JP2006169432A - Polyester and method for producing polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester produced by a production method using a catalyst containing metal components other than antimony, germanium and titanium as main metal components, forming little insoluble foreign materials, and exhibiting its characteristic features in the field of ultrafine fiber, highly transparent film for optical use, a hollow molded article, etc., and provide a molded article of the polyester. <P>SOLUTION: A polyester is produced in the presence of a polyester polycondensation catalyst composed of at least one component selected from aluminum compounds and at least one component selected from phosphorus compounds. In the polyester production process, the aluminum compound and the phosphorus compound are used in the form of solutions and the solutions are mixed immediately before adding to the polycondensation reaction system. The present invention further relates to a polyester produced by the production method, and a hollow-molded article, a fiber and a film made of the polyester. <P>COPYRIGHT: (C)2006,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 PET are excellent in mechanical strength, heat resistance, transparency and gas barrier properties, so that they are used as containers for filling beverages such as juices, carbonated drinks and soft drinks, and containers for eye drops and cosmetics. Widely used.

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

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

Further, regarding the method for producing a polyester using the polycondensation catalyst system, a polyester polycondensation catalyst comprising a solution in which at least one selected from the group consisting of carboxylic acid aluminum salts is dissolved in water and / or an organic solvent, and the polycondensation A method for producing a polyester using a catalyst is disclosed (see Patent Document 5).
JP 2003-82083 A

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

  In addition, among bottle applications, which are one of the main uses of polyester, beverages such as fruit juice drinks, mineral water, oolong tea, green tea, and black tea can be aseptically filled or sterilized at 85 ° C or higher when filled into polyester bottles. Mandatory. Generally, the latter is carried out, and heat resistance is required so as not to be deformed even when contacted with a soft drink or juice heated to 85 ° C. or higher. However, in the case of normal polyester bottles, the container shrinks and deforms during such a hot filling process, which becomes a problem. Therefore, as a method of improving the heat resistance of the polyester bottle, the preform or the bottle cap is heat treated. And a method of crystallizing the bottle (see Patent Document 6) or a method of heat-fixing the stretched blown bottle (heat setting process) to increase the degree of crystallinity of the bottle body and the like (see Patent Document 7). ) Has been proposed.

  When the crystallization of the plug portion is insufficient or the variation in crystallinity is large, deformation due to insufficient heat resistance may occur, sealing performance with the cap may deteriorate, and leakage of contents may occur. Moreover, when the heat setting process of the bottle body is insufficient, the body may be deformed, which causes a problem.

In the method of improving heat resistance by heat-treating such plugs and barrels, the time and temperature of the crystallization treatment greatly affect the productivity, the treatment can be performed at a low temperature in a short time, and the crystallization speed is increased. A fast polyester resin is preferred. However, even if the crystallization rate is too fast, the shrinkage rate due to the plug portion crystallization treatment fluctuates, the plug portion size after crystallization deviates from the specified value, the sealing performance with the cap decreases, and the contents leak. Etc. may occur. In addition, glass-like transparency is required for parts other than the bottle cap, but if the crystallization rate of the polyester is too high, the preform will crystallize and stretch in the process of heating the preform to the stretching temperature. There may be a problem that the appearance of blow-molded bottles becomes cloudy.
Therefore, the crystallization rate of the polyester may cause a problem if it is too fast or too slow, and it is essential to control it within a certain range.

  Further, in order to improve the heat resistance of the bottle body, a method of heat-treating the stretch blow mold at a high temperature is employed. By such a method, many bottles are continuously formed using the same blow mold. And the bottle obtained with a long driving | operation will whiten, transparency will fall, and only a bottle with no commercial value will be obtained. In particular, in recent years, the molding speed has been increased along with the downsizing of the bottle, and shortening of the heating time for crystallization of the plug portion is required from the viewpoint of productivity.

  Various proposals have been made as methods for increasing the crystallization rate. For example, a method of copolymerizing polyethylene terephthalate with polyethylene or the like (see Patent Document 8), a method of bringing a polyethylene terephthalate resin into contact with a crystalline thermoplastic resin member such as polyethylene under flow conditions (see Patent Document 9), a polyethylene terephthalate resin A method of blending a trace amount of a crystalline thermoplastic resin member such as polyethylene (see Patent Document 10), a method of containing a trace amount of a polyolefin resin or a polyamide resin in a polyester composed of antimony and a titanium catalyst, and lowering the temperature rise crystallization temperature (Tc1) ( (See Patent Document 11). However, these methods have problems in terms of quality and productivity, such as variations in the dimensions of the plug portion after crystallization, transparency of the trunk portion, and an increase in the number of processes, and are not fully satisfactory. .

JP 55-79237 A Japanese Examined Patent Publication No.59-6216 JP-A-5-9275 JP-A-9-71639 JP-A-9-151308 JP 2002-294056 A

  For the reasons mentioned above, the plug part is heated and crystallized in a short time, and has excellent dimensional stability, high productivity at the time of molding, and transparency and coloring problems as a bottle in the bottle. A polyester resin and a method for producing the same are desired.

  The present invention was made in the background of the problems of the prior art, and is a polycondensation catalyst having a metal component other than antimony, germanium and titanium as the main metal component of the catalyst, polycondensation catalyst activity, color tone, transparency and thermal stability. Thus, it is possible to provide a method for producing a polyester capable of stably producing a polyester in which Tc1 can be controlled in a wide temperature range and foreign matter generation due to a polycondensation catalyst is small. In addition, regarding a polyester obtained by a polycondensation catalyst comprising an aluminum compound and a phosphorus compound having a metal component other than antimony, germanium and titanium as the main metal component of the catalyst, a polyester derived from aluminum which is the main metal element of the polycondensation catalyst Therefore, the present invention provides a polyester and its molded body that have few insoluble foreign matters and can exhibit the characteristics in the fields of ultrafine fibers, optically highly transparent films or hollow molded bodies.

