TW202222902A - Polyester resin composition, method for manufacturing same, and polyester film using same - Google Patents

Abstract

Provided is a polyester resin composition whereby catalyst cost is reduced even when a polymerization catalyst comprising an aluminum compound and a phosphorus compound is used, and there is little foreign matter in the polyester resin composition. A polyester resin composition including a polyester resin and insoluble particles which are particles that are insoluble in the polyester resin, the polyester resin composition being characterized in that the polyester resin includes an aluminum compound and a phosphorus compound, and the polyester resin composition satisfies (1) through (4). (1): The content ratio of elemental aluminum in the polyester resin composition is 9-19 mass ppm. (2): The content ratio of elemental phosphorus in the polyester resin composition is 13-31 mass ppm. (3): The mole ratio of elemental phosphorus to elemental aluminum in the polyester resin composition is 1.32-1.80. (4): The content ratio of the insoluble particles in the polyester resin composition is 500-2000 mass ppm.

Description

Polyester resin composition, method for producing the same, and polyester film using the same

The present invention relates to a polyester resin composition, a method for producing the same, and a polyester film using the same.

Polyester resins represented by polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) have excellent mechanical and chemical properties. Due to the properties of each polyester resin, it is widely used in various fields such as fibers for clothing and industrial materials, various films and sheets for packaging and industrial use, and molded articles such as bottles and engineering plastics.

Typical polyester resins are polyester resins that use units derived from aromatic dicarboxylic acids and alkanediols as main constituents, such as in the case of polyethylene terephthalate (PET). Dicarboxylic acid or dimethyl terephthalate is esterified or transesterified with ethylene glycol to produce bis(2-hydroxyethyl terephthalate), which is polycondensed by using a catalyst under high temperature and vacuum The polycondensation method is used for industrial production.

Conventionally, antimony compounds or germanium compounds have been widely used as polyester polymerization catalysts used in the polymerization of such polyester resins. Antimony trioxide, which is an example of an antimony compound, is an inexpensive catalyst with excellent catalytic activity. However, when it is used as a main component, that is, in an amount sufficient to exhibit a practical polymerization rate, metal is precipitated during polymerization. Antimony, thus producing darkening and foreign matter in polyester resins, also causes surface defects in films. In addition, when used as a raw material such as a hollow molded product, it is difficult to obtain a hollow molded product excellent in transparency. Based on such ins and outs, a polyester resin containing no antimony compound at all or no antimony compound as a main component is desired as a catalyst.

A germanium compound has been put into practical use as a catalyst other than the antimony compound, which has excellent catalytic activity and can be given to a polyester resin which does not have the above-mentioned problems. However, the germanium compound has problems that it is very expensive and easy to distill from the reaction system to the outside of the system during polymerization, so that the catalyst concentration of the reaction system changes and the control of polymerization becomes difficult. There are problems in using it as the main component of the catalyst. .

The research on polymerization catalysts to replace antimony-based catalysts or germanium-based catalysts was also carried out. Titanium compounds represented by tetraalkoxy titanate have been proposed, but polyester resins produced using the titanium compounds are liable to be thermally deteriorated at the time of melt-molding, and the polyester resins have problems of remarkably coloring.

Based on the above-mentioned ins and outs, a polymerization catalyst is desired, which is a polymerization catalyst having metal components other than antimony, germanium, and titanium as the main metal component of the catalyst, which is excellent in catalytic activity, and excellent in color tone and thermal stability. , and can impart excellent transparency to the molded product of polyester resin.

For example, Patent Documents 1 and 2 disclose catalysts composed of aluminum compounds and phosphorus compounds as novel polymerization catalysts. Moreover, patent documents 3 and 4 disclose polyester films which consist of polyester resins produced using catalysts consisting of an aluminum compound and a phosphorus compound. By using the above-mentioned polymerization catalyst, a polyester resin and a polyester film having good color tone, transparency, and thermal stability can be obtained. However, in Patent Documents 1 to 4, in order to obtain high polymerization activity, a large amount of the catalyst is added, and the cost of the catalyst necessary for the polymerization increases. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2007/032325 [Patent Document 2] Japanese Patent Laid-Open No. 2006-169432 [Patent Document 3] Japanese Patent Laid-Open No. 2002-249565 [Patent Document 4] Japanese Patent Laid-Open No. 2002-249602

[The problem to be solved by the invention]

The present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide a polyester resin composition with reduced catalyst cost and less foreign matter even when a polymerization catalyst composed of an aluminum compound and a phosphorus compound is used. thing. Moreover, a polyester film formed by film-forming the polyester resin composition is provided. [Means to solve the problem]

The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, they have found that by reducing the amount of the aluminum element contained in the polyester resin composition and setting the molar ratio of the phosphorus element to the aluminum element to an appropriate range, The present invention has been accomplished to achieve the object.

When polymerization catalysts such as antimony compounds and germanium compounds are used in polyester polymerization, the polymerization activity is usually proportional to the amount of catalyst added. However, in the polymerization catalyst composed of the aluminum compound and the phosphorus compound, the polymerization activity is affected by the complex formation reaction of the aluminum compound and the phosphorus compound, so the relationship between the polymerization activity and the catalyst addition amount cannot be simplified.

Therefore, the inventors of the present invention conducted an analysis of the control factor of the catalyst activity with respect to the polymerization catalyst composed of an aluminum compound and a phosphorus compound. As a result, it was found that by reducing the amount of the aluminum element in the polyester resin composition and setting the molar ratio of the phosphorus element to the aluminum element in an appropriate range, it was possible to suppress the cost of the catalyst and reduce the aluminum content. The present invention is accomplished by increasing the amount of foreign matter and improving the polymerization activity.

That is, this invention consists of the following structures. 1. A polyester resin composition comprising a polyester resin composition and insoluble particles of particles insoluble in the polyester resin, characterized in that the polyester resin contains an aluminum compound and a phosphorus compound, and the above The polyester resin composition satisfies the following (1) to (4); (1) The content of aluminum element in the polyester resin composition is 9 to 19 ppm by mass (2) The content of phosphorus element in the polyester resin composition is 13 to 31 ppm by mass (3) The molar ratio of phosphorus element to aluminum element in the polyester resin composition is 1.32 or more and 1.80 or less (4) The content rate of the said insoluble particle in the said polyester resin composition is 500-2000 mass ppm. 2. The polyester resin composition according to 1. above, wherein the content of aluminum element corresponding to the aluminum-based foreign matter in the polyester resin is 3000 mass ppm or less. 3. The polyester resin composition according to 1. or 2. above, wherein the intrinsic viscosity (IV) is 0.56 dl/g or more. 4. The polyester resin composition according to any one of 1. to 3. above, wherein the phosphorus compound has a phosphorus element and a phenol structure in the same molecule. 5. The polyester resin composition according to any one of the above 1. to 4., wherein the volume average particle diameter of the insoluble particles is 0.5 to 3.0 μm. 6. The polyester resin composition according to any one of 1. to 5. above, wherein the insoluble particles are silica. 7. A method for producing a polyester resin composition, which is a method for producing a polyester resin composition according to any one of the above 1. to 6., characterized by having a synthetic polycondensation method. The first step in which the polyester or its oligomer is used as an intermediate, and the second step in which the intermediate is further polycondensed, after the first step and before the second step, an aluminum compound is added to the intermediate. The solution A1 and the solution B1 in which the phosphorus compound is dissolved, the addition amounts of the solution A1 and the solution B1 satisfy the following (5) to (7), and the insoluble particles are added during the first step or after the first step. , the addition amount of the aforementioned insoluble particles satisfies the following (8); (5) The amount of aluminum added to the polyester resin produced is 9 to 19 ppm by mass (6) The amount of phosphorus added to the polyester resin produced is 18 to 38 ppm by mass (7) The molar ratio of the addition amount of the phosphorus element in the above (6) to the addition amount of the aluminum element in the above (5) is 1.50 or more and 2.30 or less (8) The addition amount of the said insoluble particle with respect to the said polyester resin produced|generated is 500-2000 mass ppm. 8. The method for producing a polyester resin composition according to 7. above, wherein the polyester resin composition is produced by a batch polymerization method. 9. The method for producing a polyester resin composition according to 7. above, wherein the polyester resin composition is produced by a continuous polymerization method, and the solution A1 and the solution B1 are added to the final esterification reaction tank or The transfer line between the final esterification reaction tank and the initial polymerization reaction tank. 10. The method for producing a polyester resin composition according to any one of the above 7. to 9., wherein the solution A1 is a glycol solution, and the maximum absorption wavelength of the solution A1 is 562.0 to 572.0 nm. 11. The method for producing a polyester resin composition according to 10. above, wherein the solution B1 is a dihydric alcohol solution, and the solution B1 is a maximum absorption wavelength of 460.0 to 463.0 nm. 12. The method for producing a polyester resin composition according to 11. above, wherein the diol solution B1 is heat-treated at 170 to 196° C. for a phosphorus compound in a diol solution for 125 to 240 minutes. 13. The method for producing a polyester resin composition according to any one of 7. to 12., wherein the solution A1 and the solution B1 are glycol solutions, and the glycol solution A1 and the glycol are The maximum absorption wavelength of the mixed solution of solution B1 was 559.5-560.8 nm. 14. A polyester film comprising the polyester resin composition according to any one of 1. to 6. above. 15. The polyester film according to 14. above, wherein an electrostatic adhesiveness imparting agent is further added to the polyester resin composition. [Effect of invention]

