JP2005112875A - Polyester and method for producing polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester by using a polycondensation catalyst containing a metal component other than antimony, germanium and titanium as a main metal component of the catalyst, maintaining color tone, transparency and thermal stability, having an ultralow content of carboxy terminal groups and excellent hydrolytic resistance, etc., with slight production of foreign materials caused by the catalyst and having a low content of cyclic trimers when a polyester obtained by melt polycondensation is subjected to solid-phase polycondensation. <P>SOLUTION: The method for producing the polyester comprises using a polyester polycondensation catalyst composed of at least one kind selected from the group consisting of aluminum and its compounds and at least one kind selected from phosphorus compounds. In the method, a dicarboxylic acid and/or its ester-forming derivative are reacted with a diol and/or its ester-forming derivative to provide a product in which the ratio of hydroxy terminal groups based on the whole terminal groups is ≥76 mol%. The resultant product is then polycondensed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing polyester, and more particularly to a polyester polycondensation method using a novel polyester polycondensation catalyst that does not use germanium or an antimony compound as a catalyst main component, and a polyester product thereof.

  Polyesters typified by polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc. are excellent in mechanical properties and chemical properties. Depending on the properties of each polyester, for example, Used in a wide range of fields such as textiles for clothing and industrial materials, films and sheets for packaging, magnetic tape, optics, bottles that are hollow molded products, casings for electrical and electronic components, and other engineering plastic molded products Has been. In particular, bottles made of saturated polyesters such as 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 a reaction, and this is produced by liquid phase polycondensation using a catalyst at a high temperature under vacuum.

  Conventionally, antimony or germanium compounds have been widely used as the polyester polycondensation catalyst used in such polycondensation of polyester. Antimony trioxide is an inexpensive catalyst with excellent catalytic activity. However, if it is used in an amount of such a main component, that is, a practical 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.

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

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

Moreover, regarding the method for producing a polyester using the polycondensation catalyst system, preferred addition times of the polycondensation catalyst system are disclosed (see, for example, Patent Documents 5 and 6).
JP 2002-322250 A JP 2002-327052 A

Moreover, regarding the polyester obtained by the polycondensation catalyst system, a polyester subjected to solid phase polycondensation is also disclosed (see Patent Document 7).
JP 2002-322259 A

  The polyester obtained by the polycondensation catalyst system has good color tone, transparency and thermal stability, and meets the above requirements. However, even if a method of reducing the cyclic trimer by solid-phase polycondensation is taken, it is difficult to make it 2900 ppm or less, and there remains a problem that it cannot answer the high market demand of 2500 ppm or less, The improvement was strongly envyed.

  The present invention has been made against the background of the problems of the prior art, and maintains color tone, transparency and thermal stability with a polycondensation catalyst having a metal component other than antimony, germanium and titanium as the main metal component, and It has very few carboxyl end groups and is excellent in hydrolysis resistance, etc., produces little foreign matter due to the polycondensation catalyst, and has a cyclic trimer content when the polyester obtained by melt polycondensation is subjected to solid phase polycondensation. The present invention provides a polyester capable of producing a low-quality polyester and a method for producing the polyester.

  In order to solve the above-mentioned problems, the present invention has finally been completed as a result of intensive studies. That is, the present invention relates to a method for producing a polyester using a polyester polycondensation catalyst comprising at least one selected from the group consisting of aluminum and a compound thereof and at least one selected from a phosphorus compound, and a dicarboxylic acid and / or an ester thereof. A diol and / or an ester-forming derivative thereof is reacted to obtain a product in which the ratio of hydroxyl end groups to all end groups is 76 mol% or more, and the product is polycondensed It is a manufacturing method of polyester to make. Moreover, this invention is the polyester manufactured by this method, and its molding.