In order to solve the above-mentioned problems, the present invention has finally been completed as a result of intensive studies. That is, the present invention provides a method for producing a polyester in the presence of a polyester polycondensation catalyst comprising at least one selected from the group consisting of aluminum compounds and at least one selected from phosphorus compounds. A method for producing a polyester characterized in that both solutions are mixed and added immediately before being added to the polycondensation reaction system.
In this case, it is preferable to mix the aluminum compound solution and the phosphorus compound solution with a homomixer type mixer in which the peripheral speed of the outer periphery of the stirring blade is 2 to 400 m / sec.
In this case, it is preferable that the aluminum compound solution and the phosphorus compound solution are mixed and added to the polycondensation reaction system so that the molar ratio of aluminum atoms and phosphorus atoms satisfies the following formula.
1 ≦ P / Al (molar ratio) ≦ 5
[Wherein Al is the number of moles of aluminum atoms in the aluminum compound, and P is the number of moles of phosphorus atoms in the phosphorus compound]
In this case, the NMR spectrum peak of the phosphorus bond substituted with the hydroxyl group of the mixed solution of the aluminum compound and the phosphorus compound is higher than the NMR spectrum peak of the phosphorus bond substituted with the hydroxyl group of the single solution of the phosphorus compound before mixing. It is preferable that the solution consists of a solution in which the peak becomes broad and the peak becomes broad.
In this case, the integrated value of the shifted peak is 10% or more with respect to the integrated value of the NMR spectrum peak of the phosphorus bond substituted with the hydroxyl group of the phosphorus compound single solution before mixing with the aluminum compound solution. Preferably it is.

  Moreover, this invention is the polyester manufactured with the said manufacturing method.

  Moreover, this invention is the hollow molded object, fiber, and film which consist of said polyester.

  The polyester production method according to the present invention is a polycondensation catalyst in which a metal component other than antimony, germanium and titanium is used as the main metal component of the catalyst and maintains the polycondensation catalyst activity, color tone, transparency, thermal stability, etc. Can be controlled in a wide temperature range, and a polyester with less foreign matter generation due to the polycondensation catalyst can be obtained. Accordingly, the polyester obtained by the production method of the present invention includes, for example, fibers for clothing and industrial materials, films and sheets for packaging, magnetic tape and optics, bottles that are hollow molded articles, electrical / electronic components, etc. Can be suitably used in a wide range of fields such as casings and other engineering plastic molded articles. Further, since the polyester of the present invention has a feature that the generation of foreign matter due to the polycondensation catalyst is small, it exhibits the feature in the field of ultrafine fibers, highly transparent films for optical use or hollow molded articles, etc. Has the advantage of being able to

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

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

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

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

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

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

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

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

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

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

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

  As the polyester of the present invention, PET, PBT, polypropylene terephthalate, poly (1,4-cyclohexanedimethylene terephthalate), PEN, polybutylene naphthalate, polypropylene naphthalate and copolymers thereof are preferable, and among these, polyethylene terephthalate and This copolymer is 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. PET is particularly preferred.

  The aluminum compound constituting the polycondensation catalyst of the present invention is not limited as long as it dissolves in a solvent, but aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, Carboxylates such as aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, aluminum tartrate, aluminum salicylate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate , Inorganic acid salts such as aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum Aluminum chelate such as muiso-propoxide, aluminum n-butoxide, aluminum t-butoxide, aluminum alkoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate diiso-propoxide, trimethylaluminum , Organoaluminum compounds such as triethylaluminum and their partial hydrolysates, reaction products composed of aluminum alkoxides and aluminum chelate compounds and hydroxycarboxylic acids, aluminum oxide, ultrafine aluminum oxide, aluminum silicate, aluminum and titanium or silicon, Composite with zirconium, alkali metal, alkaline earth metal, etc. Product and the like. 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. Examples of basic aluminum acetate stabilizers include urea and thiourea in addition to boric acid.

The above aluminum compound is preferably solubilized in a solvent such as water or glycol.
Solvents that can be used in the present invention are water and alkylene glycols. Examples of alkylene glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylene glycol, ditrimethylene glycol, tetramethylene glycol, ditetramethylene glycol, neopentyl glycol, and the like. . Preferably, they are ethylene glycol, trimethylene glycol, tetramethylene glycol, more preferably ethylene glycol. It is preferable to use those solubilized in water and / or ethylene glycol because the effects of the present invention can be remarkably exhibited.

In the present invention, it is preferable to use the above aluminum compound dissolved in ethylene glycol, and the integrated value of the peak appearing at -15 to 30 ppm in the ²⁷ Al-NMR spectrum determined by the following method is the integral of the reference peak. It is more preferable to use an ethylene glycol solution of an aluminum compound having a ratio to the value of 0.3 or more.
[Method of measuring NMR spectrum of aluminum compound ethylene glycol solution]
The NMR spectrum of an aluminum glycol solution of an aluminum compound is measured by the following method.
Sample: Ethylene glycol solution of aluminum compound (concentration: source of aluminum)
2.65g / l as a basic quantity)
Apparatus: Fourier transform nuclear magnetic resonance apparatus (AVANCE500 manufactured by BRUKER)
Measurement solution: 20 parts by volume of deuterated dimethylsulfoxy with respect to 80 parts by volume of the sample.
Add sid
²⁷ Al resonance frequency: 130.33 MHz
Detection pulse flip angle: 90 °
Data acquisition time: 1.0 seconds Delay time: 1.0 seconds Proton decoupling: not implemented Integration count: 500-1000 times Measurement temperature: room temperature On the other hand, aluminum chloride hexahydrate (AlCl ₃ .6H ₂ O) The peak integral value when measuring a 1.3 mmol / l heavy aqueous solution under the above conditions is 1.0 as a standard, and the peak integral appearing at −15 to 30 ppm of the ethylene glycol solution of the aluminum compound measured by the above method Display as a ratio of values.
The integral value ratio of the peak is more preferably 0.35 or more, further preferably 0.40 or more, and particularly preferably 0.50 or more. If the integral value ratio of the peak is less than 0.30, the amount of aluminum-based foreign matter insoluble in polyester described later increases, and it is not possible to secure 3500 ppm or less, which is not preferable.

The method for setting the integral value ratio of the peak to 0.3 or more is not limited, but it is a preferred embodiment that the temperature of the solution does not become 110 ° C. or higher when the aluminum compound is made into a solution. 105 ° C. or lower is more preferable, and 100 ° C. or lower is further preferable. As described above, the aluminum compound is preferably finally added to the reaction system as an ethylene glycol solution. The method for preparing the ethylene glycol solution is not limited, however, after the aluminum compound is once dissolved in water, ethylene glycol is added to the aqueous solution, and the resulting water / ethylene glycol mixed solvent is heated to remove water. It is a preferable embodiment to carry out by a liquid replacement method for distilling off.
Here, the solution formation includes all steps related to solution formation such as dissolution or liquid replacement. As a method for lowering the temperature in the liquid replacement, it is a preferred embodiment that the lowering is carried out under reduced pressure and both the lowering of the temperature and the shortening of time are performed. Considering the efficiency of liquid replacement, 55 to 105 ° C is preferable, and it is particularly preferable to perform at 60 to 100 ° C.

