JP2005325164A - Polyester polymerization catalyst and polyester manufactured using the same, and manufacturing method of polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester polymerization catalyst exhibiting excellent catalytic activities and providing a polyester which is excellent in color tones and thermal stability, gives a molded article excellent in transparency and, in particular, contains a few foreign matters, a polyester manufactured using the same and a manufacturing method of the polyester. <P>SOLUTION: The polyester polymerization catalyst comprises at least one selected from the group consisting of aluminum and its compounds and at least one selected from among phosphorous compounds, and is obtained by preparing an alkylene glycol solution or a slurry of each component and compounding them. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyester polymerization catalyst, a polyester produced using the same, and a method for producing the polyester. More specifically, the present invention is excellent in catalytic activity, excellent in color tone, thermal stability and transparency, and particularly improved in terms of foreign matter. The present invention relates to a polyester polymerization catalyst for providing a polyester, a polyester produced using the same, and a method for producing the 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, It is used in a wide range of fields such as textiles for clothing and industrial materials, films and sheets for packaging and magnetic tape, bottles that are hollow molded products, casings for electrical and electronic parts, and other engineering plastic molded products. . In particular, bottles made of saturated polyesters such as polyethylene terephthalate are excellent in mechanical strength, heat resistance, transparency and gas barrier properties, so containers for filling beverages such as juices, carbonated drinks and soft drinks, and containers for eye drops, cosmetics, etc. As widely used.

  For example, in the case of polyethylene terephthalate (PET), a polyester mainly composed of aromatic dicarboxylic acid and alkylene glycol, which is a typical polyester, is an esterification reaction or transesterification of terephthalic acid or dimethyl terephthalate and ethylene glycol. An oligomer mixture such as bis (2-hydroxyethyl) terephthalate is produced by reaction, and this is subjected to liquid phase polycondensation using a catalyst at high temperature and under vacuum, and after granulation, solid phase polycondensation is performed to produce pellets for molding. The The polyester pellets thus manufactured are manufactured by injection molding to produce a preform, and then the preform is blow-molded, biaxially stretched, and molded into a bottle shape.

  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 polymerization rate, metal antimony is used during polycondensation. As a result of precipitation, 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, Since it is easy to distill out of the reaction system from the reaction system during the polymerization, there is a problem that the catalyst concentration in the reaction system changes and it becomes difficult to control the polymerization.

  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.

  Although it is known that an aluminum compound is generally inferior in catalytic activity (see, for example, Patent Document 1), it is known that the catalytic activity of an aluminum compound is improved by using a phosphorus compound in combination with the aluminum compound ( For example, see Patent Document 2.) When the catalyst is used, a polyester excellent in color tone and thermal stability can be obtained, but there still remains a problem that the transparency of the molded article or the problem of foreign matters is insufficient.

Japanese Patent Publication No. 46-40711 (page 1-2) JP 2001-131276 (page 3-4)

  With the above circumstances, it is a polymerization catalyst that uses metal components other than antimony, germanium, and titanium as the main metal component of the catalyst, and has excellent catalytic activity, excellent color tone and thermal stability, and excellent transparency of molded products. In particular, there is a demand for a polymerization catalyst that gives a polyester with less foreign matter.

The object of the present invention is to contain the above-mentioned disadvantageous antimony compound, germanium compound and titanium compound as the main component of the catalyst, use an aluminum compound as the catalyst metal component, and have excellent catalytic activity, excellent color tone and thermal stability. Another object of the present invention is to provide a polyester polymerization catalyst that gives a polyester excellent in transparency of a molded article and has particularly few foreign matters, a polyester produced using the same, and a method for producing the polyester.

As a result of intensive studies aimed at solving the above-mentioned problems, the authors of the present invention have found that an alkylene glycol of a phosphorus compound in a ³¹ P-NMR spectrum of the mixture comprising an alkylene glycol solution of an aluminum compound and an alkylene glycol solution of a phosphorus compound. In the ²⁷ Al-NMR spectrum of the mixture comprising a polymerization catalyst in which the peak position is chemically shifted with respect to the peak of the solution alone and / or an alkylene glycol solution of an aluminum compound and an alkylene glycol solution of a phosphorus compound, an aluminum compound The present inventors found that a polymerization catalyst obtained by chemically shifting the peak position with respect to the peak of the alkylene glycol solution alone was effective in reducing foreign matter.

  That is, the present invention is a polyester polymerization catalyst comprising at least one selected from the group consisting of an aluminum compound and at least one selected from a phosphorus compound as a solution to the above-mentioned problem, wherein the aluminum compound and the phosphorus compound are previously contained in a solvent. A polyester polymerization catalyst, a polyester produced using the same, and a method for producing the polyester, comprising mixing the solution and / or slurry of the obtained aluminum compound and the phosphorus compound after heat treatment with provide.

ADVANTAGE OF THE INVENTION According to this invention, the polyester polymerization catalyst which is excellent in catalyst activity, is excellent in the transparency of a molded article, and gives especially polyester with few foreign materials, the polyester manufactured using this, and the manufacturing method of polyester are provided.