  The polyester production method according to the present invention is a polycondensation catalyst having a metal component other than antimony, germanium and titanium as the main metal component of the catalyst, and has good color tone, transparency, thermal stability, etc., and is derived from the polycondensation catalyst. For example, fibers for clothing and industrial materials, films and sheets for packaging, magnetic tape and optics, bottles that are hollow molded products, casings for electrical and electronic parts, and other engineering plastic molding It can be suitably used in a wide range of fields such as products. Furthermore, when the polyester obtained by the present invention is subjected to solid phase polycondensation, a polyester having a low cyclic trimer content can be obtained. Accordingly, the polyester obtained by the production method of the present invention has strict requirements on the content of by-products such as cyclic trimers, for example, beverage containers such as mineral water, juice, wine and whiskey, and metal It can be particularly useful as a raw material polyester for a beverage can lining film and an electrical insulation film. Further, since the polyester produced by the method of the present invention has a significantly low carboxyl end group and a product having excellent durability such as hydrolysis resistance is obtained, fibers that are highly demanded of durability such as industrial materials, There exists an advantage that it can be used especially suitably in the field of a film and a molded article.

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

Dicarboxylic acids include succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1,3 -Cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, etc. Saturated aliphatic dicarboxylic acids exemplified, or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid, etc., or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid Acid, 5 -(Alkali metal) sulfoisophthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid Acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylsulfonedicarboxylic acid, 4
4'-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p
Examples include aromatic dicarboxylic acids exemplified by '-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like, and ester-forming derivatives thereof.

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

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

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

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

  Moreover, you may use together hydroxycarboxylic acid. Examples of the hydroxycarboxylic acid include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or these And ester-forming derivatives thereof.

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

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

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

  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. As a copolymer, what consists of 50 mol% or more of ethylene terephthalate units is preferable, and 70 mol% or more is more preferable.

  As the aluminum or aluminum compound constituting the polycondensation catalyst of the present invention, known aluminum compounds can be used without limitation in addition to metallic aluminum.

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 aluminum compounds such as trimethylaluminum and triethylaluminum 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, and aluminum acetate, aluminum chloride, and aluminum hydroxide chloride are more preferable from the viewpoint of solubility. Furthermore, the use of aluminum acetate is particularly preferred from the viewpoint of not corroding the device.

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

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

  The aluminum or aluminum compound may be added in the form of powder, but is preferably added in the form of a slurry or solution. In particular, it is preferable to add it in the form of a solution from the viewpoint of catalytic activity and the quality of the obtained polyester. That is, it is preferable to use those solubilized in a solvent such as water or glycol, particularly those solubilized in water and / or ethylene glycol.

The method for dissolving the aluminum compound is exemplified below.
(1) Preparation example of aqueous solution of basic aluminum acetate Water is added to basic aluminum acetate and stirred at 50 ° C. or lower for 3 hours or longer. The stirring time is more preferably 6 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 100 ° C. The stirring time is preferably 1 hour or longer. The concentration of the aqueous solution is preferably 10 g / l to 30 g / l, particularly preferably 15 g / l to 20 g / l.

(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 0.5 to 5 times the volume ratio of the aqueous solution. More preferably, the amount is 1 to 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 200 ° C. or lower. More preferably, the water is distilled off by stirring at 90 to 150 ° C. for several hours. The system may be depressurized during distillation. By reducing the pressure, ethylene glycol can be rapidly distilled off at a lower temperature. In other words, the distillation can be performed at 80 ° C. or lower under reduced pressure, and the heat history applied to the system can be further reduced.

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

  The amount of aluminum or aluminum compound used in the present invention is preferably 0.001 to 0.05 mol%, more preferably 0.005 to 0, based on the number of moles of all structural units of the carboxylic acid component of the polyester obtained. 0.03 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. Thus, even if the addition amount of the aluminum component is small, the polycondensation catalyst of the present invention has a great feature in that it exhibits sufficient catalytic activity. As a result, the thermal stability and thermal oxidation stability are excellent, and foreign matters and coloring caused by aluminum are reduced.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of R ¹ include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R2 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, and substitution. And a phenyl group, a naphthyl group, a group represented by —CH ₂ CH ₂ OH, and the like. Examples of R ³ O— include hydroxide ions, alcoholate ions, acetate ions, and acetylacetone ions.

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

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

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

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

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

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

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

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

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

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

Examples of R1 include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R2 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, and substitution. And a phenyl group, a naphthyl group, a group represented by —CH ₂ CH ₂ OH, and the like.

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

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

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

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

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

  Specific examples of these phosphorus compounds are shown below.

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

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

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

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

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

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

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

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

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

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

(In formula (Chemical Formula 34), Mn + represents an n-valent metal cation. N represents 1, 2, 3 or 4.)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Among these alkali metals, alkaline earth metals or their compounds, when using strongly alkaline ones such as hydroxides, these tend to be difficult to dissolve in diols such as ethylene glycol or organic solvents such as alcohols. 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 product such as the characteristics, processability, and color tone of the polyester. 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.

