JP2007254660A - Method for continuous production of copolyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for continuously producing a high-quality copolyester stably over a long period at a low cost while suppressing the variation of quality. <P>SOLUTION: The method for the continuous production of a copolyester comprises 1: a slurry preparation step, 2: an esterification reaction step and 3: polycondensation reaction step, and a phosphorus compound is supplied once or more through the steps 1 to 3. In the step 1, new solid neopentyl glycol is introduced into a slurry preparation tank in molten state and/or in the form of ethylene glycol solution after filtering the molten or dissolved material, in the step 2, a glycol component containing neopentyl glycol is additionally supplied in or after the second esterification reaction tank while setting the reaction temperature of the esterification reaction tank to receive the additional glycol component to be lower than the reaction temperature of the esterification reaction tank of the former stage and recycling and reusing the distilled glycol component at or after the supply of the phosphorus compound after reducing the phosphorus atom content of the glycol component to ≤10 ppm by a distillation column. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for continuously producing a copolyester.

  Polyesters represented by polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc. are excellent in mechanical properties and chemical properties. These polyesters, depending on the respective properties, for example, fibers for clothing and industrial materials, packaging, magnetic tape, optical films and sheets, bottles that are hollow molded products, casings for electrical and electronic parts, It is used in a wide range of other fields such as engineering plastic moldings.

  In recent years, due to the diversification of the market, copolyesters obtained by copolymerizing the above polyesters with other glycol components have attracted attention (see, for example, Patent Documents 1 and 2). In particular, a copolyester containing a neopentyl glycol residue is characterized by being amorphous and having a high glass transition point, and is widely used in the field of films and the like.

  One of the uses of the copolyester is a film or a sheet. In these films and sheets, thickness uniformity is a very important characteristic, and how to ensure this characteristic becomes a problem. In addition, since the productivity of films and the like directly depends on the casting speed, how to increase the casting speed is an important issue for improving the productivity.

  In order to solve this problem, when a sheet-like material melt-extruded from a T-die is rapidly cooled on the surface of the rotary cooling drum, it is necessary to improve the adhesion between the sheet-like material and the drum surface. As a method for improving the adhesion between the sheet-like material and the drum surface, a wire-like electrode is provided between the T-die and the rotary cooling drum, and a high voltage is applied to deposit static electricity on the unsolidified sheet-like material surface. Thus, a method (electrostatic adhesion casting method) in which the sheet is rapidly cooled while closely contacting the surface of the cooling body is effective.

  In order to effectively carry out the electrostatic contact casting method, it is necessary to improve the electrostatic adhesion between the sheet-like material and the drum surface. To that end, how much charge is deposited on the surface of the sheet-like material. It is important to make it happen. In order to increase the amount of charge, it is effective to modify the copolyester to lower the specific resistance, and many studies have been made heretofore. For example, regarding the copolyester, methods for improving electrostatic adhesion are disclosed in Patent Documents 1 and 2 described above.

  By the way, in producing polyester, a continuous method is generally used from the viewpoint of productivity. In such a continuous production method, a two-stage reaction comprising an esterification reaction step and a polycondensation reaction step is performed. Specifically, first, an oligomer having higher reactivity is obtained by esterification directly from a dicarboxylic acid such as terephthalic acid and a glycol component such as ethylene glycol, or by transesterification from the dicarboxylic acid ester and the glycol component. Next, this oligomer is polycondensed by transesterification at high temperature and under reduced pressure to produce a high molecular weight copolymer polyester.

  In recent years, in the esterification reaction step, a direct esterification method having a lower production cost has become mainstream. In both steps, the viscosity of the reaction solution increases as the degree of polymerization increases. Therefore, in order to use the reaction tank according to the viscosity or to advance the reaction uniformly, a multi-stage reaction using a plurality of reaction tanks is performed.

  In the direct esterification method, an esterification reaction is performed using a dicarboxylic acid and a glycol component as raw materials. At this time, since the aromatic dicarboxylic acid is solid and insoluble in the glycol component, a slurry is first prepared from the dicarboxylic acid and the glycol component and supplied to the esterification reactor. In order to ensure, more glycol than the theoretical amount is required. Furthermore, when the oligomer is subjected to a polycondensation reaction to obtain a high molecular weight polyester, a glycol component is generated by a deglycolization reaction. These glycol components need to be recovered and reused. Since such recovery and reuse methods greatly affect the production cost of polyester, various methods have been studied.

  For example, Patent Document 3 discloses a method in which a low-boiling fraction of the distillate in an esterification reaction tank is rectified and removed and recycled to a slurry preparation tank, and Patent Document 4 discharges from the esterification reaction tank. Rectifying and removing the low boiling fraction of ethylene glycol and supplying it to the ethylene glycol storage tank, using a part of it as the circulating liquid of the wet condenser provided in the polycondensation reaction tank, supplying the condensate to the ethylene glycol storage tank, A method of reusing ethylene glycol retained in the ethylene glycol storage tank for slurry preparation is disclosed.

  Patent Document 5 discloses that a distillate generated from a polycondensation reaction tank is condensed by a wet condenser and sent to a distillation tower provided in an esterification reaction tank to remove a low-boiling fraction, and then a slurry blending tank. In Patent Document 6, the distillate generated in the polycondensation reaction tank is continuously subjected to simple distillation, and the bottom extracted liquid of the continuous simple distillation can is used as a batch simple distillation can. A method of using the distilled liquid from which the initial distillation portion has been removed as a part of the refrigerant liquid for condensation of the polycondensation reaction gas is disclosed in Patent Document 7 as an esterification reaction tank distillate. And some of the polycondensation reaction tank distillate removes the low-boiling distillate, and the remaining part of the polycondensation reaction tank distillate removes the low-boiling distillate and the high-boiling distillate. Describes how to circulate and reuse.

  Furthermore, Patent Document 8 discloses a method in which the distillate discharged from the reaction vessel at the second stage of the esterification reaction is directly reused as a part or all of the raw material without being purified by distillation. A method is disclosed in which a distillate from a polycondensation reaction tank is subjected to rectification removal of a low-boiling fraction by flash distillation and reused as a part of raw material glycol.

  As described above, various studies have been made on the continuous production method of polyester in order to improve the efficiency of the method of reducing the production cost of polyester by recovering and reusing distillate glycol. However, these continuous production methods described in Patent Documents 3 to 9 relate to homopolyesters and do not describe copolymerized polyesters.

  In the production of polyester, a phosphorus compound such as trimethyl phosphate is often added. The addition of such a phosphorus compound may include blocking of a metal compound used for an esterification or transesterification reaction, generation of so-called internal particles in which fine particles are precipitated by, for example, reaction with a metal compound in a polyester production process, or electrostatic adhesion of a polyester. For the purpose of improving the performance. For example, in order to improve the electrostatic adhesion of polyester, a metal compound containing an alkaline earth metal or the like is added. By adding an appropriate amount of a phosphorus compound, the electrostatic adhesion can be further enhanced. .

  However, some of these phosphorus compounds are mixed in the distillate glycol component. Therefore, when the distillate glycol component is reused, the amount of phosphorus compound contained in the polyester varies unless the amount of phosphorus compound mixed in the recovered glycol component is controlled. Moreover, the structure of the phosphorus compound mixed in the recovered glycol component may be changed. As a result, there arises a problem that the action and effect that should be originally exhibited by the added phosphorus compound cannot be reproducibly imparted to the polyester. Therefore, it is necessary to prevent or control the mixing of the phosphorus compound into the distillate glycol. However, in the techniques disclosed in the above Patent Documents 3 to 9, the mixing of the phosphorus compound into the glycol that is recycled and reused is completely different. There is no consideration.

  On the other hand, as a method for solving the problem of the above phosphorus compound, Patent Documents 10 and 11 disclose that ethylene glycol distilled from the polyester production process is water in the presence of an alkali compound or water having the same capacity or more as ethylene glycol. A method of heat-treating by adding is disclosed. Patent Document 12 describes a method of using ethylene glycol recovered by distillation after adding 0.2 to 10 wt% of water to distillate ethylene glycol and heat-treating it.

However, although the methods of Patent Documents 10 to 12 are effective methods for preventing the phosphorus compound from being mixed into the recovered ethylene glycol, it is economical because an alkali compound is added or a heat treatment step is required. There is a problem that it is disadvantageous in terms of.
JP 2004-256819 A JP 2004-67733 A Japanese Patent Laid-Open No. 53-126096 JP-A-55-56120 JP-A-60-163918 JP-A-8-325363 JP-A-11-505551 Japanese Patent Laid-Open No. 10-279777 WO01 / 088382 JP 57-14619 A JP 57-14620 A JP 59-96124 A

  As described above, copolymerized polyester is known as an excellent material that can be widely applied to films and the like, and various studies have been made on a continuous production method of polyester. In addition, a phosphorus compound is used for producing the polyester, but a method for removing the phosphorus compound from the recovered glycol component is also known in order to control the amount of the phosphorus compound mixed in the final polyester.

