JP2008013664A - Copolyester and its molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copolyester which is produced by using a catalyst not containing a metal compound such as a titanium compound, an antimony compound, a tin compound, or a germanium compound, as the main catalyst component and is excellent in transparency, color tone, and moldability. <P>SOLUTION: The copolyester is produced by polycondensation using a polycondensation catalyst containing an aluminum compound. The main component of the copolyester is recurring units each consisting of an aromatic dicarboxylic acid and an aliphatic glycol, and the copolyester contains 1.0-20.0 mol% at least one copolymerization component selected from among terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, bisphenol A, and an ethylene oxide adduct of bisphenol A. The intrinsic viscosity of the copolyester is 0.90-1.50 dL/g. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is excellent in transparency, color tone, and moldability using a polycondensation catalyst mainly composed of an aluminum compound, which does not use a metal compound such as a tin compound, an antimony compound, a germanium compound and a titanium compound as a main catalyst component. The present invention relates to a copolyester and a molded body comprising the same.

  Polyesters represented by polyethylene terephthalate (hereinafter simply referred to as “PET”), polybutylene terephthalate (hereinafter simply referred to as “PBT”), polyethylene naphthalate (hereinafter simply referred to as “PEN”), Excellent in properties and chemical properties, depending on the properties of each polyester, such as hollow molded products such as bottles, films for packaging and magnetic tape, sheets for packaging, etc., for electrical and electronic parts, etc. It is used in a wide range of fields such as molding materials.

  Among these polyesters, polyethylene terephthalate is particularly soft drinks such as carbonated drinks, juices, mineral waters and the like due to its excellent transparency, mechanical strength, heat resistance, gas barrier properties and the like. It is used as a material for containers for cosmetics, pharmaceuticals, detergents, etc., and its spread is remarkable.

  When manufacturing plastic bottles, melt-plasticized resin is extruded through a die orifice because of ease of molding, high productivity, and relatively low equipment costs for molding machines and molds. A so-called extrusion blow molding method (extrusion blow method) in which a cylindrical parison is formed and sandwiched between molds and air is blown into the interior is now generally employed. In the case of this extrusion blow molding, it is necessary to avoid that the parison extruded in the molten state is drawn down during blow molding in order to perform the molding smoothly, and therefore, the resin used requires a high melt viscosity. In general, vinyl chloride resins and polyolefins having a high melt viscosity are widely used in this extrusion blow molding technique.

  As a method of manufacturing a hollow molded body made of polyester resin, an injection molding method in which a molten polyester resin is directly injected into a mold to make a molded body as it is, or a sealed parison (preform) by injecting a molten resin into a mold. In general, an injection blow method is used in which an air blow is inserted into a blow mold and air is blown. However, the injection molding method and the injection blow method require high technology in the production and molding of molds, and it is difficult to manufacture a container having a complicated shape having thin objects, deep objects, large objects, and handles. Has the disadvantages. In addition, these molding methods are suitable for mass-produced containers due to high equipment costs such as molds and molding equipment, but have a problem that they are not suitable for multi-product / small-volume production. For these reasons, the extrusion blow molding method of PET or copolymerized PET is employed for molding pharmaceutical containers such as eye drops, and high molecular weight PET or high molecular weight copolymerized PET is used (for example, (See Patent Documents 1, 2, 3, etc.).

  In general, PET and copolymerized PET used for such applications mainly use terephthalic acid and ethylene glycol as raw materials, and use a germanium compound, an antimony compound, a titanium compound and a mixture thereof as a polycondensation catalyst. Manufactured.

Among the above-mentioned catalysts, the antimony catalyst is a catalyst that is inexpensive and has excellent catalytic activity. However, when it is used in a main component, that is, in an added amount such that a practical polymerization rate is exhibited. Because antimony is deposited during polycondensation, darkening and foreign matter occur in the polyester, and the resulting PET has a faster crystallization rate and superior transparency compared to the case where a germanium compound or a titanium compound is used as a catalyst. It is very difficult to obtain a hollow molded body, particularly a large hollow molded body or a thick extruded blow hollow molded body.
Recently, environmental problems related to antimony safety have been pointed out. Under such circumstances, a polyester that does not contain antimony at all or does not contain antimony as a main catalyst component is desired.

  As a method for solving the above problems, attempts have been made to use antimony trioxide as a catalyst and suppress the occurrence of darkening and foreign matter in PET. For example, by using a compound of antimony trioxide, bismuth and selenium as a polycondensation catalyst, generation of black foreign matters in PET is suppressed (for example, see Patent Document 4). Further, as another technique, it is disclosed that the use of antimony trioxide containing sodium and iron oxides as a polycondensation catalyst suppresses the precipitation of metal antimony (see, for example, Patent Document 5). However, these polycondensation catalysts cannot achieve the purpose of reducing the content of antimony in the polyester after all.

For applications requiring transparency such as PET bottles, as a method for solving the problems of antimony catalysts, a method is disclosed in which transparency is improved by defining the use amount ratio of antimony compound and phosphorus compound. (See, for example, Patent Document 6). However, it cannot be said that the hollow molded body made of polyester obtained by this method has sufficient transparency.
Moreover, the continuous manufacturing method of polyester excellent in transparency using an antimony trioxide, phosphoric acid, and a sulfonic acid compound is disclosed (for example, refer patent document 7). However, the polyester obtained by such a method has a problem that the thermal stability is poor and the acetaldehyde content of the obtained hollow molded article is high.

  Polycondensation catalysts to replace antimony-based catalysts such as antimony trioxide have been studied, and titanium compounds and tin compounds typified by tetraalkoxy titanate have already been proposed. There is a problem that it is susceptible to thermal degradation during melt molding and the polyester is markedly colored.

As an attempt to overcome such problems when a titanium compound is used as a polycondensation catalyst, for example, a method of using tetraalkoxy titanate simultaneously with a cobalt salt and a calcium salt has been proposed (see, for example, Patent Document 8). ). In addition, a method has been proposed in which tetraalkoxy titanate is used simultaneously with a cobalt compound as a polycondensation catalyst and an optical brightener is used (see, for example, Patent Document 9). However, with these techniques, although coloring of PET when tetraalkoxy titanate is used as a polycondensation catalyst is reduced, it has not been achieved to effectively suppress thermal decomposition of PET.
As another attempt to suppress thermal deterioration during melt molding of a polyester polymerized using a titanium compound as a catalyst, a method of adding a phosphorus compound after polymerizing the polyester using the titanium compound as a catalyst has been disclosed (for example, (See Patent Document 10). However, it is not only technically difficult to effectively add the additive to the polymer after polymerization, but also the cost is increased and it is not put into practical use.

  Aluminum compounds are generally known to have poor catalytic activity. Among aluminum compounds, aluminum chelate compounds have been reported to have higher catalytic activity as polycondensation catalysts than other aluminum compounds, but they have sufficient catalytic activity compared to the antimony compounds and titanium compounds described above. However, no example has been known in which a polyester polymerized using an aluminum compound as a catalyst is used for a hollow molded body or a film.

  A germanium compound has already been put to practical use as a catalyst that gives a polyester having excellent catalytic activity other than antimony compounds and excellent thermal stability and thermal oxidation stability. However, this catalyst is very expensive. There are problems and problems that the catalyst concentration in the reaction system changes due to easy distilling out of the reaction system during the polymerization, making it difficult to control the polymerization. is there.

  Moreover, the method of removing a catalyst from polyester is also mentioned as a method for suppressing thermal degradation during melt molding of polyester. As a method for removing the catalyst from the polyester, a method in which the polyester resin is brought into contact with an extractant that is a supercritical fluid in the presence of an acidic substance is disclosed (for example, see Patent Document 11). However, such a method using a supercritical fluid is not preferable because it is technically difficult and increases costs.

As described above, a high-molecular-weight copolymer polyester obtained by using a polymerization catalyst having a metal (component) other than antimony and germanium as a main metal component of the catalyst, and an inexpensive, non-colored and transparent material comprising the same. An extrusion blow molded article having excellent properties is desired.
JP-A-4-59822 Japanese Patent Laid-Open No. 5-65338 JP-A-7-207003 Japanese Patent No. 2666502 JP 9-291141 A JP-A-6-279579 Japanese Patent Laid-Open No. 10-36495 JP-A-55-116722 JP-A-8-73581 JP-A-10-259296 Japanese Patent Application Laid-Open No. 10-251394

  An object of the present invention is to solve the above-described problems of the conventional techniques, and a catalyst that does not contain a metal compound such as a titanium compound, an antimony compound, a tin compound, a germanium compound, etc. as a main component of the catalyst is used. Provided is a copolyester having excellent transparency, color tone, and moldability using a condensed copolyester, that is, a so-called heavy metal catalyst, a catalyst capable of polycondensation at a speed that does not cause any problems in productivity. For the purpose.

  In order to solve the above-mentioned problems, the present invention has been completed as a result of intensive studies. That is, the copolyester of the present invention has as a main component a repeating unit composed of an aromatic dicarboxylic acid and an aliphatic glycol, polycondensed using a polycondensation catalyst containing at least one selected from the group consisting of aluminum and its compounds. As a copolymerization component different from the aromatic dicarboxylic acid and the aliphatic glycol, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1.4-cyclohexanedicarboxylic acid, ethylene At least one selected from the group consisting of glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, bisphenol A, and an ethylene oxide adduct of bisphenol A. Polymerization Based on the total moles of all the structural units of the ester contains 1.0 to 20.0 mol%, a copolymerized polyester, wherein the intrinsic viscosity of 0.90~1.50dl / g.

In this case, the aromatic dicarboxylic acid may be any one of terephthalic acid or 2,6-naphthalenedicarboxylic acid.
In this case, the aliphatic glycol can be a kind selected from the group consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol.
In this case, a trifunctional or higher polyfunctional compound component can be included.
In this case, the melt flow rate (MFR) can be in the range of 0.5-10.0 g / 10 min.

In this case, the polycondensation catalyst can be composed of at least one selected from the group consisting of aluminum compounds and at least one selected from phosphorus compounds.
In this case, the polycondensation catalyst may be composed of at least one selected from the group consisting of aluminum compounds and an alkali metal and / or an alkaline earth metal.
In this case, the aluminum compound may be a carboxylic acid-containing compound.
In this case, the phosphorus compound includes at least one of a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphonous acid compound, a phosphinic acid compound, and a phosphine compound. be able to.
In this case, the alkali metal and alkaline earth metal may be at least one selected from Li, Na, Mg or a compound thereof.

  In this case, the copolymer polyester can be used as a molded body, and the molded body can be a molded body obtained by extrusion blow.

  The copolymerized polyester of the present invention is not a so-called heavy metal catalyst, but uses a catalyst capable of polycondensation at a speed that does not cause a problem in terms of productivity. The molded body can be suitably used as a material useful for other applications.

  The present invention will be described in detail below.

  As an aluminum compound which comprises the polycondensation catalyst used for the copolymerization polyester of this invention, a well-known aluminum compound other than metallic aluminum can be used without limitation.

  Specific examples of the aluminum compound include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, and aluminum lactate. , Carboxylates such as aluminum citrate, aluminum salicylate, inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum Aluminum such as n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-butoxide Aluminum alkoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethyl acetoacetate diiso-propoxide, organoaluminum compounds such as trimethylaluminum, triethylaluminum and their partial hydrolysates And aluminum oxide. Of these, carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

  As the usage-amount of the aluminum compound used for the copolyester of this invention, it is 0.001-1 with respect to the mol number of all the structural units of carboxylic acid components, such as dicarboxylic acid and polyhydric carboxylic acid, of the copolyester obtained. 0.0 mol% is preferable, and 0.005 to 0.5 mol% is more preferable. Thus, the amount of the aluminum component to be added is required to be wide because the catalytic activity varies greatly depending on the type and combination of the polyvalent carboxylic acid and diol used, and the polycondensation method. This shows the same tendency with other polycondensation catalysts. In particular, when polycondensation is not performed under reduced pressure, the amount of polycondensation catalyst needs to be greatly increased. The polycondensation catalyst used in the copolymerized polyester of the present invention exhibits sufficient catalytic activity, and as a result, the resulting copolymerized polyester is excellent in thermal stability, thermal oxidation stability, and hydrolysis resistance and is attributed to aluminum. Generation of foreign substances and coloring are suppressed.