As the aluminum compound constituting the polymerization catalyst of the present invention, known aluminum compounds can be used without limitation.
Specific examples of aluminum compounds include aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, Carboxylates such as aluminum tartrate and aluminum salicylate, inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate and aluminum phosphonate, aluminum methoxide, aluminum Etoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxa Id, aluminum alkoxide such as aluminum t-butoxide, aluminum acetylacetonate, aluminum acetyl acetate, aluminum ethyl acetoacetate, aluminum ethyl acetoacetate diiso-propoxide, and other organic chelate compounds; And their partial hydrolysates, reaction products comprising aluminum alkoxides and aluminum chelate compounds and hydroxycarboxylic acids, aluminum oxide, ultrafine aluminum oxide, aluminum silicate, aluminum and titanium, silicon, zirconium, alkali metals and alkaline earths Examples thereof include complex oxides with metals. Of these, carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

  Among these aluminum compounds, aluminum acetate, aluminum chloride, aluminum hydroxide, and aluminum hydroxide chloride having a high aluminum content are preferable. From the viewpoint of solubility, aluminum acetate, basic aluminum acetate, aluminum chloride, and aluminum hydroxide chloride are preferable. preferable. Furthermore, the use of aluminum acetate or basic aluminum acetate is particularly preferred from the viewpoint of not corroding the device.

Here, aluminum hydroxide chloride is a general term for what is generally called polyaluminum chloride or basic aluminum chloride, and those used for water supply can be used. These are represented by, for example, the general structural formula [Al ₂ (OH) _n Cl _6-n ] _m (where 1 ≦ n ≦ 5). Among these, those having a low chlorine content are preferable from the viewpoint of not corroding the device.

  The above-mentioned aluminum acetate is a general term for those having a structure of an aluminum salt of acetic acid represented by basic aluminum acetate, aluminum triacetate, aluminum acetate solution, etc. Among these, from the viewpoint of solubility and solution stability The use of basic aluminum acetate is preferred. Of the basic aluminum acetates, aluminum monoacetate, aluminum diacetate, or those stabilized with boric acid are preferred. When using the one stabilized with boric acid, it is preferable to use one stabilized with boric acid in an amount of equimolar or less with respect to basic aluminum acetate, and in particular, 1/2 to 1/3 molar amount. The use of basic aluminum acetate stabilized with boric acid is preferred. Examples of basic aluminum acetate stabilizers include urea and thiourea in addition to boric acid. Any of the above basic aluminum acetates solubilized in a solvent such as water or glycol, particularly those solubilized in water and / or ethylene glycol are preferably used from the viewpoint of catalytic activity and the quality of the resulting polyester.

  Solvents that can be used in the present invention are water and alkylene glycols. Examples of alkylene glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylene glycol, ditrimethylene glycol, tetramethylene glycol, ditetramethylene glycol, neopentyl glycol, and the like. . Preferably, they are ethylene glycol, trimethylene glycol, tetramethylene glycol, more preferably ethylene glycol.

Below, the specific example of the preparation method of a basic aluminum acetate solution is shown.
(1) Preparation example of aqueous solution of basic aluminum acetate Water is added to basic aluminum acetate and stirred at room temperature for several hours or more. 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 10 g / l to 30 g / l, particularly preferably 15 g / l to 20 g / l. In order to exert a foreign matter reducing effect, it is necessary to confirm a chemical shift in ²⁷ Al-NMR spectrum measurement in the state of the aqueous solution of the aluminum compound. For example, heating at 90 ° C. or more for a long time is an unfavorable aspect that causes the chemical shift to disappear.
(2) Preparation Example of Ethylene Glycol Solution of Basic Aluminum Acetate Ethylene glycol is added 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. More preferably, heating is performed under reduced pressure and / or an inert gas atmosphere such as nitrogen or argon, and water is distilled off to prepare a catalyst solution or slurry.

  It is preferable to use the basic aluminum acetate solubilized in a solvent such as water or glycol, particularly those solubilized in water and / or ethylene glycol, from the viewpoint of catalytic activity and reduction of foreign matters in the resulting polyester.

  Below, the specific example of the preparation method of the ethylene glycol solution of basic aluminum acetate is shown. Preparation of an aqueous solution of basic aluminum acetate 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.

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

  The solvent used when the phosphorus compound constituting the polyester polymerization catalyst of the present invention is preliminarily heat-treated is preferably at least one selected from the group consisting of water and alkylene glycol, and a solvent that dissolves the phosphorus compound is used. It is preferable. 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. Moreover, it is not necessary for the compound to retain the original structure after the heat treatment.

(Method for preparing phosphorus compound)
The preheating treatment of the phosphorus compound alkylene glycol solution or slurry is an important step in order to easily form a complex between the aluminum compound and the phosphorus compound by being mixed with the alkylene glycol solution or slurry of the aluminum compound in a subsequent step. That is, the phosphorus compound can obtain at least one hydroxyl group capable of forming a complex in one molecule by heat treatment. The hydroxyl group here is an OH group, a hydroxylalkyl group or the like contained in the molecule of the phosphorus compound. Specifically, a phosphorus compound having two alkoxy groups in its molecule such as phosphonic acid is introduced with a hydroxyl group in the form of dealkoxylation or hydroxyethylation by, for example, heat treatment in ethylene glycol. In particular, the introduction of hydroxyethylation leads to an increase in the molecular weight of the phosphorus compound, which is a preferred embodiment for complex formation with an aluminum compound effective for reducing foreign matter in addition to reducing scattering during polymerization of the phosphorus compound. 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.

  It is possible to obtain a solution or slurry polymerization catalyst by stirring and mixing an ethylene glycol solution or slurry of an aluminum compound and an ethylene glycol solution or slurry of the phosphorus compound. Furthermore, you may heat-process the said solution or slurry. The solution or slurry obtained by these operations can be used as the polymerization catalyst of the present invention.

The ethylene glycol solution or slurry of the above aluminum compound and the ethylene glycol solution or slurry of the above phosphorus compound are stirred and mixed, and the solution-like or slurry-like polymerization catalyst is measured by ³¹ P-NMR spectrum measurement and / or ²⁷ Al-NMR. In the spectrum measurement, a chemical shift is recognized in the mixed catalyst system with respect to the peak positions of the phosphorus compound and the aluminum compound alone as the respective standard substances.

