivity and less disturbance using a glycol or slurry sample with known moisture, and create a calibration curve appropriately. For example, it is preferable to use a wavelength of 1922 nm. Moreover, you may calculate from the analytical curve which combined the some wavelength.

  The installation location is not limited. For example, in the case of the distillation control method, it may be installed at any location from the bottom of the distillation column to just before the supply to the slurry preparation tank. Further, the moisture content may be controlled by measuring the moisture content in the slurry and feeding it back to the distillation condition control described below. In the case of the moisture adjustment method, it may be installed at any location from the slurry preparation tank to immediately before being supplied to the esterification reaction tank. In the case of the distillation control method, the water content in both the recovered glycol and the slurry may be measured online with a near-infrared spectrophotometer to increase the control accuracy.

  In the present invention, the amount of water in the recovered glycol, which is a distillate residual liquid of the distillate (A) from the esterification reaction tank described above, is X ± 2.0% by mass (where X is a number of 2 or more and 3 or less. It is preferable to perform distillation within a controlled range. Within X ± 1.5% by mass (where X represents a number of 2 or more and 3 or less) is more preferable, and within X ± 1.0% by mass (where X represents a number of 2 or more and 3 or less) is more preferable. On the other hand, the lower limit of the fluctuation range is most preferably ± 0%, which is unchanged, but is preferably ± 0.03% by mass, more preferably ± 0.05% by mass from the viewpoint of cost performance. By carrying out by this method, even if the mixing ratio of the recovered glycol in the glycol used for slurry preparation is varied within a wide range of 50 to 66% by mass, the amount of water in the slurry can be adjusted without adjusting the water content of the slurry. Can be kept within the preferred range of the present invention as described above, and it is possible to stabilize the management of the amount of water in the slurry. Further, controlling the water content X in the recovered glycol at 2 to 3% by mass can be said to be an excellent method of cost performance because the recovery cost is reduced as compared with the method of lowering the water content.

  The method for setting the amount of water in the recovered glycol to the above range is not limited, but the pressure and temperature of the distillation column are controlled to control the amount of water in the residue of the fraction taken from the bottom of the distillation column. preferable.

  The pressure in the distillation column is not limited, but it is preferable to set the pressure in the esterification reaction tank, which is a generation source of glycol supplied to the distillation column by adjusting the pressure in the distillation column. The pressure setting is preferably carried out in a normal pressure to a slightly pressurized state from the viewpoint of the overall performance such as the influence on the esterification reaction and the balance between the distillation efficiency and the energy required for distillation.

  In the above method, it is preferable to maintain the top pressure of the distillation column at normal pressure to 300 kPa (absolute pressure, hereinafter, pressure is expressed as absolute pressure). 20-280 kPa is more preferable, and 40-260 kPa is more preferable. Under reduced pressure, the temperature control accuracy of the distillation column is reduced. On the other hand, when it exceeds 300 kPa, it leads to the fall of fractionation precision. Further, in the method of adjusting the pressure in the esterification reaction tank with the tower top pressure, by-product of diethylene glycol in the esterification reaction step is increased, which is not preferable. Furthermore, an increase in the pressure of the esterification reaction tank increases the degree of influence on the esterification reaction due to the pressure fluctuation, and therefore the fluctuation of the esterification reaction increases.

  The method for controlling the top pressure of the distillation column is not limited. For example, a pressure regulating valve is installed in the vent pipe of a distillation column, and the method of adjusting with the pressure regulating valve, the method of adjusting the vent pipe with water, and adjusting by changing the position of the liquid surface of the water seal or the pipe of the water sealed portion, etc. Is mentioned.

  The present invention is preferably applied to a method for producing a polyester using ethylene glycol as the glycol. When ethylene glycol is used as the glycol, the middle temperature of the distillation column is preferably controlled to 106 ± 3 ° C. in the distillation. In general, the control of the distillation column is controlled by the top temperature of the distillation column. However, in order to control the amount of water in the residue taken out from the bottom of the distillation column by controlling the top temperature, a very narrow range is required. It is necessary to control the temperature. On the other hand, for example, when the temperature is controlled at the temperature at the bottom of the column disclosed in Patent Document 2, the temperature at the top of the column is determined, and the amount of ethylene glycol in the low-boiling fraction mainly composed of water taken out from the column top. Fluctuation increases. In general, since the low boiling fraction is discarded, an increase in the amount of ethylene glycol in the low boiling fraction is not preferable because it leads to a change in the treatment load of the waste liquid and the environmental load increases. The above problems can be balanced by controlling the temperature of the middle stage of the distillation column. In addition, the middle stage temperature means a substantially central part of the shelf of the distillation column. That is, when the number of shelves is an odd number, the temperature is at the center shelf, and when the number is even, it indicates the temperature of one of the shelves on the center side of each of the divided parts. The temperature range is more preferably 106 ± 2 ° C. If the temperature is less than 103 ° C., the amount of water in the residue is more than the above range, which is not preferable. On the other hand, when the temperature exceeds 110 ° C., the amount of water in the residue is less than the above range, and the amount of ethylene glycol in the low-boiling fraction is increased. Since it increases, it is not preferable.

  The esterification conditions, the characteristics of the esterification reaction product and the polycondensation reaction conditions in the present invention may be appropriately set in consideration of the quality and productivity of the polyester, but in the present invention, the recovered glycol is circulated as described above. Since it is reused, even if the amount of water in the recovered glycol is controlled within the above range, since the fluctuation of the esterification reaction is increased as compared with a production method in which a conventionally known recovered glycol is circulated and not reused, It is preferred to incorporate suppression of reaction fluctuations.

  In the present invention, it is preferable to control the amount of heat per unit time of the reactant staying in the esterification reaction tank to be within ± 1.5% of the set value. The fluctuation range of the amount of heat per unit time of the reaction product staying in the esterification reaction tank is more preferably within ± 1.3%, and further preferably within ± 1.1%. 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. When the above fluctuation range exceeds ± 1.5%, the fluctuation of the carboxyl end group concentration of the esterification reaction product at the outlet of the esterification reaction tank becomes large, resulting in the carboxyl end group concentration and color tone of the final polyester. This is not preferable because quality fluctuations increase. In addition, depending on the type of polycondensation catalyst used, the polycondensation catalyst activity may vary, and the quality variation of the polyester may be further increased.