  In addition, the quality of the aluminum compound used for dissolution is also important as a method for setting the integral value ratio of the peak to 0.3 or less. It is also an effective method to select one with a low degree of association. The method for suppressing the association of the aluminum compound before dissolution is not limited. For example, when preparing an aluminum compound, an additive that suppresses association is added, the concentration and drying temperature of the liquid when the aluminum compound is taken out as a solid in the preparation process, or the drying at the time of drying is reduced. It is effective to make the product in a state of reducing the degree and containing moisture. It is also a preferred embodiment that the aluminum compound is used in the form of a solution such as an aqueous solution without isolation.

  As selection criteria for an aluminum compound having a low degree of association, for example, the amount of insoluble components when the aluminum compound is dissolved in water is specified, the crystallinity of the aluminum compound is specified, and the amount of water of crystallization of the aluminum compound is specified. And the like. It is also a preferred embodiment to use an additive that improves the solubility of the aluminum compound in a solvent such as water and a compound that improves the stability of the aluminum compound against hydrolysis and the like.

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 50 ° C. or higher, and preferably 110 ° C. or lower. More preferably, the water is distilled off by stirring at 55 to 105 ° C. for several hours. It is particularly preferable to carry out at 60 to 100 ° C. It is preferred to reduce the system pressure during the 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 50 ° C. or higher, and preferably 110 ° C. or lower. More preferably, the water is distilled off by stirring at 55 to 105 ° C. for several hours. It is particularly preferable to carry out at 60 to 100 ° C. As in the case of basic aluminum acetate, it is preferable to perform liquid replacement with an ethylene glycol solution under reduced pressure.

In the present invention, removing the insoluble foreign matter such as contaminants present in the solution by a method such as filtration, centrifugation or ultracentrifugation of the aluminum compound solution obtained by the above method is a preferable implementation.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of R ¹ include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of 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 Formula (Chemical Formula 33), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or R ⁴ represents a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group, R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group, or a carbonyl group including carbonyl. Examples of R ⁴ O ⁻ include hydroxide ion, alcoholate ion, acetate ion, acetylacetone ion, etc. l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation, n represents an integer of 1 or more, and the hydrocarbon group includes an alicyclic structure such as cyclohexyl, a branched structure, and an aromatic ring structure such as phenyl or naphthyl. Moyo .)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  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.

It is preferable that the polyester in this invention is 3500 ppm or less of the aluminum type foreign substance insoluble in the polyester quantified by the evaluation method shown below.
[Aluminum-based foreign substance evaluation method insoluble in polyester]
30 g of polyester pellets after melt polycondensation and 300 ml of parachlorophenol / tetrachloroethane (3/1: weight ratio) mixed solution are put into a round bottom flask with a stirrer, and the pellets are added to the mixed solution at 100 to 105 ° C. for 2 hours. Stir and dissolve. The solution was allowed to cool to room temperature, and a polytetrafluoroethylene membrane filter (Advantec PTFE membrane filter, product name: T100A047A) having a diameter of 47 mm / a pore size of 1.0 μm was used, and the total amount was under a pressure of 0.15 MPa. Use to filter out foreign objects. The effective filtration diameter was 37.5 mm. After completion of the filtration, the product is subsequently washed with 300 ml of chloroform, and then dried under reduced pressure at 30 ° C. for a whole day and night. The amount of aluminum element was quantified on the filtration surface of the membrane filter using a scanning X-ray fluorescence analyzer (manufactured by RIGAKU, ZSX100e, Rh tube 4.0 kW). The quantification is performed on a portion having a diameter of 30 mm at the center of the membrane filter. The calibration curve of the fluorescent X-ray analysis method is obtained using a polyethylene terephthalate resin having a known aluminum element content, and the apparent aluminum element amount is expressed in ppm. The measurement is carried out by measuring Al-Kα ray intensity under the conditions of PHA (wave height analyzer) 100-300, using pentaerythritol as a spectral crystal, PC (proportional counter) as a detector, with an X-ray output of 50 kV-70 mA. . The amount of aluminum element in the polyethylene terephthalate resin for the calibration curve is quantified by high frequency inductively coupled plasma emission spectrometry.

  The amount of aluminum-based foreign matter insoluble in polyester measured by the above evaluation method is more preferably 2500 ppm or less. 1500 ppm or less is more preferable. When the amount of aluminum-based foreign matter insoluble in polyester exceeds 3500 ppm, fine foreign matters that are insoluble in the polyester cause the haze of the molded product to deteriorate when molded as a molded product such as a film or bottle. Therefore, it is not preferable. Moreover, it leads to the subject that the filter clogging at the time of filtration of polyester in a polycondensation process or a molding process increases.

The amount of the aluminum-based foreign substance insoluble in the polyester measured by the above evaluation method is a converted value to the last, and the content relative to the total amount of the polyester used for the above evaluation becomes a very small amount of ppb level. The transparency of the molded product deteriorates due to the amount of this very small amount of foreign matter. The aluminum-based foreign matter that is insoluble in polyester measured by the above evaluation method has low affinity for polyester. It is presumed that a void is formed at the interface between the aluminum-based foreign material and light is scattered by the void and the transparency of the molded body is lowered.

  In order to satisfy the above characteristics, it is preferable to use an ethylene glycol solution of an aluminum compound having the above-described characteristics, but it is important to use a mixed solution obtained by mixing the solution and the above-described phosphorus compound solution. The correspondence stabilizes the polyester in which the amount of aluminum-based foreign matter insoluble in the polyester is within a preferable range even when the addition time, location, and characteristics of the added polyester oligomer of the polycondensation catalyst of the present invention are changed. Can be obtained. In this case, it is a preferred embodiment that the phosphorus compound contains a hydroxyl group. Accordingly, a structural compound having at least one hydroxyl group in one molecule of the phosphorus compound is preferable. For example, among the above phosphorus compounds, acid compounds and acid / ester mixed compounds of acids and esters are applicable. In the case of a fully esterified compound in which all the hydroxyl groups of the phosphorus compound are esterified, the phosphorus compound is pretreated with a water-containing solvent such as water or alkylene glycol, and the ester bond is hydrolyzed to partially convert the ester bond to a hydroxyl group. It is a preferred embodiment to use the converted one. The amount of conversion to hydroxyl groups in this case is not limited, but the amount of insoluble foreign matter to the polyester is very small, and the effect of reducing the amount of insoluble foreign matter to the polyester by introducing the hydroxyl group is manifested in a very small amount. Even an amount of about% is effective.