  In recent years, as for copolyesters, there has been an increasing demand for reduction in production costs as the usage and amount of use increase. Therefore, it is conceivable to use a continuous production method for the copolyester, and to recover and reuse the excess glycol component. However, if the glycol component is recovered and reused in the continuous production of the copolyester, stable operation may not be possible, and the product quality may deteriorate.

  In collecting and reusing the glycol component, it is necessary to remove the phosphorus compound from the distilled glycol component in order to maintain product quality. However, the conventional method is not efficient because it requires a new step of adding an alkali compound or water.

  Therefore, the problem to be solved by the present invention is a method capable of stably and continuously producing a copolyester over a long period of time, and a method capable of producing a high-quality copolyester at low cost while suppressing quality fluctuations. Is to provide.

  In order to solve the above-mentioned problems, the inventors of the present invention have made extensive researches on the configuration of the continuous production method. As a result, the following knowledge was found and the present invention was completed.

  First, when continuously producing a copolyester by a conventional method, if a glycol component is additionally supplied to compensate for the distillate in the esterification reaction, foaming may occur and stable production may not be continued. Incidentally, in a normal polyester continuous production method, the viscosity of the reaction solution gradually increases with the progress of esterification or polymerization, and therefore it is common knowledge that the reaction temperature is made higher at the later stage or at least the same as the previous stage. It was. On the other hand, it discovered that foaming can be suppressed by controlling the reaction temperature in the case of addition.

  Moreover, in the case of neopentyl glycol copolymer polyester, if the raw material neopentyl glycol is supplied to the slurry preparation tank in a solid state, the quality of the final product may be lowered. Therefore, we succeeded in improving the product quality by filtering it once in a molten state.

  Furthermore, it has been found that the removal of the phosphorus compound can be efficiently performed without adding a process by using an existing distillation column.

That is, the continuous production method of the copolyester according to the present invention is:
Step 1: a step of preparing a slurry by introducing at least terephthalic acid, ethylene glycol, and neopentyl glycol into a slurry preparation tank;
Step 2: The prepared slurry is continuously introduced into two or more esterification reaction vessels connected in series, and subjected to esterification to obtain an oligomer compound; and Step 3: the obtained oligomer compound is overlapped. A step of producing a copolyester by subjecting to a condensation reaction,
Supplying the phosphorus compound at least once through steps 1 to 3,
In step 1, the novel solid neopentyl glycol is filtered and introduced into the slurry preparation tank in the molten state and / or after being made into an ethylene glycol solution,
In Step 2, a glycol component containing neopentyl glycol is additionally supplied after the second esterification reaction tank,
The reaction temperature of the esterification reaction tank to be additionally supplied is set lower than the reaction temperature of the esterification reaction tank in the previous stage, and the phosphorus atom content of the distilled glycol component after the supply of the phosphorus compound is distilled. Recycle and reuse after reducing to 10ppm or less by
It is characterized by.

  In the above method, it is preferable that neopentyl glycol in a molten state or an ethylene glycol solution is filtered through a filter having an average pore diameter of 20 μm or less. If filtration is performed with such a filter after it is in a molten state or the like, coarse particles contained in the finally obtained copolymer polyester can be suppressed, and a high-quality product can be obtained.

  Moreover, it is preferable to make the reaction temperature of the stage which additionally supplies the glycol component containing neopentyl glycol in the said process 2 5-15 degreeC lower than the reaction temperature of a previous step. If the reaction temperature is lowered above 15 ° C, the esterification reaction may not be carried out efficiently, while foaming may occur at temperatures below 5 ° C.

  The addition of the phosphorus compound is preferably performed after the second esterification reaction tank. Moreover, the refinement | purification of the glycol component to distill is the distillate (B) distilled from the reaction tank before adding a phosphorus compound, and the distillate (B) distilled from the reaction tank after adding a phosphorus compound. ) Is preferably performed separately. Originally, this eliminates the possibility of the phosphorus compound being mixed into the effluent (A) where there is no room for the phosphorus compound to be mixed, and the phosphorus compound removal operation is limited to glycol distillate containing the phosphorus compound. This is because it is more efficient.

  About the production | generation of the glycol component from a distillate (A), it is preferable to carry out the distillative removal of the low boiling point fraction from a distillate (A), and to recycle a residue (A ') as a recovery glycol component. . This is because the impurities to be removed from the distillate (A) are mainly low boiling point compounds such as water and acetaldehyde.

  It is also a preferred embodiment that a part of the residue (A ′) extracted from the bottom of the distillation column for fractionating the distillate (A) is circulated to the distillation column. It is for purifying more effectively.

  From the distillate (B), it is preferable to distill and remove the high-boiling fraction and the low-boiling fraction containing the phosphorus compound, and to recycle and reuse the obtained middle distillate (B ′) as recovered glycol. . The distillate (B) contains a phosphorus compound that cannot be removed at a relatively low temperature in addition to impurities having a low boiling point, and this changes the amount of the phosphorus compound finally mixed into the copolyester, resulting in a product. In particular, it is necessary to remove the high-boiling fraction because it causes the quality to be increased.

  In the same manner as in the case of the distillate (A), a part of the distillation column residual liquid extracted from the bottom of the distillation column for fractionating low-boiling components from the distillate (B) is also circulated to the distillation column. Is preferred.

  In the purification of the distillate (B), first, the low-boiling fraction is removed from the distillate (B) by distillation using a distillation tower, and then the high-boiling fraction containing a phosphorus compound is separated by another distillation tower. It is preferable to carry out by distilling off and to recycle the middle distillate (B ′) obtained. This is because the removal of the low-boiling fraction and the removal of the high-boiling fraction are more efficient when performed using separate distillation columns.

  A part of the residue (A ′) and middle distillate (B ′) purified from the distillate (A) and the distillate (B), respectively, is supplied after the second esterification reaction tank in step 2. It is preferable. The glycol component is continuously supplied from the slurry preparation tank to the first esterification reaction tank, and the recovered glycol component is more effective when reused after the second esterification reaction layer where the loss of glycol component is large. Is expensive. Further, since the temperature of the recovered glycol component is relatively high, it is difficult to lower the reaction temperature, and it can be supplied as it is without adjusting the composition, so that it is more convenient than the novel glycol component.

  Since the continuous production method of the copolymerized polyester according to the present invention suppresses the mixing of foreign matters, it is possible to obtain a copolymerized polyester with high clarity. In addition, the production method according to the present invention suppresses quality fluctuations of the copolymer composition and the like and suppresses process troubles even if continuous production is performed over a long period of time in the continuous polycondensation method. There is an advantage that the polymerized polyester can be stably produced in a form in which quality fluctuation is suppressed. Furthermore, the production method according to the present invention is economical by using a distillation column in which a glycol component distilled during production is connected to a production apparatus without lowering the quality of the copolyester, particularly electrostatic adhesion and polycondensation activity. Therefore, it is highly economical and has excellent cost performance. Therefore, the continuous production method of the present invention is extremely useful industrially as a high quality copolyester can be produced stably at low cost over a long period of time.

The continuous production method of the copolyester according to the present invention,
Step 1: a step of preparing a slurry by introducing at least terephthalic acid, ethylene glycol, and neopentyl glycol into a slurry preparation tank;
Step 2: The prepared slurry is continuously introduced into two or more esterification reaction vessels connected in series, and subjected to esterification to obtain an oligomer compound; and Step 3: the obtained oligomer compound is overlapped. A step of producing a copolyester by subjecting to a condensation reaction,
Supplying the phosphorus compound at least once through steps 1 to 3,
In step 1, the novel solid neopentyl glycol is filtered and introduced into the slurry preparation tank in the molten state and / or after being made into an ethylene glycol solution,
In Step 2, a glycol component containing neopentyl glycol is additionally supplied after the second esterification reaction tank,
The reaction temperature of the esterification reaction tank to be additionally supplied is set lower than the reaction temperature of the esterification reaction tank in the previous stage, and the phosphorus atom content of the distilled glycol component after the supply of the phosphorus compound is distilled. Recycle and reuse after reducing to 10ppm or less by
It is characterized by. Below, it demonstrates in order from the process 1. FIG.

Step 1) Slurry Preparation Step In the present invention, first, at least terephthalic acid, ethylene glycol, and neopentyl glycol are introduced into a slurry preparation tank to prepare a slurry.

  The content ratio of these components in the slurry is not particularly limited as long as the slurry has sufficient fluidity to be transported to the esterification reaction vessel, but the terephthalic acid residue in the copolymerized polyester is 95 mol% or more, ethylene. It is preferable to blend such that the glycol residue is 60 to 75 mol% and the neopentyl glycol residue is 25 to 35 mol%. More specifically, the total amount of ethylene glycol and neopentyl glycol is preferably 1 to 3 moles, more preferably 1.5 to 2.5 moles per 1 mole of terephthalic acid. . From the slurry satisfying the composition of the above acid component and glycol component, a copolyester having the characteristics of being amorphous and having a high glass transition point can be produced. Such a copolyester can be suitably used, for example, as various molded articles such as a polyester film or a polyester sheet, or a modifier thereof.