  In the present invention, the above-mentioned dicarboxylic acid and / or ester-forming derivative thereof is reacted with diol and / or ester-forming derivative thereof, and the ratio of hydroxyl end groups to all end groups (hereinafter abbreviated as OHV%). It is important to obtain a product in which) is 76 mol% or more and to polycondense the product. 85 mol or more is preferable and 95 mol% or more is more preferable. If it is less than 76 mol%, the degree of reduction of the cyclic trimer contained in the polyester is low even if the polyester obtained by the melt polycondensation of the present invention is subsequently subjected to the solid phase polycondensation method. Is less than 2900 ppm. On the other hand, a low oligomerized polyester having a cyclic trimer content of 2500 ppm or less can be obtained by solid-phase polycondensation using the polyester obtained by the method of the present invention.

  Further, the polyester produced by the method of the present invention has a feature that a carboxyl end group is remarkably low and a product having excellent durability such as hydrolysis resistance can be obtained. This effect is not manifested in conventionally known polycondensation catalyst systems such as antimony compounds, germanium compounds, and titanium compounds. Therefore, it is one of the major characteristics inherent in the polycondensation catalyst of the method of the present invention.

  In the present invention, the method for setting the OHV% within the above range is arbitrary without limitation. For example, the esterification reaction is performed by the reaction of dicarboxylic acid and diol, so-called direct esterification reaction, and the esterification reaction is stopped and the polycondensation reaction is started when the ratio of the hydroxyl end groups is reached. A method of transferring to a can and initiating a polycondensation reaction is mentioned. The esterification reaction may be carried out by either a batch method or a continuous method. Further, the esterification reaction may be carried out at normal pressure or pressure. It is preferable to carry out by normal pressure or slight pressure from the viewpoint that generation of side reaction products such as diethylene glycol can be suppressed.

  When the batch method and the pressure esterification method are used, tertiary amines such as triethylamine, tri-n-butylamine and benzyldimethylamine, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, hydroxylated When a small amount of a quaternary ammonium hydroxide such as trimethylbenzylammonium and a basic compound such as lithium carbonate, sodium carbonate, potassium carbonate or sodium acetate is added, for example, in the case of polyethylene terephthalate, This is preferable because the proportion of dioxyethylene terephthalate component units can be maintained at a relatively low level (5 mol% or less with respect to all diol components).

The production method by the direct esterification method is exemplified below.
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 / cm2G, preferably 0 to 1.3 kg / cm2G. 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 final stage. The increase in the reaction rate of these esterification reactions is preferably distributed smoothly at each stage. Ultimately, it is desirable that the esterification reaction rate reaches 90% or more, preferably 93% or more. By these esterification reactions, low-order condensates having a molecular weight of about 500 to 5,000 are obtained. In this method, the esterification reaction is stopped when the above OHV% is reached, and subsequently transferred to a polycondensation reactor to carry out polycondensation.

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

  In addition, it is a preferred embodiment to use a transesterification product obtained by a reaction between an ester-forming derivative such as dimethyl ester of dicarboxylic acid and a diol, a so-called transesterification reaction. OHV% may be adjusted by adding a dicarboxylic acid to the transesterification reaction product to carry out an esterification reaction. In the transesterification reaction, methanol produced by the reaction is treated in a rectifying column under the condition that ethylene glycol is distilled back using an apparatus in which one or two transesterification reactors are connected in series. Carry out while removing outside. 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.

  Another method for setting the OHV% within the above range is a dihydroxyalkyl ester derivative of dicarboxylic acid obtained by chemical decomposition recovery from a polyester resin, for example, bishydroxyethyl terephthalate obtained by chemical decomposition recovery of a recovered PET bottle ( BHET) is the preferred embodiment. An esterification reaction may be carried out by adding a dicarboxylic acid such as terephthalic acid to the BHET. During the reaction, ethylene glycol or other glycols may be added to adjust OHV% or composition.

  In the present invention, not only BHET but also the use of recycled raw materials such as terephthalic acid, dimethyl terephthalate or ethylene glycol obtained by the chemical decomposition recovery method for recovered PET bottles is preferable because it helps save resources and protect the environment. This is an embodiment.