  As described above, the effect of the present invention can be expressed more efficiently by using one that has been previously heat-treated in at least one solvent selected from the group consisting of water and alkylene glycol. However, since the effect of improving the polycondensation catalyst activity is exhibited by the heat treatment, it is recommended as a particularly preferred embodiment.

  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 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.

  In the present invention, the NMR spectrum peak of the phosphorus atom to which the hydroxyl group is bonded in the mixed solution is shifted to a higher magnetic field side than the NMR spectrum peak of the phosphorus atom to which the hydroxyl group is bonded in the phosphorus compound single solution before mixing, and the peak is broadened. It is preferable to become. Furthermore, the integrated value of the NMR spectrum peak of the phosphorus atom to which the hydroxyl group of the mixed solution is bonded is 10% or more with respect to the integrated value of the NMR spectrum peak of the phosphorus atom to which the hydroxyl group of the phosphorus compound single solution before mixing is bonded. Is a preferred embodiment. 15% or more is more preferable, and 20% or more is more preferable. If it is less than 10%, the effect of suppressing the production of foreign substances insoluble in the polyester resulting from the aluminum polycondensation catalyst is reduced, and the content of foreign substances insoluble in the polyester is increased. For example, when molded as a molded body such as a film or bottle, This is not preferable because the haze of the molded body deteriorates. Moreover, it leads to the subject that the filter clogging at the time of filtration of polyester in a polycondensation process or a molding process increases. In addition, it is preferable that 90 mol% or more of the solvent of said mixed solution is ethylene glycol.

  By mixing an ethylene glycol solution of the above aluminum compound and a phosphorus compound solution, the NMR spectrum peak of the phosphorus atom to which the hydroxyl group is bonded shifts to the high magnetic field side. This is because the hydroxyl group in the phosphorus compound is aligned with the aluminum atom in the aluminum compound. It is presumed that it is caused by the formation of a complex.

  The mixed solution of the aluminum compound solution and the phosphorus compound solution described above causes gelation of the aluminum compound or a complex of the aluminum compound and the phosphorus compound when stored at a high temperature. Added to the polycondensation reaction system because it is necessary to manage its storage method. Preferably, it is performed immediately before.

  When carried out by this method, it is preferable to accelerate the reaction between the aluminum compound and the phosphorus compound. In the case of a phosphorus compound having a hydroxyl group, the reaction proceeds almost instantaneously. Therefore, in the case of an ester type phosphorus compound in which all hydroxyl groups are esterified, the hydroxyl group is generated in advance by the method described above. It is preferable to do this.

When mixing the ethylene glycol solution and the phosphorus compound solution of the above aluminum compound, the mixing ratio of the aluminum compound and the phosphorus compound is preferably such that the molar ratio of the aluminum atom and the phosphorus atom is represented by the formula (1). .
0.5 ≦ P / Al (molar ratio) ≦ 20 (1)
Exceeding the range of the above formula (1) is not preferable because the polycondensation catalyst activity is lowered and the effect of suppressing the formation of foreign matters insoluble in the polyester is lowered. P / Al (molar ratio) is preferably 0.8 to 10, more preferably 1.0 to 5.

The mixing method of the aluminum compound solution and the phosphorus compound solution is not limited, but it is preferable to use a homomixer type mixer in which the peripheral speed of the outer periphery of the stirring blade is 2 to 400 m / sec. The mixer is preferably, for example, a commercially available pipeline homomixer.
The peripheral speed of the outer periphery of the stirring blade is more preferably 5 to 200 m / second, and further preferably 10 to 100 m / second. Further, it is preferable to use a stirring blade having a high stirring efficiency such as a disk turbine blade. By this method, the effect of the present invention is stably expressed.

  The mixing temperature is not limited. The temperature control of the homomixer is not particularly necessary. However, since the phosphorus compound solution may precipitate at a low temperature depending on the type of the phosphorus compound, it is preferable to supply the phosphor compound solution after heating to around 70 ° C.

  In the present invention, the mechanism that the content of foreign matter insoluble in polyester is reduced by satisfying the above requirements has not been clarified, but the hydroxyl group in the phosphorus compound is coordinated to the aluminum atom of the aluminum compound, and the aluminum compound It is presumed that the formation of a complex of a phosphorus compound is caused by the formation of foreign matters insoluble in the polyester derived from the aluminum compound.

As described above, due to the effect of the present invention, the conventional problem that the amount of foreign matter insoluble in the polyester obtained by the difference in the manufacturer and lot of the aluminum compound greatly fluctuates can be solved,
Without reducing the polycondensation activity and increasing side reactions during polyester formation, this problem has been solved and the amount of foreign matter insoluble in polyester has always been stably maintained at a low level.

  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. When M is less than 1 × 10 ⁻⁶ , the effect is not clear even when added.

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

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

  The polycondensation catalyst of the present invention is a polycondensation catalyst such as an antimony compound, a germanium compound, or a titanium compound, and the addition of these components does not cause problems in the 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 order to improve the color tone of the polyester of the present invention, it is also a preferred embodiment to use a color tone improving agent other than the cobalt compound. The color tone improving agent refers to a substance that changes color tone when added. The color tone improving agent of the present invention is not particularly limited, but inorganic and organic pigments, dyes, fluorescent whitening agents and the like are preferable.

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

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

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

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

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

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

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

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

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

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

It is preferable that the haze value of the uniaxially stretched film evaluated by the evaluation method shown below is 2% or less.
[Haze value of uniaxially stretched film]
The polyester resin was dried under vacuum at 130 ° C. for 12 hours and 1000 ±±
Create a 100 μm sheet. The heat press temperature, pressure and time are 320 ° C., 100 kg / cm ² G and 3 seconds, respectively. After pressing, the sheet is put into water and rapidly cooled. The obtained sheet is uniaxially stretched 3.5 times by a batch type stretching machine (manufactured by TM LONG CO., INC, FILM STRETCHER) to obtain a uniaxially stretched film of 300 ± 20 μm. The stretching temperature is blow temperature 95 ° C / plate temperature 100 ° C. The stretching speed is 15,000% / min. The haze of the obtained uniaxially stretched film is measured according to JIS-K7136 using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., 300A). The measurement is performed 5 times and the average value is obtained. The haze value is displayed as a converted value of a film thickness of 300 μm.
1.8% or less is more preferable, and 1.6% or less is more preferable. A haze value exceeding 2% is not preferable because a molded body having high transparency cannot be obtained with respect to a molded body formed by molding with stretching such as a film or a bottle.