Below, the phosphorus compound which comprises the polymerization catalyst of this invention is illustrated. Although not particularly limited, phosphoric acid and phosphoric acid esters such as trimethyl phosphoric acid, triethyl phosphoric acid, phenyl phosphoric acid, triphenyl phosphoric acid, phosphorous acid and trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tris ( And phosphites such as 2,4-di-tert-butylphenyl) phosphite and tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylenediphosphite.
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, in the present invention, a metal salt compound of phosphorus is particularly preferable as the phosphorus compound. The phosphorus metal salt compound is not particularly limited as long as it is a metal salt of a phosphorus compound. However, when a metal salt of a phosphonic acid compound is used, the physical properties improving effect and catalytic activity improving effect of the polyester, which are the problems of the present invention, are improved. Largely preferred. Examples of the metal salt of the phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.

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

  As the phosphorus metal salt compound of the present invention, it is preferable to use at least one selected from the compounds represented by the following general formula (Chemical Formula 16) 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 (l + m And n represents an integer greater than or equal to 1. 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 contains an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl. May be good.)

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

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

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

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

Among the phosphorus compounds described above, in the present invention, a phosphorus compound having at least one P—OH bond is particularly preferable as the phosphorus compound. In addition to particularly enhancing the physical properties improving effect of the polyester by containing these phosphorus compounds, the catalytic activity is improved by using these phosphorus compounds in combination with the aluminum compound of the present invention at the time of polymerization of the polyester. Seen large.
The phosphorus compound having at least one P—OH bond is not particularly limited as long as it is a phosphorus compound having at least one P—OH in the molecule. Among these phosphorus compounds, use of a phosphonic acid compound having at least one P—OH bond is preferable 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 (Formula 19) is a compound containing an aromatic ring structure.

  Specific examples of these phosphorus compounds are shown below.

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

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

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

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

(In the formulas (Chemical Formula 26) to (Chemical Formula 28), R ¹ is a carbon having 1 to 50 carbon atoms including a phenol part, a substituent such as a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a phenol part. 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, R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and the like. 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. May be good.)

  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 represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m represents M is an (l + m) -valent metal cation, n is an integer of 1 or more, and the hydrocarbon group is an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl. May be included.)

  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 [ethyl 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- Butyl-4-hydroxybenzylphosphonate methyl], strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], barium bis [3,5-di-tert-butyl] Phenyl-4-hydroxybenzylphosphonate], manganese bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], nickel bis [3,5-di-tert-butyl-4-hydroxybenzyl] Ethyl phosphonate], copper bis [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], zinc bis [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] and the like. Can be mentioned. Among these, lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [ Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

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

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

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

(In 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 selected from the compounds represented by the following General Formula (Chemical Formula 38) because the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are high.

(In the above formula (Chemical Formula 38), R ³ and R ⁴ each independently 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). Chemicals) is commercially available and can be used.

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

The amount of P compound used The amount of the phosphorus compound used in the production of the polyester according to the method of the present invention is 0.0001 to 0.1 mol relative to the number of moles of all the structural units of the polycarboxylic acid component of the obtained polyester. % Is preferable, and 0.005 to 0.05 mol% is more preferable.

  By using the phosphorus compound of the present invention in combination, a catalyst exhibiting a sufficient catalytic effect can be obtained even when the amount of addition as aluminum in the polyester polymerization catalyst is small. When the addition amount of the phosphorus compound is less than 0.0001 mol%, the addition effect may not be exhibited, and when added over 0.1 mol%, the catalytic activity as a polyester polymerization catalyst may be reduced. There is a tendency of the change depending on the amount of aluminum used.

In the ³¹ P-NMR spectrum of the mixture comprising an alkylene glycol solution of an aluminum compound and an alkylene glycol solution of a phosphorus compound, the polymerization catalyst that can be used in the present invention is at a peak position relative to the peak of the alkylene glycol solution of the phosphorus compound alone. In the ²⁷ Al-NMR spectrum of the mixture consisting of an alkylene glycol solution of an aluminum compound and an alkylene glycol solution of a phosphorus compound, a chemical shift is observed, and a peak relative to the peak of the aluminum glycol solution of the aluminum compound alone It is required that a chemical shift of the position be observed.

  The polymerization catalyst of the present invention preferably contains no alkali metal, alkaline earth metal, or these compounds.

  On the other hand, in the present invention, it is preferable that at least one selected from a small amount of an alkali metal, an alkaline earth metal, and the compound in addition to aluminum or a compound thereof coexists as the second metal-containing component. The coexistence of such a second metal-containing component in the catalyst system is effective in improving productivity by obtaining a catalyst component having an increased reaction rate in addition to an effect of suppressing the formation of diethylene glycol, and thus a higher reaction rate. .

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

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

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

  Among these alkali metals, alkaline earth metals or their compounds, when using strongly alkaline ones such as hydroxides, these tend to be difficult to dissolve in diols such as ethylene glycol or organic solvents such as alcohols. However, it must be added to the polymerization system in an aqueous solution, which may cause a problem in the polymerization process. Furthermore, when a strongly alkaline material such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during the polymerization, and the polymerized polyester tends to be colored, and the hydrolysis resistance also decreases. Tend to. Accordingly, the alkali metal or their compounds or alkaline earth metals or their compounds suitable for the present invention are preferably saturated aliphatic carboxylates, unsaturated aliphatic carboxylates, aromatics of alkali metals or alkaline earth metals. Aromatic carboxylates, halogen-containing carboxylates, hydroxycarboxylates, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromic acid Selected inorganic acid salts, organic sulfonates, organic sulfates, chelate compounds, and oxides. Among these, from the 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 products such as polyester characteristics, processability, and color tone as described above. Coexistence within the range of the addition amount is effective and preferable in improving productivity by shortening the polymerization time.