  An acid other than terephthalic acid may be added to the slurry, preferably at 5 mol% or less in the acid component. For example, orthophthalic acid, isophthalic acid, terephthalic acid, 5- (alkali metal) sulfoisophthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ) Aromatic dicarboxylic acids such as ethane-p, p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid , Decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedica Boric acid, hexadecanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2, Saturated aliphatic dicarboxylic acids such as 5-norbornane dicarboxylic acid and dimer acid; unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid and the like may be used in combination.

  If the slurry is within the above range, for example, a trifunctional or higher polyfunctional compound such as trimellitic acid, pyromellitic acid or glycerol; a compound such as a monofunctional compound such as benzoic acid or phenyl isocyanate may be used in combination. Also good.

  Moreover, you may use together hydroxycarboxylic acid. Examples of the hydroxycarboxylic acid include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, and 4-hydroxycyclohexanecarboxylic acid. .

  Furthermore, as a glycol component, as long as the other glycol component residue in a copolyester is 5 mol% or less, you may contain another glycol compound. Another glycol component includes diethylene glycol (DEG). This DEG is different from other glycol components in that it is by-produced in the process of producing a copolyester without being actively added and is taken into the copolyester. Furthermore, the DEG residue in the copolyester affects properties such as thermal oxidation stability. In particular, when the copolymerized polyester of the present invention is used as a raw material for a heat-shrinkable polyester film, it greatly affects the solvent adhesion, which is one of the important characteristics of the film. Therefore, it is preferable to control the DEG residue in the range of 1.3 to 2.5 mol%. More preferably, it is 1.5-2.3 mol%. When the DEG residue is less than 1.3 mol%, the solvent adhesion may be deteriorated, which is not preferable. On the other hand, if it exceeds 2.5 mol%, it is not preferable because it may adversely affect the heat shrinkability and heat resistance of the film.

  The method for controlling the DEG residue content is not particularly limited. For example, since DEG is produced as a by-product in the production process by dimerization of ethylene glycol, the amount of DEG produced as a by-product in the production process of the copolyester may be controlled by optimizing the esterification reaction conditions. However, since the optimum range of the DEG residue content in the copolyester is narrow as described above, the manufacturing conditions are set so as to suppress the production amount in the manufacturing process as much as possible, and then a sufficient amount of DEG is added to the preferable range. It is preferable. In this case, the addition place of DEG is not limited. You may add to a slurry preparation tank, and you may add at an esterification reaction process. Further, the addition amount of DEG in this case may be appropriately adjusted according to the desired amount of DEG residues in the copolymerized polyethylene. For example, it is 0.1 to 1.0 mol% with respect to the produced copolymerized polyester. can do.

  In recent years, quality requirements for films and sheets made of copolyesters have become more stringent, and accordingly, increasing thickness accuracy has become an important requirement, and this is another important characteristic of copolyesters. One.

  Further, in the present invention, it is preferable to optimize the melt specific resistance at 275 ° C. of the finally obtained copolymer polyester to enhance its electrostatic adhesion and the like.

  The melt specific resistance at 275 ° C. of the copolyester is a measure of the electrostatic adhesion of the copolyester. The electrostatic adhesion is a characteristic required at the time of casting when, for example, a copolymerized polyester is molded into a film or sheet by a melt extrusion method. That is, when a film-like material melt-extruded from an extrusion die is rapidly cooled with a rotary cooling drum, an electrostatic charge is deposited on the surface of the film-like material, and the film-like material adheres to the surface of the cooling drum with an electrostatic force. The adhesion method is known. However, in this method, when the rotation speed of the cooling drum is increased in order to increase the production capacity, the adhesion between the film-like material and the cooling drum decreases, so that gas is caught between the film-like material and the cooling drum. As a result, pinner bubbles are generated, resulting in thickness spots and appearance defects. Electrostatic adhesion is a characteristic of a copolyester that can provide a large electrostatic adhesion force in this electrostatic adhesion method and can produce a film-formed product with high thickness accuracy even when casting at high speed.

  This electrostatic adhesion correlates with the melt specific resistance of the copolyester. By reducing the melt specific resistance of the copolyester, the maximum casting speed that can be cast while suppressing the occurrence of pinner bubbles in the electrostatic cohesive casting method. That is, electrostatic adhesion can be improved. Therefore, optimization of the melt specific resistance of the copolyester is very important from the viewpoint of film productivity.

The melt specific resistance of the copolyester is preferably 0.5 × 10 ⁸ Ω · cm or less. If the melt specific resistance is higher than 0.5 × 10 ⁸ Ω · cm, the electrostatic adhesion is deteriorated, the casting speed is lowered, and the productivity is deteriorated. Preferably, it is 0.4 × 10 ⁸ Ω · cm or less, more preferably 0.3 × 10 ⁸ Ω · cm. On the other hand, the lower limit is preferably 0.05 × 10 ⁸ Ω · cm, particularly preferably 0.09 × 10 ⁸ Ω · cm from the viewpoint of heat resistance and coloring.

  A method for setting the melt specific resistance of the copolyester to the above range is not limited, but it is preferable to carry out by adding a magnesium compound and a sodium compound.

  The added amount of the magnesium compound is preferably 3 to 300 ppm, more preferably 100 to 250 ppm in terms of magnesium atomic weight. When the magnesium atom content is less than 3 ppm, the melt specific resistance of the copolyester increases, and the electrostatic adhesion may easily deteriorate. On the other hand, when it exceeds 300 ppm, the thermal stability of the copolyester tends to decrease, and the color of the copolyester may increase.

  Moreover, 0.5-50 ppm is preferable and, as for the addition amount of a sodium compound in conversion of sodium atomic weight, 3-30 ppm is more preferable. When the sodium atom content is less than 0.5 ppm, the melt specific resistance of the copolyester increases, and the electrostatic adhesion may easily deteriorate. Furthermore, the condensation reaction between glycol components, which are side reactions, is increased, leading to, for example, an increase or fluctuation in the amount of DEG by-product, which may adversely affect the control of the amount of DEG, which is an important composition of the copolymer polyester of the method of the present invention. . On the other hand, when it exceeds 50 ppm, there is a possibility that the decrease in the melt specific resistance of the copolymer polyester or the effect of suppressing the condensation reaction between glycol components will reach its peak, and the color of the copolymer polyester may increase and the color tone may decrease. is there.

  The magnesium compound or sodium compound may be added in the form of a compound containing magnesium or the like. Examples of such compounds include saturated aliphatic carboxylates such as formic acid, acetic acid, propionic acid, butyric acid and oxalic acid; unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid; and aromatics such as benzoic acid. Group-containing carboxylates; 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, hydrogen phosphate, hydrogen sulfide, Inorganic acid salts such as sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid and bromic acid; organic sulfonic acid salts such as 1-propanesulfonic acid, 1-pentanesulfonic acid and naphthalenesulfonic acid; organic such as lauryl sulfuric acid Sulfate; alkoxa such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butoxy De, chelate compounds and acetylacetonate; hydride; oxides; and hydroxides.

  The addition of the magnesium compound or the like is not limited to the slurry preparation step, and may be added in an esterification reaction step or a polycondensation reaction step.

  In the present invention, it is preferable to add a phosphorus compound in order to further improve the electrostatic adhesion of the copolymerized polyester that is the object. Such a phosphorus compound is not limited to the slurry preparation step, like the magnesium compound, but may be added in an esterification reaction step or a polycondensation reaction step described later, or between these steps. It is preferable to add in the step after the esterification reaction tank outlet.

  In particular, the phosphorus compound is preferably added after the second esterification reaction. This is because the glycol component distilled from the reaction tank before the phosphorus compound is added and the glycol component distilled from the reaction tank after the addition can be distinguished and purified. As will be described later, the phosphorus compound is distilled together with the glycol component distilled from the esterification reaction tank or the polycondensation reaction tank. Since it is extremely difficult to control the amount of the phosphorus compound mixed in the recovered glycol component, the quality of the copolymerized polyester as the target compound may be adversely affected. Therefore, purification of the distilled glycol component should be performed after distinguishing between the glycol component recovered from the reaction system not containing the phosphorus compound and the reaction system containing the glycol component, and then reusing the recovered glycol component. In addition, there is an effect that the amount of the distillate glycol component that must be removed by distilling not only the low-boiling fraction but also the high-boiling phosphorus compound and the like for reuse can be reduced.

  However, the addition of the phosphorus compound in the polycondensation reaction step of step 3 should be avoided because the residual amount of the phosphorus compound is reduced because of the reduced pressure system. Therefore, it is preferable to add the phosphorus compound by a method in which a line mixer is installed in the final stage of the esterification reaction process or a transfer line from the final stage to the polycondensation process and added to the line mixer.

  Examples of such phosphorus compounds include phosphoric acid and phosphoric acid esters such as trimethyl phosphoric acid, triethyl phosphoric acid, phenyl phosphoric acid, triphenyl phosphoric acid; phosphorous acid and trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tris ( Phosphites such as 2,4-di-tert-butylphenyl) phosphite and tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylenediphosphite.

  The addition amount of the phosphorus compound is preferably 0.1 to 1.0, more preferably 0.2 to 0.8, in terms of the atomic ratio of phosphorus atom / metal contained in the magnesium compound. If the atomic ratio of phosphorus atom / metal atom is less than 0.1, the thermal stability of the copolyester may be easily lowered. On the other hand, when the atomic ratio of phosphorus atom / the metal atom exceeds 1.0, the melt specific resistance of the copolyester is increased, and the electrostatic adhesion may be deteriorated.

