JP2005187555A - Polyester and manufacturing method of polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester-manufacturing method which allows stable manufacture of a polyester retaining color tones, transparency and thermal stability, having a Tc1 within an appropriate temperature range and containing a few foreign matters derived from a polycondensation catalyst using a polycondensation catalyst comprising metal components mainly composed of metal components other than antimony, germanium and titanium in a continuous polycondensation method. <P>SOLUTION: In the manufacturing method of the polyester by the continuous polycondensation method in the presence of the polyester polycondensation catalyst comprising at least one selected from aluminum compounds and at least one selected from phosphorous compounds, the aluminum compound is added to an oligomer having an acid value AVo of at least 3,000 eq/ton and the phosphorous compound is added after the completion of the esterification reaction. The polyester is manufactured by the method. A molded product of the same is also provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a polyester, and more particularly to a polyester polycondensation method using a novel polyester polycondensation catalyst that does not use germanium, antimony, and a titanium compound as the main catalyst components, and a polyester product thereof. It is.

  Polyesters typified by polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc. are excellent in mechanical properties and chemical properties. Depending on the properties of each polyester, for example, Used in a wide range of fields such as textiles for clothing and industrial materials, packaging, magnetic tape, optical films and sheets, bottles that are hollow molded products, casings for electrical and electronic parts, and other engineering plastic molded products. ing. In particular, bottles made of saturated polyesters such as PET are excellent in mechanical strength, heat resistance, transparency and gas barrier properties, so that they are used as containers for filling beverages such as juices, carbonated drinks and soft drinks, and containers for eye drops and cosmetics. Widely used.

  For example, in the case of PET, a polyester having aromatic dicarboxylic acid and alkylene glycol as main components as a typical polyester is bis ((ester) by esterification reaction or transesterification reaction between terephthalic acid or dimethyl terephthalate and ethylene glycol. An oligomer mixture such as 2-hydroxyethyl) terephthalate is produced, and this is produced by liquid phase polycondensation using a catalyst at high temperature under vacuum.

  Conventionally, antimony or germanium compounds have been widely used as the polyester polycondensation catalyst used in such polycondensation of polyester. Antimony trioxide is an inexpensive catalyst with excellent catalytic activity. However, if it is used in an amount of such a main component, that is, a practical polycondensation rate, a metal is used during polycondensation. Since antimony is deposited, darkening and foreign matter are generated in the polyester, which may cause film surface defects. Further, when a raw material such as a hollow molded product is used, it is difficult to obtain a hollow molded product having excellent transparency. Under such circumstances, a polyester that does not contain antimony at all or does not contain antimony as a main catalyst component is desired.

  Germanium compounds have already been put to practical use as catalysts that give polyesters that have excellent catalytic activity other than antimony compounds and do not have the above problems, but the problem that this catalyst is very expensive, It is difficult to control the polycondensation because the concentration of the catalyst in the reaction system changes due to easy distilling from the reaction system to the outside during the polycondensation, and there is a problem in using it as the main component of the catalyst. .

  Polycondensation catalysts to replace antimony or germanium catalysts have been studied, and titanium compounds typified by tetraalkoxy titanates have already been proposed. Polyesters produced using these compounds are subject to thermal degradation during melt molding. There is a problem that the polyester is easily colored and the polyester is remarkably colored.

  With the above circumstances, it is a polycondensation catalyst that uses metal components other than antimony, germanium, and titanium as the main metal components of the catalyst, and has excellent catalytic activity, excellent color and thermal stability, and transparency of molded products. There is a need for polycondensation catalysts that provide excellent polyesters.

As a novel polycondensation catalyst that meets the above requirements, a catalyst system comprising an aluminum compound and a phosphorus compound has been disclosed and attracted attention (for example, see Patent Documents 1 to 4).
JP 2001-131276 A JP 2001-163963 A JP 2001-163964 A JP 2002-220446 A

Regarding a method for producing polyester using the polycondensation catalyst system, a method is disclosed in which the polycondensation catalyst is added to an oligomer having an intrinsic viscosity of less than 0.4 (see Patent Document 5). The patent document discloses that the polycondensation catalyst is preferably added to an oligomer having an acid value AV ₀ of 10 ≦ AV ₀ ≦ 3000 (eq / ton).
JP 2002-322255 A

Further, regarding the method for producing a polyester using the polycondensation catalyst system, a polyester polycondensation catalyst comprising a solution in which at least one selected from the group consisting of carboxylic acid aluminum salts is dissolved in water and / or an organic solvent, and the polycondensation A method for producing a polyester using a catalyst is disclosed (see Patent Document 6).
JP 2003-82083 A

  The polyester obtained by the method disclosed in the above patent document has good color tone, transparency, and thermal stability, and meets the above requirements. However, the polyester obtained by this method has a problem that the content of foreign matters insoluble in the polyester cannot always be stably obtained at a low level. Ultrafine fibers, highly transparent films for optical use, The highly transparent molded body and the like did not reach a sufficiently satisfactory level, and the improvement was strongly envyed.

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

In addition, in the case of beverages that require hot filling, such as fruit juice beverages, oolong tea, and mineral water, a method of crystallizing by heat treatment of a preform or a molded bottle cap portion is generally used ( For example, see Patent Documents 7 and 8). Such a method, that is, a method of improving the heat resistance by heat-treating the plug portion and the shoulder portion, the time and temperature for the crystallization treatment greatly affect the productivity, and can be processed at a low temperature in a short time. It is preferable that the conversion rate is PET. On the other hand, the body portion is required to be transparent even if heat treatment is performed at the time of molding so as not to deteriorate the color tone of the contents of the bottle, and the mouthpiece portion and the body portion must have contradictory characteristics. On the other hand, if the crystallization speed is too high, the crystallization becomes non-uniform and distortion occurs in the plug portion, leading to leakage of the filling liquid.
JP 55-79237 A JP 58-110221 A

As a solution to such a problem, there is a method of optimizing the crystallization rate of PET, and it is known that the crystallization temperature at the time of temperature rise of PET, which is a measure of the crystallization rate, so-called Tc1 is in the optimum range. Yes. Although the appropriate crystallization speed slightly changes depending on the bottle production process equipment, a Tc1 product at 150 to 170 ° C. is desired from the market. The polycondensation catalyst system composed of the above aluminum compound and phosphorus compound is disclosed, for example, that PET of 150 to 170 ° C., which is the optimum Tc1, can be obtained unlike the antimony polycondensation catalyst that has been widely used conventionally. (See, for example, Patent Document 9). Certainly, this method can stably obtain PET with the above characteristics for the batch polycondensation method, but when applied to the continuous polycondensation method, the above characteristics may not be in the preferred range. The establishment of a method that can be obtained stably was strongly envyed.
JP 2002-249568 A

  The present invention has been made against the background of the problems of the prior art. It is a polycondensation catalyst having a metal component other than antimony, germanium and titanium as the main metal component of the catalyst, maintaining color tone, transparency and thermal stability, and continuously. The present invention provides a method for producing a polyester that can stably produce a polyester in which Tc1 is in an appropriate temperature range in the formula polycondensation method and the generation of foreign matter due to the polycondensation catalyst is small.

  In order to solve the above-mentioned problems, the present invention has finally been completed as a result of intensive studies. That is, the present invention provides a method for producing a polyester by a continuous polycondensation method in the presence of a polyester polycondensation catalyst comprising at least one selected from aluminum compounds and at least one selected from phosphorus compounds. It is a method for producing a polyester characterized in that it is added to an oligomer having an acid value Avo of 3000 eq / ton or more, and the phosphorus compound is added after the esterification reaction. Moreover, this invention is the polyester manufactured by this method, and its molding.

  The polyester production method according to the present invention is a polycondensation catalyst in which a metal component other than antimony, germanium and titanium is used as a main metal component in a continuous polycondensation method excellent in economic efficiency, color tone, transparency and thermal stability. Therefore, there is an advantage that both quality and economical efficiency can be achieved since polyester having a low Tc1 temperature range and less foreign matter generation due to the polycondensation catalyst can be obtained. Accordingly, the polyester obtained by the production method of the present invention includes, for example, fibers for clothing and industrial materials, films and sheets for packaging, magnetic tape and optics, bottles that are hollow molded articles, and electrical / electronic components. Can be suitably used in a wide range of fields such as casings and other engineering plastic molded articles. Since the polyester obtained in the present invention has an optimum Tc1 that greatly affects the crystallization of the polyester, it is particularly suitable for use in fields in which the crystallization characteristics of the polyester such as heat-resistant bottle raw materials are important. can do.

Hereinafter, the present invention will be described in detail.
The polyester referred to in the present invention refers to a polyester comprising a dicarboxylic acid and / or an ester-forming derivative thereof and a diol and / or an ester-forming derivative thereof.

Dicarboxylic acids include succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1,3 -For cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, etc. Saturated aliphatic dicarboxylic acids exemplified, or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid, etc., or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid 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 Acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylsulfonedicarboxylic acid, 4
4'-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p
Examples thereof include aromatic dicarboxylic acids exemplified by '-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like, and ester-forming derivatives thereof.

  Of these dicarboxylic acids, terephthalic acid and naphthalenedicarboxylic acid, particularly 2,6-naphthalenedicarboxylic acid, are preferable from the viewpoint of the physical properties of the resulting polyester, and other dicarboxylic acids are used as constituents as necessary.

In addition to these dicarboxylic acids, a polyvalent carboxylic acid may be used in combination if the amount is small. Examples of the polyvalent carboxylic acid include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3, 4, 3 ′, 4′-biphenyltetracarboxylic acid, and these Examples thereof include ester-forming derivatives.

As glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4 -Butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethyl Aliphatic glycols exemplified by tylene glycol and polytetramethylene glycol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) ) Sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2 , 5-naphthalenediol, aromatic glycols exemplified by ethylene glycol added to these glycols, and the like.

  Of these glycols, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol are preferred.

  In addition to these glycols, polyhydric alcohols may be used in combination in small amounts. Examples of the polyhydric alcohol include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol, and the like.

  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, 4-hydroxycyclohexanecarboxylic acid, or These ester-forming derivatives are exemplified.

  Moreover, combined use of cyclic ester is also permitted. Examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, and lactide.

  Examples of ester-forming derivatives of polyvalent carboxylic acids or hydroxycarboxylic acids include alkyl esters and hydroxylalkyl esters of these compounds.

  Examples of ester-forming derivatives of diols include esters of diols with lower aliphatic carboxylic acids such as acetic acid.

  As the polyester of the present invention, PET, PBT, polypropylene terephthalate, poly (1,4-cyclohexanedimethylene terephthalate), PEN, polybutylene naphthalate, polypropylene naphthalate and copolycondensates thereof are preferable, and among these, polyethylene terephthalate And this copolycondensate is particularly preferred. The copolycondensate is preferably composed of 50 mol% or more of ethylene terephthalate units, more preferably 70 mol% or more. As described in claim 4, PET is particularly preferable.

  The polyester production method in the present invention needs to be a continuous polycondensation method. The continuous polycondensation method is advantageous in terms of quality uniformity and economy compared to the batch polycondensation method. Further, the continuous polycondensation method in the present invention needs to be a so-called direct esterification method which is produced by a reaction between a dicarboxylic acid and a diol. The number and size of the reactors in the esterification and polycondensation steps, the production conditions in each step, etc. can be appropriately selected without limitation.

Hereafter, a manufacturing method is illustrated about a polyethylene terephthalate.
A slurry containing 1.02 to 1.5 mol, preferably 1.03 to 1.4 mol, of ethylene glycol with respect to 1 mol of terephthalic acid was prepared, and this was continuously added to the esterification reaction step. To supply.

In the esterification reaction, water produced by the reaction is removed out of the system using a rectification column under conditions where ethylene glycol is refluxed using a multistage apparatus in which 1 to 3 esterification reactors are connected in series. While carrying out. The temperature of the first stage esterification reaction is 240 to 270 ° C., preferably 245 to 265 ° C., and the pressure is 0.2 to 3 kg / cm ² G, preferably 0.5 to ² kg / cm ² G. The temperature of the esterification reaction in the final stage is usually 250 to 290 ° C, preferably 255 to 275 ° C, and the pressure is usually 0 to 1.5 kg / cm ² G, preferably 0 to 1.3 kg / cm ² G. . When carried out in three or more stages, the reaction conditions for the esterification reaction in the intermediate stage are preferably intermediate conditions between the reaction conditions in the first stage and the reaction conditions in the final stage. The increase in the reaction rate of these esterification reactions is preferably distributed smoothly at each stage. Ultimately, it is desirable that the esterification reaction rate reaches 90% or more, preferably 93% or more. By these esterification reactions, oligomers having a molecular weight of about 500 to 5,000 are obtained.

  The characteristic value of the oligomer obtained by the said esterification process is set suitably. When emphasizing the productivity of polyester, polycondensation is preferably started when OHV%, which is the ratio of the amount of hydroxyl end groups to the amount of all end groups of the oligomer, is 55 to 75%. On the other hand, when importance is given to the polyester quality such as the acid end group amount and cyclic oligomer content of the resulting polyester, it is preferable to start polycondensation when the OHV% is 75% or more.

  For the above OHV%, a bypass flow path is provided in the transfer line from the final esterification reactor to the polycondensation reactor, and the amount of hydroxyl end groups and amount of carboxyl end groups of the reaction product are measured online by the nuclear magnetic resonance method. The reaction product may be fed back to the reaction conditions, or the reaction product may be intermittently removed from the system, and the hydroxyl end group amount and carboxyl end group amount of the removed sample may be measured offline and fed back to the reaction conditions. good.

  Subsequently, it is transferred to a polycondensation reactor to carry out polycondensation. The number of reactors in the polycondensation step is not limited. Generally, a two-stage system of initial polycondensation and late polycondensation is taken. The polycondensation reaction conditions are as follows: the first stage polycondensation reaction temperature is 250 to 290 ° C., preferably 260 to 280 ° C., and the pressure is 500 to 20 Torr, preferably 200 to 30 Torr. The temperature is 265 to 300 ° C., preferably 275 to 295 ° C., and the pressure is 10 to 0.1 Torr, preferably 5 to 0.5 Torr. When the reaction is carried out in three or more stages, the reaction conditions for the intermediate polycondensation reaction are preferably intermediate 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.

  As the aluminum compound constituting the polycondensation catalyst of the present invention, known aluminum compounds can be used without limitation, but those that can be dissolved in water and / or an organic solvent are preferable. Specifically, aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, aluminum tartrate, salicylic acid Carboxylates such as aluminum, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate, aluminum phosphonate, and other inorganic acid salts, aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-but Aluminum alkoxides such as side, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethyl acetoacetate, aluminum ethyl acetoacetate diiso-propoxide, etc., aluminum chelate compounds, trimethylaluminum, organic aluminum compounds such as triethylaluminum and their partial hydrolysis Examples include decomposition products, reaction products composed of alkoxides of aluminum and aluminum chelate compounds and hydroxycarboxylic acids. Of these, carboxylates are particularly preferred.

  Among these aluminum compounds, an aluminum carboxylate compound is particularly preferable from the viewpoint of solubility and corrosion of the apparatus.

  Specific examples of the carboxylic acid aluminum salt used in the present invention include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, and benzoic acid. Examples include aluminum, aluminum trichloroacetate, aluminum lactate, aluminum citrate, aluminum tartrate, and aluminum salicylate. Of these, aluminum acetate, basic aluminum acetate and other aluminum acetate structures and aluminum lactate From the viewpoint of solubility and catalytic activity.

  Polyesters obtained by the methods disclosed in the aforementioned Patent Documents 5 and 6 have good color tone, transparency and thermal stability, and metal components other than antimony, germanium and titanium are used as the main metal components of the catalyst. It is highly practical as a polycondensation catalyst. However, the polyester obtained by this method sometimes has a high content of foreign matters insoluble in the polyester, and the foreign matter content insoluble in the polyester cannot always be stably obtained at a low level. Therefore, the ultrafine fiber, the highly transparent film for optical use, the ultrahighly transparent molded article, etc. did not reach a sufficiently satisfactory level, and the improvement thereof was strongly desired. The present invention has been made by earnestly studying and establishing a technique for stably obtaining a content of foreign matters insoluble in polyester at a low level.

  In the present invention, in the above-mentioned continuous polycondensation method, it is important to add the aluminum compound to an oligomer having an acid value Avo of 3000 eq / ton or more. 3200 eq / ton or more is preferable, and 3400 eq / ton or more is more preferable. If an oligomer having an acid value Avo of less than 3000 eq / ton is added, the content of foreign matters insoluble in polyester increases. For example, when molded as a molded body such as a film or a bottle, the haze of the molded body deteriorates. Therefore, it is not preferable. Moreover, it leads to the subject that the filter clogging at the time of filtration of polyester in a polycondensation process or a molding process increases.

In the present invention, the method of adding to the oligomer having the above characteristics is not limited, but it is a preferred embodiment that the esterification reaction tank is multi-staged and added to the oligomer portion satisfying the above characteristics. For example, reaction conditions are set so that an oligomer satisfying the above characteristics can be obtained in the first esterification reaction tank with two stages of esterification reaction tanks.
There is a method in which an inline mixer is installed in a transfer line to an esterification reaction tank, and an aluminum compound solution is added to the inline mixer.

In the polycondensation of polyester, when a metal-based polycondensation catalyst that forms a salt with the constituent components of the polyester as in the present invention is used, if it is added to an oligomer having a high acid value AVO, The common sense is that metal reacts with the acid terminus of the oligomer to form a metal salt, and the metal salt has poor solubility in polyester, so the content of foreign matter insoluble in polyester increases. It is.

  In the present invention, the hydroxyl value OHVo of the oligomer to which the aluminum compound is added can be arbitrarily set depending on various polymerization catalysts, polyester compositions, conditions for adding the additive, etc., but it should be 800 eq / ton or more. It may be preferable. When the hydroxyl value OHVo of the oligomer is less than 800 eq / ton, the content of foreign matters insoluble in the polyester may increase. For example, when molded as a molded body such as a film or a bottle, the haze of the molded body may be deteriorated. is there.

  According to the above-described embodiment, the problem that the amount of foreign matter insoluble in the polyester, which has been left as a problem in the above-described conventional technology, has been solved.

  In the polycondensation of polyester, when a metal-based polycondensation catalyst that forms a salt with the constituent components of the polyester as in the present invention is used, if it is added to an oligomer having a high acid value AVO, The common sense is that metal reacts with the acid terminus of the oligomer to form a metal salt, and the metal salt has poor solubility in polyester, so the content of foreign matter insoluble in polyester increases. Is

  Although the reason why the addition conditions that overturn the above general common sense are preferable is not clear, the generation of foreign matters insoluble in the polyester is not the aluminum compound itself, but the trace amount of impurities contained in the aluminum compound or the aluminum compound This is due to alteration or aggregation of the crystal transformation, etc., and when the polycondensation catalyst made of an aluminum compound is added, the trace component reacts with the polyester oligomer and changes into a compound soluble in the polyester. It is presumed that this is caused by the deterioration and aggregation of insoluble components with respect to polyester being suppressed and, as a result, the generation of insoluble foreign matters with respect to polyester being suppressed.