Although the polyester resin composition of the present invention uses a polymerization catalyst composed of an aluminum compound and a phosphorus compound, the cost of the catalyst can be kept low, and foreign matter derived from the catalyst contained in the polyester resin composition can be reduced at the same time. , so the cost of the polyester resin composition can be reduced and the quality can be improved. In addition, by setting the acidity and basicity of the solution in which the aluminum compound added as a catalyst is dissolved, the solution in which the phosphorus compound added as a catalyst is dissolved, and the mixed solution thereof into a preferable range (the The maximum absorption wavelengths of the solution and the mixed solution are set in a preferred range), which can further suppress the increase in the amount of aluminum-based foreign matter. In addition, since the polyester resin composition of the present invention can be obtained at low cost and is of high quality, the production cost of the polyester film obtained by forming the polyester resin composition of the present invention into a film can also be reduced, and the polyester The quality of the film is improved. In addition, since this polyester film is excellent in running properties, abrasion resistance, optical properties, and the like, it can be used in a wide range of applications such as packaging films and industrial films.

The present invention will be described in detail below.

The polyester resin composition of the present invention contains insoluble particles of a polyester resin and particles insoluble in the polyester resin. Moreover, the said polyester resin contains an aluminum compound and a phosphorus compound.

[Polyester resin composition] The polyester resin composition of the present invention satisfies the following (1) to (4). (1) The content of aluminum element in the polyester resin composition is 9 to 19 ppm by mass (2) The content of phosphorus element in the polyester resin composition is 13 to 31 ppm by mass (3) The polyester The molar ratio of the phosphorus element to the aluminum element in the resin composition is 1.32 or more and 1.80 or less (4) The content rate of the insoluble particles in the polyester resin composition is 500 to 2000 mass ppm , mass ppm means 10 ^-4 mass %.

[polyester resin] The polyester resin used in the present invention includes a polyester resin composed of at least one selected from polycarboxylic acids and ester-forming derivatives thereof and at least one selected from polyols and ester-forming derivatives thereof.

As a polyester resin, it is preferable that the main polyhydric carboxylic acid component is a dicarboxylic acid.

The polyester resin whose main polycarboxylic acid component is dicarboxylic acid is preferably a polyester resin containing more than 70 mol% of dicarboxylic acid relative to the total polycarboxylic acid component, more preferably 80 mol% % or more of the polyester resin, more preferably 90 mol% or more of the polyester resin. Moreover, when using two or more types of dicarboxylic acid, it is preferable that the sum total of these is in the said range.

Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, sebacic acid, dodecanedioic acid Alkanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3- Saturated aliphatic dicarboxylic acids exemplified by cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, etc., or their ester-forming derivatives; Unsaturated aliphatic dicarboxylic acids or their ester-forming derivatives exemplified by fumaric acid, maleic acid, itaconic acid, etc.; phthalic acid, isophthalic acid, terephthalic acid, 5-( Alkali metal) sulfoisophthalic acid, biphthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, 7-Naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenylenedicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 1,2-bis(phenoxy)ethane Aromatic dicarboxylic acid exemplified by -p,p'-dicarboxylic acid, pamoic acid, anthracenedicarboxylic acid, etc., or an ester-forming derivative thereof.

More preferably, the main polyvalent carboxylic acid component is terephthalic acid or its ester-forming derivative, or naphthalenedicarboxylic acid or its ester-forming derivative. As naphthalenedicarboxylic acid or its ester-forming derivative, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7 - Naphthalenedicarboxylic acid, or ester-forming derivatives of these.

Polyester resin whose main polyhydric carboxylic acid component is terephthalic acid or its ester-forming derivative or naphthalenedicarboxylic acid or its ester-forming derivative, and contains 70 mol in total relative to all polyvalent carboxylic acid components % or more of the polyester resin of terephthalic acid or its ester-forming derivative and naphthalene dicarboxylic acid or its ester-forming derivative is preferably, more preferably 80 mol% or more of the polyester resin, even more preferred It is a polyester resin containing more than 90 mol%.

Particularly preferred are terephthalic acid, 2,6-naphthalenedicarboxylic acid, or ester-forming derivatives of these. Other dicarboxylic acid can also be used as a structural component as needed.

As the polyvalent carboxylic acid other than these dicarboxylic acids, a trivalent or higher polyvalent carboxylic acid and a hydroxycarboxylic acid may be used together as long as the amount is small, and trivalent to tetravalent polyvalent carboxylic acid is preferable. Examples of polyvalent carboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3',4'-biphenyl Tetracarboxylic acid, ester-forming derivatives thereof, and the like. The trivalent or more polyvalent carboxylic acid is preferably 20 mol % or less, more preferably 10 mol % or less, and further preferably 5 mol % or less with respect to the total polyvalent carboxylic acid component. Moreover, when using 2 or more types of trivalent or more polyvalent carboxylic acid, it is preferable that the sum total of these is in the said range.

Examples of hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, glycolic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and 4-hydroxycyclohexane Formic acid, or their ester-forming derivatives, and the like. The hydroxycarboxylic acid is preferably 20 mol % or less, more preferably 10 mol % or less, and further preferably 5 mol % or less with respect to the total polyvalent carboxylic acid component. Moreover, when using two or more types of hydroxycarboxylic acid, it is preferable that the sum total of these is in the said range.

Examples of ester-forming derivatives of polyvalent carboxylic acids or hydroxycarboxylic acids include such alkyl esters, acyl chlorides, acid anhydrides, and the like.

As the polyester resin, it is preferable that the main polyol component is a diol.

The polyester resin (A) whose main polyol component is diol is preferably a polyester resin containing more than 70 mol% of diol relative to the total polyol component, more preferably 80 mol% It is more preferable to contain 90 mol% or more of the polyester resin in an amount of 90 mol% or more of the polyester resin. Moreover, when using two or more types of dihydric alcohols, it is preferable that the sum total of these should fall within the said range.

As the dihydric alcohol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3- Cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol Alkanediols exemplified by alkanediethanol, 1,10-decanediol, 1,12-dodecanediol, etc.; aliphatic diols exemplified by polyethylene glycol, polypropylene glycol, polybutylene glycol, etc. ;Hydroquinone, 4,4'-dihydroxybisphenol, 1,4-bis(β-hydroxyethoxy)benzene, 1,4-bis(β-hydroxyethoxyphenyl)benzene, bis(p-hydroxy) Phenyl) ether, bis (p-hydroxyphenyl) bismuth, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5-naphthalene Aromatic diols such as diphenols, diols in which ethylene oxide is added to these diols, and the like are exemplified.

Among these diols, alkanediol is preferable, and ethylene glycol, 1,3-propanediol, 1,4-butanediol, or 1,4-cyclohexanedimethanol is more preferable. Moreover, the said alkanediol may contain a substituent and an alicyclic structure in a molecular chain, and may use 2 or more types together.

As polyhydric alcohols other than these dihydric alcohols, a trivalent or higher polyhydric alcohol may be used in combination as long as it is a small amount, and trivalent to tetravalent polyhydric alcohols are preferable. Trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol, etc. are mentioned as a trivalent or more polyhydric alcohol.

The trivalent or higher polyol is preferably 20 mol % or less, more preferably 10 mol % or less, and further preferably 5 mol % or less with respect to the total polyol component. Moreover, when using 2 or more types of trivalent or more polyhydric alcohols, it is preferable that the sum total of these is in the said range.

In addition, the combined use of cyclic esters is also acceptable. Examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, lactide, and the like. Moreover, as ester-forming derivatives of polyhydric alcohol, the ester of polyhydric alcohol and lower aliphatic carboxylic acid, such as acetic acid, is mentioned.

The cyclic ester is preferably 20 mol % or less, more preferably 10 mol % or less, and further preferably 5 mol % or less with respect to the total of the total polyvalent carboxylic acid component and the total polyol component. Moreover, when using two or more types of cyclic esters, it is preferable that the total of these is within the above-mentioned range.

The polyester resin used in the present invention is selected from the group consisting of ethylene terephthalate, butylene terephthalate, propylene terephthalate, and 1,4-cyclohexane terephthalate. A polymer consisting of only one monomer of dimethyl naphthalate, ethylene naphthalate, butylene naphthalate, or propylene naphthalate, or a copolymer consisting of two or more of the above-mentioned monomers is Preferably, the polyester resin used in the present invention is polyethylene terephthalate or a copolymer composed of at least one of the above monomers other than ethylene terephthalate and ethylene terephthalate More preferably, polyethylene terephthalate is particularly preferred. A copolymer composed of ethylene terephthalate and at least one of the above monomers other than ethylene terephthalate contains 70 mol% or more of components derived from ethylene terephthalate monomers More preferably, it is more preferable to contain 80 mol% or more, and it is still more preferable to contain 90 mol% or more.