  In the present invention, the method of setting the haze value of the uniaxially stretched film to 2% or less is not limited, but the haze value is greatly affected by the amount of aluminum-based foreign matter insoluble in the polyester, so that the characteristic value is within the above range. It is preferable to optimize.

  The method for producing polyester in the present invention can be applied to both a batch polycondensation method and a continuous polycondensation method. The continuous polycondensation method is advantageous in terms of quality uniformity and economy compared to the batch polycondensation method. The polycondensation method in the present invention is either a so-called direct esterification method produced by a reaction between a dicarboxylic acid and a diol, or a so-called transesterification method produced by a reaction between an ester-forming derivative of a dicarboxylic acid and a diol. It does not matter. Further, the number and size of the reactors in the esterification, transesterification and polycondensation steps, production conditions in each step, and the like can be appropriately selected without limitation.

  A production method by a continuous direct esterification method, which is one preferred embodiment, is exemplified below.

  A slurry containing 1.02 to 1.5 moles, preferably 1.03 to 1.4 moles of ethylene glycol per mole of terephthalic acid was prepared, and this was continuously added to the esterification reaction step. To supply.

  The esterification reaction is carried out using a multistage apparatus in which 1 to 3 esterification reaction tanks are connected in series while removing water generated by the reaction from the system with a rectification column. The temperature of the esterification reaction in the first stage is 240 to 270 ° C., preferably 245 to 265 ° C., and the pressure is normal pressure to 0.29 MPa, preferably 0.005 to 0.19 MPa. The temperature of the esterification reaction at the final stage is usually 250 to 290 ° C, preferably 255 to 275 ° C, and the pressure is usually 0 to 0.15 MPa, preferably 0 to 0.13 MPa. 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. A low-order condensate having a molecular weight of about 500 to 2000 is obtained by these esterification reactions. Subsequently, it is transferred to a polycondensation reaction tank to carry out polycondensation. The number of reaction tanks in the polycondensation step is not limited. In general, a three-stage system of initial polycondensation, intermediate polycondensation and late polycondensation is employed. As for the polycondensation reaction conditions, the reaction temperature of the first stage polycondensation is 250 to 290 ° C., preferably 260 to 280 ° C., and the pressure is 0.065 to 0.0026 MPa, preferably 0.026 to 0.0039 MPa. In the final stage, the temperature of the polycondensation reaction is 265 to 300 ° C., preferably 275 to 295 ° C., and the pressure is 0.0013 to 0.000013 MPa, preferably 0.00065 to 0.000065 MPa. 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 transesterification method, the transesterification reaction is performed by continuously supplying, for example, dimethyl terephthalate and ethylene glycol to the reactor using an apparatus in which one or two transesterification reactors are connected in series. The methanol produced by the reaction is removed from the system by a rectification column. The temperature of the first stage transesterification is 180 to 250 ° C, preferably 200 to 240 ° C. The temperature of the transesterification reaction at the final stage is usually 230 to 270 ° C, preferably 240 to 265 ° C. As the transesterification catalyst, it is preferable to use fatty acid salts such as Zn, Cd, Mg, Mn, Co, Ca, Ba, carbonates, and the like.

  When the transesterification method is used, it is preferable to block the transesterification catalyst by adding a phosphorus compound at the end of the transesterification reaction. In general, phosphoric acid, phosphorous acid, and ester derivatives thereof are used as the phosphorus compound, but the above phosphorus compounds may be used.

  In the present invention, the addition location of the polycondensation catalyst solution composed of the mixed solution of the aluminum compound solution and the phosphorus compound solution is not limited.

  In the continuous polycondensation method, for example, when a compound containing a hindered phenol residue such as Chemical Formula 39 or Chemical Formula 40 is used as the phosphorus compound, the temperature rise crystallization temperature ( Tc1) changes. The influence of the heat history after the addition is large, and Tc1 decreases as the heat history increases. Tc1 increases as it is added later in the polycondensation step. Depending on the type of phosphorus compound, when the polyester is PET, Tc1 is around 140 ° C. in the initial addition of the esterification reaction, but is 165 ° C. or more in the case of addition after the completion of the esterification reaction. Therefore, Tc1 can be controlled in a wide range by changing the addition location of the mixed solution of the aluminum compound and the phosphorus compound, and it is possible to lead to the solution of the problems in the bottle molding described above. In the method of the present invention, even when the addition location of the polycondensation catalyst solution is changed, the quality such as polycondensation catalyst activity, color tone, and the amount of aluminum-based foreign matter insoluble in polyester does not change. Therefore, by changing the addition location of the polycondensation catalyst solution, Tc1 can be controlled in a wide range while maintaining the above characteristics.

  Although the cause of the change in Tc1 due to the change in the addition position of the polycondensation catalyst is unclear, the polycondensation catalyst, in particular, the alteration due to the thermal reaction in the polycondensation reaction step of the phosphorus compound is involved. I guess. In particular, it is speculated that the contribution of elimination of the t-butyl group in the hindered phenol residue is large.

  The polycondensation catalyst solution may be added to the reaction tank or may be added to a transfer pipe between the reaction tanks. In the case of adding to the transfer pipe, it is a preferred embodiment that an in-line mixer is installed and added to the in-line mixer. The structure of the in-line mixer used in this method is not limited as long as a uniform mixing effect can be exhibited. For example, an in-line mixer for the purpose of dispersing and mixing the slurry disclosed in JP-A-8-299771 is suitable.

  The esterification or transesterification reaction conditions, the characteristics of the low-order condensate of the product, and the polycondensation reaction conditions in the present invention may be appropriately set in consideration of the quality and productivity of the polyester.

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

  The polyester obtained by the method of the present invention is heated under reduced pressure or under an inert gas stream to further proceed with polycondensation, an oligomer such as a cyclic trimer contained in the polyester resin, acetaldehyde, etc. There are no restrictions on taking measures such as removing the by-products. Further, for example, it is possible to incorporate a treatment such as purifying a polyester resin by an extraction method such as a supercritical pressure extraction method to remove impurities such as the by-products.