  In the present invention, the aluminum compound is preferably added to the polycondensation system as a solution dissolved in water and / or an organic solvent. As the organic solvent, it is preferable to use glycols, and when manufacturing PET, it is preferable to use ethylene glycol. Such solution makes it easy to add to the polycondensation reaction system, and provides a polyester having excellent catalytic activity and excellent quality.

  In order to produce a solution in which the aluminum compound of the present invention is dissolved in water and / or an organic solvent, it is preferable to use a solution in which the aluminum compound is previously dissolved in water. It is preferable to add an organic solvent such as diols to the aqueous solution as necessary. The aqueous solution may be added as it is to the polycondensation system, but in order to reduce heat shock during the addition, a solution obtained by diluting the aqueous solution with a diol such as ethylene glycol is added to the polycondensation system, or a diol It is preferable to add to a polycondensation system a solution obtained by distilling water by liquid-liquid replacement of a solution diluted with a liquid.

  When the aluminum compound aqueous solution is diluted with a diol such as ethylene glycol, it is preferable to dilute the diol with a volume ratio of 0.5 to 50 times that of water. Further, the concentration of the aluminum compound solution added to the polycondensation system is preferably 0.01 to 1 mol / liter in terms of aluminum element, since the generation of insoluble foreign matter in the resulting polyester is particularly suppressed.

  Solubility when aluminum compounds are dissolved in water and / or organic solvents, or by adding stabilizers such as boric acid, sulfuric acid, urea, thiourea and acids such as citric acid, lactic acid, oxalic acid to the dissolved solution It is also a preferred embodiment that the compound is used in combination because the stability of the solution increases.

  Below, the preparation method of the aluminum compound solution used by this invention is illustrated in the case where basic aluminum acetate is used. Add water to basic aluminum acetate and stir at room temperature for several hours. The stirring time is preferably 12 hours or longer. Thereafter, stirring is performed at 60 ° C. or more for several hours or more. The temperature in this case is preferably in the range of 60 to 80 ° C. The stirring time is preferably 3 hours or more. The concentration of the aqueous solution is preferably 5 g / l to 100 g / l, particularly preferably 10 g / l to 30 g / l.

  Add ethylene glycol to the above aqueous solution. The amount of ethylene glycol added is preferably 1 to 5 times the volume ratio of the aqueous solution. More preferably, the amount is 2-3 times. The solution is stirred at room temperature for several hours to obtain a uniform water / ethylene glycol mixed solution. Thereafter, the solution is heated and water is distilled off to obtain an ethylene glycol solution. The temperature is preferably 80 ° C. or higher, and preferably 120 ° C. or lower. More preferably, the water is distilled off by stirring at 90 to 110 ° C. for several hours.

  Moreover, the specific example of the ethylene glycol solution preparation method of aluminum lactate is shown. An aqueous solution of aluminum lactate is prepared. The preparation may be performed at room temperature or under heating, but is preferably performed at room temperature. The concentration of the aqueous solution is preferably 20 g / l to 100 g / l, particularly preferably 50 to 80 g / l. Ethylene glycol is added to the aqueous solution. The amount of ethylene glycol added is preferably 1 to 5 times the volume ratio of the aqueous solution. More preferably, the amount is 2-3 times. After stirring the solution at room temperature to obtain a uniform water / ethylene glycol mixed solution, the solution is heated and water is distilled off to obtain an ethylene glycol solution. The temperature is preferably 80 ° C. or higher, and preferably 120 ° C. or lower. More preferably, the water is distilled off by stirring at 90 to 110 ° C. for several hours.

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

Regarding the formation of foreign matters insoluble in polyester by the above aluminum compound, for example, the amount of insoluble content in water of the aluminum compound measured by the method shown below is a measure.
[Measurement method of insoluble content of aluminum compound in water]
30 g of an aluminum compound is added to 1500 ml of pure water at room temperature stirred at 200 rpm, and stirring is continued for 6 hours at room temperature. Subsequently, the liquid temperature was raised to 95 ° C., and stirring was further continued at the same temperature for 3 hours to dissolve the aluminum compound. The resulting solution was allowed to cool to room temperature, filtered through a cellulose acetate membrane filter having a pore size of 0.2 μm (cellulose acetate type membrane filter manufactured by Advantec, product name: C020A047A), and washed with 50 ml of pure water. The filter obtained by filtering the insoluble matter was dried in a vacuum dryer at 60 ° C. for 12 hours, and the insoluble matter weight (W) was determined. The insoluble content of the aluminum compound in water was calculated by the following formula. When the aluminum compound is an aqueous solution, a part of the aqueous solution is collected, the solid content in the aqueous solution is measured by evaporating the aqueous solution to dryness, and the concentration of the aluminum compound in the aqueous solution is obtained using the solid content as the weight of the aluminum compound. The amount of the aluminum compound in the aqueous solution was determined by filtering the aqueous solution in an amount of 30 g. In the case of the aqueous solution, when the concentration of the aluminum compound in the aqueous solution was higher than 2% by mass, pure water was added to dilute the aluminum so as to be 2% by mass, followed by filtration. The dilution was performed under the same conditions as the dissolution of the solid aluminum compound. The above operation was performed in a clean bench.
Insoluble content in water (ppm) = [W (mg) / 30000 (mg)] × 10 ⁶

  When using an aluminum compound whose insoluble content in water measured by the above method exceeds 700 ppm, the content of foreign matters insoluble in polyester increases. For example, when molded as a molded body such as a film or a bottle, Haze may worsen. By satisfying the above-mentioned requirements of the present invention, even when an aluminum compound having an insoluble content in water of more than 700 ppm is used, the content of foreign matters insoluble in the polyester does not increase, and high-quality polyester can always be produced stably. It becomes like this. Therefore, the effect of the present invention is more remarkably exhibited when an aluminum compound having an insoluble content with respect to water exceeding 700 ppm is used, but is not limited thereto. Even when an aluminum compound having an insoluble content in water of 700 ppm or less is used, the content of foreign matter insoluble in polyester is lower than that in the case where an aluminum compound is added outside the scope of the present invention, so that it is included in the scope of the present invention. . In the present invention, even if an aluminum compound having a large amount of insoluble matter in water is used, the content of foreign matter insoluble in polyester is suppressed, but the amount of insoluble matter in water has an upper limit. 7000 ppm or less is preferable. 6500 ppm or less is more preferable, and 6000 ppm or less is more preferable.

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

  More preferable phosphorus compound of the present invention is at least one phosphorus compound selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. It is. By using these phosphorus compounds, an effect of improving the catalytic activity is seen, and an effect of improving physical properties such as thermal stability of the polyester is seen. Among these, use of a phosphonic acid compound is preferable because of its great effect of improving physical properties and improving catalytic activity. Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

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

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

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

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

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

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

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

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

  Among the phosphorus compounds described above, a phosphorus metal salt compound is particularly preferable as the phosphorus compound in the present invention. The phosphorus metal salt compound is not particularly limited as long as it is a metal salt of a phosphorus compound. However, when a metal salt of a phosphonic acid compound is used, the physical properties improving effect and catalytic activity improving effect of the polyester, which are the problems of the present invention, are improved. Largely preferred. Examples of the metal salt of the phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.

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

  As the phosphorus metal salt compound of the present invention, it is preferable to use at least one selected from the compounds represented by the following general formula (Chemical Formula 16) because the effect of improving the physical properties and the effect of improving the catalytic activity are large.

(In the formula (Formula 16), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a hydrocarbon group having 1 to 50 carbon atoms. R ² represents , Hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and a hydrocarbon group having 1 to 50 carbon atoms, R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. A hydrocarbon group having 1 to 50 carbon atoms including a group or carbonyl, l is an integer of 1 or more, m is 0 or an integer of 1 or more, l + m is 4 or less, M is a (l + m) -valent metal Represents a cation, n represents an integer of 1 or more, and the hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

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

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

(In the formula (Chemical Formula 17), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a hydrocarbon group having 1 to 50 carbon atoms. R ³ represents , Hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl, l is an integer of 1 or more, and m is 0 or an integer of 1 or more. , L + m is 4 or less, M represents a (l + m) -valent metal cation, and the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl.

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

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

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

  Examples of the metal salt compound of phosphorus according to the present invention include lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [ethyl (1-naphthyl) methylphosphonate], potassium [ (2-naphthyl) methylphosphonate ethyl], magnesium bis [(2-naphthyl) methylphosphonate ethyl], lithium [benzylphosphonate ethyl], sodium [benzylphosphonate ethyl], magnesium bis [benzylphosphonate ethyl], beryllium bis [Ethyl benzylphosphonate], strontium bis [ethyl benzylphosphonate], manganese bis [ethyl benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonic acid], sodium [(9-anths L) ethyl methylphosphonate], magnesium bis [(9-anthryl) methylphosphonate ethyl], sodium [ethyl 4-hydroxybenzylphosphonate], magnesium bis [4-hydroxybenzylphosphonate ethyl], sodium [4-chlorobenzylphosphone] Acid phenyl], magnesium bis [4-chlorobenzylphosphonate ethyl], sodium [methyl 4-aminobenzylphosphonate], magnesium bis [4-aminobenzylphosphonate methyl], sodium phenylphosphonate, magnesium bis [phenylphosphonic acid] Ethyl], zinc bis [ethyl phenylphosphonate] and the like. Among these, lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [ethyl (1-naphthyl) methylphosphonate], lithium [ethyl benzylphosphonate], Sodium [ethyl benzylphosphonate], magnesium bis [ethyl benzylphosphonate], sodium benzylphosphonate and magnesium bis [benzylphosphonic acid] are particularly preferred.