Below, the specific example of the preparation method of the same solution using basic aluminum acetate as an aluminum compound is shown.
Examples of preparation of an aqueous solution of basic aluminum acetate are as follows. That is, water is added to basic aluminum acetate and sufficiently diffused at room temperature, and then dissolved at room temperature to 100 ° C. to prepare an aqueous solution. In this case, the temperature is preferably low, and the heating is preferably short. The concentration of the aqueous solution is preferably 10 to 30 g / l, particularly preferably 15 to 20 g / l.

Furthermore, in order to suppress the heat shock at the time of catalyst addition, it is a preferable aspect that the basic aluminum acetate aqueous solution is the same ethylene glycol solution. That is, ethylene glycol is added to the above aqueous solution. The amount of ethylene glycol added is preferably 0.5 to 5.0 times the volume ratio of the aqueous solution. More preferably, the amount is 0.8 to 2.0 times. After the solution is stirred 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 70 ° C. or higher, and preferably 130 ° C. or lower. More preferably, the water is distilled off by heating and stirring at 80 to 120 ° C. More preferably, heating is performed under reduced pressure and / or an inert gas atmosphere such as nitrogen or argon, and water is distilled off to prepare a catalyst solution.
The above ethylene glycol is an example, and other alkylene glycols can be used in the same manner.

  The basic aluminum acetate described above is solubilized in a solvent such as water or glycol, in particular, water and / or solubilized in ethylene glycol is used from the viewpoint of catalytic activity and reduction of foreign matter in the resulting copolymerized polyester. preferable.

  Although it does not specifically limit as a phosphorus compound which comprises the polycondensation catalyst used for the copolyester of this invention, Phosphate ester, such as phosphoric acid and trimethyl phosphoric acid, triethyl phosphoric acid, phenyl phosphoric acid, 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 And phosphites such as' -biphenylene diphosphite.

  More preferable phosphorus compounds used in the copolymerized polyester of the present invention are selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. At least one phosphorus compound. By using these phosphorus compounds, an effect of improving the catalytic activity is seen, and an effect of improving physical properties such as the thermal stability of the copolyester 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 used in the copolymerized polyester of the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, and diethyl benzylphosphonate. Etc. Examples of the phosphinic acid compound used in the copolymerized polyester 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 used in the copolymerized polyester of the present invention include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide.

  Among the phosphinic acid-based compounds, phosphine oxide-based compounds, phosphonous acid-based compounds, phosphinic acid-based compounds, and phosphine-based compounds, the phosphorus compounds used in the copolymerized polyester of the present invention include the following formulas (Chemical Formula 7) to The compound represented by (Chemical Formula 12) is 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.

  Moreover, as a phosphorus compound used for the copolymer polyester of this invention, when the compound represented by the following general formula (Chemical Formula 13)-(Chemical Formula 15) is used, the physical property improvement effect and the catalytic activity improvement effect are especially large and preferable.

(In the formulas (Chemical Formula 13) to (Chemical Formula 15), 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. R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl.)

As the phosphorus compound used for the copolyester of the present invention, compounds 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) are particularly used. preferable.

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

  Among the phosphorus compounds described above, in the present invention, a metal salt compound of phosphorus is particularly preferable as the phosphorus compound. The phosphorus metal salt compound is not particularly limited as long as it is a metal salt of a phosphorus compound. However, when a metal salt of a phosphonic acid compound is used, the physical property improvement effect and catalytic activity of the copolymerized polyester, which are the problems of the present invention, are improved The effect is large and preferable. 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 part 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 metal salt compound of phosphorus used in the copolymerized polyester 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 physical property improving effect and the catalytic activity improving effect are great. .

(In the formula (Chem. 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. A hydrocarbon group having 1 to 50 carbon atoms including a group or carbonyl, l is an integer of 1 or more, m is 0 or an integer of 1 or more, l + m is 4 or less, M is (l + m And n represents an integer greater than or equal to 1. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

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

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

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

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

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

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

  Examples of the metal salt compound of phosphorus used in the copolymerized polyester of the present invention include lithium [(1-naphthyl) methylphosphonate ethyl], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [(1-naphthyl) methylphosphone. Acid ethyl], potassium [ethyl (2-naphthyl) methylphosphonate], magnesium bis [ethyl (2-naphthyl) methylphosphonate], lithium [ethyl benzylphosphonate], sodium [ethyl benzylphosphonate], magnesium bis [benzylphosphone] Acid ethyl], beryllium bis [ethyl phosphophosphonate], strontium bis [ethyl benzyl phosphonate], manganese bis [ethyl benzyl phosphonate], sodium benzyl phosphonate, magnesium bis [benzyl phosphone] ], Sodium [ethyl (9-anthryl) methylphosphonate], magnesium bis [ethyl (9-anthryl) methylphosphonate], sodium [ethyl 4-hydroxybenzylphosphonate], magnesium bis [ethyl 4-hydroxybenzylphosphonate], Sodium [phenyl 4-chlorobenzylphosphonate], magnesium bis [ethyl 4-chlorobenzylphosphonate], sodium [methyl 4-aminobenzylphosphonate], magnesium bis [methyl 4-aminobenzylphosphonate], sodium phenylphosphonate Magnesium bis [ethyl phenylphosphonate], 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 property improving effect of the copolymer polyester by containing these phosphorus compounds, these phosphorus compounds coexist with the aluminum compound used in the copolymer polyester of the present invention during the polycondensation of the copolymer polyester. As a result, the effect of improving the catalytic activity is greatly seen.
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 facilitates complex formation with an aluminum compound, and is highly preferable for improving the physical properties and improving the catalytic activity of the copolyester. .

  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 used in the copolymerized polyester of the present invention, at least one selected from the compounds represented by the following general formula (Formula 18) is used. The improvement effect is greatly preferred.

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

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

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

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

  As a preferable phosphorus compound used for the copolyester of the present invention, a phosphorus compound represented by the chemical formula (Chemical Formula 19) may be mentioned.

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

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

  Specific examples of these phosphorus compounds are shown below.

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

  The phosphorus compound used in the copolymerized polyester of the present invention is preferably a phosphorus compound having a phenol moiety in the same molecule. In addition to improving the physical property improvement effect of the copolymer polyester by containing a phosphorus compound having a phenol part in the same molecule, by using a phosphorus compound having a phenol part in the same molecule during polycondensation of the copolymer polyester The effect of increasing the catalytic activity is greater, and therefore the productivity of the copolyester 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 two 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 and the catalytic activity of the copolymerized polyester are greatly preferred. Among these, the use of a phosphonic acid compound having one or two or more phenol moieties in the same molecule is particularly preferable because the physical properties improving effect and catalytic activity improving effect of the copolyester are particularly large.

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

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

  Examples of the phosphorus compound having a phenol moiety used in the copolymerized polyester of the present invention in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, and p-hydroxy. Diphenyl phenylphosphonate, bis (p-hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, phenyl bis (p-hydroxyphenyl) phosphinate, p-hydroxyphenylphenylphosphinic acid, p-hydroxyphenylphenyl Methyl phosphinate, phenyl p-hydroxyphenylphenylphosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, p-hydroxyphenylphosphinic acid Nyl, bis (p-hydroxyphenyl) phosphine oxide, tris (p-hydroxyphenyl) phosphine oxide, bis (p-hydroxyphenyl) methylphosphine oxide, and compounds represented by the following formulas (Chemical 29) to (Chemical 32) Etc. 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 used in the copolymerized polyester of the present invention in the same molecule, at least one selected from a metal salt compound of a specific phosphorus represented by the following general formula (Formula 33) is particularly preferable.

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

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

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

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

  Specific phosphorus metal salt compounds used in the copolymerized polyester of the present invention include lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert- Ethyl butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], potassium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] ], Magnesium bis [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3, Methyl 5-di-tert-butyl-4-hydroxybenzylphosphonate], strontium bis [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], Barium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate phenyl], manganese bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], nickel bis [3,5 -Ethyl di-tert-butyl-4-hydroxybenzylphosphonate], copper bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], zinc bis [3,5-di-tert-butyl -Ethyl 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 a phenol moiety used in the copolyester of the present invention in the same molecule, selected from specific phosphorus compounds having at least one P—OH bond represented by the following general formula (Formula 35) At least one is particularly preferred.

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

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

(In the formula (Chemical Formula 36), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group containing 1 to 50 carbon atoms. 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 used in the copolymerized polyester of the present invention include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert -Methyl butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate isopropyl, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate phenyl, 3,5 -Octadecyl di-tert-butyl-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 used in the copolymerized polyester 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 each independently represent 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 formula (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 and the catalytic activity of the copolyester 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 used in the copolyester of the present invention include diisopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid Examples include di-n-butyl, 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 used in the copolymerized polyester of the present invention in the same molecule, a particularly desirable compound in the present invention is at least one selected from compounds represented by chemical formulas (Chemical Formula 39) and (Chemical Formula 40). The phosphorus compound.

  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 Chemicals) is available. Chemicals) is commercially available and can be used.

  Other phosphorus compounds that are preferably used in the present invention are represented by the following phosphonic acid compounds having a linking group (X) represented by (Chemical Formula 41) or (Chemical Formula 42) or (Chemical Formula 43). Examples thereof include phosphonic acid compounds having no linking group (X).

Embedded image R ¹ —X— (P═O) (OR ² ) (OR ³ )
[In the formula (Formula 41), R ¹ represents an aromatic ring structure having 6 to 50 carbon atoms or a heterocyclic structure having 4 to 50 carbon atoms, and the aromatic ring structure or the heterocyclic structure may have a substituent. Good. X is a linking group, an aliphatic hydrocarbon having 1 to 10 carbon atoms (which may be linear, branched or alicyclic), or an aliphatic having 1 to 10 carbon atoms containing a substituent. Hydrocarbon (which may be linear, branched or alicyclic), —O—, —OCH ₂ —, —SO ₂ —, —CO—, —COCH ₂ —, —CH ₂ OCO—, It is selected from —NHCO—, —NH—, —NHCONH—, —NHSO ₂ —, —NHC ₃ H ₆ OCH ₂ CH ₂ O—. R ² and R ³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. ]

  The substituent of the aromatic ring structure and the heterocyclic structure of the phosphorus compound represented by the formula (Chemical Formula 41) is a hydrocarbon group having 1 to 50 carbon atoms (an alicyclic structure, a branched structure, an aromatic ring even if it is linear) Or a hydroxyl group, a halogen group, a C1-C10 alkoxyl group or an amino group (C1-C10 alkyl or alkanol-substituted). Or nitro group, carboxyl group, aliphatic carboxylic acid ester group having 1 to 10 carbon atoms, formyl group, acyl group, sulfonic acid group, sulfonic acid amide group (alkyl group having 1 to 10 carbon atoms or alkanol substitution) 1 or 2 selected from phosphoryl-containing groups, nitrile groups, and cyanoalkyl groups. More than a seed.

