JP2008001855A - Polyester and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester polycondensed by using a catalyst containing no metallic compound such as a titanium compound, an antimony compound, a tin compound and a germanium compound, that is, a polyester excellent in transparency, color tone and moldability or a polyester having barrier property, and using no heavy metal catalyst but a catalyst capable of polycondensing at a rate causing no problem on productivity. <P>SOLUTION: The polyester comprises polycarboxylic acid ingredients comprising 15.5-100 mol% isophthalic acid and polyhydric alcohol ingredients comprising 30-100 mol% ethylene glycol, wherein the polyester is polycondensed by using a polycondensation catalyst containing one or more selected from a group consisting of aluminum and compounds thereof. <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 applications such as a polyester having a barrier property or a polyester having a barrier property, and a molded article comprising the polyester.

  Polyesters represented by polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc. are excellent in mechanical properties and chemical properties. These polyesters, depending on the respective properties, for example, fibers for clothing and industrial materials, packaging, magnetic tape, optical films and sheets, bottles that are hollow molded products, casings for electrical and electronic parts, It is used in a wide range of other fields such as engineering plastic moldings.

  In recent years, due to the diversification of the market, copolymer polyesters obtained by copolymerizing the above polyester with other glycol components have attracted attention and are used in various fields. For example, it is used as an adhesive (for example, see Patent Document 1), as a paint (for example, see Patent Document 2), and as a coating agent (for example, see Patent Document 3).

  In particular, copolyesters composed of isophthalic acid have a wide range of properties, from crystalline polyesters with a slow crystallization rate to amorphous polyesters, depending on the amount of isophthalic acid copolymerized, and more transparent and gas barrier properties than the above homopolyesters. Have disclosed the possibility of use in the field of packaging materials (for example, Patent Documents 5 and 6) such as a hollow molded body (see, for example, Patent Document 4) and multilayer sheets and multilayer films.

However, such copolyesters have the following problems depending on the polycondensation catalyst species.
(1) Tin compounds and antimony compounds as polycondensation catalysts are so-called heavy metals and are never preferred catalysts.
(2) The antimony compound is darkened in the obtained copolyester resin, and when the copolyester resin is dissolved in a solvent to form a varnish, aggregates containing reduced antimony and antimony settle and cause problems as a paint. In the case of forming or forming a molded body, the transparency may be changed due to foreign matters caused by the catalyst metal.
(3) When a titanium compound is used as a polycondensation catalyst, the polyester resin is colored. When an aliphatic dicarboxylic acid such as adipic acid or sebacic acid is used as a copolymerization component, the heat resistance is poor and the resin The coloration is remarkable, for example, the white color cannot be obtained with white paint.
(4) The germanium compound can be used effectively as the polycondensation catalyst, but the price is extremely high.

In order to solve such problems, a technique (for example, see Patent Document 7) containing a specific amount of an antimony compound, a germanium compound, a cobalt compound and a phosphorus compound, or a specific amount of a cobalt compound is included. Resins with improved coloring (for example, see Patent Documents 8 and 9) have been disclosed. However, with the expansion of the market, for example, in the field of molded articles for optical containers and the like that require a high-class feeling such as cosmetic containers. Therefore, there is an increasing demand for improvement in color tone and transparency with higher transparency. Based on the above background, it is desired to develop an aromatic polyester having higher transparency and color tone or barrier property.
JP-A-48-034231 JP 52-042528 A Japanese Patent Laid-Open No. 54-141810 JP 2003-40987 A JP-A-2-269152 JP 59-67049 A JP-A-11-209465 JP 2001-98058 A Japanese Patent Laid-Open No. 2001-214045

  An object of the present invention is to solve the above-mentioned problems of the prior art, using a catalyst that does not contain a metal compound such as a titanium compound, an antimony compound, a tin compound, or a germanium compound as a main catalyst component. Condensed polyester, that is, a polyester that is not a so-called heavy metal catalyst and that can be polycondensed at a speed that does not cause any problems in terms of productivity, has excellent transparency, color tone and moldability, or has a barrier property The object is to provide polyester.