Among the phosphorus compounds described above, in the present invention, a phosphorus compound having at least one P—OH bond is particularly preferable as the phosphorus compound. In addition to particularly enhancing the physical properties improving effect of the polyester by containing these phosphorus compounds, the catalytic activity is improved by using these phosphorus compounds in combination with the aluminum compound of the present invention at the time of polymerization of the polyester. Seen large.
The phosphorus compound having at least one P—OH bond is not particularly limited as long as it is a phosphorus compound having at least one P—OH in the molecule. Among these phosphorus compounds, the use of a phosphonic acid compound having at least one P—OH bond is preferred because of its great effect of improving the physical properties and improving the catalytic activity of the polyester.

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

  As the phosphorus compound having at least one P—OH bond of the present invention, it is preferable to use at least one selected from the compounds represented by the following general formula (Chemical Formula 18) because the physical property improving effect and the catalytic activity improving effect are large. .

(In the formula (Chemical Formula 18), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a hydrocarbon group having 1 to 50 carbon atoms. R ² represents , Hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, n represents an integer of 1 or more, and the hydrocarbon group is an alicyclic structure such as cyclohexyl. And may contain an aromatic ring structure such as a branched structure or phenyl or naphthyl.)

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

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

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

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

(In the formula (Chemical Formula 19), R ¹ represents a hydrocarbon group having ¹ to 49 carbon atoms, or a hydrocarbon group having ¹ to 49 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and R ² , R ³ each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, which has an alicyclic structure, a branched structure or an aromatic ring structure. May be included.)

More preferably, at least one of R ¹ , R ² and R ^{3 in} the chemical formula (Chemical Formula 19) is a compound containing an aromatic ring structure.

  Specific examples of these phosphorus compounds are shown below.

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

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

  The phosphorus compound having a phenol moiety in the same molecule is not particularly limited as long as it is a phosphorus compound having a phenol structure, but a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound having a phenol moiety in the same molecule. When one or more compounds selected from the group consisting of a compound, a phosphonous acid compound, a phosphinic acid compound, and a phosphine compound are used, the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are greatly preferred. Among these, when a phosphonic acid compound having one or two or more phenol moieties in the same molecule is used, the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are particularly large and preferable.

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

(In the formulas (Chemical Formula 26) to (Chemical Formula 28), R ¹ is a carbon having 1 to 50 carbon atoms including a phenol part, a substituent such as a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a phenol part. Represents a hydrocarbon group having a number of 1 to 50. R ⁴ , R ⁵ and R ⁶ each independently represents a substituent such as hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group or an amino group. Represents a hydrocarbon group having 1 to 50 carbon atoms, and R ² and R ³ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, or an alkoxyl group. Represents a hydrocarbon group, provided that the hydrocarbon group may contain a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl, and the ends of R ² and R ⁴ are bonded to each other. Moyo Yes.)

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

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

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

(In Formula (Chemical Formula 33), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or R ⁴ represents a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group, R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group, or a carbonyl group including carbonyl. Examples of R ⁴ O ⁻ include hydroxide ion, alcoholate ion, acetate ion, acetylacetone ion, etc. l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation, n represents an integer of 1 or more, and the hydrocarbon group includes an alicyclic structure such as cyclohexyl, a branched structure, and an aromatic ring structure such as phenyl or naphthyl. Moyo .)

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

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

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

  Specific phosphorus metal salt compounds of the present invention include lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzyl] Ethyl phosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], potassium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [3 , 5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di-tert- Methyl butyl-4-hydroxybenzylphosphonate], strontium bis [3,5-di-te t-butyl-4-hydroxybenzylphosphonate ethyl], barium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate phenyl], manganese bis [3,5-di-tert-butyl-4- Ethyl hydroxybenzylphosphonate], nickel bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], copper bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate] Zinc bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate] and the like. Among these, lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [ Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

  Among the phosphorus compounds having the phenol moiety of the present invention in the same molecule, at least one selected from specific phosphorus compounds having at least one P—OH bond represented by the following general formula (Formula 35) is particularly preferable.

(In formula (Chemical Formula 35), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or A hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group is represented, and n represents an integer of 1 or more.
The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

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

(In formula (Chemical Formula 36), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group is a fatty acid such as cyclohexyl. (It may contain a ring structure, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

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

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

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

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

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

(In the above formula (Chemical Formula 38), R ³ and R ⁴ each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

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

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

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

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

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

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

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

  When the phosphorus compound is previously heat-treated in a solvent, the aluminum compound of the present invention may coexist. Alternatively, the aluminum of the present invention or a compound thereof may be added in a powder form, a solution form, or a slurry form to a phosphorus compound that has been previously heat-treated in a solvent. Furthermore, you may heat-process the solution or slurry after addition. The solution or slurry obtained by these operations can be used as the polycondensation catalyst of the present invention.

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

  In the present invention, if the above aluminum compound and phosphorus compound are used in combination, a highly practical polycondensation catalytic activity can be expressed, but a further small amount of alkali metal, alkaline earth metal and at least selected from the compounds are used. It is a preferred embodiment that one type is allowed to coexist as the second metal-containing component. The coexistence of such a second metal-containing component in the catalyst system is effective in improving productivity by obtaining a catalyst component having an increased reaction rate in addition to an effect of suppressing the formation of diethylene glycol, and thus a higher reaction rate. .

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

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

  In the present invention, the alkali metal or alkaline earth metal constituting the second metal-containing component preferably used in addition to aluminum or a compound thereof includes Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr. , Ba is preferable, and among these, at least one selected from Li, Na, Mg or a compound thereof is more preferable. Examples of the alkali metal and alkaline earth metal compounds include saturated aliphatic carboxylates such as formic acid, acetic acid, propionic acid, butyric acid, and succinic acid, and unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid. , Aromatic carboxylates such as benzoic acid, halogen-containing carboxylates such as trichloroacetic acid, hydroxycarboxylates such as lactic acid, citric acid and salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphorus Inorganic acid salts such as acid hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid and bromic acid, and organic sulfonates such as 1-propanesulfonic acid, 1-pentanesulfonic acid and naphthalenesulfonic acid , Organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butyl Alkoxides such as alkoxy, chelate compounds and the like acetylacetonate, hydrides, oxides, and hydroxides and the like.

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

  The polycondensation catalyst of the present invention is a polycondensation catalyst such as an antimony compound, a germanium compound, or a titanium compound, and the addition of these components does not cause problems in the product such as the characteristics, processability, and color tone of the polyester. Coexistence within the range of the addition amount is effective in improving productivity by shortening the polycondensation time, and is preferable.

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

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

  The titanium compound is preferably added in an amount of 5 ppm or less as a titanium atom with respect to the polyester obtained by polycondensation. A more preferable addition amount is 3 ppm or less, and further preferably 1 ppm or less. If the amount of titanium added is 5 ppm or more, the resulting polyester is markedly colored, and the thermal stability is significantly reduced, which is not preferable.

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

  The titanium compound that can be used in the present invention is not particularly limited, but tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetra Phenyl titanate, tetrabenzyl titanate, lithium oxalate titanate, potassium oxalate titanate, ammonium oxalate titanate, titanium oxide, composite oxide of titanium and silicon, zirconium, alkali metal, alkaline earth metal, etc., titanium orthoester or Condensed ortho ester, titanium ortho ester or reaction product of condensed ortho ester and hydroxycarboxylic acid, titanium ortho ester or condensed ortho ester and hydroxy carbonate A reaction product composed of an acid and a phosphorus compound, a titanium ortho ester or a condensed ortho ester and a polyhydric alcohol having at least two hydroxyl groups, a reaction product composed of a 2-hydroxycarboxylic acid and a base, etc. Of these, a composite oxide of titanium and silicon, a composite oxide of titanium and magnesium, a reaction product composed of titanium orthoester or condensed orthoester, hydroxycarboxylic acid and phosphorus compound is preferable.

  In addition, as tin compounds, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin sulfide, Examples thereof include dibutylhydroxytin oxide, methylstannoic acid, and ethylstannic acid, and the use of monobutylhydroxytin oxide is particularly preferable.

  In the polyester of the present invention, it is preferable to add a cobalt compound as a cobalt atom in an amount of less than 10 ppm with respect to the polyester for the purpose of improving the color tone. More preferably, it is 5 ppm or less, More preferably, it is 3 ppm or less. The cobalt compound is not particularly limited, and specific examples include cobalt acetate, cobalt nitrate, cobalt chloride, cobalt acetylacetonate, cobalt naphthenate, and hydrates thereof. Of these, cobalt acetate tetrahydrate is particularly preferred.

  In order to improve the color tone of the polyester of the present invention, it is also a preferred embodiment to use a color tone improving agent other than the cobalt compound. The color tone improving agent refers to a substance that changes color tone when added. The color tone improving agent of the present invention is not particularly limited, but inorganic and organic pigments, dyes, fluorescent whitening agents and the like are preferable.

  When a pigment or a dye is used, when the amount used is increased, there arises a problem that the brightness of the polycondensate decreases as a result. This causes the problem of being unacceptable for many applications. Therefore, the total amount of pigments and dyes used is preferably 20 ppm or less, more preferably 10 ppm or less, still more preferably 5 ppm or less, based on the polyester obtained. In such a region, the coloring can be effectively eliminated without reducing the brightness of the polycondensate.