  Examples of the phosphorus compound represented by the formula (Chemical Formula 41) include the following. Specifically, benzylphosphonic acid, benzylphosphonic acid monoethyl ester, 1-naphthylmethylphosphonic acid, 1-naphthylmethylphosphonic acid monoethyl ester, 2-naphthylmethylphosphonic acid, 2-naphthylmethylphosphonic acid monoethyl ester, 4-phenyl, Benzylphosphonic acid, 4-phenyl, benzylphosphonic acid monoethyl ester, 2-phenyl, benzylphosphonic acid, 2-phenyl, benzylphosphonic acid monoethyl ester, 4-chloro, benzylphosphonic acid, 4-chloro, benzylphosphonic acid mono Ethyl ester, 4-chloro, benzylphosphonic acid diethyl ester, 4-methoxy, benzylphosphonic acid, 4-methoxy, benzylphosphonic acid monoethyl ester, 4-methoxy, benzylphosphonic acid diethyl ester, 4-methyl, benzyl Sulphonic acid, 4-methyl, benzylphosphonic acid monoethyl ester, 4-methyl, benzylphosphonic acid diethyl ester, 4-nitro, benzylphosphonic acid, 4-nitro, benzylphosphonic acid monoethyl ester, 4-nitro, benzylphosphonic acid Diethyl ester, 4-amino, benzylphosphonic acid, 4-amino, benzylphosphonic acid monoethyl ester, 4-amino, benzylphosphonic acid diethyl ester, 2-methyl, benzylphosphonic acid, 2-methyl, benzylphosphonic acid monoethyl ester 2-methyl, benzylphosphonic acid diethyl ester, 10-anthranylmethylphosphonic acid, 10-anthranylmethylphosphonic acid monoethyl ester, 10-anthranylmethylphosphonic acid diethyl ester, (4-methoxyphenyl-, ethoxy-) me Ruphosphonic acid, (4-methoxyphenyl-, ethoxy-) methylphosphonic acid monomethyl ester, (4-methoxyphenyl-, ethoxy-) methylphosphonic acid dimethyl ester, (phenyl-, hydroxy-) methylphosphonic acid, (phenyl-, hydroxy-) Methylphosphonic acid monoethyl ester, (phenyl-, hydroxy-) methylphosphonic acid diethyl ester, (phenyl-, chloro-) methylphosphonic acid, (phenyl-, chloro-) methylphosphonic acid monoethyl ester, (phenyl-, chloro-) methylphosphonic acid Diethyl ester, (4-chlorophenyl) -iminophosphonic acid, (4-chlorophenyl) -iminophosphonic acid monoethyl ester, (4-chlorophenyl) -iminophosphonic acid diethyl ester, (4-hydroxyphenyl-, diphenyl-) Tylphosphonic acid, (4-hydroxyphenyl-, diphenyl-) methylphosphonic acid monoethyl ester, (4-hydroxyphenyl-, diphenyl-) methylphosphonic acid diethyl ester, (4-chlorophenyl-, hydroxy-) methylphosphonic acid, (4- Chlorphenyl-, hydroxy-) methylphosphonic acid monomethyl ester, (4-chlorophenyl-, hydroxy-) methylphosphonic acid dimethyl ester, and other phosphorus compounds containing a heterocyclic ring include 2-benzofuranylmethylphosphonic acid diethyl ester, 2 -Benzofuranylmethylphosphonic acid monoethyl ester, 2-benzofuranylmethylphosphonic acid, 2- (5-methyl) benzofuranylmethylphosphonic acid diethyl ester, 2- (5-methyl) benzofuranylmethylphosphonic acid monoe Glycol ester, such as 2- (5-methyl) benzo furanyl methyl phosphonic acid. The phosphorus compound which has said coupling group is a preferable aspect at the point of polymerization activity.

  Other compounds having a linking group (X) that are preferably used in the present invention include phosphorus compounds represented by the formula (Formula 42).

(R 42) (R ⁰ ) _m —R ₁ — (CH ₂ ) _n — (P═O) (OR ² ) (OR ³ )
[In the formula (Chemical Formula 42), R ⁰ represents a hydroxyl group, a C1-C10 alkyl group, —COOH group or —COOR ⁴ (R ⁴ represents a C1-C4 alkyl group), alkylene glycol group or monoalkoxyalkylene. Represents a glycol group (monoalkoxy represents C1-C4, alkylene glycol represents C1-C4 glycol). R ¹ represents an aromatic ring structure such as benzene, naphthalene, biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenyl methane, diphenyl dimethyl methane, diphenyl ketone, anthracene, phenanthrene and pyrene. R ² and R ³ each independently represent a hydrogen atom, a C1-C4 hydrocarbon group, a hydroxyl group or a C1-C4 hydrocarbon group having an alkoxyl group. m represents an integer of 1 to 5, and when R ⁰ is plural, it may be the same substituent or a combination of different substituents. n represents 0 or an integer of 1 to 5. ]

  Among the phosphorus compounds represented by the formula (Chemical Formula 42) used for the copolymerized polyester of the present invention, the following are examples of phosphorus compounds having a substituent aromatic ring structure of benzene. That is, 2-hydroxybenzylphosphonic acid diethyl ester, 2-hydroxybenzylphosphonic acid monoethyl ester, 2-hydroxybenzylphosphonic acid, 4-hydroxybenzylphosphonic acid diethyl ester, 4-hydroxybenzylphosphonic acid monoethyl ester, 4-hydroxy Benzylphosphonic acid, 6-hydroxybenzylphosphonic acid diethyl ester, 6-hydroxybenzylphosphonic acid monoethyl ester, 6-hydroxybenzylphosphonic acid, and the like include, but are not limited to, benzylphosphonic acids having a hydroxyl group introduced into the benzene ring. It is not a thing.

  Also, 2-n-butylbenzylphosphonic acid diethyl ester, 2-n-butylbenzylphosphonic acid monomethyl ester, 2-n-butylbenzylphosphonic acid, 3-n-butylbenzylphosphonic acid diethyl ester, 3-n-butylbenzyl Phosphonic acid monoethyl ester, 3-n-butylbenzylphosphonic acid, 4-n-butylbenzylphosphonic acid diethyl ester, 4-n-butylbenzylphosphonic acid monoethyl ester, 4-n-butylbenzylphosphonic acid, 2,5 -N-dibutylbenzylphosphonic acid diethyl ester, 2,5-n-dibutylbenzylphosphonic acid monoethyl ester, 2,5-n-dibutylbenzylphosphonic acid, 3,5-n-dibutylbenzylphosphonic acid diethyl ester, 3, 5-n-dibutylbenzylphosphonic acid monoethyl ester, 3,5-n-dibutylben Benzyl phosphonic acids was introduced alkyl benzene ring such as Ruhosuhon acid but not limited thereto.

  Further, 2-carboxybenzylphosphonic acid diethyl ester, 2-carboxybenzylphosphonic acid monoethyl ester, 2-carboxybenzylphosphonic acid, 3-carboxybenzylphosphonic acid diethyl ester, 3-carboxybenzylphosphonic acid monoethyl ester, 3-carboxy Benzylphosphonic acid, 4-carboxybenzylphosphonic acid diethyl ester, 4-carboxybenzylphosphonic acid monoethyl ester, 4-carboxybenzylphosphonic acid, 2,5-dicarboxybenzylphosphonic acid diethyl ester, 2,5-dicarboxybenzylphosphone Acid monoethyl ester, 2,5-dicarboxybenzylphosphonic acid, 3,5-dicarboxybenzylphosphonic acid diethyl ester, 3,5-dicarboxybenzylphosphonic acid Ethyl ester, 3,5-dicarboxybenzylphosphonic acid, 2-methoxycarbonylbenzylphosphonic acid diethyl ester, 2-methoxycarbonylbenzylphosphonic acid monoethyl ester, 2-methoxycarbonylbenzylphosphonic acid, 3-methoxycarbonylbenzylphosphonic acid diethyl Ester, 3-methoxycarbonylbenzylphosphonic acid monoethyl ester, 3-methoxycarbonylbenzylphosphonic acid, 4-methoxycarbonylbenzylphosphonic acid diethyl ester, 4-methoxycarbonylbenzylphosphonic acid monoethyl ester, 4-methoxycarbonylbenzylphosphonic acid, 2,5-dimethoxycarbonylbenzylphosphonic acid diethyl ester, 2,5-dimethoxycarbonylbenzylphosphonic acid monoethyl ester Carboxyl on the benzene ring such as 2,5-dimethoxycarbonylbenzylphosphonic acid, 3,5-dimethoxycarbonylbenzylphosphonic acid diethyl ester, 3,5-dimethoxycarbonylbenzylphosphonic acid monoethyl ester, 3,5-dimethoxycarbonylbenzylphosphonic acid, etc. Benzylphosphonic acids into which a group or a carboxylic acid ester group has been introduced may be mentioned, but the invention is not limited thereto.

  Further, 2- (2-hydroxyethoxy) benzylphosphonic acid diethyl ester, 2- (2-hydroxyethoxy) benzylphosphonic acid monoethyl ester, 2- (2-hydroxyethoxy) benzylphosphonic acid, 3- (2-hydroxyethoxy) ) Benzylphosphonic acid diethyl ester, 3- (2-hydroxyethoxy) benzylphosphonic acid monoethyl ester, 3- (2-hydroxyethoxy) benzylphosphonic acid, 4- (2-hydroxyethoxy) benzylphosphonic acid diethyl ester, 4- (2-hydroxyethoxy) benzylphosphonic acid monoethyl ester, 4- (2-hydroxyethoxy) benzylphosphonic acid, 2,5-di (2-hydroxyethoxy) benzylphosphonic acid diethyl ester, 2,5-di (2- Hydroxyethoxy) benzylphosphonic acid monoethyl Ester, 2,5-di (2-hydroxyethoxy) benzylphosphonic acid, 3,5-di (2-hydroxyethoxy) benzylphosphonic acid diethyl ester, 3,5-di (2-hydroxyethoxy) benzylphosphonic acid monoethyl Ester, 3,5-di (2-hydroxyethoxy) benzylphosphonic acid, 2- (2-methoxyethoxy) benzylphosphonic acid diethyl ester, 2- (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 1- (2 -Methoxyethoxy) benzylphosphonic acid, 3- (2-methoxyethoxy) benzylphosphonic acid monomethyl ester, 3- (2-methoxyethoxy) benzylphosphonic acid diethyl ester, 3- (2-methoxyethoxy) benzylphosphonic acid monoethyl ester 3- (2-methoxyethoxy) benzylphosphonic acid, 4 (2-methoxyethoxy) benzylphosphonic acid diethyl ester, 4- (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 4- (2-methoxyethoxy) benzylphosphonic acid, 2,5-di (2-methoxyethoxy) Benzylphosphonic acid diethyl ester, 2,5-di (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 2,5-di (2-methoxyethoxy) benzylphosphonic acid, 3,5-di (2-methoxyethoxy) Benzenephosphonic acid diethyl ester, 3,5-di (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 3,5-di (2-methoxyethoxy) benzylphosphonic acid and other benzene rings such as alkylene glycol groups or monoalkoxylation And benzylphosphonic acids introduced with an alkylene glycol group. The