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

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

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

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

  Among these, polyester is particularly suitable for various beverages as a pressure-resistant container, a heat-resistant pressure-resistant container, and an alcohol-resistant container utilizing the hygiene and strength 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.

  As described above, since the polyester obtained by the method of the present invention has an optimized Tc1 that greatly affects the crystallization of the polyester, the crystallization characteristics of the polyester as the raw material for the heat-resistant bottle are regarded as important. It can be particularly preferably used for the field to be used.

  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 co-extrusion method, using a several extruder, assigning various functions to 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 simultaneously in the longitudinal direction and the transverse direction. In addition to using a linear motor as the driving method for simultaneous biaxial stretching, several times in the same direction, such as horizontal / longitudinal / longitudinal stretching, longitudinal / horizontal / longitudinal stretching, and longitudinal / vertical / horizontal stretching It is possible to adopt a multistage stretching method in which the stretching is performed separately.

  Further, after the completion of stretching, in order to reduce the thermal shrinkage rate of the film, a heat setting treatment is performed at a temperature of (melting point−50 ° C.) to less than the melting point within 30 seconds, preferably within 10 seconds. % 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, infrared absorption, antibacterial properties, scratch resistance, etc., the surface of the oriented polyester film may be coated with a polymer resin by a coating method. Good. Moreover, it is good also as a slippery highly transparent polyester film by making an inorganic and / or organic particle | grain contain only in a coating layer. Furthermore, an inorganic vapor deposition layer can be provided to provide various barrier functions such as oxygen, water, and oligomer, or a conductive layer can be provided by a sputtering method or the like to provide conductivity. In addition, inorganic and organic salt particles or heat-resistant polymer resin particles are added in the polyester polymerization process in order to improve the handling properties such as slipping property, running property, wear resistance, and winding property of the oriented polyester film. Then, irregularities may be formed on the film surface. These particles may be either inorganic / organic or hydrophilic / hydrophobic surface-treated or non-surface-treated particles. For example, particles that have been surface-treated for the purpose of improving dispersibility. There are cases where it is preferable to use.

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

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

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

    A method for incorporating the inert particles in the polyester as the base film is not limited, but (a) the inert particles are dispersed in a slurry form in a diol which 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 vent type twin screw extruder in a melt extrusion step of a polyester film, (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. Moreover, when preparing 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 the polyester or after polymerization, or at any stage after the formation of the polyester film. 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 ear part of the film produced in the stretching process or a nonstandard film 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 decorative 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, Reflective For prevention film, for conductive film, for separator, for ultraviolet 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 JP-A-6-184337 can be used. Examples of the easy-adhesive film include JP-B-07-108563, JP-A-10-235820, JP-A-11-323271, and examples of cards include JP-A-10-171958 and JP-A-11-010815. The technique can be applied to the film of the present invention. For the dummy can, for example, instead of the sheet-like cylinder described in JP-A-10-101103, a design obtained by printing a design on the film of the present invention to form a cylinder or a half cylinder can be used. For building materials, decorative plates for building materials, and decorative materials, for example, the film of the present invention can be used as a base sheet described in JP-A No. 05-200927 and a transparent sheet described in JP-A No. 07-314630. it can. As the OHP (for overhead projector), the film of the present invention can be used as the transparent resin sheet described in JP-A No. 06-297831 and the transparent polymer synthetic resin film described in JP-A No. 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 No. 05-088400. For thermal transfer recording, the film of the present invention can be used by the methods described in JP-A-07-032754, for thermal recording, and JP-A-11-034503, respectively. For printed circuit boards, for example, the film of the present invention can be used as a polyester film described in JP-A-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, plasma display), for example, the film of the present invention can be used by the method described in JP-A-11-231126. For transparent conductive films and touch panels, the film of the present invention can be used by the method described in JP-A-11-224539, for example. 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 the retardation 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. As an agricultural film, it can be obtained by applying the film of the present invention to a polyethylene terephthalate film described in JP-A-10-166534. The pressure-sensitive adhesive sheet can be obtained, for example, by applying the oriented polyester film of the present invention to a polyethylene terephthalate film described in JP-A-06-122856.

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

1. Measurement of NMR spectrum of ethylene glycol solution of aluminum compound NMR spectrum of ethylene glycol solution of aluminum compound was measured by the following method.
Sample: Ethylene glycol solution of aluminum compound (concentration: source of aluminum)
2.65g / l as a basic quantity)
Apparatus: Fourier transform nuclear magnetic resonance apparatus (AVANCE500 manufactured by BRUKER)
Measurement solution: 20 parts by volume of deuterated dimethyl sulfoxide with respect to 80 parts by volume of the sample
Add
²⁷ Al resonance frequency: 130.33 MHz
Detection pulse flip angle: 90 °
Data acquisition time: 1.0 seconds Delay time: 1.0 seconds Proton decoupling: not implemented Integration count: 500-1000 times Measurement temperature: room temperature On the other hand, aluminum chloride hexahydrate (AlCl ₃ .6H ₂ O) The peak integral value when measuring a 1.3 mmol / l heavy aqueous solution under the above conditions is 1.0 as a standard, and the peak integral appearing at −15 to 30 ppm of the ethylene glycol solution of the aluminum compound measured by the above method Displayed as a ratio of values.

2. Method for measuring NMR spectrum of mixed solution (polycondensation catalyst solution) of aluminum compound and phosphorus compound Device: Fourier transform nuclear magnetic resonance device (AVANCE500 manufactured by BRUKER)
Measurement solution: 20 parts by volume of deuterated dimethylsulfoxy with respect to 80 parts by volume of the sample
Added.
³¹ P resonance frequency: 202.47 MHz
Detection pulse flip angle: 45 °
Data acquisition time: 2.0 seconds Delay time: 0.5 seconds Proton decoupling: Proton complete decoupling Integration count: 2000 to 10000 times Measurement temperature: Room temperature

3. Measurement of intrinsic viscosity (IV) It measured at 30 degreeC using the phenol / tetrachloroethane (60:40, weight ratio) mixed solvent.