  Further, it is preferable to use a fluorescent brightening agent alone or in combination with another color tone improving agent because the color tone is improved and, for example, the amount of the pigment or dye used may be small. As the fluorescent brightening agent, one commonly used one may be used, or two or more kinds may be used in combination. The amount added is preferably 50 ppm or less, more preferably 5 to 25 ppm, based on the polyester obtained.

  The inorganic pigment of the present invention is not particularly defined as long as it can change the color tone, for example, titanium dioxide, carbon black, iron black, nickel titanium yellow, yellow iron oxide, cadmium yellow, chrome lead, chrome titanium yellow, Examples include zinc ferrite pigments, dials, cadmium red, molybdenum red, chromium oxide, spinel green, chrome orange, cadmium orange, ultramarine blue, bitumen, and cobalt blue. Of these, chromium oxide, ultramarine blue, bitumen, and cobalt blue are preferable, and ultramarine blue and cobalt blue are more preferable. One or more of these inorganic pigments may be used in combination as necessary.

  The organic pigments and dyes of the present invention are not specified as long as they can change the color tone, but, for example, Pigment Red 5, 22, 23, 31, 38, 48: 1, 48: 2 displayed by a color index. , 48: 3, 48: 4, 52, 53: 1, 57: 1, 122, 123, 144, 146, 151, 166, 170, 177, 178, 179, 187, 202, 207, 209, 213, 214 , 220, 221, 247, 254, 255, 263, 272, Pigment Orange 13, 16, 31, 36, 43, 61, 64, 71, Pigment Brown 23, Pigment Yellow 1, 3, 12, 13, 14, 17 , 55, 73 , 74, 81, 83, 93, 94, 95, 97, 109, 110, 128, 130, 133, 136, 138, 147, 150, 151, 154, 180, 181, 183, 190, 191, 191: 1 , 199, Pigment Green 7, 36, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15.4, 15: 6, 29, 60, 64, 68, Pigment Violet 19, 23, 37, 44, Solvent Red 52, 117, 135, 169, 176, Disperse Red 5, Solvent Orange 63, 67, 68, 72, 78, Solvent Yellow 98, 103, 105, 113, 116, Di perseYellow 54, 64, 160, Solvent Green 3, 20, 26, Solvent Blue 35, 45, 78, 90, 94, 95, 104, 122, 132, Solvent Violet 31, and the like. Other anthraquinone, phthalocyanine, quinacridone, isoindolinone, dioxazine, quinophthalone, perylene, perinone, benzimidazolone, diarylide, bat, indigo, quinophthalone, diketopyrrolo Examples include pyrrole and anthrapyrrolidone dyes / pigments.

  Among these, Pigment Red 187, 263, Pigment Blue 15: 1, 15: 3, 29, 60, Pigment Violet 19, Solvent Red 135, Solvent Blue 45, 90, 104, 122, and anthraquinone and phthalocyanine dyes / Pigments are preferred. Furthermore, anthraquinone and phthalocyanine dyes / pigments are particularly preferred.

  The selected pigments and / or dyes preferably satisfy the following conditions. First, the pigments and dyes must be non-extractable from the polycondensate for maximum safety. It is stable to sunlight and a wide range of temperature and humidity conditions. Furthermore, it does not cause sublimation or hue changes as a result of the extremely high temperatures encountered during the production of polyester. Furthermore, it is preferable that these pigments and dyes do not adversely affect the physical properties of the polyester polymer.

  A pigment and / or a dye satisfying these conditions is not particularly limited as long as it improves the color tone of the polyester. For example, in Japanese Translation of PCT International Publication No. 2000-511111, a certain blue 1,4-bis (2,6-dialkylanilino) is used. ) Color tone improvers that mainly use anthraquinone and combine red anthraquinone and anthrapyridone (3H-dibenzo [fi, j] isoquinoline-2,7-dione) compounds according to the hue are exemplified. be able to. These dyes have suitable color characteristics, are stable to heat, light, humidity and various environmental factors and can be included in the polyester polymer structure during polycondensation, and are known organic dyes. Overcome many of the problems you encounter. It is stable to UV light, high temperature, glycolysis and hydrolysis. Furthermore, the amount of the blue component and the red component can be changed as necessary so as to work effectively for polyesters having different degrees of coloring.

  As the optical brightener of the present invention, those generally used may be used alone or in combination. For example, benzoxazoline-based fluorescent brighteners, preferably UVITEX OB, UVITEX OB-P, UVITEX OB-ONE, CHIARI Specialty Chemicals, Ltd., HOTALUX KS, manufactured by Clariant, and those described in JP-A-10-1563 Can be preferably used.

  Since the above-described color tone improving agent achieves an achromatic hue, it can be used in any combination of types and addition ratios. Further, the color tone improving agent may be added at any stage of the polycondensation, after the polycondensation reaction, or at any stage from the end of the polycondensation reaction to the time of molding. . Further, the addition method is preferably added after dissolving in powder or one of polyester monomers during polycondensation. Furthermore, after completion of the polycondensation reaction, it is preferably added as a powder or a master batch.

Moreover, when a problem arises in the dispersibility of pigments or the like, it may be preferable to use a dispersant as necessary. The dispersant is not particularly defined as long as it aids in dispersing the pigment. For example, N, N′-ethylenebismyristic acid amide, N, N′-ethylenebisstearic acid amide, N, N′-ethylenebisoleic acid N, N′-methylenebismyristic acid amide, N, N′-methylenebisstearic acid amide, N, N′-methylenebisoleic acid amide, and other N, N′-alkylenebisfatty acid amides. Among these, N, N′-methylenebisstearic acid amide is preferable. The amount added depends on the performance, but it is 10 to 200% by mass, preferably 40 to 150% by mass, based on the pigment.

  In the present invention, as described in claim 5, it is preferable that the degree of crystallinity (Tc1) of the polyester when heated is 150 ° C. or higher. It is more preferable that it is 150-170 degreeC.

  Polyester Tc1 is an important characteristic because it is a measure of the crystallization speed when polyester is heated and greatly affects the transparency and heat resistance of the molded article when the polyester is molded. As described above, for example, when PET is used as a raw material for a heat-resistant bottle, the Tc1 is preferably 150 to 170 ° C.

  In the present invention, it is important to add the phosphorus compound for the polycondensation catalyst after completion of the esterification reaction. Thus, a polymer having a Tc1 of the obtained polyester in a range suitable for molding the polyester, for example, in the range of 150 to 170 ° C. when the polyester is polyethylene terephthalate, can be stably obtained. If added before the end of the esterification reaction, it becomes Tc1 around 130 ° C., which is about the same as that of polyethylene terephthalate obtained with an antimony catalyst. Although the cause of this is not clarified, it is presumed that this is caused by a slight change in the reaction of the phosphorus compound with the aluminum compound or the polyester oligomer depending on the addition timing of the phosphorus compound.

  As long as the addition timing of the phosphorus compound is satisfied after the esterification reaction is completed, the addition place and addition method are not limited at all. For example, it may be added to the transfer line from the esterification reactor to the polycondensation reactor or may be added in the polycondensation step, but it is installed in the transfer line from the esterification reactor to the polycondensation reactor. It is a preferred embodiment to be added to the in-line mixer. This method is a preferred embodiment because the added phosphorus compound and the esterification reaction product can be mixed uniformly, and the effects of the present invention can be expressed more efficiently. The structure of the in-line mixer used in this method is not limited as long as a uniform mixing effect can be exhibited. For example, an in-line mixer for the purpose of dispersing and mixing the slurry disclosed in JP-A-8-299771 is suitable.

  In the case of adding to the polycondensation reactor, in order to prevent the scattering of the additive, for example, it is preferable to carry out by a capsule addition method in which a phosphorus compound is enclosed in a container made of the same polyester as the product and added. .

  Moreover, since the fluctuation | variation of the fluctuation | variation of Tc1 tends to become more stable by making the temperature of the polycondensation process after adding the said phosphorus compound low, it is better to perform a polycondensation process as low temperature as possible. Of course, when adding to the above-mentioned transfer line, it is preferable to make the temperature of the addition site as low as possible.

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

  The polyester obtained by the method of the present invention is heated in a solid phase under reduced pressure or under an inert gas stream to further proceed with polycondensation, or a cyclic trimer contained in the polyester resin. There are no restrictions on taking measures such as removal of by-products such as oligomers and acetaldehyde. In order to promote crystallization before the solid phase polycondensation, the molten polycondensed polyester may be subjected to heat crystallization after moisture absorption, or may be heated and crystallized by spraying water vapor directly onto the polyester chip. Further, for example, it is possible to incorporate a treatment such as purifying a polyester resin by an extraction method such as a supercritical pressure extraction method to remove impurities such as the by-products.

  The polyester of the present invention can contain organic, inorganic, and organometallic toners, and a fluorescent brightening agent. By containing one or more of these, the yellowness of the polyester, etc. Can be suppressed to an even better 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.