  Among the phosphorus compounds represented by (Chemical Formula 42), the phosphorus compound in which the aromatic ring structure having a substituent is benzene is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the copolymerized polyester of the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure as naphthalene include the following. 1- (5-hydroxy) naphthylmethylphosphonic acid diethyl ester, 1- (5-hydroxy) naphthylmethylphosphonic acid monoethyl ester, 1- (5-hydroxy) naphthylmethylphosphonic acid, 1- (5-hydroxy) naphthylmethylphosphonic acid Diethyl ester, 1- (5-hydroxy) naphthylmethylphosphonic acid monoethyl ester, 1- (5-hydroxy) naphthylmethylphosphonic acid, 1- (5-n-butyl) naphthylmethylphosphonic acid diethyl ester, 1- (5-n- Butyl) naphthylmethylphosphonic acid monoethyl ester, 1- (5-n-butyl) naphthylmethylphosphonic acid, 1- (4-carboxy) naphthylmethylphosphonic acid diethyl ester, 1- (4-carboxy) naphthylmethylphosphonic acid monoethyl ester Ter, 1- (4-carboxy) naphthylmethylphosphonic acid, 1- (4-methoxycarbonyl) naphthylmethylphosphonic acid diethyl ester, 1- (4-methoxycarbonyl) naphthylmethylphosphonic acid monoethyl ester, 1- (4-methoxycarbonyl) Naphthylmethylphosphonic acid, 1- [4- (2-hydroxyethoxy)] naphthylmethylphosphonic acid diethyl ester, 1- [4- (2-hydroxyethoxy)] naphthylmethylphosphonic acid monoethyl ester, 1- [4- (2-hydroxy) Ethoxy)] naphthylmethylphosphonic acid, 1- (4-methoxyethoxy) naphthylmethylphosphonic acid diethyl ester, 1- (4-methoxyethoxy) naphthylmethylphosphonic acid monoethyl ester, 1- (4-methoxyethoxy) naphthylmethylphosphonic acid Acid, 1- (5-hydroxy) naphthylmethylphosphonic acid diethyl ester, 2- (6-hydroxy) naphthylmethylphosphonic acid diethyl ester, 2- (6-hydroxy) naphthylmonoethylphosphonic acid, 2- (6-hydroxy) naphthylmethylphosphonic acid Acid, 2- (6-n-butyl) naphthylmethylphosphonic acid diethyl ester, 2- (6-n-butyl) naphthylmethylphosphonic acid monoethyl ester, 2- (6-n-butyl) naphthylmethylphosphonic acid, 2- (6 -Carboxy) naphthylmethylphosphonic acid diethyl ester, 2- (6-carboxy) naphthylmethylphosphonic acid monoethyl ester, 2- (6-carboxy) naphthylmethylphosphonic acid, 2- (6-methoxycarbonyl) naphthylmethylphosphonic acid diethyl ester, 2- ( 6-methoxycarbonyl) naphthylmethylphosphonic acid monoethyl ester, 2- (6-methoxycarbonyl) naphthylmethylphosphonic acid, 2- [6- (2-hydroxyethoxy)] naphthylmethylphosphonic acid diethyl ester, 2- [6- (2- Hydroxyethoxy)] naphthylmethylphosphonic acid monoethyl ester, 2- [6- (2-hydroxyethoxy)] naphthylmethylphosphonic acid, 2- (6-methoxyethoxy) naphthylmethylphosphonic acid diethyl ester, 2- (6-methoxyethoxy) naphthyl Alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monoalkoxyalkylene glycol on naphthalene ring such as methylphosphonic acid monoethyl ester and 2- (6-methoxyethoxy) naphthylmethylphosphonic acid Although like phosphonic acids and the like are introduced is not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42), the phosphorus compound in which the aromatic ring structure having a substituent is naphthalene is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the copolymerized polyester of the present invention, the following compounds can be cited as phosphorus compounds having a substituted aromatic ring structure of biphenyl. That is, 4- (4-hydroxyphenyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenyl) benzylphosphonic acid, 4- (4-n- Butylphenyl) benzylphosphonic acid diethyl ester, 4- (4-n-butylphenyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenyl) benzylphosphonic acid, 4- (4-carboxyphenyl) benzylphosphone Acid diethyl ester, 4- (4-carboxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyl) benzylphosphonic acid, 4- (4-methoxycarbonylphenyl) benzylphosphonic acid diethyl ester, 4- (4 -Methoxycarbonylph Nyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyl) benzylphosphonic acid, 4- (4-hydroxyethoxyphenyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxyethoxyphenyl) benzylphosphonic acid mono Ethyl ester, 4- (4-hydroxyethoxyphenyl) benzylphosphonic acid, 4- (4-methoxyethoxyphenyl) benzylphosphonic acid diethyl ester, 4- (4-methoxyethoxyphenyl) benzylphosphonic acid monoethyl ester, 4- ( 4-methoxyethoxyphenyl) phosphones in which an alkyl group, a carboxyl group, a carboxylic ester group, an alkylene glycol group, a monomethoxyalkylene glycol group or the like is introduced into a biphenyl ring such as benzylphosphonic acid Although s and the like are not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42), the phosphorus compound in which the aromatic ring structure having a substituent is biphenyl is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the copolymerized polyester of the present invention, the following compounds may be mentioned as phosphorus compounds having a substituted aromatic ring structure as diphenyl ether. That is, 4- (4-hydroxyphenyloxy) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenyloxy) benzylphosphonic acid, 4- (4 -N-butylphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-butylphenyloxy) benzylphosphonic acid, 4- (4- Carboxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyloxy) benzylphosphonic acid, 4- (4-methoxycarbonylphenyloxy) Benji Phosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyloxy) benzylphosphonic acid, 4- (4-hydroxyethoxyphenyloxy) benzylphosphonic acid Monoethyl ester, 4- (4-hydroxymethoxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenyloxy) benzylphosphonic acid, 4- (4-methoxyethoxyphenyloxy) benzylphosphonic acid monoethyl An alkyl group on a diphenyl ether ring such as ester, 4- (4-methoxyethoxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenyloxy) benzylphosphonic acid, Rubokikishiru group, a carboxylic acid ester group, an alkylene glycol group, and a phosphonic acids like are introduced monomethoxy polyalkylene glycol groups are not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42), the phosphorus compound in which the aromatic ring structure having a substituent is diphenyl ether is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the copolymerized polyester of the present invention, the following compounds are examples of the phosphorus compound having a substituted aromatic ring structure as diphenthioether. That is, 4- (4-hydroxyphenylthio) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenylthio) benzylphosphonic acid, 4- (4 -N-butylphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-butylphenylthio) benzylphosphonic acid, 4- (4- Carboxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenylthio) benzylphosphonic acid, 4- (4-methoxycarbonylphenylthio) Benzylphosphonic acid monoethyl Ester, 4- (4-methoxycarbonylphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenylthio) benzylphosphonic acid, 4- (4-hydroxyethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenylthio) benzylphosphonic acid, 4- (4-methoxyethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenylthio) benzylphosphonic acid and other diphenylthioether rings have an alkyl group, a carboxyl group, a carboxylic acid ester Group, alkylene glycol group, and a phosphonic acids like are introduced monomethoxy polyalkylene glycol groups are not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42), the phosphorus compound in which the aromatic ring structure having a substituent is diphenylthioether is not limited to the above-mentioned single substituent species. A mixture of a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the copolymerized polyester of the present invention, the following compounds can be cited as phosphorus compounds having a substituted aromatic ring structure of diphenylsulfone. 4- (4-hydroxyphenylsulfonyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenylsulfonyl) benzylphosphonic acid, 4- (4-n -Butylphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-butylphenylsulfonyl) benzylphosphonic acid, 4- (4-carboxyphenyl) Sulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenylsulfonyl) benzylphosphonic acid, 4- (4-methoxycarbo) Ruphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenylsulfonyl) benzylphosphonic acid, 4- (4-hydroxyethoxyphenyl) Sulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenylsulfonyl) benzylphosphonic acid, 4- (4-methoxyethoxyphenylsulfonyl) Benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenylsulfonyl) ) Phosphonic acids in which an alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monomethoxyalkylene glycol group, etc. are introduced into a diphenylsulfone ring such as benzylphosphonic acid, but are not limited thereto. .

  Among the phosphorus compounds represented by the formula (Chemical Formula 42), the phosphorus compound in which the aromatic ring structure having a substituent is diphenylsulfone is not limited to the above-mentioned single substituent species. A mixture of a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the copolymerized polyester of the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure of diphenylmethane include the following. That is, 4- (4-hydroxybenzyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxybenzyl) benzylphosphonic acid, 4- (4-n- Butylbenzyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylbenzyl) benzylphosphonic acid monoethyl ester, 4- (4-butylbenzyl) benzylphosphonic acid, 4- (4-carboxybenzyl) benzylphosphonic acid Monoethyl ester, 4- (4-carboxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxybenzyl) benzylphosphonic acid, 4- (4-methoxycarbonylbenzyl) benzylphosphonic acid monoethyl ester, 4- ( 4-methoxycarbonyl Benzyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylbenzyl) benzylphosphonic acid, 4- (4-hydroxyethoxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxybenzyl) benzylphosphonic acid Monoethyl ester, 4- (4-hydroxymethoxybenzyl) benzylphosphonic acid, 4- (4-methoxyethoxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxybenzyl) benzylphosphonic acid monoethyl ester, 4 An alkyl group, a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group or the like is introduced into a diphenylmethane ring such as-(4-methoxyethoxybenzyl) benzylphosphonic acid. And the like phosphonic acids include but are not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42), the phosphorus compound in which the aromatic ring structure having a substituent is diphenylmethane is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the copolymerized polyester of the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure of diphenyldimethylmethane include the following. That is, 4- (4-hydroxyphenyldimethylmethyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenyldimethylmethyl) benzylphosphonic acid, 4 -(4-n-butylphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-butylphenyldimethylmethyl) benzylphosphonic acid 4- (4-carboxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyldimethylmethyl) Benzylphosphonic acid, 4- (4-methoxycarbonylphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylphenyldimethylmethyl) ) Benzylphosphonic acid, 4- (4-hydroxyethoxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenyldimethyl) Methyl) benzylphosphonic acid, 4- (4-methoxyethoxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenyldimethylmethyl) benzene Alkyl groups, carboxyxyl groups, carboxylic acid ester groups, alkylene glycol groups, monomethoxyalkylene glycol groups, etc. were introduced into diphenylmethane rings such as diphosphonic acid monoethyl ester and 4- (4-methoxyethoxyphenyldimethylmethyl) benzylphosphonic acid. Examples thereof include, but are not limited to, phosphonic acids.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42), the phosphorus compound in which the aromatic ring structure having a substituent is diphenyldimethylmethane is not limited to the above-mentioned single substituent species. , A hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group may be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the copolymerized polyester of the present invention, examples of the phosphorus compounds having a substituted aromatic ring structure as diphenyl ketone include the following. That is, 4- (4-hydroxybenzoyl) benzylphosphonic acid diethyl ester, 4- (4-hydroxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxybenzoyl) benzylphosphonic acid, 4- (4-n- Butylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-butylbenzoyl) benzylphosphonic acid, 4- (4-carboxybenzoyl) benzylphosphonic acid Monoethyl ester, 4- (4-carboxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxybenzoyl) benzylphosphonic acid, 4- (4-methoxycarbonylbenzoyl) benzylphosphonic acid monoethyl ester, 4- ( 4 Methoxycarbonylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylbenzoyl) benzylphosphonic acid, 4- (4-hydroxyethoxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxybenzoyl) benzyl Phosphonic acid monoethyl ester, 4- (4-hydroxymethoxybenzoyl) benzylphosphonic acid, 4- (4-methoxyethoxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxybenzoyl) benzylphosphonic acid monoethyl ester , 4- (4-methoxyethoxybenzoyl) benzylphosphonic acid and the like on an alkyl group, carboxy group, carboxylic acid ester group, alkylene glycol group, monomethoxy group Although such phosphonic acids such as alkylene glycol group is introduced are exemplified but not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42), the phosphorus compound whose aromatic ring structure having a substituent is diphenyl ketone is not limited to the above-mentioned single substituent species. A mixture of a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the copolymerized polyester of the present invention, examples of the phosphorus compound having an anthracene substituted aromatic ring structure include the following. That is, 9- (10-hydroxy) anthrylmethylphosphonic acid diethyl ester, 9- (10-hydroxy) anthrylmethylphosphonic acid monoethyl ester, 9- (10-hydroxy) anthrylmethylphosphonic acid, 9- (10-n- Butyl) anthrylmethylphosphonic acid diethyl ester, 9- (10-n-butyl) anthrylmethylphosphonic acid monoethyl ester, 9- (10-n-butyl) anthrylylmethylphosphonic acid, 9- (10-carboxy) anthryl Methylphosphonic acid diethyl ester, 9- (10-carboxy) anthrylmethylphosphonic acid monoethyl ester, 9- (10-carboxy) anthrylmethylphosphonic acid, 9- (10-carboxy) 9- (2-hydroxyethoxy) anthrylmethylphosphone Acid di Chill ester, 9- (2-hydroxyethoxy) anthrylmethylphosphonic acid monoethyl ester, 9- (2-hydroxyethoxy) anthrylmethylphosphonic acid, 9- (2-methoxyethoxy) anthrylmethylphosphonic acid diethyl ester, 9- (2 -Methoxyethoxy) anthrylmethylphosphonic acid monoethyl ester, 9- (2-methoxyethoxy) anthrylmethylphosphonic acid, 9- (2-methoxycarbonyl) anthrylmethylphosphonic acid diethyl ester, 9- (2-methoxycarbonyl) anthryl Anthracene rings such as methylphosphonic acid monoethyl ester and 9- (2-methoxycarbonyl) anthrylmethylphosphonic acid have alkyl groups, carboxyxyl groups, carboxylic acid ester groups, alkylene glycol groups, monomethoxy groups. Although such phosphonic acids such as alkylene glycol group is introduced are exemplified but not limited thereto.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42), the phosphorus compound whose aromatic ring structure having a substituent is anthracene is not limited to the above-mentioned single substituent species. A mixture of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the copolymerized polyester of the present invention, the following can be given as the phosphorus compounds having a substituted aromatic ring structure as phenanthrene. 1- (7-n-butyl) phenanthrylmethylphosphonic acid diethyl ester, 1- (7-n-butyl) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-n-butyl) phenanthrylmethylphosphone Acid, 1- (7-carboxy) phenanthrylmethylphosphonic acid diethyl ester, 1- (7-carboxy) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-carboxy) phenanthrylmethylphosphonic acid, 1- (7 -Hydroxyethoxy) phenanthrylmethylphosphonic acid diethyl ester, 1- (7-hydroxyethoxy) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-hydroxyethoxy) phenanthrylmethylphosphonic acid, 1- (7-methoxyethoxy) ) Phenanthryl 1- (7-methoxyethoxy) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-methoxyethoxy) phenanthrylmethylphosphonic acid, 1- (7-methoxycarbonyl) phenanthrylmethylphosphonic acid diethyl ester Ester, 1- (7-methoxycarbonyl) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-methoxycarbonyl) phenanthrylmethylphosphonic acid, etc., phenanthrene ring, alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol Examples thereof include, but are not limited to, phosphonic acids into which a group or a monomethoxyalkylene glycol group has been introduced.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42), the phosphorus compound in which the aromatic ring structure having a substituent is phenanthrene is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the copolymerized polyester of the present invention, examples of the phosphorus compounds having an aromatic ring structure having a substituent as pyrene include the following. 1- (5-hydroxy) pyrenylmethylphosphonic acid diethyl ester, 1- (5-hydroxy) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-hydroxy) pyrenylmethylphosphonic acid, 1- (5-n- Butyl) pyrenylmethylphosphonic acid diethyl ester, 1- (5-n-butyl) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-n-butyl) pyrenylmethylphosphonic acid, 1- (5-carboxy) pyrenyl Methylphosphonic acid diethyl ester, 1- (5-carboxy) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-carboxy) pyrenylmethylphosphonic acid, 1- (5-hydroxyethoxy) pyrenylmethylphosphonic acid diethyl ester, 1- ( 5-hydroxyethoxy) pyrenylmethylphosphonate Ethyl ester, 1- (5-hydroxyethoxy) pyrenylmethylphosphonic acid, 1- (5-methoxyethoxy) pyrenylmethylphosphonic acid diethyl ester, 1- (5-methoxyethoxy) pyrenylmethylphosphonic acid monoethyl ester, 1- ( 5-methoxyethoxy) pyrenylmethylphosphonic acid, 1- (5-methoxycarbonyl) pyrenylmethylphosphonic acid diethyl ester, 1- (5-methoxycarbonyl) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-methoxycarbonyl) Examples include, but are not limited to, phosphonic acids in which an alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monomethoxyalkylene glycol group, etc. are introduced into a pyrene ring such as pyrenylmethylphosphonic acid. No.

