JP2005187557A - Polyester and manufacturing method of polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester which retains color tones, transparency and thermal stability, has a fast polycondensation rate, contains a few foreign matters derived from a polycondensation catalyst and satisfies both qualities and economical efficiency by using a polycondensation catalyst comprising metal components mainly composed of metal components other than antimony, germanium and titanium, a polyester product and a manufacturing method of the polyester. <P>SOLUTION: In the manufacturing method of the polyester in the presence of the polyester polycondensation catalyst comprising at least one selected from the group consisting of aluminum compounds and at least one selected from phosphorous compounds, an aluminum compound whose aqueous solution has an absorbance of at most 0.0132 as measured by a specific method is employed as the aluminum compound. 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 using a novel polyester polycondensation catalyst that does not use germanium or an antimony compound as a catalyst main component. More specifically, the present invention relates to a polyester, polyester product, The present invention relates to a method for producing polyester.

  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, films and sheets for packaging, magnetic tape, optics, bottles that are hollow molded products, casings for electrical and electronic components, and other engineering plastic molded products Has been. 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 precipitated, darkening and foreign matter are generated in the polyester, which causes surface defects of the film. 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

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 aluminum carboxylates 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 5).
JP 2003-82083 A

  The polyester obtained by the polycondensation catalyst system 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.

  The present invention has been made against the background of the problems of the prior art, and maintains color tone, transparency and thermal stability with a polycondensation catalyst having a metal component other than antimony, germanium and titanium as the main metal component, and The present invention provides a polyester, a polyester product, and a method for producing a polyester that have a high polycondensation rate, and that are less likely to produce foreign substances due to a polycondensation catalyst, and that are compatible with quality and economy.

  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 relates to a method for producing a polyester in the presence of a polyester polycondensation catalyst comprising at least one selected from the group consisting of aluminum compounds and at least one selected from phosphorus compounds. A polyester production method using an aluminum compound having an absorbance of an aqueous solution of an aluminum compound to be measured of 0.0132 or less. 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 metal components other than antimony, germanium and titanium are used as the main metal components of the catalyst, maintaining color tone, transparency, thermal stability, etc., and having a high polycondensation rate. Furthermore, there is an advantage that the production of foreign matter due to the polycondensation catalyst is small and both quality and economy can be achieved. 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, electrical / electronic components, etc. Can be suitably used in a wide range of fields such as casings and other engineering plastic molded articles. In particular, the polyester of the present invention has the feature that there is little generation of foreign matter due to the polycondensation catalyst, so it exhibits the feature in the fields of ultrafine fibers, optically transparent films or ultra-highly transparent molded products. 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-phthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalene Dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylsulfonedicarboxylic acid, 4,
4'-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p '
-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 And ester-forming derivatives thereof.

  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.

  The aluminum compound in the present invention is not limited as long as it can be dissolved in water and / or an organic solvent. 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 and basic aluminum acetate and other aluminum acetate structures and aluminum lactate are used. From the viewpoint of solubility in water and catalytic activity.

  Examples of using an aluminum salt of a carboxylic acid as a polyester polycondensation catalyst include aluminum acetate, basic aluminum acetate, aluminum lactate, aluminum benzoate and the like, and these are all soluble in polyester. Therefore, the catalyst activity is inferior, and insoluble foreign matter is generated in the resulting polyester, and there is a problem in using these compounds as a catalyst as they are. As a method for solving this problem, the present inventors can give sufficient catalytic activity by using those previously dissolved in water and / or an organic solvent as a catalyst. Yes. The present invention is based on the technique disclosed in Patent Document 5. That is, the polyester obtained by this technique has good color tone, transparency and thermal stability, and is highly practical as a polycondensation catalyst having a metal component other than antimony, germanium and titanium as the main metal component of the catalyst. Is. 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. The present invention has been accomplished through earnest studies on the establishment of a technique for suppressing the fluctuation of the content of fine foreign matter insoluble in polyester, and satisfies the demand.