＜Polymerization catalyst＞ The polyester resin of the present invention contains a component derived from an aluminum compound and a component derived from a phosphorus compound in a catalytic amount. That is, the polyester resin of this invention is manufactured using the polymerization catalyst which consists of an aluminum compound and a phosphorus compound.

＜Aluminum compound＞ The aluminum compound constituting the above-mentioned polymerization catalyst is not limited as long as it is dissolved in a solvent, and known aluminum compounds can be used without limitation. 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 lactic acid. Aluminum, aluminum citrate, aluminum tartrate, aluminum salicylate and other carboxylates; aluminum chloride, aluminum hydroxide, aluminum chloride hydroxide, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate, aluminum phosphonate and other inorganic acid salts ; Alumina methoxide, aluminum ethoxide, n-propoxide aluminum, isopropoxide aluminum, n-butyrate aluminum, tertiary butyrate aluminum alkoxide, etc.; Chelate compounds such as aluminum diisopropoxide; organoaluminum compounds such as trimethylaluminum, triethylaluminum, and their partial hydrolyzates, aluminum alkoxides, and reactions composed of aluminum chelate compounds and hydroxycarboxylic acids Products, alumina, ultrafine particle alumina, aluminum silicate, composite oxides of aluminum and titanium, silicon, zirconium, alkali metals, alkaline earth metals, etc. Among them, at least one selected from carboxylates, inorganic acid salts, and chelate compounds is preferred, and among these, aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, At least one of aluminum chloride hydroxide and aluminum acetylacetonate is more preferably selected from the group consisting of aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum chloride hydroxide, and aluminum acetylacetonate One is further preferred, at least one selected from aluminum acetate and basic aluminum acetate is particularly preferred, and basic aluminum acetate is most preferred.

The above-mentioned aluminum compound is preferably an aluminum compound soluble in solvents such as water and glycol. Solvents that can be used in the present invention are water and alkanediols. Examples of the alkanediols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol, dipropylene glycol, butylene glycol, dibutylene glycol, and neopentyl glycol. Preferably it is at least 1 sort(s) chosen from ethylene glycol, propylene glycol, and butylene glycol, More preferably, it is ethylene glycol. It is preferable to use a solution in which the aluminum compound is dissolved in water or ethylene glycol because the effect of the present invention can be significantly exhibited.

The content rate of the aluminum element in the polyester resin composition must be 9 to 19 mass ppm, preferably 10 to 19 mass ppm, more preferably 10 to 17 mass ppm, still more preferably 12 to 17 mass ppm. If the aluminum element is less than 9 mass ppm, there is a possibility that the polymerization activity cannot be fully exhibited. On the other hand, when it exceeds 19 mass ppm, there exists a possibility that the amount of aluminum-type foreign material may increase.

＜Phosphorus compound＞ The phosphorus compound constituting the polymerization catalyst of the present invention is not particularly limited, but if a phosphonic acid-based compound or a phosphinic acid-based compound is used, it is preferable because the effect of improving the catalyst activity is large. If a phosphonic acid-based compound is used, the effect of improving the catalytic activity is particularly great and better.

Among the above-mentioned phosphorus compounds, phosphorus compounds having a phosphorus element and a phenol structure in the same molecule are preferable. It is not particularly limited as long as it is a phosphorus compound having a phosphorus element and a phenol structure in the same molecule, but if a phosphonic acid-based compound having a phosphorus element and a phenol structure in the same molecule is used, a phosphorus element and a phenol structure in the same molecule are used. One or more than two kinds of compounds in the group consisting of phosphinic acid-based compounds of the structure have a large and better catalytic activity improvement effect. Phosphonic acid compounds have a very large and better catalytic activity improvement effect.

Moreover, as a phosphorus compound which has a phosphorus element and a phenol structure in the same molecule, P(=O)R ¹ (OR ² )(OR ³ ) and P(=O)R ¹ R ⁴ (OR ² ) are exemplified. Represented compounds, etc. R ¹ represents a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as a hydroxyl group, a halogen group, an alkoxy group or an amine group, and a phenol structure. R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as a hydroxyl group, a halogen group, an alkoxy group or an amine group. R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, and a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as a hydroxyl group or an alkoxy group. However, the hydrocarbon group may include branched structures, alicyclic structures such as cyclohexyl, and aromatic ring structures such as phenyl and naphthyl. The termini of R ² and R ⁴ may also be bonded to each other.

Examples of the phosphorus compound having a phosphorus element and a phenol structure in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, and p-hydroxyphenylphosphonate. Diphenyl phosphonate, Bis(p-hydroxyphenyl)phosphinic acid, Methyl bis(p-hydroxyphenyl)phosphinate, Phenyl bis(p-hydroxyphenyl)phosphinate, p-hydroxyphenylphosphinic acid , methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid represented by the following (Formula 1) Alkyl esters, etc. As a phosphorus compound having a phosphorus element and a phenolic structure in the same molecule, a phosphorus compound having a hindered phenolic structure is particularly preferred, among which 3,5-di-tertiary butyl group represented by the following (Formula 1) is used Dialkyl 4-hydroxybenzylphosphonates are preferred.

[hua 1]

(In (Formula 1), X ¹ and X ² represent hydrogen and an alkyl group having 1 to 4 carbon atoms, respectively.)

The carbon number of the alkyl groups of X ¹ and X ² is preferably 1-4, more preferably 1-2. In particular, the ethyl ester compound having 2 carbon atoms is commercially available as Irganox 1222 (manufactured by BASF Corporation), and is preferably readily available.

In addition, as the phosphorus compound in the present invention, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dialkyl ester represented by the above-mentioned (chemical formula 1) is preferable, but it may be other than In addition, the modified product of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dialkyl ester is also included. Details of the modified product will be described later.

The content rate of phosphorus element in the said polyester resin composition is 13-31 mass ppm, Preferably it is 15-29 ppm. If the phosphorus element is less than 13 mass ppm, the polymerization activity may decrease and the amount of aluminum-based foreign matter may increase. On the other hand, when it exceeds 31 mass ppm, the polymerization activity may fall, the addition amount of a phosphorus compound will increase, and the catalyst cost will increase, which is unfavorable.

<Molar ratio of phosphorus element to aluminum element in polyester resin composition> In the polyester resin composition of the present invention, the molar ratio of phosphorus element relative to aluminum element is controlled (hereinafter referred to as "relative molar ratio of phosphorus element relative to aluminum element" in order to distinguish it from "added molar ratio of phosphorus element relative to aluminum element" described later). The residual molar ratio of phosphorus to aluminum is also important, and must be 1.32 to 1.80, preferably 1.38 to 1.68. As described above, the aluminum element and the phosphorus element in the polyester resin composition are derived from the aluminum compound and the phosphorus compound, respectively, which are used as the polymerization catalyst of the polyester resin composition. By using these aluminum compounds and phosphorus compounds together in a specific ratio, a complex having catalytic activity can be functionally formed in a polymerization system, and sufficient polymerization activity can be exhibited. If the residual molar ratio of phosphorus element to aluminum element is less than 1.32, thermal stability and thermal oxidation stability may decrease, and the amount of aluminum-based foreign matter may increase. On the other hand, when the residual molar ratio of phosphorus element with respect to aluminum element exceeds 1.80, since the addition amount of a phosphorus compound will become too large, a catalyst cost will increase.

In the present invention, in addition to the above-mentioned aluminum compound and phosphorus compound, an antimony compound, a germanium compound, and a titanium compound may be used in combination within the range in which the properties, processability, and color tone of the polyester resin composition of the present invention do not cause problems in products. and other polycondensation catalysts. The content rate of antimony element in the polyester resin composition is preferably 30 mass ppm or less, and the content rate of germanium element in the polyester resin composition is preferably 10 mass ppm or less. The content of titanium element in the composition is preferably 3 mass ppm or less. However, based on the purpose of the present invention, it is preferable not to use the other polycondensation catalysts mentioned above as much as possible.

The intrinsic viscosity (IV) of the polyester resin composition of the present invention is preferably above 0.56dl/g, preferably 0.56-0.65dl/g, more preferably 0.58-0.64dl/g. When the intrinsic viscosity of the polyester resin composition is less than the above, there is a possibility that the mechanical strength and impact resistance of the molded product will become insufficient. On the other hand, when the intrinsic viscosity of the polyester resin composition exceeds the above-mentioned range, it is unfavorable because the economical efficiency is lowered.

[Manufacturing method of polyester resin composition] As a method for producing the polyester resin composition of the present invention, in addition to using a polyester polymerization catalyst composed of an aluminum compound and a phosphorus compound as a catalyst, adding a polymerization catalyst so as to satisfy the following (5) to (7), The addition of the insoluble particles by the method described later can be performed by a method including a well-known procedure.