  The method for controlling the amount of heat per unit time of the reactant staying in the esterification reaction tank is not limited. For example, the following methods are mentioned.

  The first method measures the temperature and flow rate of the reactants retained in the esterification reaction tank, the slurry temperature and the flow rate, so that the amount of heat per unit time of the reactants retained in the esterification reaction tank is constant. It is preferable to carry out by controlling the amount of heat per unit time brought into the slurry. In this method, as a method of controlling the amount of heat per unit time brought into the slurry, there is a method of controlling the slurry temperature, the slurry supply amount, and both, but if the slurry supply amount is changed, the liquid level fluctuation of the esterification reaction tank etc. Since this causes fluctuations in factors affecting the esterification reaction, it is preferable to control the slurry temperature so that the slurry flow rate is constant. In the case of carrying out by this method, it is preferable to control the slurry supply amount within a set value ± 3.0%. 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 number of revolutions of the feed pump so as to achieve a set flow rate using a flow meter, a bypass line that returns to the slurry preparation tank is provided after the feed pump of the feed line, and the number of revolutions of the feed pump is adjusted. A 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 providing a difference in height between the slurry preparation tank and the esterification reaction tank. Then, the slurry is fed by the head pressure, and adjustment is performed by adjusting the opening of the control valve provided in the liquid feeding line so that the flow rate of the flow meter provided in the liquid feeding line becomes 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 an esterification reaction tank may become fixed. Moreover, it is preferable to measure the temperature inside the reaction tank of 200 to 400 mm from the can wall at the bottom of the reaction tank.

  The amount of reactant passing through the esterification reactor is measured by measuring the reactant flow rate at the outlet of the esterification reactor using a high-temperature flow meter, or the amount of slurry supplied to the esterification reactor The method etc. which are computed from the liquid level of an esterification reaction tank are mentioned.

  In the second method, the temperature and the liquid level of the reaction product staying in the esterification reaction tank are controlled to be within ± 3.0% and ± 0.2% of the set values, respectively, In this method, the amount of heat per unit time of the slurry supplied to the chemical reaction tank is controlled to be within ± 2.0% of the set value.

  Since the variation of the carboxyl end group concentration of the esterification reaction product at the outlet of the esterification reaction tank is affected by the temperature and residence time of the esterification tank (in the limited polyester production line, the liquid level of the reaction tank), The factor is preferably controlled within the above range. For example, the temperature is more preferably within a set value ± 2.0%. 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 preferable to control the amount of heat per unit time of the slurry supplied to the esterification reaction tank to be within ± 2.0% of the set value after satisfying the above requirements. Within ± 1.7% is more preferred, and within ± 1.4% 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.

  In the third method, as in the second method, the temperature and the liquid level of the reactant staying in the esterification reaction tank are within ± 3.0% and ± 0.2% of the set values, respectively. And the temperature difference between the temperature of the reactant staying in the esterification reaction tank and the slurry temperature supplied to the esterification reaction tank, the slurry flow rate, and the specific heat of the slurry are supplied to the esterification reaction tank. It is preferable to control the amount of heat per unit time of the slurry to be within ± 2.0% of the set value. The fluctuation range of the amount of heat per unit time of the slurry supplied into the esterification reaction tank obtained by the above method is more preferably within ± 1.7%, and further preferably within ± 1.4%. The lower limit is most preferably ± 0%, which is unchanged, but is preferably ± 0.1%, more preferably ± 0.3% from the viewpoint of cost performance.

  In this method, the calorie fluctuation per unit time of the reactant staying in the esterification reaction tank can be approximated by the temperature of the reactant staying in the esterification reaction tank, and the fluctuation of the calorific value is in the esterification reaction tank. The amount of heat per unit time of the slurry supplied to the esterification reaction tank is obtained from the temperature difference between the temperature of the reactant staying in the slurry and the slurry temperature supplied to the esterification reaction tank, the slurry flow rate and the specific heat of the slurry. This is based on finding out that it can be suppressed by making it smaller. That is, if the fluctuation of the amount of heat brought in by the slurry supplied to the esterification reaction tank is suppressed, the fluctuation of the amount of heat per unit time of the reactant staying in the esterification reaction tank can be suppressed, and the supply to the esterification reaction tank If the variation in the amount of heat carried by the slurry is increased, an over-response of the temperature control of the esterification reaction tank may occur, and it becomes difficult to control the temperature of the reactant staying in the esterification reaction tank. This leads to avoidance of the over-response, suppresses the fluctuation of the esterification reaction in the esterification reaction tank, and suppresses the fluctuation of the carboxyl end group concentration of the esterification reaction product at the outlet of the esterification reaction tank.

  The method for controlling the amount of heat per unit time of the slurry supplied into the esterification reaction tank in the above method is not limited. For example, there is a method of measuring the temperature and slurry flow rate of the slurry supplied into the esterification reaction tank and controlling the slurry temperature and / or slurry flow rate. The method of controlling the slurry flow rate is a reaction in the esterification reaction tank. Since this leads to fluctuations in factors affecting the esterification reaction such as fluctuations in the liquid level of the material, it is preferable to control the slurry temperature so that the slurry flow rate is constant. In the case of carrying out by this method, it is preferable to control the slurry supply amount within a set value ± 3.0%. 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 number of revolutions of the feed pump so as to achieve a set flow rate using a flow meter, a bypass line that returns to the slurry preparation tank is provided after the feed pump of the feed line, and the number of revolutions of the feed pump is adjusted. A 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 providing a difference in height between the slurry preparation tank and the esterification reaction tank. Then, the slurry is fed by the head pressure, and adjustment is performed by adjusting the opening of the control valve provided in the liquid feeding line so that the flow rate of the flow meter provided in the liquid feeding line becomes 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 an esterification reaction tank may become fixed.