  The low-order condensate or BHET, which is a product having an OHV% of 76 mol% or more, is subsequently supplied to the melt polycondensation step. The melt polycondensation step may be either a batch method or a continuous method. The number of reactors in the process is not limited. Generally, a two-stage system of initial polycondensation and late polycondensation is taken. The polycondensation reaction conditions are as follows: the first stage polycondensation reaction temperature is 250 to 290 ° C., preferably 260 to 280 ° C., and the pressure is 500 to 20 Torr, preferably 200 to 30 Torr. The temperature is 265 to 300 ° C., preferably 275 to 295 ° C., and the pressure is 10 to 0.1 Torr, preferably 5 to 0.5 Torr. When 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 the case of the batch method, the so-called single-can method may be used in which the polycondensation reaction is advanced by reducing the pressure of the low-order condensate reactor.

  In the present invention, the timing of addition of the polycondensation catalyst to the reaction system is not limited, but it is added at the end of the low-order condensate production reaction to increase the polycondensation activity and cause the polycondensation catalyst. This is preferable because formation of insoluble foreign matter is suppressed. The polycondensation catalyst may be added directly to the reactor of the low-order condensate or may be added to a transfer line between the reactors. When adding to a transfer line, it is preferable to install a mixer such as a line mixer and add to the mixer to achieve uniform mixing. Further, the addition time of aluminum or its compound and the phosphorus compound constituting the polycondensation catalyst is not limited, but adding the phosphorus compound at the same time or the phosphorus compound first suppresses the polycondensation activity and insoluble foreign matter formation caused by the polycondensation catalyst. Etc. are preferable. Moreover, the addition time of the conventionally well-known polycondensation catalyst and the cobalt compound of a color tone improving agent is not limited, and is arbitrary. That is, the addition timing of these polycondensation catalysts and additives can be appropriately set depending on the structure of the target polyester and the desired properties of the resulting polyester. In this case, OHV% is calculated using the low-order condensate after various polymerization catalysts and various additives are added, that is, immediately before the polycondensation reaction.

  The polyester obtained by the method of the present invention is heated under a reduced pressure or under an inert gas stream, and the method of further proceeding polycondensation is the cyclic trimer contained in the polyester resin. There are no restrictions on the removal of by-products such as oligomers and acetaldehyde. Since the polyester obtained by the present invention can efficiently reduce the cyclic trimer content by the solid-phase polycondensation method, it is recommended as a preferred embodiment to take this means. In addition, it is not excluded to incorporate a treatment such as purifying a polyester resin by an extraction method such as a supercritical pressure extraction method to remove impurities such as the by-products.

  The polyester of the present invention can contain organic, inorganic, and organometallic toners, and a fluorescent brightening agent. By containing one or more of these, the yellowness of the polyester, etc. Can be suppressed to an even better level. It also contains other optional polymers, antistatic agents, antifoaming agents, dyeability improvers, dyes, pigments, matting agents, fluorescent brighteners, stabilizers, antioxidants, and other additives. Also good. As antioxidants, aromatic amine-based and phenol-based antioxidants can be used, and as stabilizers, phosphoric acid and phosphate ester-based phosphorus-based, sulfur-based, amine-based stabilizers, etc. Can be used.

  These additives can be added at any stage during or after polymerization of the polyester, or at the time of molding the polyester. Which stage is suitable depends on the structure of the target polyester and the requirements of the resulting polyester. What is necessary is just to select suitably according to performance, respectively.

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

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

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

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

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

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

  Among these, polyester is particularly suitable for various beverages as a pressure-resistant container, a heat-resistant pressure-resistant container, and an alcohol-resistant container utilizing the hygiene and strength and solvent resistance of polyester. The hollow molded body 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, or melted after melt polymerization. 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 product obtained by a molding machine such as the above-described extrusion molding machine or injection molding machine can be used as a final hollow container.

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

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

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

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

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

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

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

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

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

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

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

  In addition, in order to provide various functions such as adhesion, releasability, antistatic properties, infrared absorption, antibacterial properties, scratch resistance, etc., the surface of the oriented polyester film may be coated with a polymer resin by a coating method. Good. Moreover, it is good also as a slippery highly transparent polyester film by making an inorganic and / or organic particle | grain contain only in a coating layer. Furthermore, an inorganic vapor deposition layer can be provided to provide various barrier functions such as oxygen, water, and oligomer, or a conductive layer can be provided by a sputtering method or the like to provide conductivity. In addition, inorganic and organic salt particles or heat-resistant polymer resin particles are added in the 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.