The method for producing the polyester resin composition of the present invention includes a first step of using a polyester having a synthetic polycondensate (low-order condensate) or an oligomer thereof as an intermediate, and a second step of further polycondensing the intermediate. 2 steps are preferred.

Furthermore, it is preferable to add the solution A1 in which the aluminum compound is dissolved and the solution B1 in which the phosphorus compound is dissolved to the intermediate product after the first step and before the second step so as to satisfy the following (5) to (7). . Polycarboxylic acids and their ester-forming derivatives used in the production of polyester resins, hydroxycarboxylic acids and their ester-forming derivatives that can be added in small amounts, and cyclic esters that can be added in small amounts do not escape from the polymer during polymerization. The reaction system is distilled to the outside of the system, and almost 100% of the amount initially added to the system as a catalyst remains in the polyester resin produced by polymerization. Therefore, the "generated polyester resin" can be calculated from the input amount. of quality. (5) The amount of aluminum added to the polyester resin produced is 9 to 19 ppm by mass (6) The amount of phosphorus added to the polyester resin produced is 18 to 38 ppm by mass (7) The molar ratio of the added amount of the phosphorus element in the above (6) to the added amount of the aluminum element in the above (5) (hereinafter referred to as "the added molar ratio of the phosphorus element relative to the aluminum element") ) is 1.50 or more and 2.30 or less

It does not specifically limit as a manufacturing method of the polyester or its oligomer of the low-order condensate (oligomer) used in this invention.

In the method for producing the polyester resin used in the present invention, in addition to using a polyester polymerization catalyst composed of an aluminum compound and a phosphorus compound as a catalyst, and adjusting the content of aluminum element and phosphorus element in the polyester resin so as to be within a specific range Except for the content ratio and the molar ratio of the phosphorus element with respect to the aluminum element, it can be carried out by a method including a conventionally known procedure. For example, when producing polyethylene terephthalate, by directly reacting terephthalic acid with ethylene glycol, and other copolymerization components as required, distilling off water and esterifying it, it can be carried out under normal pressure or reduced pressure. The direct esterification method of polycondensation under low temperature; or react dimethyl terephthalate with ethylene glycol and other copolymerization components as needed to distill off methanol and transesterify them, then carry out under normal pressure or reduced pressure. Produced by the transesterification method of polycondensation. Further, solid-phase polymerization may be performed in order to increase the intrinsic viscosity according to need. The polymerization may be a batch polymerization method or a continuous polymerization method. Moreover, the quantity (mass) of the polyester resin produced|generated can be calculated from the quantity (mass) of the polyvalent carboxylic acid containing dicarboxylic acid etc. used as a raw material.

In these forms, either the esterification reaction or the transesterification reaction may be carried out in one stage, or may be carried out in multiple stages. In the melt polymerization reaction, the number and size of the reactors and the manufacturing conditions of each step can be appropriately selected without limitation, and can be carried out in one stage or divided into multiple stages, and 2 to 5 stages are preferred. 3 to 4 stages are more preferable, and 3 stages are more preferable. The aforementioned melt polymerization reaction is preferably carried out using a continuous reaction apparatus. The continuous reaction apparatus connects the reaction vessel of esterification reaction or transesterification reaction with the melt polymerization reaction vessel by piping, and carries out the continuous feeding of raw materials so that each reaction vessel is not empty, transported to the melt polymerization reaction vessel by piping, and then from the reaction vessel. A method of extracting resin from a melt polymerization reaction vessel. In addition, in this case, it is not necessary to continuously inject the raw materials to extraction at any time, and it may be intermittently performed in a small amount (for example, about 1/10 of the amount of the reaction vessel). When the polyester resin composition is produced by an esterification reaction or a transesterification reaction in multiple stages and by a continuous polymerization method, the solution A1 in which the aluminum compound is dissolved and the solution B1 in which the phosphorus compound is dissolved are added to the multistage The conveying line between the final reaction tank (final esterification reaction tank or final esterification reaction tank) and the initial polymerization reaction tank is preferred.

In addition, the polyester resin produced by the melt polymerization method may be additionally polymerized by the solid phase polymerization method. The solid-phase polymerization reaction can be carried out using a continuous apparatus similarly to the melt polycondensation reaction.

In the case of a continuous polycondensation apparatus consisting of three or more reactors (the three-stage polymerization method of the initial stage, the middle stage, and the later stage), the first stage is set as the initial stage, the final stage is set as the later stage, and the The previous stage from the second stage to the final stage is regarded as an intermediate stage, and the reaction conditions of the polymerization reaction in the intermediate stage are preferably those between the reaction conditions of the initial stage and the reaction conditions of the final stage. It is preferable that the increase in the intrinsic viscosity attained in these polymerization steps is distributed smoothly.

In the present invention, the acid end group concentration of the intermediate (lower-order condensate) produced in the first step is preferably 400 to 1500 eq/ton. More preferably, it is 500-1200eq/ton. By setting the setting value of the acid end group concentration of the above-mentioned oligomer to the above-mentioned range, the activity of the polymerization catalyst can be sufficiently induced.

Furthermore, in the present invention, the ratio (OH %) of hydroxyl end groups relative to the total end group concentration of the intermediate is preferably 45 to 70 mol %, more preferably 55 to 65 mol %. If the ratio of the hydroxyl end of the oligomer is less than 45 mol %, the polycondensation activity may become unstable and the amount of aluminum-based foreign substances may increase. On the other hand, when the ratio of the hydroxyl end of the oligomer exceeds 70 mol %, the polycondensation activity may decrease.

When using an aluminum compound and a phosphorus compound as a catalyst, they are preferably added in the form of a slurry or a solution, and a solution dissolved in a solvent such as water and glycol is more preferable, and those made into water and/or glycol are further Preferably, a solution dissolved in ethylene glycol is used.

In the present invention, after the esterification reaction or the transesterification reaction is completed, the content (residual amount) of the aluminum element and the phosphorus element in the polyester resin composition is added so that the content (residual amount) of the above-mentioned (1) to (3) may be satisfied. The solution A1 in which the aluminum compound is dissolved and the solution B1 in which the phosphorus compound is dissolved are preferable.

By adding the aluminum compound-dissolved solution A1 and the phosphorus compound-dissolved solution B1 so that the content ratios (remaining amounts) of the aluminum element and the phosphorus element in the polyester resin composition satisfy the above (1) to (3), It can functionally form complexes with catalytic activity in the polymerization system and exhibit sufficient polymerization activity. Moreover, generation|occurrence|production of aluminum-type foreign material can also be suppressed.

In addition, even if the aluminum element in the aluminum compound that functions as a catalyst is placed under a reduced pressure environment during the polymerization of the polyester resin, almost 100% of the amount of the catalyst initially added to the system remains as a catalyst by polymerization. in the polyester resin produced. That is, since the amount of the aluminum compound hardly changes before and after the polycondensation, if it is set so as to be 9 to 19 mass ppm with respect to the addition amount of the aluminum element in the intermediate product, the content of the aluminum element in the polyester resin composition will be reduced. The rate is also 9 to 19 mass ppm.

In addition, when the phosphorus compound, which functions as a catalyst together with the aluminum compound, is placed in a reduced pressure environment during the polymerization of the polyester resin, it is initially added to the system as a part of the catalyst (about 10 to 40%) and removed. out of the system, but the removal ratio is due to the added molar ratio of phosphorus element relative to aluminum element, the basicity and acidity of the added aluminum-containing diol solution and phosphorus-containing diol solution, and the aluminum-containing diol solution. The method of adding the solution and the phosphorus-containing solution (adding after liquefaction, or adding separately) etc. varies. Therefore, it is preferable to appropriately set the addition amount of the phosphorus compound so that the content rate of the phosphorus element in the polyester resin composition to be the final product satisfies the above-mentioned (2).

In the present invention, it is preferable to add the solution A1 in which the aluminum compound is dissolved and the solution B1 in which the phosphorus compound is dissolved at the same time. For B1, a mixed solution is first prepared, and a liquefied mixed solution is added to the aforementioned intermediate, which is a better embodiment. By implementing in this aspect, the effect of the present invention can be exhibited more stably. As a method of liquefying in advance, the method of mixing each solution in a tank, the method of merging the piping for adding a catalyst in the middle, and mixing, etc. are mentioned. In addition, in the case of adding to the reaction vessel, it is preferable to improve the stirring of the reaction vessel. In the case of adding the piping between the reaction vessels, it is preferable to install an in-pipe mixer or the like to quickly and uniformly mix the added catalyst solution. When adding the solution A1 in which the aluminum compound is dissolved and the solution B1 in which the phosphorus compound is dissolved, a large amount of foreign matter caused by the aluminum compound is easily generated, and the crystallization temperature becomes lower when the temperature rises, the crystallization temperature increases when the temperature is lowered, and sufficient contact is not obtained. The case of mediator activity. By adding the aluminum compound and the phosphorus compound at the same time, the complex of the aluminum compound and the phosphorus compound that brings the polymerization activity can be formed quickly and without waste. Moreover, there exists a possibility that the aluminum compound which cannot generate|occur|produce a complex with a phosphorus compound may precipitate as a foreign material. In addition, the solution A1 in which the aluminum compound is dissolved and the solution B1 in which the phosphorus compound is dissolved are preferably added after the completion of the esterification reaction or the transesterification reaction, and the intermediate is added after the first step and before the second step. It is more preferable to add the solution A1 in which the aluminum compound is dissolved and the solution B1 in which the phosphorus compound is dissolved. If added before the completion of the esterification reaction or the transesterification reaction, the amount of aluminum-based foreign substances may increase.