  Moreover, the control method of the slurry temperature in the case of implementing with the said method is not limited. For example, it is preferable to detect and control the temperature of the slurry preparation tank and / 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. In addition, a slurry storage tank may be provided between the slurry preparation tank outlet and the esterification reaction tank so as to increase 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 the present invention, as described later, it is preferable that the recovered glycol recovered by the implant is recycled and reused. The recovered glycol is preferably circulated in a heated state from the viewpoint of energy efficiency. Therefore, since the recovered glycol is in a warmed state, the set temperature is preferably a warmed state, and more preferably 70 to 150 ° C. In the present invention, the temperature variation of the recovered glycol that is recycled and reused affects the slurry temperature variation. Therefore, temperature management and supply amount management of the recovered glycol are important management items.

  In the present invention, it is preferable to control the esterification reactor pressure to be within a set value ± 4%. Within ± 3% is more preferable. Within ± 2% 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. When the esterification reaction tank pressure exceeds a set value ± 4%, even if the above control is performed, the fluctuation of the carboxyl end group concentration of the esterification reaction product at the outlet of the esterification reaction tank may exceed the range described later. This is not preferable.

  The set value of the esterification reaction tank pressure is not limited, but is preferably from atmospheric pressure to 300 kPa as described above. 20-280 kPa is preferable, 40-260 kPa is more preferable, and it is preferable to adjust by the tower top pressure adjustment method of the distillation column which performs fractional distillation of the distilled glycol as mentioned later.

  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.

  In the present invention, it is preferable that the carboxyl end group concentration of the esterification reaction product at the outlet of the esterification reaction tank is within a set value ± 5%. Within ± 4% is more preferred, and within ± 3% is even more preferred. When the carboxyl end group concentration fluctuation exceeds ± 5%, the fluctuation of the subsequent polycondensation reaction is increased, and the uniformity of the quality of the obtained polyester is lowered. 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 esterification reaction product 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.

  The method of setting the esterification reaction product carboxyl end group concentration at the outlet of the esterification reaction tank to the above range is not limited. For example, production equipment factors such as the structure of the esterification reaction apparatus, composition ratio of dicarboxylic acid and glycol in the slurry supplied to the esterification reaction tank, 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.

  For example, in the case of a titanium, tin and aluminum based polycondensation catalyst, the higher the carboxyl end group concentration of the esterification reaction product at the start of the polycondensation reaction, the higher the polycondensation activity and the higher the carboxyl end group concentration. Even when polycondensation was carried out, a polycondensation catalyst system was used in which the esterification reaction proceeded during the polycondensation reaction, and the increase in the concentration of the final polyester was suppressed more than when polycondensation was performed with other polycondensation catalyst systems. One of the preferred embodiments is applied to a method for producing polyester. In the polycondensation catalyst system, it is possible to increase the productivity without deteriorating the polyester quality by performing the polycondensation reaction in a state where the carboxyl end group of the esterification reaction product at the start of the polycondensation reaction is increased. It is advantageous in terms of performance. However, in the polycondensation reaction in a state where the carboxyl end group concentration of the esterification reaction product at the start of the polycondensation reaction is increased, the polycondensation reaction is carried out in a state where the carboxyl end group concentration is usually reduced. Compared to the starting method, fluctuations in the carboxyl end group concentration of the esterification reaction product have a great influence on the subsequent polycondensation reaction and polyester quality. Production of polyesters under normal conditions with reduced carboxyl end group concentration of esterification reaction products 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 esterification reaction product is increased is applied to a composite polycondensation catalyst system composed of an aluminum compound and a phosphorus compound described later, the obtained polyester The use of the polycondensation catalyst system is one of the preferred embodiments because it leads to the expression of a double effect that the effect of improving the transparency of the film is also added when producing a stretched film using a resin. It is.

  When carrying out with the polyester manufacturing method in the area | region which raised the carboxyl terminal group density | concentration of this esterification reaction product, the average value of the carboxyl terminal group density | concentration of the esterification reaction product of an esterification reaction tank exit is 500-900 eq / ton. It is preferable to be in the range.

  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, for example, when a polycondensation catalyst system having a large influence of the carboxyl end group concentration of the esterification reaction product on the polycondensation reaction activity is used, the polycondensation catalyst Since activity falls, it 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 hydrolysis stability of polyester, it is not preferable.

  When the polyester production method is used in the region where the carboxyl end group concentration of the esterification reaction product is increased, the ratio of the carboxyl end group concentration to the total end group concentration of the esterification reaction product at the outlet of the final esterification reaction tank is 35. More than 49% is preferable, 37 to 48% is more preferable, and 39 to 47% is particularly preferable. When the ratio of the carboxyl end group concentration is 35% or less, for example, when a polycondensation catalyst system having a large influence of the carboxyl end group concentration of the esterification reaction product on the polycondensation reaction activity is used, the polycondensation catalyst activity is increased. Since it falls, 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 fluctuation of the characteristics of the esterification reaction product to the target range by the above method, and further, in the esterification reaction step, the carboxyl end group concentration of the esterification reaction product Alternatively, the control accuracy and stability may be improved by measuring the hydroxyl end group concentration online and feeding it back to the slurry temperature control system.

  Although the measuring method of this esterification reaction product characteristic is not limited, It is preferable to measure using the near-infrared spectrophotometer. The near-infrared spectrophotometer is preferably installed in a portion where the esterification reaction product is flowing, for example, a reaction vessel or piping, and continuously measured. 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 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 higher polycondensation activity when the carboxyl end group concentration of the esterification reaction product at the start of the polycondensation reaction is higher, and the carboxyl end groups Even if polycondensation is carried out in a high concentration 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 where polycondensation is carried out with other polycondensation catalyst systems. Performing the polycondensation reaction in a state where the carboxyl end group of the esterification reaction product at the start of the polycondensation reaction is increased is advantageous from the viewpoint of economy. However, polycondensation in a state where the carboxyl end group concentration of the esterification reaction product is increased has a large influence on the carboxyl end group concentration on the polycondensation catalyst activity and the like. It is necessary to reduce the fluctuation of the base concentration. 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, the method for producing the polyester of the present invention can control the carboxyl end group concentration of the esterification reaction product with extremely high accuracy. Even if polycondensation is carried out in a state where the carboxyl end group concentration is increased, the polycondensation reaction can be stabilized and the quality of the polyester can be stabilized, so that it is possible to produce polyesters using titanium, tin and aluminum based polycondensation catalysts. This is a preferred embodiment because the effect of the present invention can be further utilized by applying. Of course, even in the method of performing polycondensation in a state where the carboxyl end group concentration of the esterification reaction product is low, suppressing the fluctuation of the carboxyl end group concentration of the esterification reaction product leads to stabilization of the quality of the polyester. Even in a general-purpose polyester method using a general-purpose polycondensation catalyst, the technology for suppressing the fluctuation of the carboxyl end group concentration of the esterification reaction product 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.