That is, the present invention is greatly characterized in that an aluminum compound having an absorbance of 0.0132 or less of an aqueous solution of an aluminum compound measured by the following method is used as the aluminum compound. In addition, the measuring method of the light absorbency of the aqueous solution of the aluminum compound in this invention is the following method.
[Absorbance measurement method of aluminum compound aqueous solution]
The aluminum compound is dissolved in pure water at a concentration of 2.7 g / l in terms of the amount of aluminum element, and the absorbance is measured at a wavelength of 680 nm. The dissolution is performed by stirring at room temperature for 6 hours, raising the internal temperature to 95 ° C., and stirring for another 3 hours. The absorbance is measured using a quartz cell having a cell length of 1 cm and pure water as a control solution.

  The absorbance is preferably 0.0088 or less, more preferably 0.0044 or less, and further preferably 0.022 or less. An absorbance of 0 is most preferred. When the absorbance exceeds 0.0132, the content of foreign matters insoluble in polyester increases, and for example, when molded as a molded body such as a film or a bottle, the haze of the molded body deteriorates. 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 absorbance of the aluminum compound aqueous solution is a measure for evaluating the amount of insoluble components in a very small amount of water contained in the aluminum compound. By setting the absorbance within the range of the present invention, the generation of the insoluble foreign matter content in the polyester is suppressed because the insoluble matter in the form of fine particles, which is an insoluble component in a very small amount of water, contained in the aluminum compound itself. Alternatively, it is presumed that the insoluble matter becomes the nucleus and is caused by the generation of insoluble foreign matter in the polyester due to transformation or aggregation into a foreign matter insoluble in the polyester in the polyester polycondensation step. .

  In the present invention, the method for adjusting the absorbance of the aqueous aluminum compound solution to 0.0132 or less is not limited, but it is preferable to select a carboxylic acid aluminum salt compound that is soluble in high-purity water. In addition, when it is difficult to obtain a high-purity product, an aluminum compound may be used as an aqueous solution after removing components insoluble in water by filtration, centrifugation, or ultracentrifugation.

  The aluminum compound of the present invention is preferably added to the polycondensation system in a state of being previously dissolved in water and / or an organic solvent before being added to the polyester polycondensation system. As the organic solvent, it is preferable to use glycols, and when manufacturing PET, it is preferable to use ethylene glycol.

  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. In addition, 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 formation of insoluble foreign matter in the obtained polyester is particularly suppressed.

  When an aluminum compound is dissolved in water and / or an organic solvent, or by adding a stabilizer such as boric acid or an acid such as citric acid, lactic acid, or succinic acid to the dissolved solution, the solubility and the stability of the solution are increased. Therefore, it is a preferred embodiment to use the compound in combination.

  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. In this method, it is preferable to carry out using a method in which the basic aluminum acetate satisfying the absorbance within the range of the present invention is evaluated in advance according to the absorbance measurement method of the aqueous aluminum compound solution. On the other hand, the aqueous solution dissolved by this method was purified by removing components insoluble in water by filtration or ultracentrifugation, etc., and a part of the purified solution was sampled and obtained by drying by freeze drying method The solid content may be redissolved in pure water and the absorbance may be measured to confirm that the absorbance is within the scope of the present invention.

  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.

  Below, the specific example of the preparation method of the ethylene glycol solution 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. Absorbance is evaluated in accordance with the above-described method for preparing a basic aluminum acetate solution.

  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.

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 improving the physical properties improving effect of the polyester by containing these phosphorus compounds, the catalytic activity is improved by using these phosphorus compounds in combination with the aluminum compound of the present invention during the polycondensation of the polyester. Is seen greatly.
The phosphorus compound having at least one P—OH bond is not particularly limited as long as it is a phosphorus compound having at least one P—OH in the molecule. Among these phosphorus compounds, 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 this invention has a large molecular weight, since it is hard to be distilled off at the time of polycondensation, an effect is large and preferable.

  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 the polyester by containing a phosphorus compound having a phenol moiety in the same molecule, the catalytic activity is enhanced by using a phosphorus compound having a phenol moiety in the same molecule during polycondensation of the polyester. Greater effect and therefore better polyester productivity.

  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, as described in claim 2, it is preferable that the phosphorus compound is preheated in at least one solvent selected from the group consisting of water and alkylene glycol. is there. The treatment improves the polycondensation catalyst activity by using the above-mentioned phosphorus compound in combination with the above-mentioned aluminum or aluminum compound, and decreases the foreign matter forming property due to the polycondensation catalyst.