  Among the phosphorus compounds represented by the formula (Chemical Formula 42), the phosphorus compound in which the aromatic ring structure having a substituent is pyrene is not limited to the above-mentioned single substituent species. A hybrid of a group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.

  Substituents such as hydroxyl group, alkyl group, carboxyl group, carboxy ester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group introduced into the series of aromatic rings are the aluminum atom at the time of polycondensation of the copolyester. It is presumed to be deeply involved in complex formation. In addition, carboxyl groups or hydroxyl groups that are functional groups at the time of forming the copolyester are also included, and since they are easily dissolved or taken into the copolyester matrix, they are particularly effective for polymerization activity, foreign matter reduction, etc. it is conceivable that.

Compared to the unsubstituted group in which R ⁰ is a hydrogen atom bonded to the aromatic ring structure (R ¹ ), the C1-C10 alkyl group, —COOH group or —COOR ⁴ (R ⁴ is R ⁴⁾ used in the copolymer polyester of the present invention. , A C1-C4 alkyl group), an alkylene glycol group or a monoalkoxyalkylene glycol group (monoalkoxy represents C1-C4, alkylene glycol represents a C1-C4 glycol), and phosphorus compounds substituted with a catalytic activity This is preferable in terms of not only improving the problem but also reducing foreign matter.
Examples of the substituent bonded to the aromatic ring structure include C1-C10 alkyl groups, carboxyl and carboxyl ester groups, alkylene glycols and monoalkoxy alkylene glycols. From the viewpoint of the effect of reducing foreign matter, carboxyl and carboxyl ester groups, alkylene glycols and monoalkoxy alkylene glycols are more preferable. The reason is unknown, but it is presumed that the compatibility with the copolymerized polyester and the alkylene glycol as the catalyst medium is improved.

  The phosphorus compound (Chemical Formula 43) having no linking group (X) that is preferably used in the present invention is as follows.

Embedded image R ¹ − (P═O) (OR ² ) (OR ³ )
(R ¹ represents an aromatic ring structure having 6 to 50 carbon atoms or a heterocyclic structure having 4 to 50 carbon atoms, and the aromatic ring structure or the heterocyclic structure may have a substituent. R ² and R ³ Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group or an alkoxyl group, and a hydrocarbon group having 1 to 20 carbon atoms, which is an alicyclic structure, branched structure or aromatic ring structure. May be included.)
The substituent of the aromatic ring structure and heterocyclic structure of the phosphorus compound represented by the formula (Chemical Formula 43) is a hydrocarbon group having 1 to 50 carbon atoms (an alicyclic structure, a branched structure, an aromatic ring even if it is linear) Or a hydroxyl group, a halogen group, a C1-C10 alkoxyl group or an amino group (C1-C10 alkyl or alkanol-substituted). Or nitro group, carboxyl group, aliphatic carboxylic acid ester group having 1 to 10 carbon atoms, formyl group, acyl group, sulfonic acid group, sulfonic acid amide group (alkyl group having 1 to 10 carbon atoms or alkanol substitution) 1 type or 2 types selected from phosphoryl-containing groups, nitrile groups, and cyanoalkyl groups. That's it. The aromatic ring structure of (Chemical Formula 43) is selected from benzene, naphthalene, biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenylmethane, diphenyldimethylmethane, anthracene, phenanthrene and pyrene. And the heterocyclic structure is selected from furan, benzofuran, isobenzofuran, dibenzofuran, naphthalane and phthalide. Moreover, it is preferable that at least one of R ² and R ^{3 in} the above formula (Formula 43) is a hydrogen atom.

Examples of the phosphorus compound represented by the formula (Formula 43) that can be used in the present invention include the following phosphorus compounds. That is, (3-nitro, 5-methyl) -phenylphosphonic acid diethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid monoethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid, ( 3-nitro, 5-methoxy) -phenylphosphonic acid diethyl ester, (3-nitro, 5-methoxy) -phenylphosphonic acid monoethyl ester, (3-nitro, 5-methoxy) -phenylphosphonic acid, (4-chloro ) -Phenylphosphonic acid diethyl ester, (4-chloro,)-phenylphosphonic acid monoethyl ester, (4-chloro) -phenylphosphonic acid, (5-chloro,)-phenylphosphonic acid diethyl ester, (5-chloro, ) -Phenylphosphonic acid monoethyl ester, (5-chloro,)-phenylphosphonic acid, (3-nitro, 5-methyl) -phenylphospho Phosphonic acid diethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid monoethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid, (4-nitro) -phenylphosphonic acid diethyl ester, (4 -Nitro) -phenylphosphonic acid monoethyl ester, (4-nitro) -phenylphosphonic acid, (5-nitro) -phenylphosphonic acid diethyl ester, (5-nitro) -phenylphosphonic acid monoethyl ester, (5-nitro) ) -Phenylphosphonic acid, (6-nitro) -phenylphosphonic acid diethyl ester, (6-nitro) -phenylphosphonic acid monoethyl ester, (6-nitro) -phenylphosphonic acid, (4-nitro, 6-methyl) -Phenylphosphonic acid diethyl ester, (4-nitro, 6-methyl) -phenylphosphonic acid monoethyl ester, (4-nitro, 6-methyl)- Phenylphosphonic acid and other phosphorus compounds represented by the formula (Chemical Formula 42), such as benzene, naphthalene, biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenyl methane, diphenyl dimethyl methane, diphenyl ketone, anthracene, phenanthrene, and pyrene A methylene chain as a linking group from each structural formula having an aromatic ring structure, that is, a phosphorus compound group in which —CH ₂ — is removed, and a heterocyclic ring-containing phosphorus compound such as 5-benzofuranylphosphonic acid diethyl ester, 5- Benzofuranylphosphonic acid monoethyl ester, 5-benzofuranylphosphonic acid, 5- (2-methyl) benzofuranylphosphonic acid diethyl ester, 5- (2-methyl) benzofuranylphosphonic acid monoethyl ester And 5- (2-methyl) benzo furanyl phosphonic acid. The phosphorus compound having no linking group described above may be slightly inferior in polymerization activity compared to the phosphorus compound having the linking group described above, but when the catalyst preparation method of the present invention is used, it is used as a copolymerized polyester polycondensation catalyst. It is possible to do.

  By using together the phosphorus compound used in the copolymerized polyester of the present invention, a catalyst that exhibits a sufficient catalytic effect can be obtained even if the amount of aluminum added in the copolymerized polyester polycondensation catalyst is small.

  Phosphorus compounds have been known as heat stabilizers for polyesters, but it has been known so far that even when these compounds are used in combination with conventional metal-containing polyester polycondensation catalysts, melt polycondensation is greatly promoted. It wasn't. In practice, when the polycondensation polyester is melt polycondensed using an antimony compound, a titanium compound, a tin compound or a germanium compound, which is a typical polyester polycondensation catalyst, as a polycondensation catalyst, the phosphorus used in the copolymer polyester of the present invention is used. The addition of the compound is not observed to promote polycondensation to a substantially useful level.

  As a usage-amount of the phosphorus compound used for the copolymerization polyester of this invention, 0.001-2.0 mol% is preferable with respect to the number-of-moles of all the structural units of the polycarboxylic acid component of the copolymerization polyester obtained, 0 More preferably, it is 0.005 to 1.0 mol%. When the addition amount of the phosphorus compound is less than 0.001 mol%, the addition effect may not be exhibited. When the addition amount exceeds 2.0 mol%, the catalytic activity as a copolyester polycondensation catalyst is reduced. In some cases, the tendency to decrease varies depending on the amount of aluminum used.

  On the other hand, in the present invention, it is preferable that at least one selected from a small amount of an alkali metal, an alkaline earth metal, and the compound in addition to aluminum or a compound thereof coexists as the second metal-containing component. The coexistence of such a second metal-containing component in the catalyst system increases the catalytic activity, and thus a catalyst component having a higher reaction rate can be obtained, which is effective in improving productivity.

When adding an alkali metal, an alkaline earth metal, or a compound thereof, the amount M (mol%) used is 1 × 10 ⁻⁶ or more to the number of moles of all polycarboxylic acid units constituting the copolymer polyester. It is preferably less than 0.0 mol%, more preferably 5 × 10 ^{−6 to} 0.5 mol%, still more preferably 1 × 10 ^{−5 to} 0.3 mol%, and particularly preferably 1 * 10 < ^-5 > -0.1 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 1.0 mol% or more, the thermal stability is lowered, the generation of foreign matter and coloring, and the hydrolysis resistance are problems in product processing. A case occurs. When M is less than 1 × 10 ⁻⁶ , the effect is not clear even when added.

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

  Among these alkali metals, alkaline earth metals or their compounds, when using strongly alkaline ones such as hydroxides, these tend to be difficult to dissolve in diols such as ethylene glycol or organic solvents such as alcohols. The solution must be added to the polycondensation system in an aqueous solution, which may cause a problem in the polycondensation process. Furthermore, when using a strongly alkaline substance such as hydroxide, the copolyester is susceptible to side reactions such as hydrolysis during polycondensation, and the polycondensed copolyester tends to be easily colored, Hydrolysis resistance also tends to decrease. Therefore, alkali metals or their compounds or alkaline earth metals or their compounds suitable for use in the copolymerized polyester of the present invention are alkali metal or alkaline earth metal saturated aliphatic carboxylates, unsaturated fats. Aromatic carboxylate, aromatic carboxylate, halogen-containing carboxylate, hydroxycarboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, An inorganic acid salt, an organic sulfonate, an organic sulfate, a chelate compound, and an oxide selected from chloric acid and bromic acid. 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.