  Moreover, in this invention, in order to improve the color tone of copolyester, you may contain a cobalt compound. Examples of the cobalt compound include cobalt acetate, cobalt chloride, cobalt benzoate, and cobalt chromate. Of these, cobalt acetate is preferable. Although a cobalt compound is contained so that it may become 50 ppm or less normally with respect to the copolyester to produce | generate, it is preferable to change suitably according to the kind of polymerization catalyst to be used.

  In addition, during the production of the copolymerized polyester of the present invention, as long as the purpose of the present invention is not hindered, inert particles such as titanium oxide, silica, calcium carbonate, pigments, heat / oxidation stabilizers, mold release agents, UV absorbers, A colorant or the like may be added as necessary.

  In addition, organic, inorganic, and organometallic toners, fluorescent brighteners, and the like may be added. By blending one or more of these, the coloration of the copolyester, such as yellowishness, can be suppressed to a more excellent level. It also contains other optional polymers, antistatic agents, antifoaming agents, dyeability improvers, dyes, pigments, matting agents, fluorescent brighteners, stabilizers, antioxidants, and other additives. Also good. 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.

  The above additives can be added at any stage through steps 1 to 3 unless otherwise specified. Which stage is suitable depends on the structure of the target copolyester and the required performance of the copolyester to be obtained. Each may be selected appropriately according to the situation.

  A predetermined amount of acid components such as terephthalic acid is supplied to the slurry preparation tank 2 from the measuring tank 1 of FIG. As for the glycol component, a novel glycol component is mostly used, but a part of the glycol component recovered and purified from Step 2 and / or Step 3 described later may be used. Other components are also appropriately added to the slurry preparation tank.

  However, in the present invention, when a novel solid neopentyl glycol is used, it is preferable to use one that has been filtered in a molten state and / or mixed with ethylene glycol. Since neopentyl glycol is solid at room temperature, it is usually packaged and distributed in paper bags. When this solid neopentyl glycol is used as a slurry raw material, foreign matters are mixed in the resulting copolymerized polyester, and the clarity thereof can be lowered. In particular, since the amount of new neopentyl glycol used for slurry preparation is large, there is a problem that if the new solid neopentyl glycol is used as it is for slurry preparation, the effect appears directly in the final copolymerized polyethylene. Then, by performing the said process, foreign material mixing is suppressed and the clarity of copolyester improves.

  For the filtration, it is preferable to use a filter having an average pore size of 20 μm or less, more preferably a filter having an average pore size of 15 μm or less, and further preferably 10 μm or less. On the other hand, the lower limit of the average pore diameter is about 1 μm from the viewpoint of the degree of clarity and the operability of filtration. The type and capacity of the filter are not limited, and may be appropriately selected in consideration of the clarity and operability of the copolyester.

  The installation place of the filtering means is not particularly limited. For example, what is necessary is just to install in the arbitrary places between the supply tank of neopentyl glycol and the manufacturing apparatus of copolyester.

  In addition, handling neopentyl glycol in a molten state or a solution state also leads to an improvement in the accuracy of the neopentyl glycol supply amount. The melting of neopentyl glycol may be carried out by installing a melting tank in the production equipment for copolymerized polyester, or a molten one may be purchased and used.

  The new neopentyl glycol may be directly supplied to the slurry preparation tank, or may be mixed with ethylene glycol or a recovered glycol component described later and supplied to the slurry preparation tank.

  In the present invention, the use of recycled raw materials such as terephthalic acid or glycol components obtained by the chemical decomposition recovery method for recovered PET bottles is a preferred embodiment because it helps save resources and protect the environment.

Step 2) Esterification reaction step The slurry obtained in the above step 1 is introduced into two or more esterification reaction vessels connected in series and subjected to esterification reaction, whereby glycols are added to the carboxyl groups at both ends of terephthalic acid. To give an oligomeric compound.

  Here, it is important that the continuous production method of the copolyester according to the present invention is continuous, including step 2 (esterification reaction) and step 3 (polycondensation reaction) described later. The continuous production method is more advantageous in terms of quality uniformity and economy than the batch production method.

  The number and size of reaction vessels in the esterification reaction step can be appropriately selected without limitation. The production conditions for each step can be appropriately selected depending on the type and amount of polycondensation catalyst and additives for improving electrostatic adhesion, the number and size of reaction vessels, and the like.

  For example, in the esterification reaction in step 2, the water produced by the reaction is distilled into a distillation column 9 using a multistage apparatus (in FIG. 1, esterification reaction tanks 3 to 5) in which a plurality of esterification reaction tanks are connected in series. It is preferable to carry out while removing from the system. The temperature of the esterification reaction is 240 to 290 ° C, preferably 245 to 280 ° C, and the pressure is a gauge pressure of normal pressure to 290 KPa, preferably 20 to 190 KPa. Ultimately, it is desirable that the esterification reaction rate reaches 90% or more, preferably 93% or more. In addition, as the esterification reaction tank, a tank provided with a weir or the like therein and multistaged in one reaction tank may be used.

  In the method of the present invention, the polycondensation reaction is continuously performed following the esterification reaction. The timing of adding the polycondensation catalyst necessary for this polycondensation reaction is not particularly limited, but it is preferable to supply from the first stage of the esterification reaction. This is because the polycondensation catalyst can also be a catalyst for the esterification reaction.

  Such a polycondensation catalyst is not particularly limited as long as it is generally used in the production of polyester. For example, an antimony compound, a titanium compound, a tin compound, a germanium compound and an aluminum compound can be used.

  As the antimony compound, antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoloxide and the like are suitable, and antimony trioxide is particularly preferred.

  Titanium compounds include tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, tetrabenzyl titanate, oxalic acid titanate Lithium, potassium oxalate titanate, ammonium oxalate titanate, titanium oxide, complex oxide of titanium and silicon, zirconium, alkali metal, alkaline earth metal, etc .; ortho or condensed ortho ester of titanium, ortho ester of titanium Or a reaction product comprising a condensed orthoester and a hydroxycarboxylic acid; a reaction product comprising a titanium orthoester or a condensed orthoester, a hydroxycarboxylic acid and a phosphorus compound. A polyhydric alcohol having an ortho ester or condensed ortho ester of titanium and at least two hydroxyl groups; a reaction product comprising 2-hydroxycarboxylic acid and a base, of which a composite oxide of titanium and silicon, A reaction product comprising a composite oxide of titanium and magnesium, an ortho ester or condensed ortho ester of titanium, a hydroxycarboxylic acid and a phosphorus compound is preferred.

  As tin compounds, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin sulfide, dibutyl Examples thereof include hydroxytin oxide, methylstannic acid, and ethylstannic acid, and the use of monobutylhydroxytin oxide is particularly preferable.

  As the germanium compound, germanium dioxide, germanium tetrachloride and the like are suitable, and germanium dioxide is particularly preferred. As germanium dioxide, both crystalline and amorphous materials can be used.

  Aluminum compounds include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, citric acid. Inorganic acid salts such as carboxylic acid salts such as aluminum acid, aluminum tartrate, and aluminum salicylate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate, and aluminum phosphonate . Of these, carboxylates are particularly preferred.

  The position and supply method for supplying such a catalyst are not particularly limited, and may be appropriately determined according to the manufacturing conditions. For example, these polycondensation catalysts may be put into a reaction vessel as they are, or may be supplied after being dissolved or suspended in a glycol component such as ethylene glycol.

  In the present invention, it is preferable to additionally supply a glycol component containing neopentyl glycol after the second esterification reaction tank in Step 2. In the production of neopentyl glycol copolymer polyester in the conventional method, the glycol component is supplied in its entirety in the slurry preparation. However, such a conventional method has a problem that the composition of the glycol component in the copolymerized polyester may fluctuate when continuously produced for a long period of time, and the establishment of such a suppression method has been desired. The present inventors have studied to solve this problem, and found that this fluctuation can be suppressed by additionally supplying a glycol component containing neopentyl glycol after the second esterification reaction tank in Step 2. It was.

  The above-mentioned additional supply may be divided into two or more times. The composition of the additionally supplied glycol component, the number of divided supplies to the esterification reaction tank, and the divided supply ratio are not particularly limited. Further, the esterification reaction tank to be added is not particularly limited as long as it is in the second stage or later. The composition of the glycol component is preferably a mixture of neopentyl glycol and ethylene glycol. The composition ratio may be appropriately determined in consideration of the intended glycol composition ratio of the copolymerized polyester and the effect of suppressing the composition fluctuation of the copolymerized polyester obtained. Moreover, it is preferable to add 2-10 mass% of the total addition amount of the glycol component in the whole manufacturing process to the esterification reaction tank after a 2nd step, and it is more preferable to add 4-8 mass%.

  The reason why the glycol component composition fluctuation in the copolyester is suppressed by the divided supply of the glycol component is unclear, but the fluctuation of the distillation rate of the glycol component outside the system in the esterification reaction is suppressed. I guess.