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

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

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

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

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

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

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

  The production of the polyester according to the present invention can be carried out by a method having a conventionally known process except that the polyester polycondensation catalyst of the present invention is used as a catalyst. For example, when manufacturing PET, direct esterification is performed by directly reacting terephthalic acid with ethylene glycol and if necessary other copolycondensation components to distill off water and esterify, then polycondensation under reduced pressure. Or by transesterification by reacting dimethyl terephthalate with ethylene glycol and other copolycondensation components as necessary to distill off methyl alcohol and transesterify, followed by polycondensation under reduced pressure. Manufactured. Further, solid phase polycondensation may be performed as necessary to increase the intrinsic viscosity. In order to promote crystallization before solid-phase polycondensation, the molten polycondensed polyester may be subjected to heat crystallization after moisture absorption, or water vapor may be directly sprayed onto the polyester chip for heat crystallization.

  The melt polycondensation reaction may be performed in a batch reactor or may be performed in a continuous reactor. In any of these methods, the esterification reaction or the transesterification reaction may be performed in one stage, or may be performed in multiple stages. The melt polycondensation reaction may be performed in one stage or may be performed in multiple stages. The solid phase polycondensation reaction can be performed by a batch type apparatus or a continuous type apparatus as in the case of the melt polycondensation reaction. Melt polycondensation and solid phase polycondensation may be carried out continuously or separately.

  The catalyst of the present invention has catalytic activity not only for polycondensation but also for esterification and transesterification. For example, polycondensation by transesterification of an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate with a glycol such as ethylene glycol is usually carried out in the presence of a transesterification catalyst such as a titanium compound or a zinc compound. The catalyst of the present invention can be used instead of or in the presence of these catalysts. The catalyst of the present invention has catalytic activity not only in melt polycondensation but also in solid phase polycondensation and solution polycondensation, and polyester can be produced by any method.

  The catalyst of the present invention may be added to the reaction system at any stage of the polycondensation reaction, for example, before the start of the esterification reaction or transesterification reaction, at any stage during the reaction, or immediately before or during the start of the polycondensation reaction. However, it is preferably added immediately before the start of the polycondensation reaction.

  The catalyst solution of the aluminum compound of the present invention and other compounds may be added as a premixed mixture, or these may be added separately. Moreover, the catalyst solution of the aluminum compound of the present invention and other compounds may be added to the polycondensation system at the same addition time, and the respective components may be added at different addition times. Further, the entire amount of the catalyst may be added at once, or may be added in a plurality of times.

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

  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. Also contains other optional polycondensates, antistatic agents, antifoaming agents, dyeability improvers, dyes, pigments, matting agents, fluorescent brighteners, stabilizers, antioxidants, and other additives. May be. As antioxidants, aromatic amine-based and phenol-based antioxidants can be used, and as stabilizers, phosphoric acid and phosphate ester-based phosphorus-based, sulfur-based, amine-based stabilizers, etc. Can be used.

  These additives can be added at any stage of polycondensation or after polycondensation of the polyester, or at the time of molding of the polyester. Which stage is suitable depends on the structure of the target polyester and the resulting polyester. Each may be selected as appropriate according to the required performance.

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.
[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. 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 tube 4.0 kW). Quantification was performed on a 30 mm diameter portion 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.

  In the present invention, the amount of aluminum 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.

  The polyester polycondensed using the polyester polycondensation catalyst of the present invention can be used for an oriented polyester film. 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, for photographic negative film, for retardation film, for polarizing film, for polarizing film protection (TAC), for protective film, for photosensitive resin film, for field-of-view film, for diffusion sheet, for reflective film, and for reflection For prevention film, conductive film, separator, UV protection, 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 a 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. Method for Measuring Absorbance of Aluminum Compound Aqueous Solution Aluminum carboxylate was dissolved in pure water so as to have a concentration of 2.7 g / l of aluminum element, and the absorbance was measured at a wavelength of 680 nm. Dissolution is carried out at room temperature for 6 hours using a 1.5 L flask (200 rpm), takes 30 minutes, raises the internal temperature to 95 ° C., and then adjusts the internal temperature to 95 ± 1 ° C. for 3 hours. This was done by stirring. The absorbance was measured by allowing the aqueous solution to cool to room temperature, using a quartz cell with a cell length of 1 cm, and using pure water as a control solution. As a measuring device, a double beam spectrophotometer (manufactured by Shimadzu Corporation; UV-210A) was used.