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

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

6. Evaluation method of aluminum insoluble matter insoluble in polyester 30g of polyester pellets after melt polycondensation and 300ml of parachlorophenol / tetrachloroethane (3/1: weight ratio) mixed solution are put into a screw-lens Erlenmeyer flask and the pellets are mixed The solution was stirred and dissolved in a sealed state at 60 to 80 ° C. for 2 hours. While maintaining the solution at 50 to 70 ° C., foreign matter was filtered off under reduced pressure using a membrane filter made of polytetrafluoroethylene having a diameter of 47 mm / pore size of 1.0 μm (PTFE membrane filter manufactured by Advantec, product name: T100A047A). . The effective filtration diameter was 37.5 mm. After completion of the filtration, the product was subsequently washed with 50 ml of chloroform, and then the filter was dried at 80 ° C. for 2 hours under normal pressure. The amount of aluminum element was quantified on the filtration surface of the membrane filter with a scanning fluorescent X-ray analyzer (manufactured by RIGAKU, ZSX100e, Rh tube 4.0 kW). The quantification was performed on a portion having a diameter of 30 mm at the center of the membrane filter. The calibration curve of the X-ray fluorescence analysis was determined using a polyethylene terephthalate resin having a known aluminum element content, and the apparent aluminum element amount was expressed in ppm. The measurement was carried out by measuring the intensity of Al-Kα rays under the conditions of PHA (wave height analyzer) 100-300 using X-ray output 50 kV-70 mA and using pentaerythritol as a spectroscopic crystal and PC (proportional counter) as a detector. . The amount of aluminum element in the polyethylene terephthalate resin for the calibration curve was determined by high frequency inductively coupled plasma optical emission spectrometry. 7. Haze value of uniaxially stretched film Polyester resin was dried at 130 ° C. for 12 hours under vacuum, and 1000 by heat press method. ±
Create a 100μm sheet. The heat press temperature, pressure and time were 320 ° C., 100 kg / cm ² G and 3 seconds, respectively. After pressing, the sheet was put into water and rapidly cooled. The obtained sheet was uniaxially stretched 3.5 times by a batch type stretching machine (manufactured by TM LONG CO., INC, FILM STRETCHER) to obtain a uniaxially stretched film of 300 ± 20 μm. The stretching temperature was blow temperature 95 ° C./plate temperature 100 ° C. The stretching speed was 15,000% / min. The haze of the obtained uniaxially stretched film was measured according to JIS-K7136 using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., 300A). In addition, the measurement was performed 5 times and the average value was calculated | required. The haze value was displayed as a converted value of a film thickness of 300 μm.

Example 1
(1) Preparation of ethylene glycol solution of phosphorus compound To a flask equipped with a nitrogen introduction tube and a cooling tube, 2.0 liters of ethylene glycol was added at room temperature and normal pressure, and then stirred at 200 rpm in a nitrogen atmosphere as a phosphorus compound. 200 g of Irganox 1222 (manufactured by Ciba Specialty Chemicals) represented by (Chemical Formula 39) was added. Further, 2.0 liters of ethylene glycol was added, the temperature was raised by changing the jacket temperature setting to 196 ° C., 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%.
(2) Preparation of aqueous solution of aluminum compound After adding 5.0 liters of pure water to a flask equipped with a cooling tube at room temperature and normal pressure, 200 g of basic aluminum acetate as a slurry with pure water while stirring at 200 rpm added. Further, pure water was added so as to be 10.0 liters as a whole, and the mixture was stirred at room temperature and normal pressure for 12 hours. Thereafter, the jacket temperature was changed to 100.5 ° C., the temperature was raised, and the mixture was stirred under reflux for 3 hours from the time when the internal temperature reached 95 ° C. or higher. Stirring was stopped and the mixture was allowed to cool to room temperature to obtain an aqueous solution.
(3) Preparation of ethylene glycol mixed solution of aluminum compound After adding an equal volume of ethylene glycol to the aqueous aluminum compound solution obtained by the above method and stirring for 30 minutes at room temperature, the internal temperature was controlled at 80 to 90 ° C, and the pressure was gradually reduced. Then, the water was distilled from the system while stirring for several hours at an arrival of 27 hPa to obtain an ethylene glycol solution of an aluminum compound of 20 g / l. The peak integrated value ratio of ²⁷ Al-NMR spectrum of the obtained aluminum solution was 2.2.

(4) Esterification reaction and polycondensation 0.45 parts by mass of ethylene glycol with respect to 1 part by mass of high-purity terephthalic acid in a continuous polyester production apparatus comprising two continuous esterification reaction tanks and three polycondensation reaction tanks The first and second esterification tanks are prepared by mixing and the slurry is continuously supplied to the first esterification tank at a reaction temperature of 250 ° C. and 0.1 MPa, and the second esterification tank at 250 ° C. and 0.1 MPa. The reaction time in the reaction tank was adjusted, and ethylene glycol was added to the second esterification reaction tank to obtain a polyester oligomer. AVO and OHVo of the oligomer at the outlet of the first esterification reactor were 1600 eq / ton and 1400 eq / ton, respectively. The oligomers AVO and OHVo at the outlet of the second esterification reactor were 650 eq / ton and 1520 eq / ton, respectively, and OHV% was 70 mol%. The oligomer is continuously transferred to a continuous polycondensation apparatus comprising three reaction vessels, and the ethylene glycol solution of the aluminum compound and the ethylene glycol solution of the phosphorus compound prepared by the above method are respectively supplied to the acid component in the polyester. A pipeline homomixer equipped with disk turbine blades at 0.015 mol% and 0.036 mol% as aluminum atoms and phosphorus atoms was installed in the addition line of the second esterification reaction tank and stirred at 5000 rpm 50 m / sec. The polycondensation catalyst solution prepared continuously was continuously added to the second esterification reaction tank simultaneously with the preparation, and the initial polycondensation reactor was 265 ° C., 0.009 MPa, and the medium-term polycondensation reactor was 265 to 275. ° C, 0.0067 MPa, final polycondensation reactor at 270-280 ° C, 0.00001 Polycondensation was carried out at 33 MPa to obtain PET with an IV of 0.62. Table 1 shows the characteristic values of the obtained PET. In addition, the temperature control of the said homomixer was not performed. Further, the phosphorus compound solution was heated to 50 to 70 ° C. to prevent precipitation of the phosphorus compound. The NMR spectrum of the mixture of the aluminum compound solution and the phosphorus compound solution at the outlet of the homomixer is in the range of 5 to 24 ppm that does not exist in the spectrum of the ethylene glycol solution of the phosphorus compound before mixing with the ethylene glycol solution of the aluminum compound. A broad peak (referred to as coordination peak) was observed. The integral value of the coordination peak is the value of the NMR spectrum peak of the phosphorus atom bonded with the hydroxyl group observed in the vicinity of 25 to 27 ppm present in the NMR spectrum of the ethylene glycol solution of the phosphorus compound before mixing with the ethylene glycol solution of the aluminum compound. It was 50% with respect to the integral value.