In the copolymerized polyester of the present invention, it is further preferable to add a cobalt compound as a cobalt atom in an amount of less than 10 ppm with respect to the copolymerized polyester.
Cobalt compounds are known to have a certain degree of polymerization activity per se, but as described above, when added to the extent that they exhibit a sufficient catalytic effect, the brightness and thermal stability of the copolyester obtained are reduced. Sexual decline occurs. The copolyester obtained according to the present invention is good in color tone and thermal stability, but by adding an addition amount such that the catalytic effect by addition of the cobalt compound is not clear in a small amount as described above, The coloring can be more effectively eliminated without causing a decrease in the brightness of the resulting copolyester. The cobalt compound in the present invention is for the purpose of eliminating coloration, and the addition time may be any stage of polycondensation, or may be after completion of the polycondensation reaction.

  The cobalt compound is not particularly limited, and specific examples include cobalt acetate, cobalt nitrate, cobalt chloride, cobalt acetylacetonate, cobalt naphthenate, and hydrates thereof. Of these, cobalt acetate tetrahydrate is particularly preferred.

  The addition amount of the cobalt compound is preferably such that the total of aluminum atoms and cobalt atoms is 50 ppm or less and the cobalt atoms are less than 10 ppm with respect to the finally obtained polymer. More preferably, the sum of aluminum atoms and cobalt atoms is 40 ppm or less, the cobalt atoms are 8 ppm or less, more preferably the sum of aluminum atoms and cobalt atoms is 25 ppm or less, and the cobalt atoms are 5 ppm or less.

  From the viewpoint of the thermal stability of the copolyester, the total of aluminum atoms and cobalt atoms is preferably less than 50 ppm, and the cobalt atoms are preferably 10 ppm or less. In order to have sufficient catalytic activity, the total amount of aluminum atoms and cobalt atoms is preferably more than 0.01 ppm.

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

  The polycondensation catalyst used in the present invention can be added to the reaction system at any stage of the polycondensation reaction. For example, it can be added to the reaction system at any stage before and during the esterification reaction or transesterification reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction. In particular, aluminum or a compound thereof is preferably added immediately before the start of the polycondensation reaction.

  The polycondensation catalyst used in the present invention is one or more polycondensation catalysts such as an antimony compound, a titanium compound, a germanium compound, and a tin compound, and the addition of these components is a copolymer polyester as described above. It is advantageous to improve the productivity by shortening the polycondensation time, and it is preferable to use it in the range of the addition amount that does not cause problems in the product such as the characteristics, processability, and color tone.

  However, the antimony compound can be added in an amount of 50 ppm or less as an antimony atom with respect to the copolyester obtained by polycondensation. More preferably, it is added in an amount of 30 ppm or less. When the addition amount of antimony is more than 50 ppm, metal antimony is precipitated, and darkening and foreign matter are generated in the copolyester.

  As a titanium compound, it is possible to add in the range of 10 ppm or less with respect to the polymer obtained by polycondensation. More preferably, it is added in an amount of 5 ppm or less, more preferably 2 ppm or less. If the amount of titanium added is more than 10 ppm, the thermal stability of the resulting resin is significantly reduced.

  Further, the germanium compound can be added so that the residual amount of germanium atoms remaining in the copolymerized polyester obtained by polycondensation is 30 ppm or less. A more preferable residual amount is 20 ppm or less. If the residual amount of germanium is 30 ppm or more, it is not preferable because it is disadvantageous in terms of cost.

The antimony compound, titanium compound, germanium compound and tin compound used in the present invention are not particularly limited.
Specifically, examples of the antimony compound include antimony trioxide, antimony pentoxide, antimony acetate, and antimony glycoloxide. Of these, antimony trioxide is preferable.

  Examples of titanium compounds include tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, and titanium oxalate. Of these, tetra-n-butoxy titanate is preferred.

  Examples of the germanium compound include germanium dioxide and germanium tetrachloride. Among these, germanium dioxide is preferable.

  The tin compounds include dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin adduct, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin Examples thereof include sulfide, dibutylhydroxytin oxide, methylstannic acid, ethylstannic acid and the like, and the use of monobutylhydroxytin oxide is particularly preferable.

  The addition method of the polycondensation catalyst used in the present invention may be addition in the form of powder or neat, or may be addition in the form of a slurry or solution of glycols such as ethylene glycol. It is not limited. Further, aluminum metal or a compound thereof and other components, preferably a phosphorus compound used in the present invention, may be added as a mixture or complex mixed in advance, or these may be added separately. Aluminum metal or a compound thereof and other components, preferably a phosphorus compound, may be added to the polycondensation system at the same addition time, and each component may be added at different addition times.

  As another embodiment of the polycondensation catalyst used in the copolymerized polyester of the present invention, an alkali metal compound and / or an alkaline earth metal glycol solution is used in combination with the glycol solution of the aluminum compound / the glycol solution of the phosphorus compound. It goes without saying that it is possible.

  Below, the specific example of the preparation method of an ethylene glycol solution at the time of using basic aluminum acetate as an aluminum compound is shown.

(1) Preparation example of ethylene glycol solution of aluminum compound Basic aluminum acetate (hydroxyaluminum diacetate; manufactured by Aldrich) was dispersed in distilled water at a concentration of 20 g / l, and heat-treated at 95 ° C. for 2 hours with stirring. And dissolved. An equal amount (volume ratio) of ethylene glycol is charged into the flask together with the aqueous solution, and water is distilled off from the system while stirring at 70 to 90 ° C. under reduced pressure (133 Pa) to obtain ethylene of 20 g / l aluminum compound. A glycol solution was prepared.

(2) Preparation Example of Phosphorus Compound in Ethylene Glycol Irganox 1222 (manufactured by Ciba Specialty Chemicals) as a phosphorus compound was charged into a flask together with ethylene glycol and heated at a liquid temperature of 160 ° C. for 12 hours with stirring under nitrogen substitution. An ethylene glycol solution of a phosphorus compound at 30 g / l was prepared.

(3) Preparation example of mixture of ethylene glycol solution of aluminum compound / ethylene glycol solution of phosphorus compound Each ethylene glycol solution obtained in Preparation Example 1 of the aluminum compound and Preparation Example 1 of the phosphorus compound was charged into a flask, A catalyst solution was prepared by mixing at room temperature such that the molar ratio of aluminum atoms and phosphorus atoms was 1: 2, and stirring for 5 hours.

(4) Preparation Example of Ethylene Glycol Solution of Alkali Metal Compound Lithium acetate (manufactured by Nacalai Co., Ltd., reagent special grade) was charged as an alkali metal compound into a flask together with ethylene glycol, and an alkali of 30 g / l at room temperature with stirring under nitrogen substitution. An ethylene glycol solution of a metal compound was prepared. )

  The copolyester of the present invention has as a main component a repeating unit composed of an aromatic dicarboxylic acid and an aliphatic glycol, polycondensed using a polycondensation catalyst containing at least one selected from the group consisting of aluminum and its compounds. Copolyester, a copolymer component different from the aromatic dicarboxylic acid and the aliphatic glycol, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, ethylene glycol, Copolymer polyester containing at least one selected from the group consisting of diethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, bisphenol A, and an ethylene oxide adduct of bisphenol A It is a copolyester containing 1.0 to 20.0 mol% based on the total moles of all the structural units of the Le.

  The amount of aromatic dicarboxylic acid relative to the total carboxylic acid component is 80 mol% or more, more preferably 85 mol% or more, and still more preferably 90 mol% or more.

  If the amount of the aromatic dicarboxylic acid is less than 80 mol%, it is not preferable because it is amorphous, resulting in problems such as difficulty in increasing the molecular weight by solid phase polymerization and inferior heat resistance.

  The aromatic dicarboxylic acid mainly used is preferably one of terephthalic acid and 2,6-naphthalenedicarboxylic acid.

  Further, the amount of aliphatic glycol relative to the total alcohol component is 80 mol% or more, more preferably 85 mol% or more, and still more preferably 90 mol% or more.

  If the amount of the aliphatic glycol is less than 80 mol%, it is not preferable because it is amorphous, and thus it becomes difficult to increase the molecular weight by solid phase polymerization.

  The aliphatic glycol mainly used is preferably one kind selected from the group consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol.

  The copolymerized polyester of the present invention includes terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, ethylene as copolymerization components other than the aromatic dicarboxylic acid and the aliphatic glycol. At least one selected from the group consisting of glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, bisphenol A, and an ethylene oxide adduct of bisphenol A. It is necessary to contain 1.0-20.0 mol% based on the total number of moles of all structural units of the polymerized polyester.

  The content of these copolymer components is preferably 2.0 to 10.0 mol% based on the total number of moles of all structural units of the copolymerized polyester, more preferably the total number of moles of all structural units of the copolymerized polyester. Based on the total number of moles of all structural units of the copolyester, it is 2.0 to 4.0 mole%.

  When the amount of the copolymerization component exceeds 20.0 mol% based on the total number of moles of all the structural units of the copolymerized polyester, it is difficult to increase the molecular weight by solid phase polymerization because of the amorphous nature. This is not preferable because it causes problems and poor heat resistance. On the other hand, if it is less than 1.0 mol%, the crystallization speed becomes too fast, and crystallization whitens at the time of molding, resulting in poor transparency of the molded product, and an unmelted product is produced, resulting in poor appearance of the molded product. Problems occur.

  Further, the copolymer polyester of the present invention has a polyfunctional compound unit derived from at least one of trifunctional or higher polyfunctional compounds based on the total number of moles of all structural units of the copolymer polyester. It is preferable to contain 0 mol%, preferably 0.01 to 1.0 mol%, more preferably 0.1 to 0.5 mol%. When the ratio of the polyfunctional compound unit is less than 0.005 mol%, the melt viscosity is not sufficiently high, and the moldability at the time of melt molding such as extrusion blow molding becomes poor. In particular, when extrusion blow molding is performed, the drawdown of the parison becomes severe, causing the parison to be clogged or crushed, making it impossible to produce a hollow molded body having a good shape. In addition, if the ratio of the polyfunctional compound unit exceeds 2.0 mol%, a gelled product is formed during melt polycondensation, and when moldings are molded, troubles such as generation of blisters and whitening occur, resulting in transparency, appearance. Etc. are damaged.

  As a trifunctional or higher polyfunctional compound, as an acid component, aroma such as trimesic acid, trimellitic acid, 1,2,3-benzenetricarboxylic acid, pyromellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid Polycarboxylic acid, 4-hydroxyisophthalic acid, 3-hydroxyisophthalic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, protocatechu Examples include acids, gallic acid, aromatic hydroxycarboxylic acids such as 2,4-dihydroxyphenylacetic acid, aliphatic hydroxycarboxylic acids such as tartaric acid and malic acid, ester-forming derivatives thereof, and the like. Methylolpropane, trimethylolethane, pentaerythritol, glycerin, , 2,4-butanetriol, aliphatic polyhydric alcohols such as 3-methyl-1,3,5-pentanetriol, 1,3,5-cyclohexanetriol, 1,2,4-cyclohexanetrimethanol, 1, Mention of alicyclic polyhydric alcohols such as 3,5-cyclohexanetrimethanol, 1,2,4,5-cyclohexanetetramethanol, 1,3,7-decalin trimethanol, 2,3,6-decalin trimethanol Trimellitic acid and trimethylolpropane are particularly advantageous.

  In addition, other dicarboxylic acids such as succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecane can be used as long as the purpose is not impaired. Dicarboxylic acid, hexadecanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2, An unsaturated dicarboxylic acid such as aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, fumaric acid and itaconic acid exemplified by 5-norbornane dicarboxylic acid, dimer acid, hydrogenated dimer acid and the like can be used.

  In addition, other glycol components, for example, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,5-pentanediol, 1,10, as long as the purpose is not impaired. -Decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, aliphatic glycols such as polypropylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4 Cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediethanol and other alicyclic glycols, 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, An aromatic glycol such as 1,2-bis (p-hydroxyphenyl) ethane can be used.

  The intrinsic viscosity of the copolyester of the present invention needs to be in the range of 0.90 to 1.50 dl / g, and the mechanical strength and appearance of the resulting molded product, moldability and production during the production of the molded product. From the viewpoint of properties, it is preferably 0.95 to 1.30 dl / g, and more preferably 1.00 to 1.20 dl / g. In particular, when extrusion blow molding is performed, if the intrinsic viscosity of the copolyester is less than 0.90 dl / g, the drawdown of the parison tends to increase during extrusion blow molding, resulting in poor molding. The mechanical strength is lowered and becomes a problem. On the other hand, if the intrinsic viscosity of the copolyester is greater than 1.50 dl / g, the melt viscosity becomes too high, and a weld line is likely to be formed in the molded body during extrusion blow molding, and the appearance of the obtained molded body is further improved. In addition, a problem arises due to molding problems such that the amount of extrusion tends to become non-uniform because the torque becomes high during extrusion.