  In the present invention, when the glycol component containing neopentyl glycol is additionally supplied after the second esterification reaction vessel in Step 2, the reaction temperature of the reaction vessel supplying the glycol component containing neopentyl glycol is the reaction in the previous stage. It is preferable to set it lower than the temperature. According to such an embodiment, foaming caused by neopentyl glycol in the reaction liquid in the esterification reaction tank additionally supplied with glycol containing neopentyl glycol is suppressed, and stable operation is possible over a long period of time. Usually, when performing esterification reaction in a plurality of reaction vessels, it is carried out by increasing the temperature in the reaction vessel according to the progress of the reaction, but in that case, the additional supply is performed by the additional supply of glycol containing neopentyl glycol. When the foaming of the reaction liquid increases, polyester oligomers may scatter in the piping to the distillation tower and the distillation tower installed in the reaction tank, making operation difficult. On the other hand, in the present invention, this problem is solved by lowering the reaction temperature in the esterification reaction tank in which such additional supply is performed, from the previous stage.

  The reaction temperature in the step of additionally supplying a glycol component containing neopentyl glycol is preferably 5 to 15 ° C. lower than that in the previous step. If the reaction temperature is lowered above 15 ° C, the esterification reaction may not be carried out efficiently, while foaming may occur at temperatures below 5 ° C.

  In Step 2 of the present invention or Step 3 described later, it is preferable to introduce the glycol component distilled from the reaction system into a distillation column, purify it, and reuse it. According to such an embodiment, since the amount of new glycol used can be reduced, the production cost of the copolyester can be greatly reduced. In addition, the recovered glycol component requires less effort to adjust its composition than when a new glycol component is added. Further, when a new glycol component is directly introduced into the reaction vessel, the reaction temperature may decrease and the production efficiency may decrease. However, since the recovered glycol component has a relatively high temperature, such heat shock is small.

  As described above, a part of the phosphorus compound added in the step 2 or step 3 of the present invention is mixed in the distilled glycol. The amount of the phosphorus compound is difficult to control, and the structure may change to change the activity. Therefore, when the distillate glycol component is purified and reused, the amount of the phosphorus compound to be blended with the copolymerized polyester, which is the target product, after preventing or suppressing the contamination of the phosphorus compound as much as possible, It is preferable to maintain the characteristics of the copolyester by controlling only the amount added.

  In particular, in the case where the magnesium compound and the sodium compound are added to the reaction system together with the phosphorus compound described above, and the electrostatic adhesion of the copolymerized polyester is improved by making these atomic ratios within a specific range, The electrostatic adhesion changes greatly due to fluctuations in the phosphorus compound content. Further, when a titanium-based, tin-based or aluminum-based catalyst is used as the polycondensation catalyst, the amount of the phosphorus compound greatly affects the polycondensation catalyst activity. Further, the phosphorus compound mixed in the distillate glycol has a structure that is different from that at the time of addition, and has the aspect of having a more prominent effect on the electrostatic adhesion and the polycondensation catalyst. Therefore, it is preferable that the phosphorus atom content in the recovered and purified glycol is recycled and reused so as to be 10 ppm or less. The content is more preferably 8 ppm or less, and further preferably 5 ppm or less. When a glycol component with a phosphorus atom content exceeding 10 ppm is used, the amount of phosphorus atoms remaining in the copolyester varies from the design value, resulting in unstable electrostatic adhesion and catalytic activity, adversely affecting quality and operability. May affect.

  The structure of the phosphorus compound added in the production process of the copolyester is changed by a chemical reaction, for example, a glycolic ester of phosphoric acid. As a result, the phosphorus compound contained in the distilling glycol component has been transformed into a compound having a boiling point higher than that of glycol. Therefore, in order to make the phosphorus atom content in the recovered glycol 10 ppm or less, it is preferable to remove the high-boiling fraction by distillation using a distillation column.

  On the other hand, if the distillate glycol component does not contain a phosphorus compound, only low-boiling contaminants such as water can be removed by fractional distillation, and high-boiling fractions can be recycled and reused without fractional removal. Since it hardly affects the quality of the polyester and the like, it is preferable to recycle and reuse without removing the high boiling fraction. Accordingly, the glycol component can be recovered and purified by distillate (A) distilled from the reaction tank before adding the phosphorus compound and distillate (B) distilled from the reaction tank after adding the phosphorus compound. It is preferable to carry out separately. Since the distillate distilled from the reaction tank before the phosphorus compound is added does not contain the phosphorus compound, separating and purifying the two separately and recycling them is economical, that is, reducing operating costs and equipment. This greatly contributes to the simplification.

  As described above, the distillate (A) distilled from the reaction tank before adding the phosphorus compound does not contain the phosphorus compound. Therefore, it is preferable to distill off the low-boiling fraction from the distillate (A) using a distillation column and to recycle the residue (A ′) as a recovered glycol component.

  Although the number and performance of the distillation column which processes the distillate (A) distilled from the reaction tank before adding a phosphorus compound are not limited, 8-18 steps are preferable and 9-15 steps are more preferable. Either a bubble column or a packed column may be used. The reflux ratio is appropriately set depending on the number of stages of the distillation column and the required quality of the recovered glycol.

  Here, the low boiling point fraction refers to a by-product having a boiling point lower than that of the glycol component released from the reaction tank along with the distillate glycol component, such as water, acetaldehyde, and methanol.

  In fractional distillation for removing the above low-boiling fraction, a part of the residue extracted from the bottom of the distillation column is circulated to the distillation column (hereinafter referred to as “distillation column liquid circulation method”). Is a preferred embodiment. By implementing this method, the occurrence of clogging of the remaining liquid feed line is suppressed, and long-term stable operation is possible. The glycol component to be distilled contains solids that are hardly soluble or insoluble in glycols made of copolymer polyester oligomers or the like due to entrainment of droplets. As a matter of course, this solid content is contained in the distillation column residue and circulated in the copolyester production process in the distillation. Therefore, when the production of the copolyester is carried out continuously for a long period of time, in the liquid feed line for the residue, the liquid feed line is fed by the solid content present in the residue or the solid content precipitated in the liquid feed line. There was a problem that liquidity was lowered and line clogging occurred, making stable operation difficult, and improvements were desired. This problem can be solved by a distillation column liquid circulation method. The reason why the above problem is solved by the implementation of this distillation column liquid circulation method is not clear, but increases the 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 solids precipitation due to the sum of a plurality of factors such as the structural change of the solids due to. Here, it is speculated that the structural change takes into account the effects of both chemical change and physical change. In other words, chemical changes include lowering the molecular weight due to glycolysis of oligomers in the solid content, resulting in improved solubility in glycol and decreased crystallinity, and physical changes include changes in solid crystallinity and the like. It is done. Moreover, the implementation of the distillation column liquid circulation method leads to improvement of fractionation accuracy in addition to suppression of line clogging.

  In the distillation tower, the setting of the liquid temperature of the residue and the temperature range, the storage capacity of the residue at the bottom of the distillation tower, the return position of the circulating liquid, the circulation amount, and the like are important. These 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. Specifically, it is determined as appropriate in the balance between the two. Moreover, it is preferable to supply the circulating liquid to the distillation tower by supplying the liquid in a sprayed state. This mode not only increases the fractionation efficiency and prevents contamination caused by entrainment of the distillation column tray, but also stabilizes the amount of the supplied liquid and suppresses clogging of the circulation line due to fluctuations in the flow rate of the circulating liquid. it can. Furthermore, in order to prevent clogging in the circulation line, it is preferable to take measures such as buffing or electrolytic polishing the inner surface of the piping of the circulation line, or increasing the bending radius of the piping. 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, and the circulation amount is preferably 30 to 75% by mass. The circulating fluid temperature is preferably 160 to 180 ° C, more preferably 164 to 173 ° C, and still more preferably 168 to 175 ° C. When the temperature is lower than 160 ° C., the line clogging frequency may increase. Conversely, when it exceeds 180 degreeC, it will lead to the increase in energy loss and will become economically disadvantageous, and it may lead to the fall of distillation precision. In order to maintain the temperature and control the temperature, it is preferable to add a temperature adjustment function to the circulation line.

  The conditions for fractionation by the distillation column are not limited, and may be appropriately set depending on the performance of each distillation column, required fractionation accuracy, and the like. For example, if water is contained in the purified recovered glycol, the esterification reaction is affected, and finally the quality of the copolyester is greatly affected. Therefore, it is preferable to control the amount of water. The amount of water in the recovered glycol and its variation may be appropriately set in consideration of the quality and economics of the copolyester. The control method is not limited.

  On the other hand, from the distillate (B) distilled from the reaction stage after the addition of the phosphorus compound, the low-boiling fraction mainly composed of water and the high-boiling fraction containing polyester oligomers, phosphorus compounds and the like are removed by distillation. The middle distillate (B ′) obtained is preferably recycled and reused as recovered glycol.

  For the distillate (B), as in the prior art, only the low-boiling fraction is fractionated and removed in the same manner as in the distillate (A), and the residue is part or all of the glycol for producing the copolyester. As a result, the phosphorus compound is mixed into the recovered glycol, and the amount of phosphorus atoms remaining in the copolymerized polyester varies from the design value. As a result, electrostatic adhesion and catalytic activity become unstable, which may adversely affect quality and operability.