  The method for incorporating the inert particles in the polyester that is the base film is not limited, but (a) the inert particles are dispersed in a slurry form in a diol that is a polyester component, A method of adding polyester to a polymerization reaction system, (b) a method of adding a water slurry of inert particles dispersed in a molten polyester resin by a vented twin screw extruder in a melt extrusion 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. Further, reaggregation between particles can be suppressed by electrical repulsion. In the case of calcium carbonate particles, hydroxyapatite particles, etc., it is preferable to add sodium tripolyphosphate or potassium tripolyphosphate to the slurry.

  In addition, when 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 film, for diffusion sheet, for reflective film, and for reflection For prevention film, conductive film, separator, UV protection, back glass It is used, for example, for Ndotepu.

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

  Furthermore, the polyester obtained by the present invention has an advantage that a polyester having a low cyclic trimer content can be obtained when solid-phase polycondensation is carried out. Accordingly, the polyester obtained by the production method of the present invention has strict requirements on the content of by-products produced as a by-product of melt polycondensation such as cyclic trimers, for example, mineral water, juice, wine It can be used particularly useful as a raw material polyester for beverage containers such as coffee and whiskey, lining films for metal beverage cans, and films for electrical insulation.

  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 Intrinsic Viscosity (IV) Measurement was performed at 30 ° C. using a mixed solvent of phenol / tetrachloroethane (60:40, weight ratio). The polyester after the solid phase polymerization was measured at 30 ° C. using a mixed solvent of p-chlorophenol / tetrachloroethane (3: 1, weight ratio).

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

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

4. Calculation of OHV% It was calculated according to the following formula from OHVo and AVO obtained by the above method.
OHV% = (OHVo / OHVo + AVo) × 100

5. Foreign matter evaluation [melt polycondensate]
A polyester chip (one grain) is sandwiched between two cover glasses, melt-pressed at 280 ° C, quenched, then observed in 20 fields of view with a 100x phase-contrast microscope, and the number of particles larger than 5 µm is counted with an image analyzer. did. When the total number of particles of 5 μm or more measured by this method was 30 or less, it was judged as 、, from 30 to 50 or less as ○, and from 50 to 100 or less as Δ.
6. Color tone [melt polycondensate]
The L value and b value of the hunter were measured using a color difference meter (manufactured by Tokyo Denshoku Co., Ltd .: Model ND-1001DP) using a polyester resin chip (length: about 3 mm, diameter: about 2 mm).

7. Polyester carboxyl end group (AVp) [melt polycondensate]
The polyester was pulverized with a handy mill (pulverizer) and dried at 70 ° C. under reduced pressure overnight. 0.20 g of the polyester was precisely weighed into a test tube, and 10 ml of benzyl alcohol was added and dissolved separately with stirring for 3 minutes, 5 minutes, and 7 minutes. After dissolution, the sample was cooled in a water bath for 15 seconds, the sample was transferred to a beaker, the test tube was washed once with 10 ml of chloroform, and the washing solution was also placed in the beaker. Titration was performed using phenol red as an indicator and an ethanol solution of N / 25-KOH. Do the same measurement on the blank without the polyester sample (only for 3 minutes). In advance, a solution obtained by mixing 5 ml of N / 10-hydrochloric acid and 10 ml of an ethanol solution of N / 25-KOH was titrated with an ethanol solution of N / 25-KOH using phenolphthalein as an indicator, and the factor (F ) According to the following formula.
F = 0.1 × f × 5 / (a + 10)
(F = factor of N / 10-hydrochloric acid, a = drop constant (ml))
The acid value (equivalent / ton) is calculated according to the following formula.
Acid value = (A−B) × F × 1000 / W
(A = titration constant (ml), B = blank titration constant (ml), F = factor of ethanol solution of N / 25-KOH, W = weight of sample (g))
The value of the intercept when extrapolating the straight line obtained by plotting the acid value to the dissolution time (3 minutes, 5 minutes, 7 minutes) at the dissolution time of 0 minutes was expressed as eq / ton as AVp.