  Further, when the aluminum-based polycondensation catalyst is used in the method of the present invention, the polyester obtained by starting polycondensation in a state where the carboxyl end group concentration of the esterification reaction product is increased. When a polyester film is produced using a resin, there is an advantage that a double effect that the effect of improving the transparency of the polyester film is also 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 chelates 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, Compound with zirconium, alkali metal, alkaline earth metal, etc. Such as an oxide, 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 by, for example, the general structural formula [Al ₂ (OH) _n Cl _6-n ] _m (where 1 ≦ n ≦ 5). Among these, those having a low chlorine content are preferable from the viewpoint of not corroding the device.

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

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

  The amount of the aluminum compound used in the production of 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 increased coloring may be a problem. As described above, the polycondensation catalyst of the present invention has a great feature in that it exhibits a sufficient catalytic activity even if the amount of the aluminum component added is small. 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 compounds of the present invention are 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 metal salt compound of phosphorus 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 portion of the metal salt is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn, the catalytic activity is improved. Is preferable. Of these, Li, Na, and Mg are particularly preferable.

  As the phosphorus metal salt compound 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), since the effect of improving physical properties and the effect of improving 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), when M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn, the effect of improving the catalytic activity is large and preferable. 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, 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 during the 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 is 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 (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 the catalytic activity by using a phosphorus compound having a phenol moiety in the same molecule during polymerization of the polyester Is larger, and therefore the productivity of polyester is excellent.

  The phosphorus compound having a phenol moiety in the same molecule is not particularly limited as long as it is a phosphorus compound having a phenol structure, but a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound having a phenol moiety in the same molecule. 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, the use of a phosphonic acid compound having one or two or more phenol moieties in the same molecule is particularly preferable because the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are particularly large.

  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 the formula (Chemical Formula 33), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl. Represents a hydrocarbon group having 1 to 50 carbon atoms including a group, and R ⁴ represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group, or a carbonyl group. Examples of R ⁴ O ⁻ include hydroxide ion, alcoholate ion, acetate ion, acetylacetone ion, etc. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation, n represents an integer of 1 or more, and the hydrocarbon group does not contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. 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] Zinc bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate] and the like. Among these, lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [ Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

  Among the phosphorus compounds having 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 the formula (Chemical Formula 35), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl. Represents a C1-C50 hydrocarbon group containing a group, n represents an integer of 1 or more, and the hydrocarbon group includes an alicyclic structure such as cyclohexyl, a branched structure, and an aromatic ring structure such as phenyl or naphthyl. May be good.)

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

  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.

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) Or a phosphoryl-containing group, a nitrile group, or a cyanoalkyl group. It is two 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, (4- Toxiphenyl-, ethoxy-) methylphosphonic acid, (4-methoxyphenyl-, ethoxy-) methylphosphonic acid monomethyl ester, (4-methoxyphenyl-, ethoxy-) methylphosphonic acid dimethyl ester, (phenyl-, hydroxy-) methylphosphonic acid, (Phenyl-, hydroxy-) methylphosphonic acid monoethyl ester, (phenyl-, hydroxy-) methylphosphonic acid diethyl ester, (phenyl-, chloro-) methylphosphonic acid, (phenyl-, chloro-) methylphosphonic acid monoethyl ester, (phenyl -, Chloro-) methylphosphonic acid diethyl ester, (4-chlorophenyl) -iminophosphonic acid, (4-chlorophenyl) -iminophosphonic acid monoethyl ester, (4-chlorophenyl) -iminophosphone Acid diethyl ester, (4-hydroxyphenyl-, diphenyl-) methylphosphonic acid, (4-hydroxyphenyl-, diphenyl-) methylphosphonic acid monoethyl ester, (4-hydroxyphenyl-, diphenyl-) methylphosphonic acid diethyl ester, (4 -Chlorophenyl-, hydroxy-) methylphosphonic acid, (4-chlorophenyl-, hydroxy-) methylphosphonic acid monomethyl ester, (4-chlorophenyl-, hydroxy-) methylphosphonic acid dimethyl ester, and other phosphorus compounds containing heterocycles As 2-benzofuranylmethylphosphonic acid diethyl ester, 2-benzofuranylmethylphosphonic acid monoethyl ester, 2-benzofuranylmethylphosphonic acid, 2- (5-methyl) benzofuranylmethylphospho Acid diethyl ester, 2 - (5-methyl) benzo furanyl methyl phosphonic acid monoethyl ester, 2 - (5-methyl) 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.

(R ⁰ ) _m -R 1-(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 in which the aromatic ring structure having a substituent is 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 acid, 6-hydroxybenzylphosphonic acid diethyl ester, 6-hydroxybenzylphosphonic acid monoethyl ester, 6-hydroxybenzylphosphonic acid, and the like include, but are not limited to, benzylphosphonic acids having a hydroxyl group introduced into the benzene ring. It is not a thing.

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

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

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

  The benzylic phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but 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 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, 4- (4-methoxyethoxyphenyl) benzylphosphonic acid diethyl ester, 4- (4-methoxyethoxyphenyl) benzylphosphonic acid monoethyl ester, 4- ( 4-methoxyethoxyphenyl) phosphones in which an alkyl group, a carboxyl group, a carboxylic ester group, an alkylene glycol group, a monomethoxyalkylene glycol group or the like is introduced into a biphenyl ring such as benzylphosphonic acid Although s and the like are not limited thereto.