  The antimony compound is preferably added in an amount of 50 ppm or less as an antimony atom to the polyester obtained by polymerization. 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 polymerization. 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 to the polyester obtained by polymerization. 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.

  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 polymerization catalyst of the present invention is used as a catalyst. For example, when producing PET, a direct esterification method in which terephthalic acid is directly reacted with ethylene glycol and, if necessary, other copolymerization components to distill off water and esterify, followed by polycondensation under reduced pressure. Alternatively, it is produced by a transesterification method in which dimethyl terephthalate is reacted with ethylene glycol and other copolymerization components as required to distill off methyl alcohol and transesterify, followed by polycondensation under reduced pressure. The Further, solid phase polymerization may be performed as necessary to increase the intrinsic viscosity. In order to promote crystallization before solid phase polymerization, the melt-polymerized polyester may be subjected to heat crystallization after moisture absorption, or may be heated and crystallized by spraying water vapor directly onto a polyester chip.

  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 polymerization reaction can be carried out by a batch type apparatus or a continuous type apparatus as in the melt polycondensation reaction. Melt polycondensation and solid phase polymerization may be carried out continuously or separately. Below, an example of the preferable manufacturing method by a continuous system is demonstrated taking PET as an example.

  First, a case where a low polymer is produced by an esterification reaction will be described. A slurry containing 1.02 to 1.5 mol, preferably 1.03 to 1.4 mol, of ethylene glycol is prepared per 1 mol of terephthalic acid or its ester derivative, and this is esterified. Supply continuously to the process.

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

  When terephthalic acid is used as a raw material, the esterification reaction can be carried out without a catalyst by the catalytic action of terephthalic acid as an acid, but may be carried out in the presence of a polycondensation catalyst.

  Also, tertiary amines such as triethylamine, tri-n-butylamine, benzyldimethylamine, quaternary ammonium hydroxides such as tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide, and lithium carbonate When a small amount of a basic compound such as sodium carbonate, potassium carbonate or sodium acetate is added, the proportion of dioxyethylene terephthalate component units in the main chain of polyethylene terephthalate is relatively low (total 5 mol% or less) with respect to the diol component.

Next, when a low polymer is produced by a transesterification reaction, 1.1 to 1.6 mol, preferably 1.2 to 1.5 mol of ethylene glycol is contained per 1 mol of dimethyl terephthalate. The prepared solution is prepared and continuously fed to the transesterification step.

In the transesterification reaction, methanol produced by the reaction is removed from the system by a rectification column under the condition that ethylene glycol is distilled back using an apparatus in which one or two transesterification reactors are connected in series. Perform while removing. The temperature of the first stage transesterification is 180 to 250 ° C, preferably 200 to 240 ° C. The temperature of the transesterification reaction in the final stage is usually 230 to 270 ° C., preferably 240 to 265 ° C., and as the transesterification catalyst, fatty acid salts such as Zn, Cd, Mg, Mn, Co, Ca, Ba, carbonates Alternatively, Pb, Zn, Sb, Ge oxide or the like is used. A low-order condensate having a molecular weight of about 200 to 500 is obtained by these transesterification reactions.

Subsequently, the obtained low-order condensate is supplied to a multistage liquid phase condensation polymerization process. The polycondensation reaction conditions are as follows: the first stage polycondensation reaction temperature is 250 to 290 ° C., preferably 260 to 280 ° C., and the pressure is 500 to 20 Torr, preferably 200 to 30 Torr. The temperature is 265 to 300 ° C., preferably 275 to 295 ° C., and the pressure is 10 to 0.1 Torr, preferably 5 to 0.5 Torr. When carried out in three or more stages, the reaction conditions for the intermediate stage polycondensation reaction are conditions between the reaction conditions for the first stage and the reaction conditions for the last stage. The degree of increase in intrinsic viscosity achieved in each of these polycondensation reaction steps is preferably distributed smoothly.

In addition, when a low acetaldehyde content or a low cyclic trimer content is required such as a low flavor beverage or a heat-resistant hollow molded product for mineral water, it was obtained in this way. The melt polycondensed polyester is solid state polymerized. The polyester is solid-phase polymerized by a conventionally known method. First, the polyester subjected to solid phase polymerization is pre-crystallized by heating at a temperature of 100 to 210 ° C. for 1 to 5 hours in an inert gas, under reduced pressure, or in an atmosphere of water vapor or water vapor-containing inert gas. The Subsequently, solid state polymerization is performed at a temperature of 190 to 230 ° C. for 1 to 30 hours in an inert gas atmosphere or under reduced pressure.

  The catalyst of the present invention has catalytic activity not only for polycondensation but also for esterification and transesterification. For example, the catalyst of the present invention can be used in the transesterification reaction between an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate and a glycol such as ethylene glycol. Further, the catalyst of the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization or solution polymerization, and polyester can be produced by any method.

  The polymerization catalyst of the present invention can be added to the reaction system at any stage of the polymerization reaction. For example, it can be added to the reaction system at any stage before and during the esterification reaction or transesterification reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction. In particular, in the case of a polymerization catalyst comprising an ethylene glycol solution of an aluminum compound and a phosphorus compound and / or a slurry-like mixed system, it is preferable to add it immediately before the start of the polycondensation reaction in terms of polymerization activity and foreign matter reduction.