8. Cyclic trimer in polyester [solid phase polycondensate]
Polyester obtained by melt polycondensation is cut into a cylindrical pellet having a length of about 3 mm and a diameter of about 2 mm, dried under reduced pressure (less than 0.1 Torr, 80 ° C., 12 hours) in a dryer, and subsequently crystallized ( The treatment was performed at 130 ° C. for 3 hours at a pressure of 0.1 Torr or less and then at 160 ° C. for 3 hours. The pellets after being allowed to cool were put into a solid phase polymerization reactor and subjected to solid phase polycondensation for a predetermined time while maintaining the oil bath temperature at 215 ° C. and the system at 0.1 Torr or less to obtain polyethylene terephthalate having an IV of 0.74.
The obtained solid phase polycondensation polyester was pulverized with a handy mill (pulverizer), and 0.10 g of the polyester was placed in an eggplant flask, 1,1,1,3,3,3-hexafluoro-2-propanol / chloroform. 3 ml of a mixed solvent of (2/3 (volume ratio)) was added and left until the polyester was dissolved. To the resulting solution, 20 ml of chloroform was added and mixed uniformly. Further, 10 ml of methanol was added, and the mixture was allowed to stand for 30 minutes or more to reprecipitate linear polyester. Next, the eggplant flask was subjected to ultrasonic waves, and then the solution was filtered. At that time, the precipitate was washed three times using a mixed solvent of chloroform / methanol (2/1 (volume ratio)) that had been well mixed beforehand, and the washings were also filtered. The obtained filtrate was concentrated to dryness on a rotary evaporator. To the concentrated dried product, 10 ml of dimethylformamide was added, and ultrasonically applied to dissolve the white dried portion. After allowing to stand for 30 minutes or more, this solution was filtered, and the filtrate was used as a cyclic trimer measurement solution. The cyclic trimer was quantified by measuring this measurement solution under the following conditions using a series 1050 type high performance liquid chromatography manufactured by Hewlett Packard, and expressed in ppm. For quantification, a standard solution in which the content of the cyclic trimer was previously known was used.
(Measurement condition)
Column: manufactured by Waters Co., Ltd., micro bonder sphere-5 μC ₁₈ -100A, 3.9 φmm × 150 mmL
Gradient solvent:
Liquid A; 2% aqueous acetic acid solution B; acetonitrile 10% → 100% (55 min), linear flow rate: 0.80 mL / min
Detection: UV detector, wavelength = 252 nm
Sample injection volume: 20 μl

9. Hydrolysis stability of polyester [melt polycondensate]
The polyester obtained by melt polymerization was pulverized with a handy mill (pulverizer) to obtain a powder of 20 mesh or less, which was dried under reduced pressure at 70 ° C. overnight. The IV of the polyester was measured ([IV] _i ). The hydrolysis test was performed using a mini color apparatus (TypeMC12.ELB manufactured by Tecsum Giken Co., Ltd.). 1.0 g of the above powder was put together with 100 ml of pure water into a special stainless beaker, and a special stirring blade was further added to make a closed system, which was set in a mini-color device, heated to 130 ° C. and stirred for 6 hours under pressurized conditions. . The polyester after the test was filtered with a glass filter, dried under reduced pressure at 70 ° C. overnight, and then measured for IV ([IV] _f ). The hydrolysis resistance parameter (HS) was calculated according to the following formula:% Expressed as BB.
HS = 0.245 {[IV] _f ^-1.47- [IV] _i ^-1.47 }