Comparative Example 1
In the method of Example 1, a comparative example was made in the same manner as in Example 1 except that the ethylene glycol solution of the aluminum compound and the ethylene glycol solution of the phosphorus compound were added so as to be added from separate supply ports without mixing. 1 PET was obtained. The properties of the obtained PET are shown in Table 1.

Example 2
In the method of Example 1, the PET of Example 2 was prepared in the same manner as in Example 1 except that the aqueous temperature of the aluminum compound was replaced with an ethylene glycol solution so that the internal temperature was controlled at 95 to 105 ° C. Obtained. The integrated value ratio of ²⁷ Al-NMR spectrum peak of the aluminum solution obtained in this example was 0.84. Further, the integrated value of the coordination peak in the NMR spectrum of the polycondensation catalyst solution is the value of the phosphorus atom bonded to the hydroxyl group observed in the vicinity of 25 to 27 ppm present in the NMR spectrum of the ethylene glycol solution of the phosphorus compound before preparation of the polycondensation catalyst. It was 25% with respect to the integrated value of the NMR spectrum peak. The properties of the obtained PET are shown in Table 1.

Comparative Example 2
In the method of Example 2, a comparative example was obtained in the same manner as in Example 2 except that the ethylene glycol solution of the aluminum compound and the ethylene glycol solution of the phosphorus compound were added so as to be added from separate supply ports without mixing. 2 PET was obtained. The properties of the obtained PET are shown in Table 1.

Example 3
In the method of Example 1, PET of Example 3 was obtained in the same manner as in Example 1 except that the addition location of the polycondensation catalyst solution was changed to the first esterification reaction tank. The properties of the obtained PET are shown in Table 1.

Comparative Example 3
In the method of Example 3, a comparative example was made in the same manner as in Example 3 except that the ethylene glycol solution of the aluminum compound and the ethylene glycol solution of the phosphorus compound were added so as to be added from separate supply ports without mixing. 3 PET was obtained. The properties of the obtained PET are shown in Table 1.

  The PET obtained in Examples 1 to 3 has high polycondensation productivity, little color tone and generation of insoluble foreign matters due to the polycondensation catalyst, and both economy and quality are compatible. The uniaxially stretched film obtained by using the PET obtained in these examples had a low haze and an excellent transparency. In addition, it can be seen from these Examples that the above-described high-quality PET can be stably obtained even if the addition position of the polycondensation catalyst is changed. Furthermore, it can be seen that by changing the addition location of the polycondensation catalyst, Tc1 can be changed in a wide range while maintaining the polycondensation catalyst activity and quality. For example, if a polycondensation catalyst is added to the transfer tube connecting the first esterification reaction tank and the second ester reaction tank, the Tc1 PET intermediate between Examples 1 and 2 and Example 3 is also used as the second ester. If a polycondensation catalyst is added to the transfer pipe from the chemical reaction tank to the first polycondensation reaction tank, PET having a Tc1 of 167 ° C. can be obtained. If the number of esterification reaction tanks is three or more, it is possible to obtain a PET having an intermediate Tc1 within the above range. On the other hand, since PET obtained in Comparative Examples 1 to 3 has many insoluble foreign matters, the transparency of the molded body is low.

The polyester production method according to the present invention is a polycondensation catalyst in which a metal component other than antimony, germanium and titanium is used as the main metal component of the catalyst and maintains the polycondensation catalyst activity, color tone, transparency, thermal stability, etc. Can be controlled in a wide temperature range, and a polyester with less foreign matter generation due to the polycondensation catalyst can be obtained. Accordingly, the polyester obtained by the production method of the present invention includes, for example, fibers for clothing and industrial materials, films and sheets for packaging, magnetic tape and optics, bottles that are hollow molded articles, electrical / electronic components, etc. Can be suitably used in a wide range of fields such as casings and other engineering plastic molded articles. Further, since the polyester of the present invention has a feature that the generation of foreign matter due to the polycondensation catalyst is small, it exhibits the feature in the fields of ultrafine fibers, highly transparent films for optical use or hollow molded articles, etc. Because it has the advantage of being able to do so, it is important to contribute to the industry.

Claims (11)

  In a method for producing a polyester in the presence of a polyester polycondensation catalyst comprising at least one selected from the group consisting of aluminum compounds and at least one selected from phosphorus compounds, the aluminum compound and the phosphorus compound are used as solutions, A method for producing a polyester comprising mixing and adding immediately before addition to a polycondensation reaction system.   2. The method for producing a polyester according to claim 1, wherein the aluminum compound solution and the phosphorus compound solution are mixed in a homomixer type mixer having a peripheral speed of 2 to 400 m / sec on the outer periphery of the stirring blade. 3. The polyester production according to claim 1, wherein the aluminum compound solution and the phosphorus compound solution are mixed and added to the polycondensation reaction system so that the molar ratio of aluminum atoms and phosphorus atoms satisfies the following formula. Method.
1 ≦ P / Al (molar ratio) ≦ 5
[Wherein Al is the number of moles of aluminum atoms in the aluminum compound, and P is the number of moles of phosphorus atoms in the phosphorus compound]   The NMR spectrum peak of the phosphorus bond substituted with the hydroxyl group of the mixed solution of the aluminum compound and the phosphorus compound is shifted to a higher magnetic field side than the NMR spectrum peak of the phosphorus bond substituted with the hydroxyl group of the phosphorus compound single solution before mixing. The method for producing a polyester according to any one of claims 1 to 3, which comprises a broad solution.   The integrated value of the shifted peak is 10% or more with respect to the integrated value of the NMR spectrum peak of the phosphorus bond substituted with the hydroxyl group of the phosphorus compound single solution before mixing with the aluminum compound solution. The manufacturing method of the polyester in any one of Claims 1-4.   6. The temperature-controlled crystallization temperature (Tc1) is adjusted by changing the addition location of the mixed solution of the aluminum compound and phosphorus compound in the continuous polycondensation method. Polyester production method.   The polyester production method according to any one of claims 1 to 6, wherein the phosphorus compound comprises a hindered phenol residue.   Polyester manufactured with the manufacturing method in any one of Claims 1-7.   A hollow molded body comprising the polyester according to claim 8.   A fiber comprising the polyester according to claim 8.   A film comprising the polyester according to claim 8.