  In the method for adding a polymerization catalyst of the present invention, addition of a solvent such as ethylene glycol in a solution and / or slurry is effective in reducing foreign matters, and a mixed system of aluminum or a phosphorus compound and other components are mixed in advance. You may add as a mixture and may add these separately. Moreover, the mixture of an aluminum compound or phosphorus compound and other components may be added to the polymerization system at the same addition time, and each component 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.

  The polyester referred to in the present invention is composed of one or more selected from polycarboxylic acids containing dicarboxylic acids and ester-forming derivatives thereof, and one or more selected from polyhydric alcohols containing glycol. Or consisting of a hydroxycarboxylic acid and an ester-forming derivative thereof, or consisting of a cyclic ester.

  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 -Cyclobutane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 2,5-norbornane dicarboxylic 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- (Al Limetal) sulfoisophthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 4,4'-biphenyl sulfone dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid Aromatic dicarboxylic acids exemplified in the above and their ester-forming derivatives.

Of these dicarboxylic acids, terephthalic acid and naphthalenedicarboxylic acid, particularly 2,6-naphthalenedicarboxylic acid, are preferred from the viewpoint of the physical properties of the resulting polyester, and other dicarboxylic acids are used as constituents if necessary.
As polyvalent carboxylic acids other than these dicarboxylic acids, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3, 4, 3 ', 4'-biphenyltetracarboxylic acid, And ester-forming derivatives thereof.

  The glycols include 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 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedi Methanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12 dodecanediol, polyethylene glycol, polytrimethyleneglycol Aliphatic glycols, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl), exemplified by alcohol and polytetramethylene glycol 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 Aromatic glycols exemplified by naphthalenediol, glycols obtained by adding ethylene oxide 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.

  Examples of polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like.

  Examples of hydroxycarboxylic acids 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 Examples thereof include ester-forming derivatives.

  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 these alkyl esters, acid chlorides, acid anhydrides, and the like.

  The polyester used in the present invention is preferably a polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalenedicarboxylic acid or an ester-forming derivative thereof, and the main glycol component is alkylene glycol.

  The polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalene dicarboxylic acid or its ester-forming derivative is terephthalic acid or its ester-forming derivative and naphthalene dicarboxylic acid or its ester formation with respect to all acid components It is preferable that the total amount of the functional derivatives is 70 mol% or more, more preferably 80 mol% or more of the polyester, and still more preferably 90 mol% or more of the polyester.

  The polyester whose main glycol component is alkylene glycol is preferably a polyester containing 70 mol% or more of alkylene glycol in total with respect to all glycol components, more preferably a polyester containing 80 mol% or more, More preferably, it is a polyester containing 90 mol% or more. The alkylene glycol referred to here may contain a substituent or an alicyclic structure in the molecular chain.

  The naphthalenedicarboxylic acid or ester-forming derivative thereof used in the present invention includes 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2 1,7-naphthalenedicarboxylic acid or their ester-forming derivatives are preferred.

  Examples of the alkylene glycol used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1, 4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-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 and the like. Two or more of these may be used at the same time.

  The polyester of the present invention is preferably polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly (1,4-cyclohexanedimethylene terephthalate), polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate and copolymers thereof. Of these, polyethylene terephthalate and this copolymer are particularly preferred.

  After polyester polymerization according to the method of the present invention, the thermal stability of the polyester can be further enhanced by removing the catalyst from the polyester or by deactivating the catalyst by adding a phosphorus compound or the like.

  The polyester of the present invention can contain organic, inorganic, and organometallic toners, and a fluorescent brightening agent. By containing one or more of these, the yellowness of the polyester, etc. Can be suppressed to an even better level. It also contains other optional polymers, antistatic agents, antifoaming agents, dyeability improvers, dyes, pigments, matting agents, fluorescent brighteners, stabilizers, antioxidants, and other additives. Also good. As antioxidants, aromatic amine-based and phenol-based antioxidants can be used. 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 during or after polymerization of the polyester or at the time of molding the polyester. Which stage is suitable depends on the characteristics of the compound and the required performance of the polyester molded body. Are different.

  The polyester polymerized using the polyester polymerization catalyst of the present invention can produce fibers 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 employed. 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 be adopted 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 above polyester fibers are used for interior and bedding fibers such as clothing fibers, curtains, carpets, futons, fiber fills, tensile cords such as tire cords and 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 of polyester and solvent resistance. The hollow molded body is manufactured by a method in which a polyester chip obtained by melt polymerization or solid phase polymerization 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 preform with a bottom is obtained by a direct molding method in which the body 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 body 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 a sheet is processed by vacuum forming, pressure forming, stamping or the like, and used as a tray or container for food or miscellaneous goods, a cup, a blister pack, a carrier tape for electronic components, or an electronic component delivery tray. 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 polymerized using the polyester polymerization 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 polymerized using the polyester polymerization catalyst of the present invention can be used for the 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.

  Further, after stretching, in order to reduce the thermal shrinkage of the film, 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. If it exceeds 1000 μm, it is too hard to handle.

  In addition, in order to provide various functions such as adhesiveness, 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 polyester polymerization process in order to improve the handling properties such as slipping property, running property, wear resistance, and winding property of the 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 homopolymers or copolymers of vinyl monomers of divinylbenzene, styrene, acrylic acid, methacrylic acid, acrylic acid or methacrylic acid. 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.

  A method for incorporating the inert particles into 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, and the inert particle slurry is used as a slurry. A method of adding polyester to a polymerization reaction system, (b) a method of adding a water slurry of inert particles dispersed in a molten polyester resin by a vent type twin screw extruder in a melt extrusion process of a polyester film, and (c) polyester Examples include a method of kneading a 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 polymerization 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. The repulsion 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 adding the diol slurry of inert particles to the polyester polymerization reaction system, heat treatment of the slurry to near the boiling point of the diol can also be applied to heat shock (addition between the slurry and the polymerization reaction system). (Temperature difference) can be reduced, which is preferable in terms of dispersibility of the particles.