(Examples 1 and 2 and Comparative Example 1)
(1) Preparation of polycondensation catalyst solution (ethylene glycol solution of phosphorus compound)
After adding 2.0 liters of ethylene glycol to a flask equipped with a nitrogen introduction tube and a cooling tube at room temperature and normal pressure, while stirring at 200 rpm in a nitrogen atmosphere, Irganox 1222 (Ciba 39) represented by -200 g of Specialty Chemicals) was added. Further, 2.0 liters of ethylene glycol was added, the jacket temperature was changed to 196 ° C., the temperature was raised, and the mixture was stirred under reflux for 60 minutes from the time when the internal temperature reached 185 ° C. or higher. Thereafter, the heating was stopped, the solution was immediately removed from the heat source, and the solution was cooled to 120 ° C. or less within 30 minutes while maintaining the nitrogen atmosphere. The mole fraction of Irganox 1222 in the obtained solution was 40%, and the mole fraction of the compound whose structure changed from Irganox 1222 was 60%.
(Ethylene glycol solution of aluminum compound)
After adding 5.0 liters of pure water to a flask equipped with a condenser under normal temperature and pressure, 200 g of basic aluminum acetate (hydroxyaluminum diacetate) was added as a slurry with pure water while stirring at 200 rpm. . Further, pure water was added so as to be 10.0 liters as a whole, and the mixture was stirred at room temperature and normal pressure for 12 hours. Thereafter, the jacket temperature was changed to 100.5 ° C., the temperature was raised, and the mixture was stirred under reflux for 3 hours from the time when the internal temperature reached 95 ° C. or higher. Stirring was stopped and the mixture was allowed to cool to room temperature. At that time, when undissolved particles were observed, the solution was filtered through a glass filter (3G) to obtain an aqueous solution of an aluminum compound.
A flask equipped with a distillation apparatus was charged with 2.0 liters of an aqueous solution of the aluminum compound and 2.0 liters of ethylene glycol at room temperature and normal pressure, and stirred at 200 rpm for 30 minutes to obtain a uniform water / ethylene glycol mixed solution. The jacket temperature was then changed to 110 ° C. and the temperature was raised, and water was distilled off from the solution. When the amount of distilled water reached 2.0 liters, the heating was stopped and the mixture was allowed to cool to room temperature to obtain an ethylene glycol solution of an aluminum compound.
(2) Esterification reaction The first ester is prepared by mixing 0.4 parts by mass of ethylene glycol with 1 part by mass of high-purity terephthalic acid in a 2-can continuous esterification reactor and continuously supplying slurry. The reaction time in the first and second esterification reactors is adjusted at a reaction temperature of 250 ° C. and 100 kPa, a second esterification reactor is 255 ° C. and 100 kPa, and ethylene glycol is added to the second esterification reaction vessel. Was added as necessary to obtain a low-order condensate.
(3) Polycondensation The above-mentioned polycondensation catalyst solution is added to the second esterification reactor from a separate supply port, and the ethylene glycol solution of the phosphorus compound and the ethylene glycol solution of the aluminum compound are phosphorous to the acid component in the polyester. 0.028 mol% as atoms and 0.021 mol% as aluminum atoms were added to obtain a desired low-order condensate of OHV%. This low-order condensate was transferred to a batch-type polycondensation reactor, and polycondensation was carried out at 280 ° C. and 13.3 Pa (0.1 Torr) to obtain polyethylene terephthalate having an IV of 0.62. The properties of the low-order condensate and polyethylene terephthalate are shown in Table 1.

Comparative Example 2
As a polycondensation catalyst solution added to the low-order condensate of Example 2, an ethylene glycol solution of antimony trioxide is added so as to be 0.04 mol% as antimony atoms with respect to the acid component in the polyester. Produced polyethylene terephthalate having an IV of 0.62 in the same manner as in Example 2. The properties of the low-order condensate and polyethylene terephthalate are shown in Table 1.

(Example 3 and Comparative Examples 3 and 4)
A continuous polycondensation apparatus comprising three reactors of the low-order condensate product to which the polycondensation catalyst solution of Example 1 was compared, Comparative Example 3 was Comparative Example 1, and Comparative Example 4 was Comparative Example 2. The initial polymerization reactor is polycondensed at 265 ° C. and 9 kPa, the medium polymerization reactor is 265 to 275 ° C. and 0.7 kPa, and the final polymerization reactor is 270 to 280 ° C. and 13.3 Pa. A polyethylene terephthalate of IV 0.62 was obtained.
The properties of the low-order condensate and polyethylene terephthalate are shown in Table 2.