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

  Among the phosphorus compounds represented by the 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 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) ) Phosphonic acids in which an alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monomethoxyalkylene glycol group, etc. are introduced into a diphenylsulfone ring such as benzylphosphonic acid, but are not limited thereto. .

  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 Alkyl groups, carboxyxyl groups, carboxylic acid ester groups, alkylene glycol groups, monomethoxyalkylene glycol groups, etc. were introduced into diphenylmethane rings such as diphosphonic acid monoethyl ester and 4- (4-methoxyethoxyphenyldimethylmethyl) benzylphosphonic acid. Examples thereof include, but are not limited to, phosphonic acids.

  The diphenyldimethylmethane-based phosphorus compound in the present invention is not limited to the above-mentioned single substituent species, but includes 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 whose aromatic ring structure having a substituent is diphenyl ketone include the following. That is, 4- (4-hydroxybenzoyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxybenzoyl) benzylphosphonic acid, 4- (4-n- Butylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-butylbenzoyl) benzylphosphonic acid, 4- (4-carboxybenzoyl) benzylphosphonic acid Monoethyl ester, 4- (4-carboxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxybenzoyl) benzylphosphonic acid, 4- (4-methoxycarbonylbenzoyl) benzylphosphonic acid monoethyl ester, 4- ( 4 Methoxycarbonylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylbenzoyl) benzylphosphonic acid, 4- (4-hydroxyethoxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxybenzoyl) benzyl Phosphonic acid monoethyl ester, 4- (4-hydroxymethoxybenzoyl) benzylphosphonic acid, 4- (4-methoxyethoxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxybenzoyl) benzylphosphonic acid monoethyl ester , 4- (4-methoxyethoxybenzoyl) benzylphosphonic acid and the like on an alkyl group, 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-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 (Chemical Formula 42) of the present invention, examples of the phosphorus compound 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., phenanthrene ring, alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol Examples thereof include, but are not limited to, phosphonic acids into which a group or a monomethoxyalkylene glycol group has been introduced.

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

  Among the phosphorus compounds represented by the 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) pyrenylmethylphosphonic 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.

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) Or a group selected from a phosphoryl-containing group, a nitrile group, and a cyanoalkyl group. It is two 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): , biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenylmethane, diphenyldimethylmethane, diphenyl ketone, anthracene, i.e. a methylene chain is a linking group from the respective structural formulas having an aromatic ring structure such as phenanthrene and pyrene, -CH 2 _- and The removed phosphorus compound group and the heterocyclic ring-containing phosphorus compound include 5-benzofuranylphosphonic acid diethyl ester, 5-benzofuranylphosphonic acid monoethyl ester, 5-benzofuranylphosphonic acid, 5- (2-methyl) Benzov Examples include ranylphosphonic acid diethyl ester, 5- (2-methyl) benzofuranylphosphonic acid monoethyl ester, and 5- (2-methyl) benzofuranylphosphonic 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 for the compound to retain 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 a high practicality can be expressed by using the above-mentioned aluminum or its compound in combination with a phosphorus compound, but further selected from a small amount of alkali metal, alkaline earth metal and compound thereof. It is a preferred embodiment that at least one of these is allowed to coexist 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 the 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 use amount M of the alkali metal, alkaline earth metal and the compound thereof is 0.1 mol% or more, deterioration of thermal stability, generation of foreign matter and coloring, and deterioration of 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 substances 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 polymerization, and the polymerized polyester tends to be easily colored, and the hydrolysis resistance is also reduced. 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 viewpoint of ease of handling, availability, and the like, it is preferable to use an alkali metal or alkaline earth metal saturated aliphatic carboxylate, particularly acetate.

  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). Quantification is performed on the membrane filter having a diameter of 30 mm at the center. 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 matter insoluble in polyester exceeds 3500 ppm, fine foreign matter insoluble in the polyester is the cause. For example, when molded as a molded body such as a film or a bottle, the haze of the molded body deteriorates. Therefore, it is not preferable. Moreover, it leads to the subject that the filter clogging at the time of filtration of the polyester in a polycondensation process or a shaping | 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 amount of insoluble components 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 can be mentioned. 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 insoluble content in the water of the aluminum compound measured by the method shown below is a measure.
[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 for 3 hours at the same temperature 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 is dried under vacuum at 130 ° C. for 12 hours, and a sheet of 1000 ± 100 μm is prepared by a heat press method. 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 LONG CO., 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. The haze value of the uniaxially stretched film is more preferably 0.5% or less. When the haze value exceeds 0.6%, it is not preferable because a highly transparent molded body cannot be obtained for a molded body formed by molding involving stretching of a film or a bottle. In particular, when a biaxially stretched film is used, the feeling of weak cloudiness evaluated by the following method is deteriorated. The weak 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.

[Weak cloudiness of biaxially stretched film]
A number of biaxially stretched films are stacked so that the thickness is about 9.4 mm (50 sheets in the case of a film thickness of 188 μm), and visually observed at an angle of 45 degrees with respect to vertical under a fluorescent lamp. Very subtle cloudiness that is evaluated when

  The method for bringing the haze value of the uniaxially stretched film and the weak cloudiness of the biaxially stretched film within the scope of the present invention is not limited. For example, the aluminum-based foreign matter insoluble in the polyester is 1000 ppm or less. In the polyester production method, this can be achieved by simultaneously satisfying that the average value of the carboxyl end group concentration of the esterification reaction product 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 properties are improved by the above-mentioned properties is unclear, but the production of aluminum-based foreign particles or aggregates that reduce the light transmittance due to the carboxyl end groups of the esterification reaction product or polyester, or polyester It is presumed that it is expressed by the promotion of solubilization in water.

  As described above, the polyester resin obtained by the method of the present invention is heated in a solid phase under reduced pressure or under an inert gas stream, and the polycondensation is further advanced, or the cyclic 3 amount contained in the polyester resin. There are no restrictions on taking measures such as removing oligomers such as body and by-products such as acetaldehyde. Further, for example, it is possible to incorporate a treatment such as purifying a polyester resin by an extraction method such as a supercritical pressure extraction method to remove impurities such as the by-products.