When the polyester resin used in the present invention is composed of at least one selected from polycarboxylic acids and their ester-forming derivatives and at least one selected from polyols and their ester-forming derivatives, a solution in which an aluminum compound is dissolved A1 is preferably a diol solution in which an aluminum compound is dissolved (hereinafter referred to as aluminum-containing diol solution A1), and solution B1 in which a phosphorus compound is dissolved is a diol solution in which a phosphorus compound is dissolved (hereinafter referred to as a diol solution A1). Preferably, it is a dihydric alcohol solution B1) containing phosphorus.

The following describes the absorption maximum wavelengths of the aluminum-containing diol solution A1 and the phosphorus-containing diol solution B1. By controlling the maximum absorption wavelengths of the aluminum-containing diol solution A1 and the phosphorus-containing diol solution B1 to a specific range, the polymerization activity can be stabilized, and a polyester resin of stable quality can be obtained. It is assumed that by controlling the maximum absorption wavelengths of the aluminum-containing diol solution A1 and the phosphorus-containing diol solution B1 to a specific range, the aluminum-containing diol solution A1 and the phosphorus-containing diol solution B1 can be The Lewis acid/base characteristic is controlled to a specific range, and the Lewis acid/base characteristic affects the complex formation reaction of the aluminum compound and the phosphorus compound, and the complex formation reaction affects the polymerization activity.

<Maximum absorption wavelength of aluminum-containing diol solution A1> The diol solution A1 containing aluminum preferably has a maximum absorption wavelength of 562.0-572.0 nm, more preferably 567.0-572.0 nm. The maximum absorption wavelength of the aluminum-containing diol solution A1 is the value obtained by measuring the absorption spectrum of the sample solution using an ultraviolet-visible spectrometer after adding the acid dye Mordant Blue 13 to the aluminum-containing diol solution A1. About the measurement method Details will be described later.

In order for the aluminum compound and the phosphorus compound to functionally form a complex compound with catalytic activity and exhibit polymerization activity, it is preferable to set the basicity of the aluminum compound contained in the aluminum-containing diol solution A1 to a specific range. .

The maximum absorption wavelength of the aluminum-containing diol solution A1 is affected by the type and addition amount of the aluminum compound used, the type of the diol, and the temperature, pressure, time, etc. at the time of preparing the diol solution. For example, it is a preferable embodiment that the aluminum content in the aluminum compound is within a specific range, and when an aqueous solution of the diol solution is solubilized in the preparation of the aluminum-containing diol solution A1, the treatment is performed under reduced pressure or a vacuum. .

When the maximum absorption wavelength of the aluminum-containing diol solution A1 does not reach the above-mentioned range, the basicity of the aluminum compound in the solution is low, and the complex with the phosphorus compound is not sufficiently formed, so the polymerization activity may decrease. and the possibility of an increase in the amount of aluminum-based foreign matter. On the other hand, it is technically difficult for the absorption maximum wavelength to exceed the above range.

<Maximum absorption wavelength of phosphorus-containing diol solution B1> The phosphorus-containing dihydric alcohol solution B1 preferably has a maximum absorption wavelength of 458.0-465.0 nm, more preferably 460.0-463.0 nm, and even more preferably 461.0-462.0 nm. The maximum absorption wavelength of the phosphorus-containing diol solution B1 is the value obtained by measuring the absorption spectrum of the sample solution using an ultraviolet-visible spectrometer after adding a basic dye Bismarck brown solution to the phosphorus-containing diol solution B1. Details of the method will be described later.

In order for the phosphorus compound and the aluminum compound to functionally form a complex having catalytic activity and exhibit polymerization activity, it is preferable to set the acidity of the phosphorus compound contained in the phosphorus-containing diol solution B1 to a specific range.

The maximum absorption wavelength of the phosphorus-containing diol solution B1 is affected by the type and amount of phosphorus compound used, the type of diol, and the temperature, pressure, time, etc. when the diol solution is prepared. When the maximum absorption wavelength of the phosphorus-containing diol solution B1 exceeds the above-mentioned range, the acidity of the phosphorus compound is low, and the complex with the aluminum compound is not sufficiently formed, so that the phosphorus compound is distilled out of the polymerization system and the aluminum-based foreign matter increases. , so not good. Conversely, when the maximum absorption wavelength is less than the above-mentioned range, the acidity of the phosphorus compound is high, and the bond with the aluminum compound becomes strong, so that the polymerization activity may be greatly reduced.

<Heat treatment of phosphorus compounds> In addition, the phosphorus compound used in the present invention is preferably one that has been heat-treated in a solvent. The solvent to be used is not limited as long as it is at least one selected from the group consisting of water and alkanediol, but as the alkanediol, it is preferable to use a solvent that dissolves a phosphorus compound, and ethylene glycol is used for purposes such as The dihydric alcohol as the constituent component of the polyester resin is more preferable. The heat treatment in the solvent is preferably performed after dissolving the phosphorus compound, but it may not be completely dissolved.

As for the conditions of the above-mentioned heat treatment, the heat treatment temperature is preferably 170 to 196°C, more preferably 175 to 185°C, and still more preferably 175 to 180°C. The heat treatment time is preferably 125 to 240 minutes, more preferably 140 to 210 minutes.

The concentration of the phosphorus compound during the above heat treatment is preferably 3 to 10% by mass.

By the above-mentioned heat treatment, the acidity of the phosphorus compound contained in the diol solution can be set to a certain value, and the polymerization activity can be improved by using it together with the aluminum compound, and the aluminum caused by the polymerization catalyst can be made. The amount of foreign matter generated is reduced.

When 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dialkyl ester of the phosphorus compound represented by the above-mentioned (Formula 1) is used as the phosphorus compound, in the above-mentioned heat treatment, (Formula 1) A portion of the 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dialkyl ester of the phosphorus compound shown was subjected to structural changes. For example: detachment of tertiary butyl group, hydrolysis of ethyl ester group and change to hydroxyethyl transesterification structure (transesterification structure with ethylene glycol), etc. Therefore, in the present invention, as the phosphorus compound, in addition to the dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate represented by (Formula 1), a phosphorus compound whose structure has been changed is also included. . In addition, the detachment of the tertiary butyl group occurs significantly at the high temperature of the polymerization step. The phosphorus compounds are shown below as 9 phosphorus compounds in which a part of 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester has undergone structural changes. The constituent amount of each of the structurally changed phosphorus compounds in the glycol solution can be quantified by P-NMR spectrometry of the solution.

[hua 2]

Therefore, as the phosphorus compound in the present invention, in addition to 3,5-di-tertiary butyl-4-hydroxybenzylphosphonic acid dialkyl ester, it also includes 9 3,5-di-tertiary compounds represented by the above chemical formula Modification of dialkyl butyl-4-hydroxybenzylphosphonate.

<Maximum absorption wavelength of a mixed solution of aluminum-containing diol solution A1 and phosphorus-containing diol solution B1> The mixed solution (hereinafter simply referred to as "mixed solution") in which the aluminum-containing diol solution A1 and the phosphorus-containing diol solution B1 are mixed has a maximum absorption wavelength of 559.0 to 560.9 nm, preferably 559.5 to 560.8 nm. More preferably, 559.7-560.6 nm is further preferable. The maximum absorption wavelength of the mixed solution is a value obtained by measuring the absorption spectrum of the sample solution using an ultraviolet-visible spectrometer after adding Mordant Blue 13, an acid dye, to the aforementioned mixed solution, and details of the measurement method will be described later.

By setting the maximum absorption wavelength of the mixed solution to the above range, the complex formation reaction of the aluminum compound and the phosphorus compound can be maintained in a state suitable for both the improvement of polymerization activity and the suppression of aluminum-based foreign substances, which is preferable. On the other hand, when the maximum absorption wavelength exceeds the above-mentioned range, the basicity of the mixed solution is high, and since the polymerization system of the polyester resin is acidic, if the mixed solution is added to the polymerization system, the aluminum compound and the polyester resin will be separated from each other. The carboxyl terminal is neutralized and foreign matter, and the amount of aluminum foreign matter may increase. Conversely, when the maximum absorption wavelength is below the above-mentioned range, the basicity of the mixed solution becomes too low, the coordination between the aluminum compound and the phosphorus compound becomes strong, and the polymerization activity may decrease.