  On the other hand, when distillate (A) is reused with a middle distillate from which both low-boiling fraction and high-boiling distillate have been removed by distillation in the same manner as distillate (B), distillate ( The treatment of A) becomes excessive, leading to an increase in equipment and operating costs, which is not preferable because it is economically disadvantageous. In general, since the amount of the distillate (A) is larger than that of the distillate (B), the economic effect of carrying out the recovery treatment by separating both of the methods of the present invention is great.

  Therefore, it is a preferred embodiment that the phosphorus compound is added after the outlet of the first esterification reaction tank as described above.

  The middle distillate fraction (B ′) may be fractionated by a method in which a low-boiling fraction and a high-boiling fraction are removed at the same time using a single distillation column. First, the low-boiling fraction is first removed by the same method as the fractional distillation of the product (A), and the obtained residue is supplied to another distillation column, and the high-boiling fraction is removed. Also good. The latter embodiment enables more efficient fractionation and leads to a reduction in operating costs. In the latter embodiment, the number of stages of the distillation column for removing the high-boiling fraction is preferably 20 to 30. The reflux ratio may be appropriately set depending on the number of stages of the distillation column and the required quality of the recovered glycol.

  In the present invention, it is preferable that the low-boiling fraction removal of the distillate from the esterification reaction tank is continuously performed by the heat of the distillate itself. This can further reduce operating costs and simplify equipment. If necessary, auxiliary heating may be performed by heating the pipe or heat exchange.

  The solid component contained in the glycol component distilled from the esterification reaction tank has a low melting point and is dissolved and reacted in the reaction system in the esterification reaction step, so that it is not necessary to be removed. However, it is preferable to prevent clogging of the liquid feed line for the residual distillation due to solid analysis by the distillation column liquid circulation method described above.

  Although the reuse method of the glycol component collect | recovered and refined by the said method is not limited, It is preferable to reuse as a glycol component for copolyester manufacture after storing in a glycol storage tank. The glycols recovered from the distillates (A) and (B) may be stored in separate storage tanks or may be stored in a lump. Moreover, you may use in the collect | recovered plant and may use it in another plant. In the case of the distillate (A), the volume at the lower part of the distillation column may be increased and stored in this part.

  As the glycol component recovered by the above method, the purified recovered glycol may be used as it is for slurry preparation. The recovered glycol component is measured for its composition, and if necessary, a predetermined amount of a new glycol component is mixed to obtain a glycol component having a desired composition necessary for slurry preparation, and then added to the slurry preparation tank. You may supply. The glycol composition of the recovered glycol is preferably evaluated by a method selected from gas chromatography analysis, near infrared absorption spectroscopy, NMR analysis, and the like.

  Part of the glycol component recovered by the above method is preferably supplied to the esterification reaction after the second stage in step 2.

  Moreover, in this invention, as an additional supply method of the glycol component containing neopentyl glycol, the residue (A ') obtained by fractionating the glycol distilled from the reaction stage before adding a phosphorus compound with a distillation column A part of may be supplied to step 2 (esterification reaction). Thereby, the fluctuation | variation suppression effect of the copolyester composition obtained by a suitable glycol composition improves. Moreover, the residue is in a heated state, and heat shock when supplied to the reaction vessel is suppressed, leading to stabilization of the reaction. Therefore, the adjustment of the glycol composition and the heating operation necessary for supplying a new glycol component become unnecessary.

  Step 2 (esterification reaction) of the present invention is performed in two or more esterification reaction tanks connected in series. Specifically, as shown in FIG. 1, a plurality of esterification reaction tanks are provided, and the reaction liquid is supplied and withdrawn so that the liquid level in each reaction tank becomes constant, and the reaction is performed in the reaction tank in the next reaction stage. Supply liquid. The reaction solution that has passed through the final stage of the esterification reaction is then supplied to step 3 (polycondensation reaction).

  In the present invention, it is preferable to filter the oligomer or polymer through a filter through step 2 or step 3 or in a pipe connecting them. Thereby, the clarity of the reaction product can be increased. The aperture, structure, capacity, installation location, and the like of the filter that can be used here are not particularly limited.

Step 3) Polycondensation Reaction Step The reaction liquid that has undergone the esterification reaction in Step 2 is subsequently transferred to a polycondensation reaction tank and subjected to a polycondensation reaction.

  The number and size of reaction vessels in the polycondensation reaction step can be appropriately selected without limitation. The production conditions for each step can be appropriately selected depending on the type and amount of the polycondensation catalyst and additives for improving electrostatic adhesion, the number and size of reaction vessels, and the like.

  For example, as shown in FIG. 1, a plurality of polycondensation reaction tanks are provided, the reaction liquid is supplied and withdrawn so that the liquid level in each reaction tank is constant, and the reaction liquid is supplied to the reaction tank in the next reaction stage. To do.

  As for the polycondensation reaction conditions, the reaction temperature of the first stage polycondensation is 250 to 290 ° C., preferably 260 to 280 ° C., and the pressure is 10 to 2.7 KPa, preferably 2.7 to 0.27 KPa. The temperature of the final 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. When carried out in three or more stages, the reaction conditions for the intermediate stage polycondensation reaction are the conditions between the reaction conditions for the first stage and the reaction conditions for the last stage. The degree of increase in intrinsic viscosity achieved in each of these polycondensation reaction steps is preferably distributed smoothly.

  The conditions for the polycondensation reaction in the present invention may be appropriately set in consideration of the quality and productivity of the copolyester.

  Since the glycol component also distills in step 3, it is preferable to recover and purify it. The detailed conditions for the recovery and purification can be the same as in step 2 above.

  However, since the distillate from the polycondensation reaction tank is recovered by cooling and condensing with a wet condenser, it must be heated and supplied to the distillation column. In addition, the solid content contained in the fraction distilled from the polycondensation reaction tank has a high melting point, and when this is recycled to the polyester production process while contained in the recovered glycol, it does not react with the polyester in the polyester production process. Since it may lead to generation | occurrence | production of a foreign material, it is not preferable. Therefore, it is preferable to take measures to prevent such solid content from being mixed into the recovered glycol. Although such a 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 to supply 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.

  There is no restriction | limiting in the usage rate of the collection | recovery glycol collect | recovered by the above method in this invention, It can set suitably and can be used. The whole amount may be used, or only a part thereof may be used.

  In the present invention, if necessary, the solid content such as the copolymerized polyester oligomer is removed by performing a treatment such as filtration on the unpurified or purified glycol inside and outside the process, and piping clogging is avoided, It is also a preferred embodiment to adopt a method such as improving the purity.

  The copolymerized polyester obtained in the final stage of step 3 is heated under reduced pressure or an inert gas stream to further proceed with polycondensation, an oligomer such as a cyclic trimer contained in the copolymerized polyester, There are no restrictions on taking measures such as removal of by-products such as acetaldehyde. Further, for example, it is possible to incorporate a treatment such as purifying the copolyester by an extraction method such as a supercritical pressure extraction method to remove impurities such as the by-products. Furthermore, a copolyester may be filtered by installing a filter having an average pore diameter of about 20 μm at the outlet of the final reaction tank.

  What is necessary is just to process the copolyester obtained through the process 3 by a conventional method. For example, the copolyester may be taken out and solidified by means such as water cooling so that the liquid level in the final reaction tank is constant. The final shape of the copolyester is not particularly limited, and for example, a solidified strand may be pelletized with a strand cutter.

  The intrinsic viscosity of the copolyester produced by the method of the present invention is preferably 0.7 to 0.8. A molded body obtained by using a copolyester having an intrinsic viscosity in this range can balance the mechanical properties and the operability during molding. Such intrinsic viscosity can be measured by a conventional method. For example, it can measure at 30 degreeC using a phenol / tetrachloroethane (60:40, weight ratio) mixed solvent.

  Further, the copolyester obtained by the method of the present invention is excellent in properties such as electrostatic adhesion, and has a high quality with a small content of coarse particles, and is particularly useful as a material for films and sheets. It is.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. It is also possible to implement, and they are all included in the technical scope of the present invention.

  In addition, evaluation in the following example was implemented with the following method.

1. Measurement of Intrinsic Viscosity (IV) Measurement was performed at 30 ° C. using a mixed solvent of phenol: tetrachloroethane = 60: 40 (weight ratio).

2. Polymer melt specific resistance (ρi)
Two electrode plates were placed in the copolyester melted at 275 ° C., the current value (i ₀ ) when a voltage of 120 V was applied was measured, and the specific resistance value ρi was determined by the following equation.
ρi (Ω · cm) = A / l × V / i ₀
Here, A = electrode area (cm ² ), l = distance between electrodes (cm), and V = voltage (V).

3. Electrostatic adhesion An electrode made of tungsten wire is provided between the die part of the extruder and the cooling drum, and casting is performed by applying a voltage of 10 to 15 KV between the electrode and the casting drum. The surface was observed with the naked eye and evaluated at the casting speed at which pinner bubble generation began. A polymer with a higher casting speed indicates better electrostatic adhesion.