  In order to solve the above-mentioned problems, the present invention has been completed as a result of intensive studies. That is, the polyester of the present invention is a polyester in which isophthalic acid is 15.5 to 100 mol% of the polyvalent carboxylic acid component and ethylene glycol is 30 to 100 mol% of the polyhydric alcohol component, Polyester characterized by being polycondensed using a polycondensation catalyst containing at least one selected from the group consisting of aluminum and its compounds.

In this case, the other polyvalent carboxylic acid component may include at least one selected from the group consisting of terephthalic acid, 2,6-naphthalenedicarboxylic acid, sebacic acid, adipic acid, and azelaic acid.
In this case, as other polyhydric alcohol components, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, It may contain at least one selected from the group consisting of 1,3-bis (2-hydroxyethoxy) benzene and bisphenol A ethylene oxide adduct.
In this case, a trifunctional or higher polyfunctional compound component can be included.
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, or 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, it can be a varnish in which the polyester is dissolved.
In this case, it can be an adhesive containing the polyester.
In this case, a paint containing the polyester can be obtained.
In this case, it can be set as the coating agent containing the said polyester.
In this case, it can be set as the molded object containing the said polyester.
In this case, it can be set as the laminated body containing the said polyester.

  The 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, and has excellent transparency, color tone and moldability, or has a barrier property. It can be suitably used as a material useful for body and other uses.

The present invention will be described in detail below.
As an aluminum compound which comprises the polycondensation catalyst used for the 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 polyester of this invention, 0.001-1.0 mol% with respect to the number-of-moles of all the structural units of carboxylic acid components, such as dicarboxylic acid and polycarboxylic acid of polyester obtained. Is more 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. Since the polycondensation catalyst used in the polyester of the present invention exhibits a sufficient catalytic activity, as a result, the resulting polyester has excellent thermal stability, thermal oxidation stability, hydrolysis resistance, and generation of foreign matters caused by aluminum. Coloring is 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 stirring the solution 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.

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

  The phosphorus compound constituting the polycondensation catalyst used in the polyester of the present invention is not particularly limited, but phosphoric acid and phosphoric acid esters such as trimethyl phosphoric acid, triethyl phosphoric acid, phenyl phosphoric acid, triphenyl phosphoric acid, Phosphoric 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 polyester of the present invention are at least selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. It is a kind of 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 thermal stability of the polyester is seen. Among these, use of a phosphonic acid compound is preferable because of its great effect of improving physical properties and improving catalytic activity. Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

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

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

  Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds, the phosphorus compounds used in the polyester of the present invention include the following formulas The compound represented by 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 polyester of this invention, when the compound represented by the following general formula (Formula 13)-(Formula 15) is used, the physical property improvement effect and the catalyst 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 in the polyester of the present invention, a compound in which R ¹ , R ⁴ , R ⁵ and R ⁶ are groups having an aromatic ring structure in the above formulas (Chemical Formula 13) to (Chemical Formula 15) is particularly preferable.

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

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

  Further, among the above-described phosphorus compounds, when the metal 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 phosphorus metal salt compound used in the 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 polyester of the present invention include lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [(1-naphthyl) methylphosphonate. ], Potassium [(2-naphthyl) methylphosphonate ethyl], magnesium bis [(2-naphthyl) methylphosphonate ethyl], lithium [benzylphosphonate ethyl], sodium [benzylphosphonate ethyl], magnesium bis [benzylphosphonate ethyl] ], Beryllium bis [ethyl benzylphosphonate], strontium bis [ethyl benzylphosphonate], manganese bis [ethyl benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonic acid], Thorium [ethyl (9-anthryl) methylphosphonate], magnesium bis [ethyl (9-anthryl) methylphosphonate], sodium [ethyl 4-hydroxybenzylphosphonate], magnesium bis [ethyl 4-hydroxybenzylphosphonate], sodium [ 4-chlorobenzylphosphonate phenyl], magnesium bis [4-chlorobenzylphosphonate ethyl], sodium [methyl 4-aminobenzylphosphonate], magnesium bis [4-aminobenzylphosphonate methyl], sodium phenylphosphonate, magnesium Examples thereof include bis [ethyl phenylphosphonate] and zinc bis [ethyl phenylphosphonate]. 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. By containing these phosphorus compounds, the effect of improving the physical properties of the polyester is particularly enhanced, and in the polycondensation of the polyester, these phosphorus compounds are used in combination with the aluminum compound used in the polyester of the present invention. A significant improvement in activity is 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, use of a phosphonic acid compound having at least one P-OH bond facilitates formation of a complex with an aluminum compound, and is highly preferable for improving the physical properties and improving the catalytic activity of the polyester.