[Insoluble particles] The content rate of the insoluble particles in the polyester resin composition of the present invention is 500 to 2000 mass ppm, preferably 700 to 1800 mass ppm. When a film is produced from the polyester resin composition of the present invention, by forming protrusions with insoluble particles on the surface of the obtained polyester film, the sliding property, running property, abrasion resistance, winding property, etc. of the film can be exhibited. Operational characteristic enhancement function. If the content rate of the insoluble particles is less than 500 mass ppm, the effect of improving the handling properties such as the sliding property, the running property, the abrasion resistance and the winding property of the film is insufficient, which is not good. On the other hand, when it exceeds 2000 mass ppm, the film defect by coarse particles etc. will increase, and there exists a possibility that the transparency of a film may become low. Moreover, there exists a possibility that the polymerization activity may fall at the time of superposition|polymerization.

The insoluble particles used in the present invention are not particularly limited as long as they are insoluble in the polyester resin, and may be either inorganic particles or organic particles. Moreover, inorganic and organic composite particles may be used.

The type of the inorganic particles is not particularly limited, and examples thereof include oxides, carbonates, silicates, sulfates, aluminates, and the like of metals such as titanium, aluminum, silicon, calcium, magnesium, and barium.

Specific examples of the types of the inorganic particles include titanium dioxide, aluminum oxide, aluminum silicate, silicon dioxide, calcium oxide, calcium carbonate, barium sulfate, and the like, and examples thereof include naturally derived talc, mica, kaolinite, and zeolite. etc., but not limited thereto.

The type of the aforementioned organic particles is not particularly limited, and examples thereof include polysiloxane-based, cross-linked polyacrylic acid-based, benzoguanidine resin-based, and the like.

The insoluble particles are preferably silica particles because a highly transparent polyester film can be obtained.

The volume average particle diameter of the insoluble particles is preferably 0.5 to 3.0 μm, more preferably 0.8 to 2.5 μm, and further preferably 2.0 to 2.5 μm. If the volume average particle diameter of the insoluble particles is less than 0.5 μm, there is a possibility that the effect of imparting handling properties such as sliding properties and walking properties to the film may be reduced. On the other hand, when the volume average particle diameter of the insoluble particles exceeds 3.0 μm, there is a possibility that the quality of the thin film is impaired by the formation of coarse protrusions. In addition, the volume average particle diameter of the insoluble particles can be obtained from the particle size distribution measured by the laser light scattering method using water or ethylene glycol as a medium, and the detailed measurement method will be described later.

<How to add insoluble particles> The insoluble particles are preferably added as a slurry dispersed in ethylene glycol. The timing of addition is not particularly limited, but the insoluble particles are preferably added during the first step or after the first step is completed. Specifically, it may be added at any timing from the initial stage of the transesterification reaction step or the esterification reaction step to the start of polycondensation in the initial stage. It may be added directly to the reaction container, or, for example, it may be added to the piping between the reaction containers using an in-pipe mixer or the like. Moreover, it is also possible to set an addition container and add it. In addition, in order to prevent the aggregation of insoluble particles, after being slurried with ethylene glycol, it is mechanically dispersed and added with alkali metal compounds, ammonium compounds, and phosphorus compounds by means of a medium stirring type disperser such as a sand mill, attritor, and ultrasonic. It is better to add it after the dispersion efficiency is improved. The insoluble particles added to the intermediate do not distill out of the polymerization system, but remain in the polyester resin composition. That is, the addition amount (addition rate) of the above-mentioned insoluble particles with respect to the produced polyester resin is the same as the content rate of the insoluble particles in the polyester resin composition. Therefore, the addition amount of the said insoluble particle with respect to the said intermediate substance is 500-2000 mass ppm, 700-1800 mass ppm is preferable.

In the present invention, the method for quantifying the insoluble particles contained in the polyester resin composition is not limited. For example, it is preferable to carry out the correspondence by using a method of quantifying by using the characteristic absorption value inherent in the insoluble particles.

The polyester resin used in the present invention is preferably 3000 mass ppm or less, more preferably 2800 mass ppm or less of the aluminum element in the polyester resin (polyester resin composition from which insoluble particles are removed), which is equivalent to aluminum foreign matter. mass ppm or less. The aluminum-based foreign matter is caused by the use of an aluminum compound as a polymerization catalyst, and is a foreign matter that is insoluble in the polyester resin. When the content rate of the aluminum-based foreign matter exceeds the above, insoluble fine foreign matter that is insoluble in the polyester resin may become a cause, and the quality of the film may deteriorate. Moreover, it is also related to the subject that the filter clogging increases at the time of polyester filtration of a polycondensation process and a film-forming process. The preferable lower limit of the content rate of the aluminum element corresponding to the aluminum-based foreign material is 0 mass ppm, but it is about 300 mass ppm due to technical difficulties. In addition, in this specification, as can be seen from the measurement of the amount of aluminum elements by the measurement method described later in the Examples, this index relatively evaluates the amount of aluminum-based foreign substances based on the amount of aluminum elements, and does not indicate the aluminum contained in the polyester resin. It is the absolute value of the amount of foreign matter.

In addition, the polyester resin can be produced by the same method as the polyester resin composition described above except that the insoluble particles are not included. The presence or absence of insoluble particles in the polyester resin composition does not affect the amount of aluminum-based foreign matter contained in the polyester resin. Therefore, the polyester resin is substantially the same as the components of the insoluble particles excluding the constituent components of the polyester resin composition. In the evaluation method described later in the Examples, when the polyester resin composition was used, the insoluble particles clogged the membrane filter, so that the filtration of the insoluble particles and the aluminum-based foreign matter could not be performed. Therefore, the amount of aluminum-based foreign matter in the polyester resin composition can be regarded as the amount of aluminum-based foreign matter in the polyester resin composition by evaluating the amount of aluminum-based foreign matter in the polyester resin that does not include insoluble particles.

[resin other than polyester resin] The polyester resin composition of the present invention preferably does not contain resins other than polyester resins, but may contain resins other than polyester resins as long as the object of the present invention is not inhibited. Resins other than polyester resins are not particularly limited, and examples thereof include polyolefin resins, polyamide resins, polyacetal resins, and the like. Resin other than the polyester resin in the polyester resin composition is preferably 20% by mass or less, more preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably 3% by mass or less, and 1% by mass or less for the best. The method of blending the above-mentioned resin with the polyester resin is not particularly limited, and examples thereof include addition in the polyester resin production step, and dry blending with the polyester resin after production, and the like can be uniformly mixed.

[Polyester film] The polyester film of the present invention is preferably a polyester film formed from a polyester resin composition, and an electrostatic adhesion imparting agent (a polyester resin composition and electrostatic adhesion imparting agent) is further added to the polyester resin composition. The polyester film formed by the agent) is more preferable, and the polyester film formed from the above-mentioned polyester resin composition and the masterbatch containing the electrostatic adhesion imparting agent is further preferable.

[Electrostatic adhesion imparting agent] If the composition of the polyester resin composition blending master batch of the present invention is made into a film, in the electrostatic adhesion casting method, the electrostatic adhesion of the flakes to the cooling cylinder can be improved, so that film production can be realized. Improve the properties and reduce the uneven thickness of the film. Thereby, the productivity and quality of the polyester film can be improved.

As a method of adding an electrostatic adhesiveness imparting agent to the polyester resin composition of the present invention, it is preferable to add a masterbatch having an electrostatic adhesiveness imparting agent to the polyester resin composition. The structure of the polyester resin constituting the masterbatch having the electrostatic adhesion imparting agent is not limited, but it is preferably a polyester resin having the same structure as that of the polyester resin used in the present invention. In addition, below, the master batch containing an electrostatic adhesiveness imparting agent may be referred to as a masterbatch containing an electrostatic adhesiveness imparting agent, or simply referred to as a "masterbatch".

The melting specific resistance of the master batch is preferably 0.005×10 ⁸ to 0.05×10 ⁸ Ω·cm, more preferably 0.005×10 ⁸ to 0.025×10 ⁸ Ω·cm. When the melting specific resistance of the master batch is higher than 0.05×10 ⁸ Ω·cm, it is necessary to add a large amount of the master batch in order to improve the film-forming property of the polyester resin composition, which causes problems such as an increase in manufacturing cost. It is technically difficult to set the melting resistivity of the master batch to be less than 0.005×10 ⁸ Ω·cm. In addition, in order to improve the film-forming properties of the polyester film, the melting specific resistance of the polyester film formed by blending the above-mentioned master batch into the polyester resin composition is 0.1×10 ⁸ to 0.3×10 ⁸ Ω・・cm is preferable, and 0.15×10 ⁸ to 0.25×10 ⁸ Ω·cm is more preferable.