  The copolyester of the present invention is 0.5-10.0 g / 10 min at 270 ° C., preferably 0.7-8.0 g / 10 min, more preferably 0.8-6.0 g / 10 min. Preferably, it has a melt flow rate (MFR) in the range of 1.0 to 5.0 dl / g. When the melt flow rate under the temperature condition is less than 0.5 g / 10 minutes, the torque during resin extrusion is too high, resulting in uneven thickness of the resulting hollow molded article and reduced productivity. On the other hand, when the melt flow rate exceeds 10.0 g / 10 minutes, the parison draw-down occurs at the time of extrusion, and the moldability deteriorates. In the present invention, the melt flow rate at a temperature of 270 ° C. was measured by a method according to JIS K 7210.

  Further, the dialkylene glycol content by-produced during the production of the copolymer polyester of the present invention and copolymerized in the main chain is preferably 1.0 to 5.0 of the glycol component constituting the copolymer polyester. It is desirable that it is mol%, More preferably, it is 1.5-4.0 mol%, More preferably, it is 1.5-3.0 mol%. When the amount of dialkylene glycol exceeds 5.0 mol%, the thermal stability is deteriorated, the molecular weight is greatly lowered during molding, and the generation of aldehydes such as acetaldehyde is increased. Further, in order to produce a copolymer polyester having a dialkylene glycol content of less than 1.0 mol%, it is necessary to select uneconomic production conditions as transesterification conditions, esterification conditions or polymerization conditions. , Cost does not fit. Here, the dialkylene glycol copolymerized in the copolyester is, for example, a by-product during production from ethylene glycol, which is a glycol, in the case of a copolyester whose main structural unit is ethylene terephthalate. Among diethylene glycols, it refers to diethylene glycol copolymerized with the copolymerized polyester. In the case of a copolymerized polyester having 1,3-propylene terephthalate as a main constituent unit, it is glycol 1 Of di (1,3-propylene glycol) (or bis (3-hydroxypropyl) ether) produced as a by-product during production from 1,3-propylene glycol, and di (1,3) copolymerized with the copolymer polyester -Propylene glycol).

  The content of aldehydes such as acetaldehyde in the copolymerized polyester of the present invention is 50 ppm or less, preferably 30 ppm or less, more preferably 10 ppm or less. When the aldehyde content exceeds 50 ppm, the effect of flavor retention of the contents such as a molded article molded from the copolymer polyester is deteriorated. Further, these lower limits are preferably 0.1 ppb from the viewpoint of production. Here, the aldehydes are acetaldehyde when the copolyester is a copolyester having ethylene terephthalate as the main constituent unit, and a copolymer having 1,3-propylene terephthalate as the main constituent unit. In the case of polyester, it is allyl aldehyde.

  Further, the content of fine contained in the copolymerized polyester of the present invention is 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.3% by weight or less, and further preferably 0.1% by weight or less. Particularly preferred is 0.05% by weight or less, and most preferred is 0.01% by weight or less.

  In general, the copolyester contains fine powder, that is, fine and film-like substances, which are generated during the production process, particularly during solid phase polymerization, in an amount of several hundred ppm to about several tens of weight%. Such fines have an intrinsic viscosity that is considerably higher than the intrinsic viscosity of the copolymerized polyester chip. Therefore, the melt viscosity is high at the time of melt extrusion blow molding, and this causes the occurrence of thickness unevenness and irregularities in the molded product due to flow spots. Often becomes.

  When the fine content exceeds 1% by weight, the above-mentioned phenomenon occurs frequently and becomes a problem.

  In the present invention, the method for reducing the fine content of the copolyester to the above range can be achieved, for example, by a method of treating fines with a sieving device.

  The solution haze of the copolymerized polyester of the present invention is 10.0% or less, preferably 5.0% or less, more preferably 3.0% or less, still more preferably 2.0% or less, and most preferably 1.5%. The following is preferable. When it exceeds 10.0%, there are many foreign substances in the copolyester, and the commercial value that does not deteriorate the transparency of the molded article is lost.

  When the copolymerized polyester of the present invention is used for a molded product, the haze of a 4 mm-thick molded plate obtained by injection molding the copolymerized polyester is 5% or less, preferably 3% or less, and most preferably 1% or less. It is desirable. When it exceeds 5%, the transparency of the molded product is poor, which is a problem.

  In addition, it is desirable that the copolymerized polyester of the present invention has a small amount of aluminum-based foreign matters insoluble in the system. Using a polytetrafluoroethylene membrane filter (Advantec PTFE membrane filter, product name: T100A047A) having a diameter of 47 mm / pore diameter of 1.0 μm, the total amount of the stirred and dissolved solution was adjusted to an effective filtration diameter of 37 under a pressure of 0.15 MPa. When it is measured by a measuring method in which a foreign matter is subjected to a filter separation test at 5 mm, it is preferably less than 5 hours. When the filtration time exceeds 5 hours, the transparency of the extrusion blow molded article is deteriorated, which causes a problem.

  The method for producing the copolyester of the present invention is not particularly limited, and the aromatic dicarboxylic acid can be produced by a direct esterification method of an aromatic dicarboxylic acid and a glycol or by an ester exchange method of an alkyl ester of an aromatic dicarboxylic acid and a glycol. Glycol ester is obtained, and then melt polycondensed in the presence of the polycondensation catalyst under normal pressure or reduced pressure to obtain the copolymer polyester prepolymer of the present invention. Next, solid phase polymerization is performed to increase the intrinsic viscosity.

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

  Hereinafter, an example of a preferable production method will be described using a polyethylene terephthalate copolymer copolymerized with isophthalic acid as an example.

First, a case where a low polymer is produced by an esterification reaction will be described. A slurry containing 1.02 to 2.0 moles, preferably 1.03 to 1.4 moles of ethylene glycol per 1 mole total of terephthalic acid and isophthalic acid was prepared and esterified. Feed continuously to the reaction process.
In the esterification reaction, water or alcohol produced by the reaction is systematized in a rectifying column under conditions where ethylene glycol is refluxed using a multistage apparatus in which at least two esterification reactors are connected in series. Carry out while removing outside. The temperature of the first stage esterification reaction is 240 to 270 ° C., preferably 245 to 265 ° C., and the pressure is 0.2 to 3 kg / cm ² G, preferably 0.5 to ² kg / cm ² G. The temperature of the esterification reaction in the final stage is usually 250 to 280 ° C, preferably 255 to 275 ° C, and the pressure is usually 0 to 1.5 kg / cm ² G, preferably 0 to 1.3 kg / cm ² G. . When carried out in three or more stages, the reaction conditions for the esterification reaction in the intermediate stage are conditions between the reaction conditions for the first stage and the reaction conditions for the final stage. The increase in the reaction rate of these esterification reactions is preferably distributed smoothly at each stage. Ultimately, it is desirable that the esterification reaction rate reaches 90% or more, preferably 93% or more. By these esterification reactions, low-order condensates having a molecular weight of about 500 to 5,000 are obtained.

When terephthalic acid is used as a raw material, the esterification reaction can be carried out without a catalyst by the catalytic action of terephthalic acid as an acid, but may be carried out in the presence of a polycondensation catalyst.
Also, tertiary amines such as triethylamine, tri-n-butylamine, benzyldimethylamine, quaternary ammonium hydroxides such as tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide, and lithium carbonate When a small amount of a basic compound such as sodium carbonate, potassium carbonate or sodium acetate is added, the proportion of dioxyethylene terephthalate component units in the main chain of polyethylene terephthalate is relatively low (total 5 mol% or less) with respect to the diol component.

Next, when producing a low polymer by transesterification, it is 1.1-2.0 mol with respect to 1 mol in total of dimethyl terephthalate and dimethyl isophthalate, Preferably it is 1.2-1.5 mol. A solution containing ethylene glycol is prepared and continuously fed to the transesterification step.
In the transesterification reaction, methanol produced by the reaction is removed from the system by a rectification column under the condition that ethylene glycol is distilled back using an apparatus in which one or two transesterification reactors are connected in series. Perform while removing. The temperature of the first stage transesterification is 180 to 250 ° C, preferably 200 to 240 ° C. The temperature of the transesterification reaction in the final stage is usually 230 to 270 ° C., preferably 240 to 265 ° C., and as the transesterification catalyst, fatty acid salts such as Zn, Cd, Mg, Mn, Co, Ca, Ba, carbonates Alternatively, Pb, Zn, Sb, Ge oxide or the like is used. A low-order condensate having a molecular weight of about 200 to 500 is obtained by these transesterification reactions.

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

  The melt-polycondensed polyester obtained above is extruded into water from a die installed in a polycondensation reaction apparatus and cut in water, or after being extruded in the atmosphere and immediately cooled with cooling water and cut. It becomes a chip and becomes a prepolymer for solid phase polymerization.

Next, the prepolymer needs to be further subjected to solid phase polymerization treatment. The polyester chip supplied to the solid phase polymerization may be preliminarily crystallized by heating to a temperature lower than the temperature at which solid phase polymerization is performed, and then supplied during the solid phase polymerization step. Such a precrystallization step can be performed by heating the polyester chip in a dry state, usually at a temperature of 100 to 200 ° C., preferably 130 to 180 ° C., or the chip is steamed or a steam-containing inert gas. It can also be performed by heating to a temperature of usually 100 to 200 ° C. in an atmosphere.
The solid-phase polymerization process to which the crystallized polyester chip is supplied consists of at least one stage. The solid-phase polymerization has a polymerization temperature of 160 to 240 ° C., preferably 180 to 235 ° C., in an inert gas atmosphere or under reduced pressure. Will be implemented. The polymerization time reaches a desired physical property in a shorter time as the temperature is higher, but is usually 1 to 50 hours, preferably 5 to 30 hours, and more preferably 10 to 25 hours.

Moreover, as a specific solid phase polymerization apparatus, a rotary vacuum solid phase polymerization apparatus or a tower type solid phase polymerization apparatus under an inert air stream can be used.
By selecting the conditions for this solid phase polymerization, a copolyester having the physical property values defined in the present invention can be obtained.

  The shape of the copolymer polyester chip of the present invention may be any of a cylinder shape, a square shape, a spherical shape, a flat plate shape, and the like. The average particle size is usually in the range of 1.0 to 5 mm, preferably 1.5 to 4.5 mm, more preferably 1.6 to 4.0 mm. For example, in the case of a cylinder type, it is practical that the length is about 1.0 to 4 mm and the diameter is about 1.0 to 4 mm. In the case of spherical particles, it is practical that the maximum particle size is 1.0 to 2.0 times the average particle size and the minimum particle size is 0.7 times or more the average particle size. The weight of the chip is practically in the range of 5 to 40 mg / piece.

  The copolymer polyester of the present invention includes polyamides such as Ny6, Ny66, and Ny-MXD6 as aldehyde reducing agents, polyesteramide, polyimide, polyamideimide, stearylamine, 2-aminobenzamide, N, N′-1,6. -Low molecular weight amino group-containing compounds such as hexanedibis (2-aminobenzamide), 4,4'-diaminodiphenylmethane, hydroxyl group-containing compounds such as polyvinyl alcohol, ethylene vinyl alcohol polymer, sugar alcohol, trimethylolpropane Hindered phenyl compounds, hindered amine compounds, benzotriazole compounds, benzophenone compounds, polyphenol compounds, phosphorus stabilizers, sulfur stabilizers, and alkali metal salts. Amide, benzophenone compounds, polyesteramides, phosphorus-based stabilizers, low molecular weight amino-containing compounds, hydroxyl group-containing compounds, benzophenone compounds, hindered phenylalanine compound may be blended with hindered amine compound. Most preferably, it is a polyamide, polyesteramide, or a low molecular weight amino group-containing compound, and the haze of the obtained polyester molded article is good.

  These polyamide compounds, low molecular weight amino group-containing compounds, hydroxyl group-containing compounds and other aldehyde reducing agents may be used alone or in admixture at an appropriate ratio. The aldehyde reducing agent is, for example, used in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the copolyester of the present invention. Can do.