(Examples 4 and 5 and Comparative Example 5)
(1) Preparation of polycondensation catalyst solution The phosphorus compound solution and the aluminum compound solution prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were mixed so that the molar ratio of phosphorus atoms to aluminum atoms was 4: 3. The mixture was stirred at room temperature for 1 day to prepare a polycondensation catalyst solution.
(2) Polycondensation High-purity BHET and high-purity terephthalic acid obtained by chemical recovery of PET bottles were charged into a 2-liter stainless steel autoclave equipped with a stirrer to carry out an esterification reaction. The esterification reaction was performed at 255 ° C. The charge ratio of high purity BHET and high purity terephthalic acid was adjusted to obtain a low-order condensate. After adding the polycondensation catalyst solution prepared by the above method to the low-order condensate such that 0.028 mol% as a phosphorus atom and 0.021 mol% as an aluminum atom with respect to the acid component in the polyester, The low order condensate of various OHV% shown in Table 2 was obtained. Subsequently, polycondensation was performed at 280 ° C. and 13.3 Pa (0.1 Torr) to obtain polyethylene terephthalate having an IV of 0.62. The properties of the low-order condensate and polyethylene terephthalate are shown in Table 3.

(Comparative Example 6)
As a polycondensation catalyst solution added to the low-order condensate of Example 5, an ethylene glycol solution of antimony trioxide is added so as to be 0.04 mol% as antimony atoms with respect to the acid component in the polyester. Produced polyethylene terephthalate having an IV of 0.62 in the same manner as in Example 5. The properties of the low-order condensate and polyethylene terephthalate are shown in Table 3.

  The polyethylene terephthalate obtained in Examples 1 to 5 has a good color tone, and the production of foreign matters due to the polycondensation catalyst is small. Moreover, there were few carboxyl terminal groups and it was excellent in hydrolysis resistance stability. Furthermore, the melt polycondensed polyethylene terephthalate obtained in these examples was subjected to solid phase polycondensation to obtain polyethylene terephthalate having a low cyclic trimer content. On the other hand, the polyethylene terephthalate obtained in Comparative Examples 1, 3 and 5 had many carboxyl end groups and was inferior in hydrolysis resistance. Moreover, even if solid phase polycondensation was performed on the polyethylene terephthalate obtained in these comparative examples, the reduction of the cyclic trimer was small and inferior to the polyethylene terephthalate obtained in the examples. Moreover, since the polyethylene terephthalate obtained in Comparative Examples 2, 4 and 6 using an antimony catalyst has a poor color tone and a large amount of foreign matter is generated due to the polycondensation catalyst, a transfer line from the esterification step to the polycondensation step and The filter of the filter installed at the outlet of the final polycondensation reactor was clogged and the polycondensation productivity was poor. In addition, there were many carboxyl end groups and the hydrolysis resistance was inferior. Furthermore, the cyclic trimer was slightly higher.

  The polyester production method according to the present invention is a polycondensation catalyst having a metal component other than antimony, germanium and titanium as the main metal component of the catalyst, and has good color tone, transparency, thermal stability, etc., and is derived from the polycondensation catalyst. For example, fibers for clothing and industrial materials, films and sheets for packaging, magnetic tape and optics, bottles that are hollow molded products, casings for electrical and electronic parts, and other engineering plastic molding It can be suitably used in a wide range of fields such as products. Furthermore, the polyester obtained by the present invention has an advantage that a polyester having a low cyclic trimer content can be obtained when solid-phase polycondensation is carried out. Accordingly, the polyester obtained by the production method of the present invention has strict requirements on the content of by-products such as cyclic trimers, for example, beverage containers such as mineral water, juice, wine and whiskey, and metal It can be particularly useful as a raw material polyester for a beverage can lining film, an electrical insulation film, and the like. Further, since the polyester produced by the method of the present invention has a significantly low carboxyl end group and a product having excellent durability such as hydrolysis resistance is obtained, fibers that are highly demanded of durability such as industrial materials, It can be particularly suitably used in the field of films and molded articles, and greatly contributes to the industry.

Claims (6)

  In a method for producing a polyester using a polyester polycondensation catalyst comprising at least one selected from the group consisting of aluminum and a compound thereof and at least one selected from a phosphorus compound, a dicarboxylic acid and / or an ester-forming derivative thereof, Production of polyester characterized by reacting diol and / or ester-forming derivative thereof to obtain a product having a ratio of hydroxyl end groups to 76 mol% or more with respect to all end groups, and subjecting the product to polycondensation Method.   2. The method for producing a polyester according to claim 1, wherein the phosphorus compound is preheated in at least one solvent selected from the group consisting of water and alkylene glycol.   A polyester produced by the production method according to claim 1.   A hollow molded body made of the polyester according to claim 3.   A fiber comprising the polyester according to claim 3.   A film comprising the polyester according to claim 3.