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

  As the phosphorus compound having at least one P—OH bond used in the polyester of the present invention, when at least one selected from the compounds represented by the following general formula (Formula 18) is used, the physical property improving effect and the catalytic activity are improved. The effect is large and preferable.

(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 polyester of the present invention include ethyl (1-naphthyl) methylphosphonate, (1-naphthyl) methylphosphonic acid, ethyl (2-naphthyl) methylphosphonate, and benzylphosphonic acid. Ethyl, benzylphosphonic acid, ethyl (9-anthryl) methylphosphonate, ethyl 4-hydroxybenzylphosphonate, ethyl 2-methylbenzylphosphonate, phenyl 4-chlorobenzylphosphonate, methyl 4-aminobenzylphosphonate, 4-methoxy Examples include ethyl benzylphosphonate. Of these, ethyl (1-naphthyl) methylphosphonate and ethyl benzylphosphonate are particularly preferred.

  A preferable phosphorus compound used in the polyester of the present invention includes a phosphorus compound represented by the chemical formula (Chemical Formula 19).

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

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

  Specific examples of these phosphorus compounds are shown below.

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

  The phosphorus compound used in the polyester of the present invention is preferably a phosphorus compound having a phenol moiety in the same molecule. In addition to enhancing the physical properties of the polyester by containing a phosphorus compound having a phenol moiety in the same molecule, the catalytic activity is enhanced by using a phosphorus compound having a phenol moiety in the same molecule during polycondensation of the polyester. Greater effect and therefore better polyester productivity.

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

  As a phosphorus compound which has the phenol part used for the 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 the phenol moiety used in the polyester of the present invention in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, and p-hydroxyphenylphosphone. Diphenyl acid, bis (p-hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, phenyl bis (p-hydroxyphenyl) phosphinate, p-hydroxyphenylphenylphosphinic acid, p-hydroxyphenylphenylphosphinic acid Methyl, phenyl p-hydroxyphenylphenylphosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate 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) Can be mentioned. 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 a phenol moiety used in the 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 polyester of the present invention include lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl- 4-hydroxybenzylphosphonic acid ethyl], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], potassium [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl], Magnesium bis [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3,5- Di-tert-butyl-4-hydroxybenzylphosphonate methyl], strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], barium Mubis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate phenyl], manganese bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], nickel bis [3,5- Di-tert-butyl-4-hydroxybenzylphosphonate ethyl], copper bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], zinc bis [3,5-di-tert-butyl- 4-hydroxybenzylphosphonic acid ethyl ester] and the like. Among these, lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [ Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

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

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

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

(In 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 polyester of the present invention include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl. Methyl 4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate isopropyl, phenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di Examples include octadecyl-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 a phenol moiety used in the 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 formulas (Chemical Formula 37), it is preferable to use at least one selected from the compounds represented by the following General Formula (Chemical Formula 38) because the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are high.

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

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

  Specific phosphorus compounds used in the polyester of the present invention include diisopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di- 3,5-di-tert-butyl-4-hydroxybenzylphosphonate. Examples include 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 a phenol moiety used in the polyester of the present invention in the same molecule, a particularly desirable compound in the present invention is at least one phosphorus selected from compounds represented by the chemical formulas (Chemical Formula 39) and (Chemical Formula 40). A 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 (Chemical 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 group 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, diphenylmethane, diphenyldimethylmethane, 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 (Formula 42) used in the polyester of the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure are benzene are as follows. 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 polyester of the present invention, examples of the phosphorus compound having an aromatic ring structure having a substituent 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 for the polyester of the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure of biphenyl include the following. 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 polyester of the present invention, examples of the phosphorus compound having a substituted aromatic ring structure as diphenyl ether include the following. 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 polyester of the present invention, examples of the phosphorus compound having a substituent aromatic ring structure as diphenthioether include the following. 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 polyester of the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure of diphenyl sulfone include the following. 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 for the 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 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 for the 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 polyester of the present invention, examples of the phosphorus compounds 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 polyester of the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure being phenanthrene include the following. 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 polyester of the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure 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 groups, alkyl groups, carboxyl groups, carboxyester groups, 2-hydroxyethoxy groups, 2-methoxyethoxy groups introduced into the series of aromatic rings are complexes with aluminum atoms during the polycondensation of the polyester. Presumed to be deeply involved in formation. In addition, a carboxyl group or a hydroxyl group that is a functional group at the time of polyester formation is also included, and since it is easily dissolved or taken into the polyester matrix, it is considered to be particularly effective for polymerization activity and foreign matter reduction.