  In the polyester of the present invention, other arbitrary polycondensates, antistatic agents, antifoaming agents, dyeability improvers, dyes, pigments, matting agents, fluorescent whitening agents, stabilizers, antioxidants, etc. The additive may be contained. As antioxidants, aromatic amine-based and phenol-based antioxidants can be used, and as stabilizers, phosphoric acid and phosphate ester-based phosphorus-based, sulfur-based, amine-based stabilizers, etc. Can be used.

  These additives can be added at any stage of polycondensation or after polycondensation of the polyester or at the time of polyester molding, and which stage is suitable depends on the structure of the target polyester and the polyester obtained. What is necessary is just to select suitably according to required performance, respectively.

  The present invention will be specifically described with reference to the following examples. In addition, these Examples illustrate this invention and are not limited. Moreover, each characteristic in the following Example was measured by the following method.

1. Recovered glycol and water content of slurry A sample corresponding to the water content in the sample was collected with a microsyringe or syringe and precisely weighed with an electronic balance, and then a KF moisture meter (MKC-, manufactured by Kyoto Electronics Industry Co., Ltd.). The amount of water was measured using 210 and calculated as mass% with respect to the sample.
2. Intrinsic viscosity After weighing 0.200 g of the sample, it 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. In the formula (1), T represents the sample solution dropping time (second), T0 represents the solvent dropping time (second), and C represents the sample solution concentration (g / dl).

Intrinsic viscosity (dl / g) = ((T / TO-1 + 3 × ln (T / TO)) / 16) / C (Formula 1)
The measurement was performed three times and the average value was used.

3. Esterification reaction product carboxyl end group concentration The esterification reaction product was pulverized by a handy mill (pulverizer) without 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. In addition, when the esterification reaction product did not dissolve in pyridine, the reaction was performed 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.

4). Hydroxyl end group concentration of esterification reaction product A sample of 9 mg was placed in a sample tube and dissolved by adding 0.3 ml of CDCl ₃ + HFIP-d2 (1 + 1). After adding 0.3 ml of CDCl ₃ and further adding 30 μl of pyridine-d5 and mixing well, centrifugation was performed, and the H-NMR spectrum of the soluble matter was measured using a 500 MHz apparatus.

5. Polymer acid value 15 mg of a sample was dissolved in 0.13 ml of a 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 1 / Using a solution to which 22 μl of 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.

6). Method for evaluating aluminum foreign matter 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, and the pellets are mixed. The solution was stirred and dissolved at 100 to 105 ° C. 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.

7). Haze value of uniaxially stretched film The polyester resin was dried at 130 ° C. for 12 hours under vacuum, and a sheet of 1000 ± 100 μm was prepared by a heat press method. 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 Co., Ltd., 300A). The haze value was displayed as a converted value of a film thickness of 300 μm. In addition, the measurement was performed 5 times and the average value was calculated | required.

8). Weak turbidity of biaxially stretched film Overlapping a plurality of biaxially stretched polyester films to a thickness of about 9.4 mm (50 stacks when the film thickness is 188 μm), an angle of 45 degrees with respect to the vertical under a fluorescent lamp The cloudiness when observed with the naked eye was observed according to the following criteria.
○: No cloudiness △: Very little cloudiness
×: There is a cloudiness

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 room temperature and normal 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 integration value ratio of ²⁷ Al-NMR spectrum of the obtained aluminum solution was 2.2.

(2) Esterification reaction and polycondensation In-line consisting of one continuous esterification reaction tank and two polycondensation reaction tanks, and having a high-speed stirrer in the transfer line from the esterification reaction tank to the polycondensation reaction tank To a continuous polyester production apparatus equipped with a mixer, 1.0 part by mass of ethylene glycol is continuously supplied to 1 part by mass of high-purity terephthalic acid to a slurry preparation tank, the reaction temperature of the esterification tank is 260 ° C., and the pressure The esterification reaction product was obtained at 180 kPa. In the esterification reaction step, the amount of heat per unit time of the reaction product staying in the esterification reaction tank is calculated from the temperature of the reaction product staying in the esterification reaction tank, the passing amount of the reaction product and the specific heat of the reaction product, The amount of heat per unit time of the slurry supplied to the esterification reaction tank was controlled so that the amount of heat was constant. The temperature of the reaction product staying in the reaction vessel was measured at a position 300 mm inside the can wall at the bottom of the reaction vessel. Moreover, the passing amount of the reactant in the esterification reaction tank was calculated from the amount of slurry supplied to the reaction tank and the liquid level of the esterification reaction tank. In addition, the slurry heat amount is adjusted by controlling the fluctuation of the slurry supply amount to be within ± 2.0% of the set value by changing the number of revolutions of the liquid feed pump using a rotary piston flow meter. Was done. The unit time for calorific value calculation was calculated per hour. In the slurry preparation, the high-purity terephthalic acid temperature supplied to the slurry preparation tank is measured in a measuring tank immediately before the supply port, and the high-purity terephthalic acid is brought in from the high-purity terephthalic acid temperature, its supply amount and specific heat. The amount of heat was determined and controlled by changing the glycol temperature supplied to the slurry preparation tank so that the slurry temperature in the slurry preparation tank was constant. The glycol temperature is set by calculating the amount of glycol heat supplied to the slurry preparation tank necessary to keep the slurry temperature in the slurry preparation tank constant, and a temperature adjustment function is added to the slurry preparation tank. The method was carried out by increasing the slurry temperature adjustment accuracy. The amount of heat fluctuation per unit time of the reactant staying in the esterification reaction tank was ± 0.8%. The slurry temperature supplied to the esterification reaction vessel was controlled in terms of calorie with 110 ° C. as the center value. In this case, ethylene glycol to be supplied to the slurry preparation tank supplies fresh ethylene glycol and recovered ethylene glycol recovered by the method described later in an approximate mass ratio of 0.37: 0.63. By adjusting the ratio, the water content in the slurry was adjusted to be within 1.8 ± 0.3% and supplied. Further, the fluctuation of 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. The pressure fluctuation in the esterification reaction tank was controlled within ± 1.3%. Moreover, the fluctuation | variation of the liquid level of the esterification reaction tank was within ± 0.2%. AVo and OHVo of the esterification reaction product at the outlet of the esterification reactor were 810 eq / ton and 982 eq / ton on average, respectively, and AV% was 45.2 mol%. The esterification reaction product is continuously transferred to a continuous polycondensation apparatus comprising three reaction tanks, and an ethylene glycol solution of an aluminum compound and a phosphorus compound prepared by the above method in an in-line mixer installed in the transfer line The ethylene glycol solution was continuously added while stirring with a stirring mixer so as to be 0.015 mol% and 0.036 mol% as aluminum atoms and phosphorus atoms, respectively, with respect to the acid component in the polyester. The polycondensation reaction tank was 265 ° C. and 9 kPa, and the late polycondensation reaction tank was 273 ° C. and 13.3 Pa to obtain a PET of IV 0.620. Table 1 shows the characteristic values of the obtained PET. The quality fluctuations of the esterification reaction product and polyester obtained in this example were small and stable. 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 a coordination peak) was observed in the range. The integrated value of the coordination peak is the NMR spectrum peak of the phosphorus atom bonded with a 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) Recovery of ethylene glycol The flow of ethylene glycol in the polyester production process is shown in FIG.
Fresh ethylene glycol and recovered ethylene glycol supplied to the slurry preparation tank 2 are approximately 0.4: 0.6 in mass ratio.