These additives can be added at any stage of polyester polymerization, after polymerization, or at the time of polyester molding. Which stage is suitable depends on the structure of the target polyester and the required performance of the resulting polyester. Each may be selected appropriately according to the situation.
The polyester obtained by the method of the present invention has a feature that the content of foreign matter due to the polycondensation catalyst is small. This feature can be evaluated by, for example, the following aluminum-based foreign matter evaluation method insoluble in polyester. Moreover, the aluminum-based foreign substance insoluble in the polyester as used in the present invention is an amount measured by the following evaluation method.
[Aluminum-based foreign substance evaluation method insoluble in polyester]
30 g of polyester pellets after melt polycondensation and 300 ml of parachlorophenol / tetrachloroethane (3/1: weight ratio) mixed solution are put into a round bottom flask with a stirrer, and the pellets are added to the mixed solution at 100 to 105 ° C. for 2 hours. Stir and dissolve. The solution was allowed to cool to room temperature, and a polytetrafluoroethylene membrane filter (Advantec PTFE membrane filter, product name: T100A047A) having a diameter of 47 mm / a pore size of 1.0 μm was used, and the total amount was under a pressure of 0.15 MPa. Use to filter out foreign objects. The effective filtration diameter is 37.5 mm. After completion of the filtration, the product is subsequently washed with 300 ml of chloroform, and then dried under reduced pressure at 30 ° C. for a whole day and night. The amount of aluminum element is quantified on the filtration surface of the membrane filter with a scanning fluorescent X-ray analyzer (manufactured by RIGAKU, ZSX100e, Rh tube 4.0 kW). Quantification is performed on the membrane filter having a diameter of 30 mm at the center. The calibration curve of the fluorescent X-ray analysis is obtained using a polyethylene terephthalate resin having a known aluminum element content, and the apparent aluminum element amount is expressed in ppm. The measurement is carried out by measuring Al-Kα ray intensity under the conditions of PHA (wave height analyzer) 100-300, using pentaerythritol as a spectral crystal, PC (proportional counter) as a detector, with an X-ray output of 50 kV-70 mA. . The amount of aluminum element in the calibration curve PET resin is quantified by high frequency inductively coupled plasma emission spectrometry.

  In the present invention, as described in claim 3, the amount of aluminum-based foreign matter insoluble in polyester measured by the above evaluation method is preferably 3500 ppm or less. 2500 ppm or less is more preferable, and 1500 ppm or less is more preferable. When the amount of aluminum-based foreign matter insoluble in polyester exceeds 3500 ppm, the content of fine foreign matter insoluble in polyester increases. For example, when molded as a molded body such as a film or a bottle, the haze of the molded body deteriorates. This is not preferable. Moreover, it leads to the subject that the filter clogging at the time of filtration of polyester in a polycondensation process or a molding process increases.

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

  The obtained fibers can be made into various fiber structures such as atypical cross-section yarns, hollow cross-section yarns, composite fibers, original yarns, etc., and well-known means such as blending, blending, etc. can also be used in yarn processing. Can do.

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

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

  The polyester of the present invention is suitably used as a hollow molded body.

  Examples of the hollow molded body include mineral water, juice, beverage containers such as wine and whiskey, milk bottles, bottled food containers, containers for hairdressing products and cosmetics, housing and dishwashing detergent containers, and the like.

  Among these, polyester is particularly suitable for various beverages as a pressure-resistant container, a heat-resistant pressure-resistant container, and an alcohol-resistant container utilizing the hygiene and strength and solvent resistance of polyester. The hollow molded body can be manufactured by a method in which a polyester chip obtained by melt polycondensation or solid phase polycondensation is dried by a vacuum drying method or the like and then molded by a molding machine such as an extrusion molding machine or an injection molding machine. A bottomed preform is obtained by a direct molding method in which the subsequent melt is introduced into a molding machine in a molten state and molded. Further, a final hollow molded body can be obtained by blow molding such as stretch blow molding, direct blow molding, and extrusion blow molding. Of course, a molded product obtained by a molding machine such as the above-described extrusion molding machine or injection molding machine can be used as a final hollow container.

  When manufacturing such a hollow molded body, waste resin generated in the manufacturing process or polyester resin recovered from the market can be mixed. Even with such a recycled resin, the polyester resin of the present invention is less deteriorated and a high-quality hollow molded product can be obtained.

  Further, such a container can have a multilayer structure in which an intermediate layer is provided with a gas barrier resin layer such as polyvinyl alcohol or polymetaxylylenediamine adipate, a light shielding resin layer or a recycled polyester layer. It is also possible to coat the inside and outside of the container with a metal such as aluminum or a layer of diamond-like carbon using a method such as vapor deposition or CVD (chemical vapor deposit).

  In addition, in order to raise crystallinity, such as a plug part of a hollow molded object, inorganic nucleating agents, such as other resin including polyethylene and talc, can also be added.

  Further, the polyester of the present invention can be extruded into a sheet-like material from an extruder to form a sheet. Such sheets are processed by vacuum forming, pressure forming, stamping, etc., and used as trays and containers for food and sundries, cups, blister packs, carrier tapes for electronic components, and electronic component delivery trays. The sheet can also be used as various cards.

  Even in the case of these sheets, it is also possible to take a multilayer structure in which a gas barrier resin layer, a light shielding resin layer, and a recycled polyester layer are provided on the intermediate layer as described above.

  Similarly, recycled resin can be mixed. Furthermore, for the purpose of forming a crystalline heat-resistant container, other resins such as polyethylene and inorganic nucleating agents such as talc can be added to enhance crystallinity.

  The polyester polycondensed using the polyester polycondensation catalyst of the present invention can be used for a film. In this method, polyester is melt-extruded and formed into a sheet shape from a T-die on a cooling rotary roll to create an unstretched sheet. In this case, for example, by applying the technique described in Japanese Patent Publication No. 6-39521 and Japanese Patent Publication No. 6-45175, high-speed film formation is possible. Moreover, it is good also as a laminated | multilayer film by a coextrusion method by using a some extruder and sharing various functions in a core layer and a skin layer.

  Polyesters polycondensed using the polyester polycondensation catalyst of the present invention can be used for oriented polyester T terfilm. The oriented polyester film can be obtained by stretching 1.1 to 6 times at least in the uniaxial direction at a temperature not less than the glass transition temperature of the polyester and less than the crystallization temperature using a known method.

  For example, in the case of producing a biaxially oriented polyester film, a sequential biaxial stretching method in which uniaxial stretching is performed in the longitudinal direction or the transverse direction and then stretching in the orthogonal direction, and a simultaneous biaxial stretching method in which stretching is performed in the longitudinal direction and the transverse direction simultaneously. In addition to using a linear motor as the driving method for simultaneous biaxial stretching, several times in the same direction, such as horizontal / longitudinal / longitudinal stretching, longitudinal / horizontal / longitudinal stretching, and longitudinal / vertical / horizontal stretching It is possible to adopt a multistage stretching method in which the stretching is performed separately.

  Furthermore, in order to reduce the thermal shrinkage rate of the film after stretching, a heat setting treatment is performed within 30 seconds, preferably within 10 seconds, at a temperature from (melting point−50 ° C.) to less than the melting point. % Longitudinal relaxation treatment, lateral relaxation treatment, etc. are preferably performed.

  The obtained oriented polyester film has a thickness of preferably 1 μm or more and 1000 μm or less, more preferably 5 μm or more and 500 μm or less, and more preferably 10 μm or more and 200 μm or less. If it is less than 1 μm, it is difficult to handle because there is no waist. Moreover, when it exceeds 1000 micrometers, it is too hard and handling is difficult.

  In addition, in order to provide various functions such as adhesion, releasability, antistatic properties, infrared absorption, antibacterial properties, scratch resistance, etc., the surface of the oriented polyester film may be coated with a polymer resin by a coating method. Good. Moreover, it is good also as a slippery highly transparent polyester film by making an inorganic and / or organic particle | grain contain only in a coating layer. Furthermore, an inorganic vapor deposition layer can be provided to provide various barrier functions such as oxygen, water, and oligomer, or a conductive layer can be provided by a sputtering method or the like to provide conductivity. In addition, inorganic and organic salt particles or heat-resistant polymer resin particles are added in the polycondensation process of polyester to improve the handling properties such as slipperiness, running property, wear resistance, and winding property of oriented polyester film. Then, irregularities may be formed on the film surface. These particles may be either inorganic / organic or hydrophilic / hydrophobic surface-treated or non-surface-treated particles. For example, particles that have been surface-treated for the purpose of improving dispersibility. There are cases where it is preferable to use.

  Inorganic particles include calcium carbonate, kaolin, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, lithium fluoride, Examples include sodium calcium aluminum silicate.

  Examples of the organic salt particles include terephthalate such as calcium oxalate, calcium, barium, zinc, manganese, and magnesium.

    Examples of the crosslinked polymer particles include divinylbenzene, styrene, acrylic acid, methacrylic acid, acrylic acid or methacrylic acid vinyl monomer alone or a copolycondensate. In addition, organic particles such as polytetrafluoroethylene, benzoguanamine resin, thermosetting epoxy resin, unsaturated polyester resin, thermosetting urea resin, and thermosetting phenol resin may be used.

    The method for incorporating the inert particles in the polyester that is the base film is not limited, but (a) the inert particles are dispersed in a slurry form in a diol that is a polyester component, A method of adding polyester to a polycondensation reaction system, (b) a method of adding a water slurry of inert particles dispersed in a molten polyester resin by a vented twin screw extruder in a melt extrusion step of a polyester film, (c) Examples include a method of kneading a polyester resin and inert particles in a molten state (d) a method of kneading a polyester resin and a master resin of inert particles in a molten state.

  In the case of the method of adding to the polycondensation reaction system, it is preferable to add the diol slurry of inert particles to the reaction system having a low melt viscosity before the esterification reaction or transesterification reaction and before the start of the polycondensation reaction. In addition, when adjusting the diol slurry of inert particles, it is preferable to perform a physical dispersion treatment such as a high-pressure disperser, a bead mill, or ultrasonic dispersion. Furthermore, in order to stabilize the dispersion-treated slurry, it is preferable to use an appropriate chemical dispersion stabilization treatment according to the type of particles used.