Compared to an unsubstituted group in which R ⁰ is a hydrogen atom bonded to the aromatic ring structure (R ¹ ), a C1-C10 alkyl group, —COOH group or —COOR ⁴ (R ⁴ is C1) used in the polyester of the present invention. Phosphorus compounds substituted with an alkylene glycol group or a monoalkoxyalkylene glycol group (monoalkoxy represents C1-C4, alkylene glycol represents a C1-C4 glycol) improve catalytic activity This is preferable in terms of the effect of 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 for this is unknown, but it is assumed that the compatibility with the alkylene glycol, which is a medium for the polyester and the catalyst, 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 have a slightly lower polymerization activity than the phosphorus compound having the linking group described above, but should be used as a polyester polycondensation catalyst when the catalyst preparation method of the present invention is used. Is possible.

  By using together the phosphorus compound used in the 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 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. Actually, when a polyester is melt-polycondensed using a polycondensation catalyst of antimony compound, titanium compound, tin compound or germanium compound, which is a typical polyester polycondensation catalyst, the phosphorus compound used in the polyester of the present invention is added. However, it is not observed that polycondensation is accelerated to a substantially useful level.

  As the usage-amount of the phosphorus compound used for 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 polyester obtained, 0.005-1 More preferably, it is 0.0 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 polyester polycondensation catalyst may be reduced. There is a tendency of the change 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 and a compound thereof, the amount M (mol%) used is 1 × 10 ⁻⁶ or more and 1.0 or more with respect to the number of moles of all polycarboxylic acid units constituting the polyester. It is preferably less than mol%, more preferably 5 × 10 ^{−6 to} 0.5 mol%, still more preferably 1 × 10 ^{−5 to} 0.3 mol%, and particularly preferably 1 × 10 6. ^{-5 to} 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 a strongly alkaline material such as hydroxide is used, the polyester tends to undergo side reactions such as hydrolysis during polycondensation, and the polycondensed polyester tends to be easily colored, and is resistant to hydrolysis. There is also a tendency to decrease. Accordingly, alkali metals or their compounds or alkaline earth metals or their compounds suitable for use in the polyester of the present invention are alkali metal or alkaline earth metal saturated aliphatic carboxylates and unsaturated aliphatic carboxylates. Acid salt, 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, chloric acid And inorganic acid salts, organic sulfonates, organic sulfates, chelate compounds, and oxides selected from 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 polyester according to 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 polyester.
It is known that the cobalt compound itself has a certain degree of polymerization activity. However, as described above, when it is added to such an extent that it exhibits a sufficient catalytic effect, the brightness of the resulting polyester is reduced and the thermal stability is reduced. A drop occurs. The polyester obtained according to the present invention has good color tone and thermal stability, but can be obtained by adding a cobalt compound in such a small amount that the catalytic effect by addition is not clear. The coloring can be more effectively eliminated without causing a decrease in the brightness of the polyester. 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 polyester, 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. Further, 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 polyester can be produced 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. Coexistence within the range of addition amounts that do not cause problems in the product, such as processability and color tone, is advantageous and preferable in improving productivity by shortening the polycondensation time.

  However, the antimony compound can be added in an amount of 50 ppm or less as an antimony atom to the polyester 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 polyester.