  A distillate distilled from the esterification reaction tank 3 is supplied to a bubble-bell type distillation column 7 having 15 stages to remove a low-boiling fraction mainly composed of water. In the distillation tower, a part of the residue taken out from the bottom was circulated to the middle part of the distillation tower. The temperature of the circulating liquid was stable at around 168 ° C. The clogging of the liquid feed line of the residual liquid taken out from the bottom of the distillation tower due to the circulation did not occur. The distillation column 7 was controlled so that the temperature detected by the temperature detector installed in the seventh stage was 106 ± 2 ° C. The obtained residue is supplied to the ethylene glycol reservoir 12. The water content in the obtained recovered ethylene glycol was controlled to 3 ± 0.5% by mass. In addition, about the distillate from the esterification reaction tank 3, since the heat | fever required for distillation needs only the calorie | heat amount which a distillate itself has, heating is unnecessary. The pressure at the top of the distillation column was 180 kPa and was controlled within ± 1.3% of this set value. The pressure was controlled by a pressure regulating valve installed in the distillation tower vent pipe.

  The distillate distilled from the two polycondensation reaction tanks 5 and 6 is supplied to the distillation column 10 to remove the low-boiling fraction mainly composed of water and supplied to the distillation column 11 for removing the high-boiling fraction. Is done. The number of stages of the distillation columns 10 and 11 is 15 and 30, respectively. However, since these distillates are generated in a reduced pressure system, they are condensed in wet condensers 8 and 9 installed in each reaction tank, supplied to ethylene glycol condensate storage tanks 13 and 14, and then supplied to distillation column 10. . For this purpose, the heat exchanger 17 supplies heat for distillation. At this time, in order to suppress the temperature rise of the ethylene glycol liquid sprayed on the wet condenser, it is cooled by the coolers 15 and 16 and supplied to the wet condenser. Although this condensate is carried out by self-circulation of the condensate itself condensed in each wet condenser, new ethylene glycol may be supplied as necessary. The phosphorus element content in the recovered ethylene glycol obtained by distilling off the high-boiling fraction in the distillation column 11 was 1.4 ppm.

(4) Film formation PET 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 kept on a metal roll maintained at a surface temperature of 20 ° C. And then solidified rapidly 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 an esterification reaction product was calculated | required by following formula (1) from the maximum value of 50 samples, the minimum value, and the average value.

[{(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 the method of Example 1, the distillate distilled from the polycondensation reaction tanks 5 and 6 is stopped from the two-stage distillation in the distillation column 10 and the distillation column 11 and supplied to the distillation column 7 to supply a high-boiling fraction. Polyester was obtained by performing polycondensation in the same manner as in Example 1 except that the ethylene glycol storage tank 12 was changed without being removed. The results are shown in Table 1.
The flow of ethylene glycol in the polyester production process in Comparative Example 1 is shown in FIG. The bottom fraction of the distillation column 7 contained 22 ppm of phosphorus element. Therefore, in this comparative example, the phosphorus compound is circulated to the polycondensation step without being removed. Furthermore, although the details of the phosphorus compound are unknown, the structure is changed in the polycondensation step. For this reason, the polyester obtained in this Comparative Example had a low Tc1 of 140 ° C. in addition to the deterioration of the quality fluctuation of the polyester. Moreover, compared with Example 1, the polycondensation catalyst activity fell and the intrinsic viscosity of polyester was as low as 0.600.

(Comparative Example 2)
In the method of Example 1, polycondensation was carried out in the same manner as in Example 1 except that the addition location of the mixed solution of the aluminum compound ethylene glycol solution and the phosphorus compound ethylene glycol solution was changed to the esterification reaction tank. Got. The results are shown in Table 1. In this comparative example, the same problem as in comparative example 1 occurred because some phosphorus compounds were mixed in the recovered glycol as in comparative example 1.

(Example 2)
In the method of Example 1, the temperature control accuracy of the distillation column 7 is improved to ± 1%, and the water content in the slurry is strengthened to be managed using a near-infrared spectrophotometer. A polyester was obtained in the same manner as in Example 1 except that the water content was changed to be within 1.8 ± 0.1%. The results are shown in Table 1.
The fluctuation | variation of the carboxyl terminal group density | concentration of the esterification reaction product 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 3)
In Example 1, the number of shelves of the distillation column 7 is set to seven, the position of the temperature detector is changed to the fourth stage space, and the temperature is controlled to be controlled at 106 ± 5 ° C. A polyester was obtained in the same manner. The water content in the recovered ethylene glycol was 3 ± 2.2% by mass, and the variation in the water content in the slurry was ± 1.3%. The results are shown in Table 1.
Compared with the method of Example 1, the fluctuation in the amount of water in the slurry increased, so the fluctuation in the carboxyl end group concentration of the esterification reaction product increased. Along with this, the transparency of the polyester resin and the film was slightly worse than in Example 1.