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

3. 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.

4. Evaluation method for aluminum-based foreign substances insoluble in polyester 30 g of polyester pellets after melt polycondensation and 300 ml of parachlorophenol / tetrachloroethane (3/1: weight ratio) mixed solution are put into a round bottom flask equipped with a stirrer, It stirred and melt | dissolved in the mixed solution at 100-105 degreeC for 2 hours. The solution was allowed to cool to room temperature, and a polytetrafluoroethylene membrane filter (Advantec PTFE membrane filter, product name: T100A047A) having a diameter of 47 mm / 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 using a scanning X-ray fluorescence analyzer (manufactured by RIGAKU, ZSX100e, Rh tube 4.0 kW). Quantification was performed on a 30 mm diameter portion at the center of the membrane filter. The calibration curve of the X-ray fluorescence analysis was determined using a PET 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 polyethylene terephthalate resin for the calibration curve was quantified by high frequency inductively coupled plasma emission spectrometry.
5. 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.

Example 1
(1) Preparation of polycondensation catalyst solution (Preparation of ethylene glycol solution of phosphorus compound)
After adding 2.0 liters of ethylene glycol to a flask equipped with a nitrogen introduction tube and a cooling tube under normal temperature and normal pressure, the mixture was stirred at 200 rpm in a nitrogen atmosphere, and Irganox 1222 (Ciba -200 g of Specialty Chemicals) was added. Further, 2.0 liters of ethylene glycol was added, the jacket temperature was changed to 196 ° C., and the temperature was raised. Thereafter, the heating was stopped, the solution was immediately removed from the heat source, and the solution was cooled to 120 ° C. or less within 30 minutes while maintaining the nitrogen atmosphere. The mole fraction of Irganox 1222 in the obtained solution was 40%, and the mole fraction of the compound whose structure changed from Irganox 1222 was 60%.
(Preparation of aqueous solution of aluminum compound)
After adding 5.0 liters of pure water to a flask equipped with a condenser under normal temperature and normal pressure, the basic aluminum acetate (hydroxyaluminum diacetate) having an absorbance of 0.0047 evaluated by the above evaluation method while stirring at 200 rpm. ) 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 to obtain an aqueous solution.
(Preparation of water / ethylene glycol mixed solution of aluminum compound)
Ethylene glycol was added to the aqueous solution of the aluminum compound 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.

(Polycondensation of polyester)
For a mixture of bis (2-hydroxyethyl) terephthalate and oligomer produced from high-purity terephthalic acid and its 2-fold molar amount of ethylene glycol according to a conventional method, water / An ethylene glycol mixed solution and an ethylene glycol solution of a phosphorus compound are added from separate feed ports so that the acid component in the polyester is 0.021 mol% as aluminum atoms and 0.028 mol% as phosphorus atoms, and nitrogen is added. The mixture was stirred at 245 ° C. for 15 minutes under atmospheric pressure. Subsequently, the temperature of the reaction system was gradually lowered while raising the temperature to 275 ° C. over 55 minutes, and the polycondensation reaction was further performed at 275 ° C. and 66.5 Pa for 130 minutes at 66.5 Pa (0.5 Torr). The properties of the obtained PET are shown in Table 1.

Comparative Example 1
In the method of Example 1, the PET of Comparative Example 1 was prepared in the same manner as in Example 1 except that the absorbance evaluated by the above evaluation method was changed to 0.0155 as basic aluminum acetate (hydroxyaluminum diacetate). Got. The properties of the obtained PET are shown in Table 1.