  As the dispersion stabilization treatment, for example, in the case of inorganic oxide particles or crosslinked polymer particles having a carboxyl group on the particle surface, an alkali compound such as sodium hydroxide, potassium hydroxide or lithium hydroxide is added to the slurry. Further, reaggregation between particles can be suppressed by electrical repulsion. In the case of calcium carbonate particles, hydroxyapatite particles, etc., it is preferable to add sodium tripolyphosphate or potassium tripolyphosphate to the slurry.

  In addition, when the diol slurry of inert particles is added to the polycondensation reaction system of the polyester, the slurry can be heat-treated to near the boiling point of the diol. (Temperature difference from the system) can be reduced, which is preferable in terms of dispersibility of the particles.

  These additives can be added at any stage during or after polycondensation of the polyester or after film formation of the polyester film. Which stage is suitable depends on the characteristics of the compound and the requirements of the polyester film. Different depending on performance.

  In addition, since the polyester of the present invention is excellent in thermal stability, for example, when a film or the like is produced using the polyester, the film ear part or nonstandard film generated in the stretching process is melted and reused. Suitable for

  The oriented polyester film of the present invention is preferably an antistatic film, an easily adhesive film, a card, a dummy can, an agricultural product, a building material, a cosmetic material, a wallpaper, an OHP film, a printing, and an inkjet recording. For sublimation transfer recording, laser beam printer recording, electrophotographic recording, thermal transfer recording, thermal transfer recording, printed circuit board wiring, membrane switch, plasma display, touch panel, masking film, photoengraving, For X-ray film, photographic negative film, retardation film, polarizing film, polarizing film protection (TAC), protective film, photosensitive resin film, field-of-view film, diffusion sheet, reflection film, reflection For prevention film, conductive film, separator, UV prevention, back glass It is used, for example, for Ndotepu.

  As the antistatic film, for example, the techniques described in Japanese Patent No. 2952677 and Japanese Patent Application Laid-Open No. 6-184337 can be used. Examples of easy-adhesive films are described in JP-B 07-108563, JP-A-10-235820, JP-A-11-323271, and those for cards are described in JP-A-10-171856 and JP-A-11-010815, for example. The technique can be applied to the film of the present invention. For the dummy can, for example, instead of the sheet-like cylinder described in Japanese Patent Application Laid-Open No. 10-101103, a design obtained by printing a design on the film of the present invention to form a cylinder or a half cylinder can be used. As a building material, a decorative plate for building material, and a decorative material, for example, the film of the present invention is used as a base sheet described in JP-A No. 05-200927 and a transparent sheet described in JP-A No. 07-314630. it can. As the OHP (for overhead projector), the film of the present invention can be used as the transparent resin sheet described in JP-A-06-297831 and the transparent polymer synthetic resin film described in JP-A-08-305065. For inkjet recording, for example, the film of the present invention can be used as a transparent substrate described in JP-A No. 05-032037. For sublimation transfer recording, for example, the film of the present invention can be used as a transparent film described in JP-A No. 2000-025349. For laser beam printers and electrophotographic recording, for example, the film of the present invention can be used as a plastic film described in JP-A-05-088400. For thermal transfer recording, the film of the present invention can be used by the methods described in JP-A-07-032754, for thermal recording, and JP-A-11-034503, respectively. For printed circuit boards, for example, the film of the present invention can be used as a polyester film described in JP-A No. 06-326453. For the membrane switch, the film of the present invention can be used, for example, by the method described in JP-A No. 05-234459. As the optical filter (for heat ray filter and plasma display), for example, the film of the present invention can be used by the method described in JP-A-11-231126. For a transparent conductive film and a touch panel, the film of the present invention can be used, for example, by the method described in JP-A-11-224539. For the masking film, the film of the present invention can be used, for example, by the method described in JP-A No. 05-273737. For photoengraving, for example, the film of the present invention can be used by the method described in JP-A No. 05-057844. As the photographic negative film, for example, the film of the present invention can be used as a polyethylene terephthalate film described in paragraph No. (0123) of JP-A No. 06-167768. For a phase difference film, for example, the film of the present invention can be used as a film described in JP-A No. 2000-162419. For the separator, for example, the film of the present invention can be used as the film described in paragraph No. (0012) of JP-A No. 11-209711. For preventing ultraviolet rays, for example, the film of the present invention can be used as a polyester film described in JP-A-10-329291. An agricultural film can be obtained by applying the film of the present invention to a polyethylene terephthalate film described in JP-A-10-166534. The pressure-sensitive adhesive sheet can be obtained, for example, by applying the oriented polyester film of the present invention to a polyethylene terephthalate film described in JP-A-06-122856.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not restrict | limited to these Examples. In addition, the evaluation method was implemented with the following method.

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

2. Measurement of OHVo (OH value) of oligomer The oligomer was pulverized with a handy mill (pulverizer) without drying. 0.50 g of a sample was precisely weighed, 10 ml of an acetylating agent (acetic anhydride pyridine solution 0.5 mol / L) was added, and immersed in a water bath at 95 ° C. or higher for 90 minutes. Immediately after taking out from a water tank, 10 ml of pure water was added and it stood to cool to room temperature. Using phenolphthalein as an indicator was titrated with _{N / 5-NaOH-CH 3} OH solution. Do the same for the blank without the sample. In advance, 20 ml of N / 10-hydrochloric acid is titrated with an N / 5-NaOH-CH ₃ OH solution using phenolphthalein as an indicator, and the factor (F) of the solution is determined according to the following formula.
F = 0.1 × f × 20 / a
(F = factor of N / 10-hydrochloric acid, a = drop constant (ml))
OHVo (eq / ton) is calculated according to the following formula.
OHVo = {(B−A) × F × 1000 / W} + AVo
(A = titration constant (ml), B = blank titration constant (ml), F = factor of N / 5-NaOH—CH ₃ OH solution, W = weight of sample (g))

3. Method for measuring insoluble content of aluminum compound in water 30 g of aluminum compound is added to 1500 ml of pure water at room temperature stirred at 200 rpm, and stirring is continued at room temperature for 6 hours. Subsequently, the liquid temperature was raised to 95 ° C., and stirring was further continued at the same temperature for 3 hours to dissolve the aluminum compound. The resulting solution was allowed to cool to room temperature, filtered through a cellulose acetate membrane filter having a pore size of 0.2 μm (cellulose acetate type membrane filter manufactured by Advantec, product name: C020A047A), and washed with 50 ml of pure water. The filter obtained by filtering the insoluble matter was dried in a vacuum dryer at 60 ° C. for 12 hours, and the insoluble matter weight (W) was determined. The insoluble content of the aluminum compound in water was calculated by the following formula. When the aluminum compound is an aqueous solution, a part of the aqueous solution is collected, the solid content in the aqueous solution is measured by evaporating the aqueous solution to dryness, and the concentration of the aluminum compound in the aqueous solution is obtained using the solid content as the weight of the aluminum compound. The amount of the aluminum compound in the aqueous solution was determined by filtering the aqueous solution in an amount of 30 g. In the case of the aqueous solution, when the concentration of the aluminum compound in the aqueous solution was higher than 2% by mass, pure water was added to dilute the aluminum so as to be 2% by mass, followed by filtration. The dilution was performed under the same conditions as the dissolution of the solid aluminum compound. The above operation was performed in a clean bench.
Insoluble content (ppm) = [W (mg) / 30000 (mg)] × 10 ⁶

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

5. Color tone Using a polyester resin chip (length: about 3 mm, diameter: about 2 mm), a color difference meter (manufactured by Tokyo Denshoku Co., Ltd .: Model ND-1001DP) was used to measure the L value and b value of the hunter.

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

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

8. Measurement of Tc1 Measurement was performed using DSC50 manufactured by Shimadzu Corporation. 10.0 mg of polyester is put into an aluminum pan, heated from room temperature to 300 ° C. at a heating rate of 20 ° C./min in a nitrogen atmosphere, held for 3 minutes after reaching 300 ° C., and immediately removed from the pan. Quenched in liquid nitrogen. The droplets adhering to the surface were removed by blowing air with an air nozzle. Thereafter, the aluminum pan containing the sample was again heated from 25 ° C. to 300 ° C. at a rate of temperature increase of 20 ° C./min, and the crystallization temperature (Tc1) at the time of temperature increase was determined. The temperature at the maximum part of the exothermic peak was defined as Tc1.