  The aldehyde reducing agent can be blended by adding a predetermined amount of an aldehyde reducing agent in any reaction stage from the production of a low-polymerization degree oligomer of a copolyester to the production of a copolyester polymer. For example, the aldehyde reducing agent may be added to a reactor such as an esterification reactor or a polycondensation reactor in an appropriate form such as a fine granule, powder, or melt, or from the reactor to a reactor in the next step. The aldehyde reducing agent or a mixture of the polyester and the polyester may be introduced in a molten state into a transport pipe for the polyester reactant. Furthermore, if necessary, it is possible to solid-phase polymerize the obtained chip under a high vacuum or an inert gas atmosphere.

Moreover, it can also obtain by the method of mixing copolyester and an aldehyde reducing agent by a conventionally well-known method, or the method of mixing an aldehyde reducing agent with 2 or more types of mixtures. For example, polyamide chips and copolyester chips are dry blended with a tumbler, V-type blender, Henschel mixer, etc., and the dry blended mixture is melt-mixed once or more with a single screw extruder, twin screw extruder, kneader, etc. And a chip obtained by solid-phase polymerization of a chip from a molten mixture under a high vacuum or an inert gas atmosphere if necessary.
Further, a method in which a solution in which the polyamide or the like is dissolved in a solvent such as hexafluoroisopropanol is attached to the surface of the copolymer polyester chip, and the copolymer polyester is used as the member in a space where the polyamide member is present. For example, a method of causing the polyamide to adhere to the surface of the copolymerized polyester chip by collision contact.

  Since the copolymerized polyester of the present invention is excellent in extrusion blow moldability as described above, even when a general-purpose extrusion blow molding apparatus such as that used in vinyl chloride resin is used, it is high by the extrusion blow molding method. It can be formed into a hollow molded body having a desired shape and size with high productivity and high uniformity. The extrusion blow molding method applied to the copolymerized polyester of the present invention is not particularly limited, and a resin is melt-extruded to form a cylindrical parison, and this parison is in a softened state while being blown. A method of expanding the parison into a predetermined shape by inserting it into a mold and blowing a fluid such as air can be employed.

  Further, the shape, structure and the like of the molded body of the present invention are not particularly limited, and may be any arbitrary shape such as a hollow molded body, a tubular body, a plate, a sheet, a film, a rod-shaped body, a mold, etc., depending on each application. The shape and structure can be used, and the dimensions are not limited. Among them, the present invention is particularly suitable for a hollow molded body by extrusion blow molding.

  The copolymerized polyester of the present invention may optionally contain other thermoplastic resin as long as it does not impair the effects of the present invention, and is generally added to the thermoplastic resin. Substances to be added (for example, stabilizers such as UV absorbers and antioxidants, antistatic agents, flame retardants, flame retardant aids, colorants such as dyes and pigments, lubricants, plasticizers, inorganic fillers, etc.) May be blended.

  The molded product obtained from the copolymerized polyester of the present invention is in the form of a laminate with other materials such as other plastics, metals, fibers, fabrics, etc., even if formed with the copolymerized polyester of the present invention alone. Alternatively, it may be a molded body having a form other than the laminated structure of the copolymerized polyester of the present invention and the other materials described above, and is not limited at all. In particular, when the molded product of the present invention is an extrusion blow molded product, for example, a single-layer hollow molded product (such as a hollow container) made only of the copolymerized polyester of the present invention, the copolymerized polyester of the present invention and polyethylene, polypropylene, It can be a multilayer hollow molded body with other plastics such as an ethylene-vinyl alcohol copolymer and polyethylene terephthalate (PET), and more specifically, for example, three layers comprising PET layer / copolymerized polyester layer / PET layer. Examples thereof include a five-layer bottle composed of a layer bottle and a PET layer / copolyester layer / PET layer / copolyester layer / PET layer. However, the molded article of the present invention is of course not limited to the above.

  Hereinafter, the present invention will be described using examples. In the examples, “parts” means “parts by weight”. Each measurement item followed the following method.

1. Intrinsic viscosity (dl / g)
A polyester sample (0.1 g) was precisely weighed, dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane = 3/2 (mass ratio), and measured at 30 ° C. using an Ostwald viscometer.

2. Composition ratio of polyester About 5 mg of a polyester sample was dissolved in 0.7 ml of a mixed solution of deuterated chloroform and trifluoroacetic acid (9/1; volume ratio), and determined using ¹ H-NMR (manufactured by varian, UNITY 50).

3. Color of polyester The polyester chip was visually evaluated and determined as follows.
○: Almost no color △: Slightly yellow or gray ×: Remarkably yellow

4). Solution haze After 5 g of polyester was dissolved in 50 cc of the mixed solvent for limiting viscosity measurement, the solution was put into a 20 mm thick cell and measured with a Nippon Denshoku Co., Ltd. haze meter, model NDH2000.

5. Polyester melt flow rate (MFR)
The melting temperature at the time of measurement was measured at 270 ° C. by a method according to JIS K 7210.

6). Extrusion Molding The obtained copolyester is dried in a dryer using dehumidified nitrogen, then supplied to an extrusion blow molding device, and extruded from an annular orifice at an extrusion temperature of 270 ° C. to form a cylindrical parison. Was softened and sandwiched with a blow mold to cut and form the bottom, and blow molded to produce a soft drink bottle with a capacity of 500 ml and an average wall thickness of 0.4 mm. The parison draw-down property and the bottle transparency in this extrusion blow molding were determined according to the following evaluation criteria.

7). Evaluation of draw-down property of parison ◎: Extruded parison has a substantially uniform cylindrical shape ○: Extruded parison has a practically practical cylindrical shape △: Draw-down A cylindrical shape with a fast and uniform diameter cannot be obtained. ×: Extruded parison is drawn down drastically and cannot be inserted into the blow mold, or clogging occurs in the parison hollow.

8). Evaluation of transparency of bottle ○: Good transparency and no appearance problem △: The whole bottle is colored yellow to brown, and there may be foreign matter. ×: Some opaque or partially whitened part XX: Opaque or dark whitened part throughout

(Example 1)
In a 10L stainless steel reaction kettle equipped with a stirrer, condenser and thermometer, isophthalic acid, terephthalic acid, ethylene glycol and ethylene glycol solution of the above aluminum compound / ethylene glycol of phosphorus compound so that each component mol% shown in Table 1 is obtained. The catalyst solution described in the preparation example of the solution mixture was charged to 0.02 mol% and 0.04 mol% in terms of aluminum and phosphorus atoms with respect to all acid components, and esterified at 150 ° C. to 220 ° C. under nitrogen. Reaction was performed. Subsequently, the pressure was reduced while gradually raising the temperature so that the temperature finally reached 280 ° C. and the pressure became 0.2 hPa. The polycondensation reaction was completed by reacting until the torque value of the stirring blade corresponding to the intrinsic viscosity reached a desired value. The copolymer polyester prepolymer obtained by the above polycondensation was cut from a die hole while cooling with water to obtain a chip (minor axis 2 mm, major axis 3.5 mm, length 3 mm). The intrinsic viscosity of the prepolymer was 0.65 dl / g.
Next, the above prepolymer is put into a double cone type rotary solid phase polymerization apparatus, and after evacuation with nitrogen under reduced pressure, crystallization is performed at 100 to 150 ° C. at a heating medium temperature of the jacket under a reduced pressure of 0.5 torr or less. Thereafter, the temperature was gradually raised, solid phase polymerization was performed at 200 to 210 ° C. under reduced pressure, and after cooling, the pressure was restored with nitrogen to obtain a solid phase polymerization polymer. Prior to molding, it was treated with a vibrating sieve to make the fine content 0.4% by weight or less.
Table 1 shows the composition and characteristic values of the obtained copolymer polyester.
The solution haze of the copolymerized polyester obtained in this example is as low as 0.8%, the color tone is good, the MFR is 3.7 g / 10 min, the drawdown property during extrusion blow molding, and the transparency of the bottle Was good and no problem.

(Examples 2 to 10)
Copolyesters having the respective compositions shown in Table 1 were obtained by a method according to the production of the copolyester of Example 1 above. Table 1 shows the composition and characteristic values of each obtained copolyester. All was fine.

(Comparative Example 1)
A copolyester was obtained by polycondensation in the same manner as in Example 1 except that the polycondensation catalyst was changed to antimony trioxide (0.04 mol% in terms of antimony atoms based on the total acid component). Table 1 shows the composition and characteristic values of the obtained copolymer polyester. The appearance coloring of the resin is grayish, the solution haze is high, and the bottle is whitened as a whole, which is a problem.

(Comparative Example 2)
A copolyester was obtained by polycondensation in the same manner as in Example 1 except that the polycondensation catalyst was changed to tetrabutyl titanate (0.0008 mol% in terms of titanium atom based on the total acid component). Table 1 shows the composition and characteristic values of the obtained copolymer polyester. Although the solution haze was low, the appearance color of the resin was markedly yellow, the bottle was also brown, and the reduction in intrinsic viscosity was large, resulting in the formation of a molded article with poor transparency.

(Comparative Example 3)
The polycondensation catalyst was changed to antimony trioxide (0.04 mol% in terms of antimony atoms with respect to the total acid component), and the polycondensation was carried out in the same manner as in Example 1 except that the solid-phase polymerization time was shortened. Got. Table 1 shows the composition and characteristic values of the obtained copolymer polyester. The appearance coloring of the resin is grayish, the solution haze is high, the drawdown is intense, the bottle is poorly shaped and whitened as a whole, which is a problem.

(Comparative Example 4)
Polyester copolymerized by polycondensation in the same manner as in Example 1 except that isophthalic acid is not copolymerized and the polycondensation catalyst is changed to antimony trioxide (0.04 mol% in terms of antimony atoms with respect to all acid components). Got. Table 1 shows the composition and characteristic values of the obtained copolymer polyester. The appearance coloring of the resin is grayish, the solution haze is high, and the bottle is whitened as a whole, which is a problem.

  The present invention does not use a metal compound such as a tin compound, an antimony compound, a germanium compound, and a titanium compound as a main component of the catalyst, and uses a polycondensation catalyst mainly composed of an aluminum compound. The present invention provides a copolyester extremely excellent in the above and a molded article comprising the same.

Claims (12)

A copolyester having, as a main component, a repeating unit composed of an aromatic dicarboxylic acid and an aliphatic glycol, polycondensed using a polycondensation catalyst containing at least one selected from the group consisting of aluminum and its compounds, As copolymer components different from aromatic dicarboxylic acid and aliphatic glycol, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, ethylene glycol, diethylene glycol, 1,3-propanediol 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, bisphenol A, at least one selected from the group consisting of ethylene oxide adducts of bisphenol A, the total moles of all structural units of the copolyester number Based contain 1.0 to 20.0 mol%, the copolymerized polyester, wherein the intrinsic viscosity of 0.90~1.50dl / g. The copolyester according to claim 1, wherein the aromatic dicarboxylic acid is either terephthalic acid or 2,6-naphthalenedicarboxylic acid. The copolyester according to claim 1 or 2, wherein the aliphatic glycol is one selected from the group consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol. The copolyester according to any one of claims 1 to 3, comprising a trifunctional or higher polyfunctional compound component. The copolymer polyester according to any one of claims 1 to 4, wherein the melt flow rate (MFR) is in the range of 0.5 to 10.0 g / 10 minutes. The copolyester according to any one of claims 1 to 5, wherein the polycondensation catalyst comprises at least one selected from the group consisting of aluminum compounds and at least one selected from phosphorus compounds. The copolyester according to any one of claims 1 to 6, wherein the polycondensation catalyst comprises at least one selected from the group consisting of aluminum compounds and an alkali metal and / or an alkaline earth metal. The copolyester according to any one of claims 1 to 7, wherein the aluminum compound is a carboxylic acid-containing compound. The phosphorus compound includes at least one of a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphonous acid compound, a phosphinic acid compound, and a phosphine compound. The copolyester according to any one of claims 6 to 8. The copolyester according to any one of claims 7 to 9, wherein the alkali metal and alkaline earth metal are at least one selected from Li, Na, Mg or a compound thereof. A molded article comprising the copolyester according to any one of claims 1 to 10. The molded body according to claim 11, wherein the molded body is an extrusion blow molded body.