  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 amount of germanium atoms remaining in the 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 polyester of the present invention, an alkali metal compound and / or an alkaline earth metal glycol solution may be 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 was charged into the flask together with the aqueous solution, and water was distilled off from the system while stirring at 70 to 90 ° C. under reduced pressure (133 Pa). 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. )

  As another aspect of the polymerization catalyst of the present invention, an alkali metal compound and / or an alkaline earth metal ethylene glycol solution may be used in combination with the ethylene glycol solution of the above aluminum compound / ethylene glycol solution of the phosphorus compound. It goes without saying that it is possible.

  The polyester of the present invention is a polyester in which isophthalic acid is 15.5 to 100 mol% of the polyvalent carboxylic acid component, and ethylene glycol is 30 to 100 mol% of the polyhydric alcohol component.

  The amount of isophthalic acid relative to the total polyvalent carboxylic acid component and the amount of ethylene glycol relative to the total polyhydric alcohol component is preferably 20 to 95 mol% and 35 to 95 mol%, respectively, more preferably 25 to 90 mol%, respectively. And 40 to 90 mol%, more preferably 35 to 80 mol% and 50 to 80 mol%, respectively.

  If the amount of isophthalic acid relative to the total polyvalent carboxylic acid component is less than 15.5 mol%, the resulting molded product has insufficient transparency, which is particularly a problem with thick molded products, and the barrier properties also deteriorate. . Moreover, if the ethylene glycol with respect to all the polyhydric alcohol components is less than 30 mol%, it exists in the tendency for mechanical strength to fall.

  Other polyvalent carboxylic acids used in the present invention include terephthalic acid, orthophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. Acid, 2,7-naphthalenedicarboxylic acid, diphenyl-4,4-dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, anthracene dicarboxylic acid Aromatic 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, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1 , 3-Cyclobutanedicarboxylic acid, 1,3-cyclo Aliphatics exemplified by ethanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, hydrogenated dimer acid, etc. Examples thereof include unsaturated dicarboxylic acids such as dicarboxylic acid, alicyclic dicarboxylic acid, fumaric acid and itaconic acid, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferable. These polyvalent carboxylic acids can be used in the range of 0 to 84.5 mol% of the total polyvalent carboxylic acid components.

  Examples of other polyhydric alcohol components used in the present invention include diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, and 1,5-pentane. Diol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, polypropylene glycol and other aliphatic glycols, 1,2-cyclohexanediol, 1,3-cyclohexane Alicyclics such as diol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol Recall, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) sulfone, bis (p-hydroxyphenyl) ether, bis ( Examples include aromatic glycols such as p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, and alkylene oxide adducts of bisphenol A. These glycols can be used in the range of 0 to 70 mol% of all polyhydric alcohol components.

  Furthermore, examples of the trifunctional or higher polyfunctional compound that can be used as a copolymerization component of the polyester include trimellitic acid and pyromellitic acid as acid components, and glycerin, pentaerythritol, trimethylolethane as glycol components. And trimethylolpropane, with trimellitic acid being particularly advantageous. The amount of copolymerization component used should be such that the polyester remains substantially linear.

  Monofunctional compounds such as benzoic acid and naphthoic acid may be copolymerized.

  Moreover, the polyester of this invention can further improve the thermal stability of polyester by removing a catalyst from this polyester after polycondensation, or making a catalyst deactivate by addition of a phosphorus compound.

  The number average molecular weight of the polyester of the present invention is preferably 2,000 or more, more preferably 5,000 to 50,000.

  When used in a molded product, the intrinsic viscosity of the present invention is preferably 0.2 to 1.5 dl / g. If it is less than 0.2 dl / g, it is a problem of inferior mechanical properties. If an attempt is made to obtain a polyester exceeding 1.5 dl / g, the reaction takes a long time and economical efficiency becomes a problem.

  Moreover, when using for uses, such as a coating material and a coating agent, it is preferable that the reduced viscosity of the polyester of this invention is 0.02-3.80dl / g. The acid value is preferably 0.01 to 5000 eq / t. If the reduced viscosity is less than 0.02 dl / g, the adhesion and film strength are inferior. On the other hand, if it exceeds 3.80 dl / g, it takes a long time for the reaction, resulting in a problem of economical efficiency.