Example 1
(1) Preparation of polycondensation catalyst solution (ethylene glycol solution of phosphorus compound)
After adding 2.0 liters of ethylene glycol to a flask equipped with a nitrogen introduction line and a cooling line at room temperature and normal pressure, stirring with 200 rpm in a nitrogen atmosphere, Irganox 1222 (Ciba 39) represented by -200 g of Specialty Chemicals) was added. Further, 2.0 liters of ethylene glycol was added, the jacket temperature was changed to 196 ° C., the temperature was raised, and the mixture was stirred under reflux for 60 minutes from the time when the internal temperature reached 185 ° C. or higher. Thereafter, the heating was stopped, the solution was immediately removed from the heat source, and the solution was cooled to 120 ° C. or less within 30 minutes while maintaining the nitrogen atmosphere. The mole fraction of Irganox 1222 in the obtained solution was 40%, and the mole fraction of the compound whose structure changed from Irganox 1222 was 60%.
(Aqueous solution of aluminum compound)
After adding 5.0 liters of pure water to a flask equipped with a cooling line at room temperature and normal pressure, 200 g of basic aluminum acetate having an insoluble content in water evaluated by the above evaluation method of 2600 ppm with stirring at 200 rpm was added. It was added as a slurry with pure water. Further, pure water was added so as to be 10.0 liters as a whole, and the mixture was stirred at room temperature and normal pressure for 12 hours. Thereafter, the jacket temperature was changed to 100.5 ° C., the temperature was raised, and the mixture was stirred under reflux for 3 hours from the time when the internal temperature reached 95 ° C. or higher. Stirring was stopped and the mixture was allowed to cool to room temperature.
(Aluminum compound water / ethylene glycol mixed solution)
To the aqueous solution of the aluminum compound, ethylene glycol was added and sufficiently mixed so that the aqueous solution / ethylene glycol = 2/3 (volume ratio) to obtain a water / ethylene glycol mixed solution of the aluminum compound.
(2) Esterification reaction and polycondensation It consists of two continuous esterification reactors and three polycondensation reactors, and a transfer line from the first esterification reactor to the second esterification reactor and the second ester Ethylene glycol 0.39 parts by mass with respect to 1 part by mass of high-purity terephthalic acid in a continuous polyester production apparatus in which an in-line mixer having a high-speed stirrer was installed in the transfer line from the polymerization reactor to the first polycondensation reactor The first esterification tank is supplied at a reaction temperature of 250 ° C. and 100 kPa, the second esterification reactor is at 255 ° C. and 100 kPa, and the reaction is performed in the first and second esterification reactors. The time was adjusted, and ethylene glycol was added to the second esterification reaction tank to obtain a polyester oligomer. The acid value Avo and hydroxyl value OHVo of the oligomer at the outlet of the first esterification reaction tank were 3500 eq / ton and 1000 eq / ton, respectively. In the line mixer installed in the transfer line from the first esterification reaction tank to the second esterification reaction tank, the water / ethylene glycol mixed solution of the aluminum compound becomes 0.021 mol% with respect to the acid component in the polyester. Was added continuously. The acid value Avo and hydroxyl value OHVo of the oligomer at the outlet of the second esterification reaction tank were 740 eq / ton and 1259 eq / ton, respectively. The oligomer is continuously transferred to a continuous polycondensation apparatus consisting of three reactors, and prepared by the above method in an in-line mixer installed in a transfer line from the second esterification reactor to the first polycondensation reactor. The ethylene glycol solution of the phosphorous compound was continuously added so as to be 0.028 mol% as phosphorus atoms with respect to the acid component in the polyester, and the initial polycondensation reactor was 265 ° C., 9 kPa, and the medium-term polycondensation reactor. Was 265-275 ° C., 0.7 kPa, and the final polycondensation reactor was 270-280 ° C., 13.3 Pa to obtain polycondensation PET of IV 0.62. Table 1 shows the characteristic values of the obtained PET.

Comparative Example 1
In the method of Example 1, the addition of a water / ethylene glycol mixed solution of an aluminum compound is prepared by mixing high-purity terephthalic acid and ethylene glycol supplied to the first esterification tank, and continuously added to the slurry. A PET of Comparative Example 1 was obtained in the same manner as in Example 1 except that the change was made. Table 1 shows the characteristic values of the obtained PET.

Comparative Example 2
In the method of Example 1, a PET of Comparative Example 2 was obtained in the same manner as in Example 1 except that the place of addition of the aluminum compound water / ethylene glycol mixed solution and the phosphorus compound ethylene glycol solution was changed. . Table 1 shows the characteristic values of the obtained PET.

Comparative Example 3
PET in Comparative Example 3 was obtained in the same manner as in Example 1 except that the ethylene glycol solution of the phosphorus compound was changed to be continuously added to the second esterification reaction tank in the method of Example 1. Table 1 shows the characteristic values of the obtained PET.

Comparative Example 4
A PET of Comparative Example 3 was obtained in the same manner as in Example 1 except that the ethylene glycol solution of the phosphorus compound was changed to be continuously added to the first esterification reaction tank in the method of Example 1. Table 1 shows the characteristic values of the obtained PET.

Comparative Example 5
In the method of Example 1, except that the water / ethylene glycol mixed solution of the aluminum compound and the ethylene glycol solution of the phosphorus compound were changed to be continuously added to the second esterification reaction tank through separate addition ports, the examples 1 was obtained in the same manner as in Example 1. Table 1 shows the characteristic values of the obtained PET.

Example 2 and Comparative Examples 6-10
(1) Ethylene glycol solution of aluminum compound A flask equipped with a distillation apparatus was charged with 2.0 liters of an aqueous solution of basic aluminum acetate and 2.0 liters of ethylene glycol prepared by the method of Example 1 at normal temperature and pressure, and 200 rpm After stirring for 30 minutes, a uniform water / ethylene glycol mixed solution was obtained. The jacket temperature was then changed to 110 ° C. and the temperature was raised, and water was distilled off from the solution. When the amount of distilled water reached 2.0 liters, the heating was stopped and the mixture was allowed to cool to room temperature to obtain an ethylene glycol solution of an aluminum compound.
(2) Esterification reaction and polycondensation PET was obtained in the same manner as in Example 1 and Comparative Examples 1 to 5, except that the aluminum compound was added in an ethylene glycol solution of the aluminum compound prepared by the above method. Table 2 shows the characteristic values of the obtained PET.

Example 3 and Comparative Example 11
Uniaxially stretched films were obtained from the PET obtained in Examples 1 and 2 and Comparative Examples 1 to 10 by the method described in the above evaluation method. Tables 1 and 2 show the haze values of the obtained uniaxially stretched films.

Example 4 and Comparative Example 12
The PET obtained in Examples 1 and 2 and Comparative Examples 1 to 5 was subjected to solid phase polycondensation by an ordinary method to IV 0.75 dl / g, and dried with a dryer using dehumidified air. A preform was molded at a resin temperature of 295 ° C. using a 150C (DM) injection molding machine. The preform plug portion was heated and crystallized for 90 seconds with a home-made plug portion crystallization apparatus, then biaxially stretch blow-molded using a LB-01E stretch blow molding machine manufactured by Corpoplast, and subsequently about 150 It was heat-set in a mold set at ° C. for about 7 seconds to obtain a 2000 cc hollow molded body (the body was circular). The obtained hollow molded body was filled with hot water at 90 ° C., capped with a capping machine, the container was tilted and allowed to stand, and then leakage of contents was examined. The deformation state of the plug after capping was also examined. Further, a sample was collected from the top surface of the preform plug portion, the density was measured, and the density of the preform plug portion by infrared heating was evaluated. The density was measured at 30 ° C. with a density gradient line of a density deviation calcium nitrate / water mixed solution. Further, the haze of the hollow molded body was measured with a haze meter, model NDH2000 manufactured by Nippon Denshoku Co., Ltd., by cutting a sample from the body (thickness: about 0.45 mm) of the hollow molded body. The evaluation results are shown in Table 3.

The PETs of Examples 1 and 2 have less generation of insoluble foreign matter due to color tone and polycondensation catalyst, and Tc1 is in an appropriate range of 150 to 170 ° C., so that both economy and quality are compatible.
The uniaxially stretched film obtained using the PET obtained in these Examples had a low haze and an excellent transparency. Moreover, a high quality bottle is obtained. On the other hand, PET of Comparative Examples 1, 2, 5, 6, 7 and 10 has a low transparency of the molded product because of many insoluble foreign matters. Moreover, PET of Comparative Examples 2-5 and 7-10 has low Tc1. Therefore, the bottle obtained from the PET of the comparative example is inferior in heat resistance.

  The polyester production method according to the present invention is a polycondensation catalyst in which a metal component other than antimony, germanium and titanium is used as a main metal component in a continuous polycondensation method excellent in economic efficiency, color tone, transparency and thermal stability. Therefore, there is an advantage that both quality and economical efficiency can be achieved since polyester having a low Tc1 temperature range and less foreign matter generation due to the polycondensation catalyst can be obtained. Accordingly, the polyester obtained by the production method of the present invention includes, for example, fibers for clothing and industrial materials, films and sheets for packaging, magnetic tape and optics, bottles that are hollow molded articles, and electrical / electronic components. Can be suitably used in a wide range of fields such as casings and other engineering plastic molded articles. In particular, since the polyester obtained in the present invention has a highly transparent molded body with little foreign matter generation due to the polycondensation catalyst, and Tc1 that greatly affects the crystallization of the polyester is optimized, Since it can be used particularly suitably for fields in which the crystallization characteristics of polyester such as bottle raw materials are regarded as important, it greatly contributes to the industry.

Claims (7)

  In the method for producing a polyester by a continuous polycondensation method in the presence of a polyester polycondensation catalyst comprising at least one selected from aluminum compounds and at least one selected from phosphorus compounds, the aluminum compound has an acid value Avo of 3000 eq. A method for producing a polyester, comprising adding to the oligomer of / ton or more and adding the phosphorus compound after completion of the esterification reaction.   A polyester produced by the production method according to claim 1.   3. The polyester according to claim 2, wherein the amount of aluminum-based foreign matter insoluble in the polyester determined by the method described in the specification is 3500 ppm or less.   The polyester according to claim 2 or 3, wherein the polyester is polyethylene terephthalate.   The polyester according to claim 4, wherein the crystallization temperature of the polyester when heated is 150 ° C. or more.   The hollow molded object which consists of polyester in any one of Claims 2-5.   A film comprising the polyester according to claim 2.