  These additives can be added at the time of polymerization of polyester or after polymerization, or at any stage after polyester film formation. Which stage is suitable depends on the characteristics of the compound and the required performance of the polyester film. It depends on each.

  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 expansion film, For diffusion sheet, For reflection film, Reflection For prevention film, conductive film, separator, UV prevention, back glass It is used, for example, for Ndotepu.

  As the antistatic film, for example, the techniques described in Japanese Patent No. 2952677 and Japanese Patent Application Laid-Open No. 6-184337 can be used. Examples of easy-adhesive films are described in JP-B-07-108563, JP-A-10-235820, JP-A-11-323271, and examples of cards are described in JP-A-10-171856 and JP-A-11-010815. 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 JP-A-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. For building materials, decorative plates for building materials, and decorative materials, for example, the film of the present invention can be 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 transparent resin sheet described in JP-A-06-297831 and the transparent polymer synthetic resin film described in JP-A-8-305065 can be used. 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 No. 05-088400. For thermal transfer recording, the film of the present invention can be used by the methods described in JP-A-07-032754 and for thermal recording, respectively, JP-A-11-034503. For printed circuit boards, for example, the film of the present invention can be used as a polyester film described in JP-A-06-326453. For the membrane switch, the film of the present invention can be used, for example, by the method described in Japanese Patent Application Laid-Open No. 05-234459. As the optical filter (for heat ray filter and plasma display), for example, the film of the present invention can be used by the method described in JP-A-11-231126. For a transparent conductive film and a touch panel, the film of the present invention can be used, for example, by the method described in JP-A-11-224539. For the masking film, the film of the present invention can be used, for example, by the method described in JP-A No. 05-273737. For photoengraving, for example, the film of the present invention can be used by the method described in JP-A No. 05-057844. As the negative film for photography, for example, the film of the present invention can be used as a polyethylene terephthalate film described in paragraph No. (0123) of JP-A No. 06-167768. For a phase difference film, for example, the film of the present invention can be used as a film described in JP-A No. 2000-162419. For the separator, for example, the film of the present invention can be used as the film described in paragraph No. (0012) of JP-A No. 11-209711. For preventing ultraviolet rays, for example, the film of the present invention can be used as a polyester film described in JP-A-10-329291. An agricultural film can be obtained by applying the film of the present invention to a polyethylene terephthalate film described in JP-A-10-166534. The pressure-sensitive adhesive sheet can be obtained, for example, by applying the oriented polyester film of the present invention to a polyethylene terephthalate film described in JP-A-06-122856.

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

⁽¹⁾ Measurement of ²⁷ Al-NMR spectrum and ³¹ P-NMR spectrum 20% DMSO-6d is added to a mixed catalyst solution of an aluminum compound and a phosphorus compound so that the phosphorus compound has a concentration of 0.05 mol / liter. After mixing at room temperature, NMR spectra were measured at room temperature using a Varian UNITY 500. As standard materials for NMR, aluminum chloride was used for ²⁷ Al-NMR (130 MHz), and orthophosphoric acid was used for ³¹ P-NMR (202 MHz).

(2) Intrinsic viscosity (IV: dl / g)
Each polyester pellet obtained by melt polycondensation and solid phase polycondensation (length: about 3 mm, diameter: about 2 mm, cylindrical shape) is made into 6/4 (weight ratio) of phenol / 1,1,2,2-tetrachloroethane. ) It melt | dissolved in the mixed solvent at 80-100 degreeC over several hours, and measured it at the temperature of 30 degreeC using the Ubbelohde viscometer. Concentration was measured at several points centered on 4 g / l, and IV was determined according to a conventional method.

(3) Molding of Hollow Molded Body The polyester was dried with a dryer using dehumidified nitrogen, and a preform was molded at a resin temperature of 295 ° C. with an M-150C (DM) injection molding machine manufactured by Meiki Seisakusho. The preform plug portion was heated and crystallized with a home-made plug portion crystallization apparatus, then biaxially stretched using a Corpoplast LB-01E stretch blow molding machine, and subsequently kept at about 140 ° C. It was heat-set in the set mold for about 7 seconds to obtain a 1500 cc hollow molded body (the body was circular).

(4) Evaluation of Transparency of Hollow Molded Body The transparency evaluation of the hollow molded body obtained by molding by the method of (3) above was evaluated using a visual three-stage evaluation method as shown below.
○: Excellent in transparency.
Δ: Slightly inferior in transparency
X: Inferior in transparency.

(5) Evaluation method of aluminum-based foreign substance 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, The pellet was stirred and dissolved in the mixed solution at 100 to 105 ° C. for 2 hours. The solution was allowed to cool to room temperature, and a polytetrafluoroethylene membrane filter (Advantec PTFE membrane filter, product name: T100A047A) having a diameter of 47 mm / pore size of 1.0 μm was used, and the total amount was under a pressure of 0.15 MPa. Foreign substances were filtered out with an effective filtration diameter of 37.5 mm. After completion of the filtration, the filtrate was washed with 300 ml of chloroform and then dried under reduced pressure at 30 ° C. for a whole day and night. The amount of aluminum element was quantified on the filtration surface of the membrane filter 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 known polyethylene terephthalate resin, and the apparent aluminum element amount was expressed in ppm. The measurement was performed under the conditions of a PHA (wave height analyzer) 100-300 using X-ray output 50 kV-70 mA, 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.
In the present invention, the amount of aluminum-based foreign matter insoluble in polyester measured by the above evaluation method is preferably 3500 ppm or less, more preferably 2000 ppm, and still more preferably 1000 ppm or less as an apparent aluminum element amount. When the foreign matter exceeds 3500 ppm as the apparent amount of aluminum element, 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 This is not preferable because it leads to the problem that the clogging of the polyester during filtration or the molding process is increased.