In order to reduce the melting specific resistance, the electrostatic adhesiveness imparting agent is preferably a magnesium compound or an alkali metal compound. Moreover, in order to disperse|distribute these metal ion components in a polyester resin composition without foreign materialization, and to further improve thermal stability, it is preferable to add a phosphorus compound. The magnesium compound is preferably 15 to 150 mass ppm, and more preferably 30 to 100 mass ppm, in the content of the magnesium element in the polyester film. If the content of magnesium element is less than the above-mentioned range, there is a possibility that the melting specific resistance will become high, the electrostatic adhesiveness will deteriorate, and the film formability will fall. On the other hand, if the content of magnesium element exceeds the above-mentioned range, the amount of insoluble magnesium-based foreign substances produced increases, and thermal stability may be lowered and the coloring of the film may be deteriorated. As for the alkali metal compound, the content of the alkali metal element in the polyester film is preferably 1.5 to 15 mass ppm, and more preferably 3 to 10 mass ppm. If the content rate of the alkali metal element is less than the above-mentioned range, the melting specific resistance may be increased, the electrostatic adhesiveness may be deteriorated, and the film formability may be lowered. On the other hand, when the content rate of an alkali metal element exceeds the said range, there exists a possibility that thermal stability will fall and the coloring of a film may deteriorate. As for the phosphorus compound, the content of the phosphorus element in the polyester film is preferably 7 to 80 mass ppm, and more preferably 20 to 50 mass ppm. If the content of phosphorus element is less than the above-mentioned range, the amount of insoluble foreign matter produced increases, and the melting specific resistance increases, the electrostatic adhesiveness deteriorates, and the film formability decreases. Furthermore, there is a possibility that the thermal stability is lowered and the coloring of the film is deteriorated. On the other hand, when the content rate of phosphorus element exceeds the said range, there exists a possibility that melting specific resistance will become high, electrostatic adhesiveness will deteriorate, and film formability may fall.

As the magnesium compound used in the present invention, a known magnesium compound can be used. For example, lower fatty acid salts such as magnesium acetate, alkoxides such as magnesium methoxide, etc., may be used alone, or two or more may be used in combination. In particular, magnesium acetate is preferred.

It is preferable to add magnesium element so that it may become 400-2700 mass ppm with respect to the polyester resin which comprises a master batch. When the amount of magnesium element is less than 400 mass ppm, the melting specific resistance becomes high, and it is necessary to add a large amount of master batch in order to improve the film-forming property of the polyester resin composition, and the efficiency as a master batch is low and the production cost increases, etc. Danger of problems. When the amount of magnesium element exceeds 2700 mass ppm, the effect of improving the melting specific resistance is saturated, and the heat resistance is lowered and the coloring of the film may be deteriorated. The amount of magnesium element is more preferably 600 to 2500 mass ppm, and still more preferably 800 to 2000 mass ppm.

Examples of the alkali metal of the alkali metal compound contained in the master batch include lithium, sodium, and potassium. In addition, as the alkali metal compound, for example, lower fatty acid salts having 2 to 4 carbon atoms such as lithium acetate and potassium acetate, and alkoxides such as potassium methoxide, etc., may be used alone. , and two or more of them may be used in combination. As an alkali metal, potassium is preferable because it has a large effect of reducing the melting specific resistance. As the alkali metal compound, a lower fatty acid salt having 2 to 4 carbon atoms is preferable, an alkali metal acetate is more preferable, and potassium acetate is further preferable.

It is preferable to add an alkali metal element so that it may become 40-270 mass ppm with respect to the polyester resin which comprises a master batch. When the amount of the alkali metal element is less than 40 ppm by mass, the melting specific resistance becomes high, and it is necessary to add a large amount of master batch in order to improve the film-forming property of the polyester resin composition, resulting in a low efficiency as a master batch and an increase in manufacturing cost. and other problems. When the amount of the alkali metal element exceeds 270 mass ppm, the effect of increasing the melting specific resistance is saturated, and the heat resistance is lowered, and the coloring of the film may be deteriorated. The amount of the alkali metal element is more preferably 60 to 250 mass ppm, and still more preferably 80 to 200 mass ppm.

As a phosphorus compound contained in the said master batch, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, phosphinic acid, and these ester compounds can be illustrated. For example, phosphoric acid, trimethyl phosphate, tributyl phosphate, triphenyl phosphate, monomethyl phosphate, dimethyl phosphate, monobutyl phosphate, dibutyl phosphate, phosphorous acid, trimethyl phosphite, Tributyl Phosphite, Methyl Phosphonic Acid, Dimethyl Methyl Phosphonate, Dimethyl Methyl Phosphonate, Dimethyl Phenyl Phosphonate, Diethyl Phenyl Phosphonate, Diphenyl Phenyl Phosphonate , ethyl diethylphosphinate, phosphinic acid, methyl phosphinic acid, dimethyl phosphinic acid, phenyl phosphinic acid, diphenyl phosphinic acid, methyl dimethyl phosphinate, diphenyl phosphinic acid Methyl phenylphosphinate, etc. In order to remarkably show the effect of the present invention, at least one selected from the group consisting of trialkyl phosphate and ethyl diethylphosphinoacetate is preferred, and trialkyl phosphate is more preferred. Among the trialkyl phosphates, it is more preferred that at least one of the alkyl groups of the alkyl ester is an alkyl group having 2 to 4 carbon atoms, and it is particularly preferred that all the alkyl groups of the alkyl ester are alkyl groups having 2 to 4 carbon atoms. As a particularly preferable phosphorus compound, a triethyl phosphate, a tripropyl phosphate, a tributyl phosphate etc. are mentioned specifically, These may be used individually by any 1 type, and may use 2 or more types together. In particular, it is considered that triethyl phosphate and magnesium ions form a complex of interaction with moderate strength, and can obtain a master batch with low melting specific resistance, few foreign substances, and excellent color tone, which is the best.

It is preferable to add phosphorus element so that it may become 200-1700 mass ppm with respect to the polyester resin which comprises a master batch. When the amount of phosphorus element is less than 200 mass ppm, the amount of insoluble magnesium-based foreign matter may increase due to the stabilization of magnesium ions and alkali metal ions and the reduction in the effect of dispersing in the polyester resin. Furthermore, since the effect of reducing the melting specific resistance is lost by the foreign-materialized magnesium, there is a possibility that the melting specific resistance may become high. Moreover, there exists a possibility that the fall of heat resistance may be incurred and the coloring of a film may deteriorate. If the amount of phosphorus element exceeds 1700 mass ppm, since excess phosphorus compound interacts with magnesium ions, the charge of magnesium ions does not contribute to the effect of reducing the melting specific resistance, and although the amount of magnesium added is large, the melting specific resistance increases. Yu. A more preferable amount of phosphorus element is 400-1000 mass ppm.

The content of magnesium atoms, alkali metal atoms, and phosphorus atoms in the master batch can be quantified by the method described in the following examples. The timing of adding the masterbatch containing the magnesium compound, the alkali metal compound, and the phosphorus compound to the polyester resin is not particularly limited. It can be added between the time point from the end of the transesterification (or transesterification) step to the start of the polycondensation step, because it can prevent the acid component of the polyester from forming a salt with magnesium ions and alkali metal ions, and it can be uniformly dispersed in the oligomer. and better. When these compounds are added during the polymerization of the polyester resin, almost the added amount of magnesium atoms and alkali metal atoms remains in the polyester resin composition, but phosphorus atoms are distilled out of the polymerization system under reduced pressure. Therefore, it is necessary to determine the addition amount of the phosphorus compound after grasping the relationship between the addition amount and the residual amount in advance.

When the polyester is a polyester having a dicarboxylic acid component and a diol component as constituent components, the amount of magnesium relative to the dicarboxylic acid component is defined as m mol %, and the amount of alkali metal element is defined as k mol. When the amount of % and phosphorus element is set to p mol%, the effect of the present invention can be obtained by satisfying the following formula. 2≦(m+k/2)/p≦3 It is considered that the phosphorus atom stabilizes the magnesium ion and the alkali metal ion without being alienated. Since the valence of the alkali metal ion is 2 relative to the magnesium ion and the valence of the alkali metal ion is 1, the sum of the amounts of the magnesium ion and the alkali metal ion is expressed as (m+k/2), which is divided by the ratio of p (m+k/ 2)/p is the relative amount of magnesium ion and alkali metal ion with respect to phosphorus atom. When the value of (m+k/2)/p exceeds 3, the amount of phosphorus element is relatively small relative to magnesium element and alkali metal element, so that magnesium ion and alkali metal ion are stabilized and dispersed in polyester resin The effect is reduced, and the amount of insoluble foreign substances (magnesium salts, alkali metal salts) produced increases. Furthermore, since the effect of reducing the melting specific resistance is lost in the foreign-materialized magnesium, the melting specific resistance becomes high relative to the amount of magnesium added. In addition, the heat resistance is lowered, and the color tone of the master batch and film containing the electrostatic adhesion imparting agent is deteriorated. When the value of "(m+k/2)/p" is less than 2, the amount of phosphorus element becomes relatively excess with respect to magnesium element and alkali metal element, and due to the interaction between the excess phosphorus compound and magnesium ion, Therefore, although the color tone reduction is improved, the charge of magnesium ions does not contribute to the effect of reducing the melting specific resistance, and the melting specific resistance becomes higher with respect to the amount of magnesium added. (m+k/2)/p is more preferably 2.3 or more and 3 or less, and more preferably 2.5 or more and 3 or less.