  The solution haze of the 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% or less. Preferably there is. In particular, when used for a molded product having a thickness of 7 mm or more, the solution haze is desirably 3.0% or less. When it exceeds 10.0%, there are many foreign substances in polyester, and the commercial value which does not worsen the transparency of a molded object will be lost.

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

  In addition, it is desirable that the polyester of the present invention has few aluminum insolubles in the system, and it was stirred and dissolved in 30 g of polyester pellets and 300 ml of a parachlorophenol / tetrachloroethane (3/1: weight ratio) mixed solution in 2 hours. Using a tetratetrafluoroethylene membrane filter (Advantec PTFE membrane filter, product name: T100A047A) with a diameter of 47 mm / pore size of 1.0 μm as the solution, the total amount is 0.15 MPa and the effective filtration diameter is 37.5 mm. Is preferably less than 5 hours. Polyesters having such characteristics can be suitably used for applications such as varnishes and various paints used by being dissolved in an organic solvent. If the filtration time exceeds 5 hours, it takes a long time to form a solution and filter through a filtration filter.

The production method of the polyester of the present invention is not particularly limited, and is a direct esterification method of dicarboxylic acid containing isophthalic acid and glycol containing ethylene glycol, or transesterification of alkyl ester such as isophthalic acid and glycol such as ethylene glycol. A glycol ester of dicarboxylic acid is obtained by the method, and then melt polycondensed under normal pressure or reduced pressure to obtain the polyester of the present invention. At this time, an esterification catalyst or the polycondensation catalyst may be used as necessary.
Furthermore, solid phase polymerization may be performed to increase the intrinsic viscosity as necessary.

  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.

  The polyester obtained in the present invention includes extender pigments such as titanium oxide, talc, barium sulfate, and clay, chromium-containing rust preventive pigments such as zinc chromate, strontium chromate, and calcium chromate, colloidal silica, and aluminum tripolyphosphate. Non-chromium rust preventive pigments such as tripolyphosphate, zinc phosphate, phosphite, phosphomolybdate, molybdate, cyanamide zinc calcium, borate, calcium silica Further, known colorants, additives such as silica and wax, flame retardants, glass fibers and the like can be blended.

  The polyester obtained in the present invention can be used as it is by a melt molding method such as injection molding or extrusion molding. Moreover, it can be used in a form dissolved in an organic solvent. Moreover, what is used in the form melt | dissolved in the organic solvent may be used. Examples of organic solvents include toluene, xylene, Solvesso 100 and 150, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol Acetate, butyl carbitol acetate, methyl ethyl ketone, cyclohexanone, isophorone, N-methylpyrrolidone, dibasic acid ester and the like are appropriately selected in consideration of solubility and evaporation rate.

  The polyester obtained in the present invention can be applied to raw materials for various modification reactions such as adhesives, paints, coating agents, polyester polyurethanes, plasticizers, molding applications, laminates, toners, binders, inks and the like.

  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. Reduced viscosity and intrinsic viscosity (dl / g)
0.1 g of a polyester sample was precisely weighed and 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 is dissolved in 0.7 ml of a mixed solution of deuterated chloroform and trifluoroacetic acid (9/1; volume ratio) and obtained using ¹ H-NMR (manufactured by varian, UNITY 50). It was.
3. Degree of appearance coloring of polyester The polyester was evaluated and judged as follows by visual observation while maintaining a sheet shape having substantially the same thickness after polycondensation.
○: Almost no color △: Slightly yellow or gray ×: Remarkably yellow

4). Solution Haze After 5 g of the polyester was dissolved in 50 cc of the mixed solvent (1), the solution was put into a 20 mm thick cell and measured with a Nippon Denshoku Co., Ltd. haze meter, model NDH2000.
5. Oxygen permeability (cc.mil/100in2/day-atm)
Measurement was performed at 20 ° C. and 0% RH using an oxygen transmission rate measuring device OX-TRAN100 manufactured by Modern Controls.