4). Composition ratio of copolymerized polyester Approximately 5 mg of a sample is dissolved in 0.7 ml of a mixed solvent of deuterated chloroform: trifluoroacetic acid = 9: 1 (volume ratio), and determined using ¹ H-NMR (manufactured by Varian, UNITY 500). It was.

5). Composition analysis of recovered glycol component 30% by volume of dimethyl sulfoxide was added to the sample solution and evaluated by ¹ H-NMR and ¹³ C-NMR measurements.

6). Quantification of phosphorus atom content in recovered glycol component The sample was incinerated at 550 ° C. in the presence of magnesium nitrate, and then quantified by high-frequency plasma emission spectrometry after preparing a 1.2 M hydrochloric acid solution.

7). Number of coarse particles in polyester (number of particles having a particle size of 5 μm or more)
A polyester chip (one grain) was sandwiched between two cover glasses, melt-pressed at 280 ° C., rapidly cooled, and observed with 20 fields of view with a 100 × phase contrast microscope, and the number of particles of 5 μm or more was counted with an image analyzer. .

Example 1
(1) Slurry preparation In a slurry preparation tank, 1 part by mass of terephthalic acid; 3.4% by mass of water recovered from the distillate (A) by the method described later, 70.8% by mass of ethylene glycol, 25.8 of neopentyl glycol 0.464 parts by mass of a recovered glycol component consisting of mass%; and 45.7 mass% of an ethylene glycol consisting of a recovered glycol component recovered from the distillate (B) and / or a new ethylene glycol and a new neopentyl glycol; 0.325 parts by mass of a mixed glycol component consisting of 54.3% by mass of neopentyl glycol was added. Here, 0.044 parts by mass of new ethylene glycol was supplied and stirred while preparing a terephthalic acid glycol slurry. The new neopentyl glycol is melted in a neopentyl glycol melting tank and mixed with ethylene glycol in a mixing tank so as to have the above composition and filtered through a filter having an average pore diameter of 5 μm, and then a slurry is prepared. It was supplied to the tank.

(2) Esterification Reaction As the esterification reaction apparatus, a continuous esterification reaction apparatus composed of a three-stage complete mixing tank having a stirrer, a distillation tower, a raw material charging port and a product outlet was used. Along with 1651 kg / hour of the terephthalic acid glycol slurry prepared in (1) above, an ethylene glycol solution of antimony trioxide (concentration: 1.3 wt%) was added to the first esterification reactor at 41 kg / hour and DEG at 2 kg / hour. The esterification reaction was carried out at an absolute pressure of 122 kpa, a temperature of 258 ° C., and an average residence time of 6 hours.

  The reaction solution was taken out so that the liquid level in the first esterification reaction tank was constant, and charged into the second esterification reaction tank. From another inlet of the second esterification reaction tank, a residue (A ′) obtained by fractionating the glycol component distilled from the first and second esterification reaction tanks in a distillation column by the method described later is used. The esterification reaction was carried out at 50 kg / hour, with an absolute pressure of 122 kpa, a temperature of 247 ° C., and an average residence time of 1.5 hours. The oligomer acid value at the outlet of the first esterification reaction tank was 1950 eq / ton on average.

  The reaction solution was taken out so that the liquid level in the second esterification reaction tank was constant, and charged into the third esterification reaction tank. From another addition port of the third esterification reaction tank, 0.051 part by mass of an ethylene glycol solution (concentration 4.3 mass%) of magnesium acetate tetrahydrate and an ethylene glycol solution of trimethyl phosphate (concentration 5) .9 mass%) 0.018 parts by mass, ethylene acetate solution of sodium acetate (concentration 1.0 mass%) 0.009 mass parts, cobalt acetate tetrahydrate ethylene glycol solution (concentration 1.76 mass%) ) At a pressure of normal pressure, a temperature of 253 ° C., and an average residence time of 1.0 hour. The acid value of the third esterification reaction vessel outlet oligomer was 350 eq / ton on average.

(3) Polycondensation The reaction solution is taken out so that the liquid level in the third esterification reaction tank is constant, and is put into the first polycondensation reaction tank, pressure 5.3 kpa, temperature 261 ° C., average residence time. The first polycondensation reaction was performed in 1.5 hours.

  The reaction solution was taken out so that the liquid level in the first polycondensation reaction tank was constant, and charged into the second polycondensation reaction tank. The second polycondensation reaction was performed at a pressure of 0.45 kpa, a temperature of 272 ° C., and an average residence time of 1.2 hours.

  The reaction solution was taken out so that the liquid level of the second polycondensation reaction product was constant, and charged into the third polycondensation reaction tank. The degree of vacuum (pressure) was adjusted so that the average intrinsic viscosity of the reaction product was 0.74 at a temperature of 272 ° C. and an average residence time of 1.2 hours. The pressure ranged from 0.06 to 0.15 kpa.

  The copolymerized polyester was taken out in a strand shape so that the liquid level in the third polycondensation reaction was constant, the copolymerized polyester was cooled with water and solidified, and pelletized with a strand cutter. A filter having an average pore diameter of 20 μm was installed at the outlet of the third polycondensation reaction tank, and the copolymerized polyester was filtered.

A continuous operation was carried out for 10 days, and samples of copolymerized polyester were obtained every 12 hours. When the properties of these samples were measured by the above method, the intrinsic viscosity was 0.73 to 0.75, the content of neopentyl glycol with respect to all glycol components was 28 to 32 mol%, and the melt resistivity was 0.17 to 0.00. The number of particles of 19 × 10 ⁸ Ω · cm, 5 μm or more was 42 to 48. The copolymer polyester has a DEG content of 1.5 mol%, an acid value of 13 eq / ton, a melting point (pour point) of 181 ° C., a cyclic trimer content of terephthalic acid and ethylene glycol of 3700 ppm, terephthalic acid. The content of cyclic dimer of acid and neopentyl glycol was 2200 ppm (both average values). The results are shown in Table 1. As a result, the copolyester obtained in this example was of high quality and the quality fluctuation was suppressed.

(4) Recovery of glycol component The flow of the glycol component in the copolymer polyester production process shown in the above (1) to (3) is shown in FIG.

  A distillate (distillate A) distilled from the first esterification reaction tank 3 and the second esterification reaction tank 4 is transferred to a bubble-bell type distillation column 9 having 15 stages, and a third esterification reaction tank. A distillate (distillation B) distilled from 5 and 3 polycondensation reaction tanks 6 to 8 is supplied to a bubble-bell type distillation column 10 having 9 stages, and is mainly composed of water. Boiling fraction was removed. In both distillation towers, a part of the residue taken out from the bottom was circulated to the middle part of each distillation tower. The temperature of the circulating fluid was stable around 168 ° C. In these distillation columns 9 and 10, the pressure at the top of the column was controlled within 100 kPa ± 1.3%. This pressure was controlled by a pressure regulating valve installed in the distillation tower vent pipe. In addition, about the distillate from the esterification reaction tanks 3-5, since the heat required for distillation was sufficient for the calorie | heat amount which distillate itself has, there was no need for a heating. This circulation did not cause clogging of the liquid feed line of the residual liquid (collected glycol component in this example) taken out from the bottom of the distillation column.

  The distillation column 9 was controlled so that the temperature detected by the temperature detector installed in the seventh stage was 130 ± 2 ° C. The obtained residue was supplied to the glycol component reservoir 17. The composition of the obtained recovered glycol component was 3.4% by mass of water, 70.8% by mass of ethylene glycol, and 25.8% by mass of neopentyl glycol on average. The recovered glycol component obtained was used for slurry preparation. Further, as described above, a part thereof was supplied to the second esterification reaction tank.

  In the distillation column 10, the low-boiling fraction mainly composed of water was removed, and the residual liquid taken out from the bottom of the distillation column was supplied to the 25-stage distillation column 14 for removing the high-boiling fraction. The water content in the recovered glycol component obtained by distilling off the high-boiling fraction in the distillation column 14 was 0.1 wt% or less, the DEG component was 0.2 wt%, and the phosphorus atom content could be particularly reduced to 1.3 ppm. New neopentyl glycol was added to the recovered glycol component to adjust the neopentyl glycol content to 54.3% by mass, and then stored in the recovered glycol component storage tank 18 to be a part of the raw material for slurry preparation.

  Since the distillate distilled from the three polycondensation reaction tanks 6 to 8 is generated in a reduced pressure system, it is condensed in the wet condensers 11 to 13 installed in each reaction tank, and the glycol component condensate storage tanks 20 to 22 are condensed. To the distillation column 10. Therefore, in the heat exchanger 26, the amount of heat necessary for distillation is imparted to the glycol component condensate. Moreover, in order to suppress the temperature rise of the glycol component liquid sprayed on the wet condenser, the glycol component liquid is cooled by the coolers 23 to 25 and then supplied to the wet condenser. Although this glycol component liquid is implemented by the self-circulation of the condensate itself condensed by each wet condenser, you may supply novel ethylene glycol as part or all.