Example 4
In the method of Example 1, a slurry storage tank having a stirrer and a temperature adjusting function is provided in the middle of the transfer line from the slurry preparation tank to the esterification reaction tank, and the slurry temperature is controlled also in the slurry storage tank. A polyester was obtained in the same manner as in Example 1, except that the temperature adjustment accuracy was changed. The variation in the amount of heat per unit time of the reactant staying in the esterification reaction tank was improved to ± 0.4%. The results are shown in Table 1.
The fluctuation | variation of the carboxyl terminal group density | concentration of the esterification reaction product 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.

(Evaluation with hollow molded body)
The polyesters obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were subjected to solid phase polycondensation by a conventional method to IV 0.75 dl / g, and dried with a dryer using dehumidified air. A preform was molded at a resin temperature of 295 ° C. using a 150C (DM) injection molding machine. The preform plug portion was heated and crystallized for 90 seconds with a home-made plug portion crystallization apparatus, then biaxially stretch blow-molded using a LB-01E stretch blow molding machine manufactured by Corpoplast, and subsequently about 150 It was heat-set in a mold set at ° C. for about 7 seconds to obtain a 2000 cc hollow molded body (the body was circular). The obtained hollow molded body was filled with hot water at 90 ° C., capped with a capping machine, the container was tilted and allowed to stand, and then leakage of contents was examined. The deformation state of the plug after capping was also examined. Further, a sample was collected from the top surface of the preform plug portion, the density was measured, and the density of the preform plug portion by infrared heating was evaluated. The density was measured at 30 ° C. with a density gradient line of a density deviation calcium nitrate / water mixed solution. Further, the haze of the hollow molded body was measured with a haze meter, model NDH2000 manufactured by Nippon Denshoku Co., Ltd., by cutting a sample from the body (thickness: about 0.45 mm) of the hollow molded body. The polyesters obtained in Comparative Examples 1 and 2 had a longer solid phase polycondensation time than the polyesters obtained in Examples 1 to 4. The evaluation results are shown in Table 2. Since the polyesters obtained in Comparative Examples 1 and 2 have a lower Tc1 than the polyesters obtained in the Examples, the bottles obtained from the polyesters are inferior in heat resistance.

(Example 5 and Comparative Example 3)
The polycondensation catalyst is tetrabutyl titanate (15 ppm of residual titanium atom), magnesium acetate (65 ppm of residual magnesium atom), sodium acetate (5 ppm of residual sodium atom) and triethyl phosphate (30 ppm of residual phosphorus atom) The polyesters of Example 5 and Comparative Example 3 were obtained in the same manner as in Example 1 and Comparative Example 1 except that the mixed catalyst system was changed. In Example 5, a polycondensation catalytic activity equivalent to that of Example 1 was obtained, and a polyester having an intrinsic viscosity of 0.62 was obtained under substantially the same conditions as in Example 1. However, in the method of Comparative Example 3, The titanium catalyst was deactivated by the influence of the phosphorus compound present in the catalyst, and the intrinsic viscosity increased only to 0.48.

  As mentioned above, although the manufacturing method of the polyester of this invention was demonstrated based on the several Example, this invention is not limited to the structure described in the said Example, The structure described in each Example is combined suitably. The configuration can be changed as appropriate without departing from the spirit of the invention.

  The method for producing a polyester according to the present invention is a method for continuously producing a polyester in the presence of a phosphorus compound and using a single esterification reaction tank. The compound is removed by a highly economical method, and it is possible to avoid the adverse effect on the polycondensation catalytic activity and quality of the polyester due to the phosphorus compound, and to recycle it, so that the operating cost of the recovery can be achieved without reducing the quality of the polyester. Reduction and simplification of equipment can be achieved. The recycling cost of the recovered glycol can greatly reduce the production cost of the polyester. Furthermore, in this production method, there is an extremely remarkable effect that high-quality polyester can be stably and continuously produced over a long period of time without reducing polycondensation productivity. Therefore, it is a very cost-effective polyester manufacturing method and greatly contributes to the industry.

It is a figure which shows the flow of the ethylene glycol in Example 1 of this invention. It is a figure which shows the flow of the ethylene glycol in the comparative example 1.

Explanation of symbols

1: Metering tank 2: Slurry preparation tank 3: Esterification reaction tank 4: Line mixer 5: First polycondensation reaction tank 6: Second polycondensation reaction tank 7, 10, 11: Distillation tower 15, 16: Wet condenser 12 : Recovered glycol storage tank 13, 14: Glycol condensate storage tank 15, 16: Cooler 17: Heat exchanger 18-28: Pump

Claims (4)

This is a method for producing polyester in the presence of a phosphorus compound. A slurry comprising dicarboxylic acid and glycol prepared in a slurry preparation tank is continuously supplied to an esterification reaction tank, and a single esterification reaction tank is used. The esterification reaction is carried out, and the resulting esterification reaction product is continuously supplied to the polycondensation reaction tank for polycondensation, and the glycol distilled from this production process is fractionated by distillation and circulated. In the manufacturing method of polyester to reuse, the manufacturing method of polyester characterized by satisfying the following requirements simultaneously.
(1) Adding a phosphorus compound to the transfer line of the esterification reaction product from the esterification reaction tank to the polycondensation reaction tank. (2) Distillation with the distillate from the esterification reaction tank and polycondensation. Divide and process the distillate from the reaction tank 2. The polyester according to claim 1, wherein a residual glycol obtained by distilling and removing a low-boiling fraction mainly composed of water from the distillate (A) distilled from the esterification reaction tank is recycled. Manufacturing method. From the distillate (B) distilled from the polycondensation reaction tank, the low-boiling fraction mainly composed of water and the middle-distilled glycol from which the high-boiling fraction containing polyester oligomers and phosphorus compounds are removed by distillation are circulated. The method for producing a polyester according to claim 1, wherein the polyester is reused. By controlling the water content of the glycol fractionated and recovered, the water content in the slurry is controlled to be X ± 1.1% by mass (where X represents a number of 1 or more and 2 or less). The method for producing a polyester according to any one of claims 1 to 3.

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