(Example A1)
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 mixture of solutions was charged, and an esterification reaction was performed at 150 ° C. to 220 ° C. under nitrogen. 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 reaction was continued until the torque value of the stirring blade corresponding to the intrinsic viscosity reached a desired value, and the polycondensation reaction was completed. The obtained molten polyester was extracted in the form of a sheet from the outlet at the bottom of the polymerization tank, cooled in water, and then obtained in a sheet state. Table 1 shows the composition and characteristic values of the obtained polyester.
The polyester obtained in this example had a polyester solution haze as low as 1.0% and a good color tone.

(Examples A2 to A10)
Polyesters having respective compositions shown in Table 1 were obtained by a method according to the synthesis of the polyester of the present invention. Table 1 shows the composition and characteristic values of each polyester obtained.

(Comparative Example A1)
Polyester was obtained by polycondensation in the same manner as in Example 1 except that the polycondensation catalyst was changed to antimony trioxide. Table 1 shows the composition and characteristic values of the obtained polyester.
The appearance coloring of the resin is grayish, and the solution haze is high and problematic.

(Comparative Example A2)
Polyester was obtained by polycondensation in the same manner as in Example 1 except that the polycondensation catalyst was changed to tetrabutyl titanate. Table 1 shows the composition and characteristic values of the obtained polyester.
Although the solution haze was low, the appearance coloring of the resin was markedly yellow, which is a problem.

(Examples B1 to B7)
Polyesters having respective compositions described in Table 2 were obtained by a method according to the synthesis of the polyester of the present invention. Table 2 shows the composition and characteristic values of each polyester obtained.
Including Comparative Examples B1 to B3, the polycondensation time was adjusted so that the intrinsic viscosity of each polyester was about 0.68 dl / g.

(Comparative Example B1)
Polyester was obtained by polycondensation in the same manner as in Example 1 except that the polycondensation catalyst was changed to antimony trioxide. Table 2 shows the composition and characteristic values of the obtained polyester.
The appearance coloring of the resin is grayish, and the solution haze is high and problematic.

(Comparative Example B2)
Polyester was obtained by polycondensation in the same manner as in Example 1 except that the polycondensation catalyst was changed to tetrabutyl titanate. Table 2 shows the composition and characteristic values of the obtained polyester.
The solution haze was as low as 0.9%, but the appearance color of the resin was extremely yellow, which is a problem.

(Comparative Example B3)
Polyester was obtained by polycondensation in the same manner as in Example 1 except that only terephthalic acid was used as the dicarboxylic acid component and antimony trioxide was used as the polycondensation catalyst. Table 2 shows the composition and characteristic values of the obtained polyester.
The appearance coloring of the resin is grayish, and the solution haze is high and problematic. The oxygen transmission rate was also high.

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. Polyester having barrier properties, molded articles made of the same, and the like

Claims (15)

Among the polyvalent carboxylic acid components, isophthalic acid is 15.5 to 100 mol%, and among the polyhydric alcohol components, the polyester is ethylene glycol 30 to 100 mol%, the group consisting of aluminum and its compounds A polyester obtained by polycondensation using a polycondensation catalyst containing at least one selected from the group consisting of 2. The polyester according to claim 1, comprising at least one selected from the group consisting of terephthalic acid, 2,6-naphthalenedicarboxylic acid, sebacic acid, adipic acid, and azelaic acid as the other polycarboxylic acid component. . Other polyhydric alcohol components include diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3- The polyester according to claim 1, comprising at least one selected from the group consisting of bis (2-hydroxyethoxy) benzene and bisphenol A ethylene oxide adduct. The polyester according to claim 1, comprising a trifunctional or higher polyfunctional compound component. The polyester according to any one of claims 1 to 4, 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 polyester 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 an alkali metal and / or an alkaline earth metal. The polyester according to claim 1, 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, or a phosphine compound. The polyester according to any one of claims 5 to 7. The polyester according to any one of claims 6 to 8, wherein the alkali metal and alkaline earth metal are at least one selected from Li, Na, Mg or a compound thereof. The varnish which melt | dissolved the polyester in any one of Claims 1-9. The adhesive agent containing the polyester in any one of Claims 1-9. The coating material containing the polyester in any one of Claims 1-9. The coating agent containing the polyester in any one of Claims 1-9. The molded object containing the polyester in any one of Claims 1-9. The laminated body containing the polyester in any one of Claims 1-9.