Comparative Example 1
Example 1 is different from the method of Example 1 except that the bottom fraction of the distillation column 10 is supplied to the distillation column 14 and then changed to be supplied to the glycol component storage tank 18 without removing the high-boiling fraction. In the same manner as above, polycondensation was performed to obtain a copolyester. The flow of the glycol component in the process for producing the copolyester according to Comparative Example 1 is shown in FIG.

  When the bottom fraction of the distillation column 10 was analyzed, 200 ppm of phosphorus atoms were contained. Moreover, the property of the copolyester obtained in this comparative example was measured by the above method. The results are shown in Table 2.

The average value of the melt specific resistance was as high as 0.88 × 10 ⁸ Ω · cm, the maximum casting speed was 28 m / min, and the electrostatic adhesion was extremely inferior. Further, when the melt specific resistance of the copolymerized polyester was determined in the same manner as in Example 1, the fluctuation range was 0.78 to 1.05 × 10 ⁸ Ω · cm as shown in Table 2, which was extremely inferior. It was. In this comparative example, the electrostatic adhesion is decreased and the fluctuation of the melt specific resistance is increased because the phosphorus compound in the recovered glycol component is circulated in the polycondensation system.

Comparative Example 2
In the method of Example 1, a copolymerized polyester of Comparative Example 2 was obtained in the same manner as in Example 1 except that the recovered glycol component was not supplied to the second esterification reaction tank. The results are shown in Table 2. As shown in Table 2, the average value of the copolyester characteristics when operated continuously for 10 days was the same, but the variation range of the neopentyl glycol content when measured every 12 hours was 26 to 34 mol%. Yes, compared to the method of Example 1.

Comparative Example 3
In the method of Example 1, it implemented by the method similar to the comparative example 1 except changing a 2nd esterification reaction tank temperature into 260 degreeC. As a result, there was much foaming of the 2nd esterification reaction tank, and long-term stable production was difficult.

Comparative Example 4
In the method of Example 1, when supplying new neopentyl glycol to the slurry preparation tank, it is the same as that of Example 1 except that it is directly added to the slurry preparation tank in the solid state without melt filtration. A copolyester was produced by the method described above. The results are shown in Table 2. As shown in Table 2, the copolymer polyester obtained in this comparative example had a large amount of coarse particles and was of low quality.

Comparative Example 5
In the method of Comparative Example 1, the circulation line to the distillation column of the residual portion extracted from the bottom of the distillation column provided in the distillation columns 9 and 10 is removed, the circulation is stopped, and the entire amount of the residual portion is sent to the respective supply destinations. It was changed as follows. When implemented in this comparative example, in addition to the problems in the method of comparative example 1, in the liquid feed line for the residual extracted from the bottom of the distillation column, line clogging due to solid analysis sometimes occurs, and stable production over a long period of time. Sometimes it was difficult to do. Therefore, it has become clear that it is more preferable to circulate a part of the distillation column residual liquid in the purification of the distillate glycol component in the distillation column.

Example 2
In the method of Example 1, antimony trioxide was changed to tetrabutyl titanate, and the addition amount thereof was changed to 15 ppm as a titanium atom with respect to the resulting copolymerized polyester. The copolymer polyester of Example 2 was obtained. The results are shown in Table 1. A copolyester having characteristics equivalent to those of the method of Example 1 could be stably produced.

Comparative Example 6
In the method of Example 2, a copolymerized polyester of Comparative Example 6 was obtained in the same manner as in Example 2 except that the method for recovering the glycol component was changed to the same method as in Comparative Example 1. As a result, due to the influence of the phosphorus compound present in the recovered glycol component, the titanium catalyst was deactivated in addition to the problem in the method of Comparative Example 1, and the intrinsic viscosity reached a peak at 0.50 and copolymerization with a predetermined intrinsic viscosity. Polyester was not obtained.

Example 3
In the method of Example 1, supply of the recovered glycol component to the second esterification reaction tank was stopped, and a new mixed solution (mass ratio) of neopentyl glycol / ethylene glycol = 73/27 was supplied instead at 50 kg / hour. The copolymerized polyester of Example 3 was obtained in the same manner as in Example 1 except that the amount was changed as described above. The results are shown in Table 1. As shown in Table 1, a copolyester having characteristics equivalent to those of Example 1 was stably produced.

Example 4
In the method of Example 1, (1) melted neopentyl glycol was filtered with a filter having an average pore size of 5 μm and then mixed with ethylene glycol, and the mixed solution was introduced into the slurry preparation tank without filtration, and ( 2) Stop the fractionation of the glycol component distilled from the third esterification reaction tank by the distillation tower 10, condense the whole amount with the condenser 16, and combine the glycol component condensate distilled from the total polycondensation reaction tank. Thus, fractionation is performed using a distillation column 15 having 30 stages, and the middle distillate obtained by cutting the low boiling fraction and the high boiling fraction is stored in the recovered glycol component storage tank 18 and used as part of the raw material for slurry preparation. A copolymerized polyester of Example 4 was obtained in the same manner as in Example 1 except that the above was changed.

  As shown in Table 1, the quality of the obtained copolyester had the same quality as the copolyester obtained in Example 1, and was high quality. The phosphorus atom content of the middle distillate was sufficiently suppressed at 1.8 ppm. The flow of the glycol component in the process for producing the copolyester in Example 4 is shown in FIG.

It is a figure which shows the flow of the glycol component in the copolyester manufacturing process which concerns on Example 1. FIG. It is a figure which shows the flow of the glycol component in the copolyester manufacturing process which concerns on the comparative example 1. FIG. It is a figure which shows the flow of the glycol component in the copolyester manufacturing process which concerns on Example 4. FIG.

Explanation of symbols

1: Metering tank 2: Slurry preparation tank 3: First esterification reaction tank 4: Second esterification reaction tank 5: Third esterification reaction tank 6: First polycondensation reaction tank 7: Second polycondensation reaction tank 8 : Third polycondensation reaction tank 9, 10, 14, 15: distillation column 16: condenser 11-13: wet condenser 17, 18: recovered glycol component storage tank 20-22: glycol component condensate storage tank 23-25: cooler 26: Heat exchanger 27-44: Pump

Claims (12)

A method for continuously producing a copolyester,
Step 1: a step of preparing a slurry by introducing at least terephthalic acid, ethylene glycol, and neopentyl glycol into a slurry preparation tank;
Step 2: The prepared slurry is continuously introduced into two or more esterification reaction vessels connected in series, and subjected to esterification to obtain an oligomer compound; and Step 3: the obtained oligomer compound is overlapped. A step of producing a copolyester by subjecting to a condensation reaction,
Supplying the phosphorus compound at least once through steps 1 to 3,
In step 1, the novel solid neopentyl glycol is filtered and introduced into the slurry preparation tank in the molten state and / or after being made into an ethylene glycol solution,
In Step 2, a glycol component containing neopentyl glycol is additionally supplied after the second esterification reaction tank,
The reaction temperature of the esterification reaction tank to be additionally supplied is set lower than the reaction temperature of the esterification reaction tank in the previous stage, and the phosphorus atom content of the distilled glycol component after the supply of the phosphorus compound is distilled. Recycle and reuse after reducing to 10ppm or less by
A method for continuously producing a copolyester characterized by the following.   The continuous production method according to claim 1, wherein neopentyl glycol in a molten state and / or an ethylene glycol solution is filtered through a filter having an average pore diameter of 20 µm or less.   The continuous production method according to claim 1 or 2, wherein the reaction temperature of the esterification reaction tank for additionally supplying a glycol component containing neopentyl glycol is 5 to 15 ° C lower than the reaction temperature of the esterification reaction tank in the previous stage.   The continuous manufacturing method in any one of Claims 1-3 which add a phosphorus compound after a 2nd esterification reaction tank.   Distillate (A) for distilling from the reaction vessel before adding the phosphorus compound, and distillate (B) for distilling from the reaction vessel after adding the phosphorus compound The continuous production method according to any one of claims 1 to 4, which is carried out separately.   The continuous production method according to claim 5, wherein a low-boiling fraction is removed from the distillate (A) by distillation, and the residue (A ') is recycled and reused as a recovered glycol component.   The continuous production method according to claim 6, wherein a part of the residue (A ') extracted from the bottom of the distillation column for fractionating the distillate (A) is circulated to the distillation column.   The continuous production method according to claim 6 or 7, wherein a part of the residue (A ') is supplied after the second esterification reaction tank in Step 2.   A low-boiling fraction and a high-boiling fraction containing a phosphorus compound are removed from the distillate (B) by distillation, and the obtained middle distillate (B ') is recycled and reused as recovered glycol. The continuous manufacturing method in any one of 5-8.   The continuous production method according to claim 9, wherein a part of the residual liquid of the distillation column extracted from the bottom of the distillation column for fractionating low-boiling components from the distillate (B) is circulated to the distillation column.   After distilling off the low-boiling fraction from the distillate (B) using a distillation column, the middle-boiling fraction (B ′) is removed by removing the high-boiling fraction containing a phosphorus compound using another distillation column. The continuous production method according to any one of claims 5 to 10, wherein the continuous production method is obtained and reused.   The continuous production method according to any one of claims 9 to 11, wherein a part of the middle distillate (B ') is supplied after the second esterification reaction tank in Step 2.

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