(Preparation example 1 of aluminum compound)
²⁷ Equivalent (volume ratio) to a 20 g / l aqueous solution of basic aluminum acetate (hydroxyaluminum diacetate; manufactured by Aldrich), whose peak position in the Al-NMR spectrum was confirmed to be chemically shifted to the low magnetic field side. ) Was added to a flask and stirred at room temperature for 6 hours, and then water was distilled off from the system while stirring at 90-110 ° C. for several hours under reduced pressure (133 Pa) to give 20 g / l of an aluminum compound of ethylene. A glycol solution was prepared.

(Preparation example 2 of aluminum compound)
As a result of preparing an aqueous solution by heat treatment at 90 ° C. for 70 hours, 20 g / l of basic aluminum acetate (hydroxyaluminum diacetate; manufactured by Aldrich) whose chemical shift cannot be confirmed to the low magnetic field side of the peak position of the ²⁷ Al-NMR spectrum. Equivalent amount (volume ratio) of ethylene glycol to the aqueous solution was added to the flask and stirred for 6 hours at room temperature. Then, water was distilled from the system while stirring at 90-110 ° C. for several hours under reduced pressure (133 Pa). Then, an ethylene glycol solution of 20 g / l aluminum compound was prepared.

(Preparation Example 1 of phosphorus compound)
Irganox1222 (manufactured by Ciba Specialty Chemicals Co., Ltd.) represented by [Chemical Formula 39] as a phosphorus compound was charged into a flask together with ethylene glycol and heated at a liquid temperature of 160 ° C. for 25 hours while stirring under a nitrogen atmosphere to obtain 50 g / l of phosphorus. An ethylene glycol solution of the compound was prepared. It was confirmed by the ³¹ P-NMR spectrum measurement that about 60 mol% was converted to a hydroxyl group.

(Preparation Example 2 of Phosphorus Compound)
All were prepared in the same manner as in Preparation Example 1 of the phosphorus compound except that [Chemical Formula 21] was used instead of [Chemical Formula 39] as the phosphorus compound. It was confirmed by the ³¹ P-NMR spectrum measurement that about 63 mol% was converted to a hydroxyl group.

(Preparation Example 3 of Phosphorus Compound)
The phosphorous compound was prepared in the same manner as in the phosphorous compound preparation example 1 except that [chemical formula 24] was used instead of [chemical formula 39]. It was confirmed by the ³¹ P-NMR spectrum measurement that about 61 mol% was converted to a hydroxyl group.

(Preparation Example 4 of phosphorus compound)
The phosphorous compound was prepared in the same manner as in the phosphorous compound preparation example 1 except that [chemical formula 25] was used instead of [chemical formula 39]. It was confirmed that about 65 mol% was converted to a hydroxyl group by ³¹ P-NMR spectrum measurement.

(Preparation Example 5 of phosphorus compound)
Irganox1222 (manufactured by Ciba Specialty Chemicals) represented by [Chemical Formula 39] as a phosphorus compound was charged into a flask together with ethylene glycol and heated at 120 ° C. for 1 hour with stirring under nitrogen purge to give 50 g / l of phosphorus. An ethylene glycol solution of the compound was prepared. It was confirmed by the ³¹ P-NMR spectrum measurement that about 13 mol% was converted to a hydroxyl group.

(Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound)
The respective ethylene glycol solutions obtained in Preparation Example 1 of the aluminum compound and Preparation Example 1 of the phosphorus compound were charged into a flask and mixed at room temperature so that the molar ratio of aluminum atoms and phosphorus atoms was 1: 2. A catalyst solution was prepared by stirring for 1 day.

(Preparation Example 2 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound)
Using the respective ethylene glycol solutions prepared by the methods of Preparation Example 1 of the above-mentioned aluminum compound and Preparation Example 2 of the phosphorus compound, “Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound” and A catalyst solution was prepared in the same manner.

(Preparation Example 3 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound)
Using the respective ethylene glycol solutions prepared by the methods of Preparation Example 1 of the above-mentioned aluminum compound and Preparation Example 3 of the phosphorus compound, “Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound” and A catalyst solution was prepared in the same manner.

(Preparation Example 4 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound)
Using the respective ethylene glycol solutions prepared by the methods of Preparation Example 1 of the above-mentioned aluminum compound and Preparation Example 4 of the phosphorus compound, “Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound” and A catalyst solution was prepared in the same manner.

(Preparation Example 5 of mixture of ethylene glycol solution of aluminum compound / ethylene glycol solution of phosphorus compound)
Using the respective ethylene glycol solutions prepared by the methods of Preparation Example 1 of the above-mentioned aluminum compound and Preparation Example 5 of the phosphorus compound, “Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound” and A catalyst solution was prepared in the same manner.

(Preparation Example 6 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound)
Using the respective ethylene glycol solutions prepared by the methods of Preparation Example 2 of the above-mentioned aluminum compound and Preparation Example 1 of the phosphorus compound, “Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound” and A catalyst solution was prepared in the same manner.

(Preparation Example 7 of mixture of ethylene glycol solution of aluminum compound / ethylene glycol solution of phosphorus compound)
Using the respective ethylene glycol solutions prepared by the methods of Preparation Example 2 of the above-mentioned aluminum compound and Preparation Example 5 of the phosphorus compound, “Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound” and A catalyst solution was prepared in the same manner.