Example 2
The aqueous solution of the aluminum compound prepared in Comparative Example 1 was subjected to ultracentrifugation at 500,000 × g for 1.5 hours to obtain an aqueous solution of purified basic aluminum acetate (hydroxyaluminum diacetate) from which water-insoluble components had been removed. A portion of the purified solution was sampled and dried by freeze drying to obtain purified basic aluminum acetate (hydroxyaluminum diacetate). The absorbance of the obtained purified basic aluminum acetate (hydroxyaluminum diacetate) evaluated by the above evaluation method was 0.0022. PET of Example 2 was obtained in the same manner as in Example 1 except that the above-described purified basic aluminum acetate (hydroxyaluminum diacetate) aqueous solution was used as the aqueous solution of the aluminum compound. The properties of the obtained PET are shown in Table 1.

Example 3
(Preparation of ethylene glycol solution of aluminum lactate)
An aqueous solution of about 67 g / l of aluminum lactate was prepared at room temperature. The obtained aluminum lactate aqueous solution was diluted with pure water, and the absorbance evaluated by the above evaluation method was 0.0177. The aqueous solution was ultracentrifugated at 500,000 Xg for 1.5 hours to obtain an aqueous solution of purified aluminum lactate from which water-insoluble components had been removed. A portion of the purified solution was sampled and dried by freeze drying to obtain purified aluminum lactate. The absorbance of the obtained purified basic aluminum acetate evaluated by the above evaluation method was 0.0017. Thereafter, ethylene glycol was added to the aqueous solution of the purified aluminum lactate, and the water was distilled off by heating at about 100 ° C. to obtain an ethylene glycol solution of about 29 g / l.
(Polycondensation of polyester)
PET of Example 3 was obtained in the same manner as in Example 1 except that the ethylene glycol solution of the purified aluminum lactate was used as the aluminum compound. The properties of the obtained PET are shown in Table 2.

Comparative Example 2
In Example 3, the same method as in Example 3 except that an aluminum glycol ethylene glycol solution obtained in the same manner as in Example 3 was used using an unpurified aqueous solution of aluminum lactate before ultracentrifugation as the aluminum compound. Thus, PET of Comparative Example 2 was obtained. The properties of the obtained PET are shown in Table 2.

Examples 4 to 6 and Comparative Examples 3 and 4
Uniaxially stretched films were obtained from the PET obtained in Examples 1 to 3 and Comparative Examples 1 and 2 by the method described in the above evaluation method. Tables 1 and 2 show the haze values of the obtained uniaxially stretched films.

  In the PET production methods of Examples 1 to 3, the activity of the polycondensation catalyst is high, and the production of foreign matters due to the polycondensation catalyst is small, so that both economy and quality are compatible. The PETs of Comparative Examples 1 and 2 are inferior in quality due to many foreign matters resulting from the polycondensation catalyst. The uniaxially stretched films obtained using the polyesters of these examples had low haze and excellent transparency. On the other hand, the uniaxially stretched film obtained using the PET of Comparative Examples 1 and 2 had high haze and poor transparency. Therefore, the PET obtained in Examples 1 to 3 was a high-quality molded product with a high transparency.

  The polyester production method according to the present invention is a polycondensation catalyst in which metal components other than antimony, germanium and titanium are used as the main metal components of the catalyst, maintaining color tone, transparency, thermal stability, etc., and having a high polycondensation rate. Furthermore, there is an advantage that the production of foreign matter due to the polycondensation catalyst is small and both quality and economy can be achieved. 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, electrical / electronic components, etc. Can be suitably used in a wide range of fields such as casings and other engineering plastic molded articles. In particular, the polyester of the present invention has the feature that there is little generation of foreign matter due to the polycondensation catalyst, so it exhibits the feature in the fields of ultrafine fibers, optically transparent films or ultra-highly transparent molded products. It is important to contribute to the industry.

Claims (5)

  In a method for producing a polyester in the presence of a polyester polycondensation catalyst comprising at least one selected from the group consisting of aluminum compounds and at least one selected from phosphorus compounds, measurement is performed by the method described in the specification as an aluminum compound. The manufacturing method of polyester characterized by using the aluminum compound whose absorbance of the aqueous solution of the aluminum compound made is 0.0132 or less.   A polyester produced by the production method according to claim 1.   A hollow molded body made of the polyester according to claim 2.   A fiber comprising the polyester according to claim 2.   A film comprising the polyester according to claim 2.