(Example 1)
A 2 liter stainless steel autoclave with a stirrer is charged with high-purity terephthalic acid and twice its amount of ethylene glycol. An esterification reaction was carried out while distilling out of the system to obtain a mixture of bis (2-hydroxyethyl) terephthalate and oligomer (hereinafter referred to as BHET mixture) having an esterification rate of about 95%. As the polycondensation catalyst for this BHET mixture, the polymerization catalyst of “Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound” is used. As 0.014 mol% and 0.028 mol%, respectively, and then stirred at 250 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Thereafter, the pressure of the reaction system was gradually reduced to 13.3 Pa (0.1 Torr) while raising the temperature to 280 ° C. over 60 minutes, and a polycondensation reaction was further performed at 280 ° C. and 13.3 Pa. After releasing the pressure, the resin under slight pressure is discharged into cold water in a strand form and rapidly cooled. After that, it is held in cold water for 20 seconds, and then cut to obtain a cylindrical pellet having a length of about 3 mm and a diameter of about 2 mm. It was. Table 1 shows the time (polymerization time) required for the polycondensation reaction and IV of the obtained polyester.
The polyester pellets obtained by melt polymerization were dried under reduced pressure (13.3 Pa or less, 80 ° C., 12 hours), and subsequently crystallized (13.3 Pa or less, 130 ° C., 3 hours, further 13.3 Pa or less, 160 ° C., 3 hours). The polyester pellets after being allowed to cool were subjected to solid phase polymerization in a solid phase polymerization reactor while maintaining the system at 13.3 Pa or less and 215 ° C. to obtain polyester pellets having an IV of 0.78 dl / g. Table 1 shows the transparency of the hollow molded body and the evaluation results of foreign matters.

(Examples 2 to 4)
In Example 1, “Preparation Example 2”, “Preparation Example 3” and “Preparation Example 4” were used instead of “Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound”. Was carried out in the same manner as in Example 1 except that each of was used. Table 1 shows the time required for the polycondensation reaction (polymerization time), the IV of the obtained polyester, the transparency of the hollow molded article formed through solid phase polymerization, the evaluation results of foreign matters, and others.

(Example 5)
The same procedure as in Example 1 was performed except that “Preparation Example 1” was used instead of “Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound”. Table 1 shows the polymerization time, IV of the obtained polyester, transparency of the hollow molded article, evaluation results of foreign matters, and the like.

(Comparative Example 1)
The same procedure as in Example 1 was performed except that “Preparation Example 6” was used instead of “Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / ethylene glycol solution of a phosphorus compound”. Table 1 shows the polymerization time, IV of the obtained polyester, transparency of the hollow molded article, evaluation results of foreign matters, and the like.

(Comparative Example 2)
The same procedure as in Example 1 was performed except that “Preparation Example 7” was used instead of “Preparation Example 1 of a mixture of an ethylene glycol solution of an aluminum compound / an ethylene glycol solution of a phosphorus compound”. Table 1 shows the polymerization time, IV of the obtained polyester, transparency of the hollow molded article, evaluation results of foreign matters, and the like.

(Comparative Example 3)
In Example 1, using the solutions obtained in Preparation Example 1 for the aluminum compound and Preparation Example 1 for the phosphorus compound, respectively, 0.014 mol% as the aluminum atom and phosphorus atom as the acid component in the polyester, respectively. The same operation as in Example 1 was performed, except that 0.028 mol% was added separately. Table 1 shows the polymerization time, IV of the obtained polyester, transparency of the hollow molded article, evaluation results of foreign matters, and the like.

(Comparative Example 4)
The same operation as in Example 1 was performed except that an ethylene glycol solution of antimony trioxide as a polycondensation catalyst was added to 0.04 mol% as antimony atoms with respect to the acid component in the polyester. Table 1 shows the polymerization time, IV of the obtained polyester, transparency of the hollow molded article, evaluation results of foreign matters, and the like.

  The polymerization catalyst of the present invention is excellent in catalytic activity, excellent in transparency, and gives a polyester molded product with less foreign matter generation.For example, fibers for clothing and industrial materials, films and sheets for packaging and magnetic tape, It can be used in a wide range of fields, such as bottles that are hollow molded products, casings for electrical and electronic parts, and other molded products for engineering plastics.

Claims (11)

In the ³¹ P-NMR spectrum of the mixture comprising an alkylene glycol solution of an aluminum compound and an alkylene glycol solution of a phosphorus compound, the peak position is chemically shifted with respect to the peak of the alkylene glycol solution of the phosphorus compound alone. A polymerization catalyst for polyester. In the ²⁷ Al-NMR spectrum of the mixture comprising an alkylene glycol solution of an aluminum compound and an alkylene glycol solution of a phosphorus compound, the peak position is chemically shifted with respect to the peak of the alkylene glycol solution of the aluminum compound alone. Polyester polymerization catalyst.   3. The polyester polymerization catalyst according to claim 1, wherein the aluminum compound and / or the phosphorus compound is an alkylene glycol solution and / or slurry.   The polyester polymerization catalyst according to any one of claims 1 to 3, wherein the alkylene glycol is ethylene glycol.   The aluminum compound is at least one member selected from aluminum acetate, basic aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate. The polyester polymerization catalyst in any one.   The phosphorus compound is at least one selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. The polyester polymerization catalyst in any one of Claims 1-5.   7. The production of polyester using the polymerization catalyst according to any one of claims 1 to 6, characterized in that the addition timing of the polymerization catalyst is from a transesterification reaction or a direct esterification reaction to a polycondensation reaction. Method.   A polyester produced by the method according to claim 7.   The hollow molded object which consists of polyester of Claim 8.   A fiber comprising the polyester according to claim 8.   A film comprising the polyester according to claim 8.