This case is based on the benefit of claiming priority based on Japanese Patent Application No. 2020-153076 filed on September 11, 2020. The entire specification of Japanese Patent Application No. 2020-153076, filed on September 11, 2020, is cited in the present case for reference. [Example]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, the evaluation method used in each Example and the comparative example is as follows.

[Evaluation method] (1) Maximum absorption wavelength of ethylene glycol solution a1 containing aluminum After adding 4 mL of ethylene glycol and 0.3 mL of 1 mmol/L Mordant Blue 13 aqueous solution to a 6 mL sample bottle, 0.1 mL of the aluminum-containing ethylene glycol solution a1 described later was added, and the sample bottle was capped and shaken for 10 seconds until the solution became uniform. After standing at room temperature (23°C) for 10 minutes, the absorption spectrum of the sample solution was measured under the following conditions using an ultraviolet-visible spectrometer, and the maximum absorption wavelength of the aluminum-containing ethylene glycol solution a1 was determined. In addition, in this measurement, room temperature was set to 15-30 degreeC, and a series of operations were performed in the room of this temperature range. Device: UV-1800 UV-Vis Spectrometer made by Shimadzu Corporation Spectral bandwidth: 1nm Sample tank: square tank (material: polymethyl methacrylate (PMMA), optical path length: 10mm) Control solution: ethylene glycol Scanning range: 400～700nm Scanning speed setting: 0.05sec Scanning pitch: 0.2nm Scan times: 1 time

(2) Maximum absorption wavelengths of phosphorus-containing ethylene glycol solutions b1 and b1' After adding 4 mL of ethylene glycol and 0.3 mL of 1 mmol/L Bismarck brown aqueous solution to a 6 mL sample bottle, add 0.1 mL of ethylene glycol solution b1 containing phosphorus, cover the sample bottle and shake for 10 seconds until the solution becomes homogeneous. After standing at room temperature (23° C.) for 10 minutes, the absorption spectrum of the sample solution was measured under the following conditions using an ultraviolet-visible spectrometer, and the maximum absorption wavelength of the phosphorus-containing ethylene glycol solution b1 was determined. In addition, in this measurement, room temperature was set to 15-30 degreeC, and a series of operations were performed in the room of this temperature range. Device: UV-1800 UV-Vis Spectrometer made by Shimadzu Corporation Spectral bandwidth: 1nm Sample tank: square tank (material: PMMA, optical path length: 10mm) Control solution: ethylene glycol Scanning range: 400～700nm Scanning speed setting: 0.05sec Scanning pitch: 0.2nm Scan times: 1 time The maximum absorption wavelength of the phosphorus-containing ethylene glycol solution b1' was determined by the same evaluation method as above except that the phosphorus-containing ethylene glycol solution b1 was changed to the phosphorus-containing ethylene glycol solution b1'.

(3) The maximum absorption wavelength of the mixed solution of the ethylene glycol solution a1 containing aluminum and the ethylene glycol solution b1 or b1' containing phosphorus After adding 4 mL of ethylene glycol and 0.3 mL of 1 mmol/L Mordant Blue 13 aqueous solution to the 6 mL sample bottle, add 0.1 mL of a mixture of 0.1 mL of ethylene glycol solution a1 containing aluminum and ethylene glycol solution b1 or b1' containing phosphorus. , cap the vial and shake for 10 seconds until the solution is homogeneous. After standing at room temperature (23° C.) for 10 minutes, the absorption spectrum of the sample solution was measured under the following conditions using an ultraviolet-visible spectrometer, and the maximum absorption wavelength was obtained. The mixing ratio of the ethylene glycol solution a1 containing aluminum and the ethylene glycol solution b1 or b1' containing phosphorus in the above mixed solution is the same as the ethylene glycol solution a1 containing aluminum and the ethylene glycol containing phosphorus in each embodiment. The mixing ratio of the solution b1 or b1' is the same. In addition, in this measurement, room temperature was set to 15-30 degreeC, and a series of operations were performed in the room of this temperature range. Device: UV-1800 UV-Vis Spectrometer made by Shimadzu Corporation Spectral bandwidth: 1nm Sample tank: square tank (material: PMMA, optical path length: 10mm) Control solution: ethylene glycol Scanning range: 400～700nm Scanning speed setting: 0.05sec Scanning pitch: 0.2nm Scan times: 1 time

(4) Volume average particle size of silica particles Using a particle size distribution analyzer (Leeds & Northrup, Microtrac HRA model: 9320-X100) using a laser light scattering method, the ethylene glycol slurry of silica particles was diluted with water and measured in a substantial water system. The volume-cumulative 50% diameter of the measurement results was defined as the volume-average particle diameter.

(5) Intrinsic viscosity (IV) of polyester resin composition The polyester resin composition was dissolved in a mixed solvent of phenol/1,1,2,2-tetrachloroethane (=3/2; mass ratio) and measured at a temperature of 30°C.

(6) Content ratio of aluminum element in polyester resin composition The polyester resin composition was weighed in a platinum crucible, and after carbonization in an electric furnace, ashing was performed in an oven furnace at 550° C. for 8 hours. The ashed sample was dissolved in 1.2 M hydrochloric acid to prepare a sample solution. The concentration of the aluminum element in the polyester resin composition was determined by the high-frequency inductively coupled plasma luminescence analysis of the prepared sample solution. Device: CIROS-120 manufactured by SPECTRO Plasma output: 1400W Plasma gas: 13.0L/min Auxiliary gas: 2.0L/min Atomizer: Cross Flow Atomizer Chamber: Cyclone Chamber Measurement wavelength: 167.078nm

(7) Content of phosphorus element in polyester resin composition The polyester resin composition was wet-decomposed with sulfuric acid, nitric acid, and perchloric acid, and then neutralized with ammonia water. After adding ammonium molybdate and hydrazine sulfate to the prepared solution, the absorbance at a wavelength of 830 nm was measured using an ultraviolet visible light absorptometer (manufactured by Shimadzu Corporation, UV-1700). The phosphorus element concentration in the polyester resin composition was determined from a calibration curve prepared in advance.

(8) Amount of aluminum foreign matter 30 g of polyester resin and 250 mL of a mixed solution of p-chlorophenol/tetrachloroethane (3/1: mass ratio) were put into a 500-mL conical flask equipped with a stirrer, and heated and dissolved at 100-105°C for 1.5 hours using a heating stirrer. . This solution was filtered using a membrane filter made of polytetrafluoroethylene having a diameter of 47 mm/pore diameter of 1.0 μm (PTFE membrane filter manufactured by Advantec, product name: T100A047A). The effective filter diameter is set to 37.5mm. After the filtration was completed, washing was continued with 50 mL of chloroform, and the filter was dried. The filtration surface of this membrane filter was quantified by the scanning type fluorescent X-ray analyzer (manufactured by RIGAKU, ZSX100e, Rh wire ball 4.0kW). The quantitative measurement was performed for a portion of the membrane filter having a diameter of 30 mm in the center portion. In addition, the calibration curve of this fluorescent X-ray analysis method was calculated|required using the polyethylene terephthalate resin whose aluminum element content rate was known, and the apparent aluminum element amount was shown in ppm. The measurement was carried out by measuring the Al-Kα ray intensity under the conditions of PHA (wave height analyzer) 100-300 using pentaerythritol as a spectroscopic crystal with an X-ray output of 50kV-70mA and a PC (proportional counter) as a detector. The aluminum element content in the polyethylene terephthalate resin for calibration lines was quantified by high-frequency inductively coupled plasma luminescence analysis.

(9) Back pressure increase coefficient (k) The polyester resin composition was vacuum-dried at 140° C. for 16 hours, then supplied to a melt extruder, the outlet pressure of the extruder was controlled to 1.96 MPa, and a filter with a filter diameter of 14 mmφ was used. A spinning test was performed for 4 hours at a spinning temperature of 295° C. with a discharge rate of 6 g/min. During the spinning test, the filter pressure was recorded every 30 minutes, and the increase in back pressure per unit time was calculated using the value of the pressure (MPa) from the start of spinning to 4 hours after the elapse of time and the value of the pressure (MPa) at the start of spinning. Differential ΔP (MPa/time). As the spinning nozzle, a nozzle having 12 orifices with a hole diameter of 0.23 mmφ and a length of 0.3 mm was used. The filter used was composed of 100-mesh gold mesh, 10 μm NASLON filter, 100-mesh gold mesh, and 50-mesh gold mesh in order from the exit side of the extruder. The back pressure increase coefficient k is calculated by the following equation from the back pressure increase difference ΔP (MPa/time) per unit time, the flow rate Q (kg/time), and the filtration area S (cm ² ). k=ΔP/(Q/S) The area S is calculated from the filter diameter, and the flow rate Q is calculated from the discharge volume.

(10) Static friction coefficient of polyester film (μs) Two identical polyester films were prepared, and in accordance with JIS K-7125, using a tensile tester (TENSILON RTG-1210 manufactured by A&D Corporation), under the environment of 23°C and 65% RH, the difference between one polyester film and the other was determined. Coefficient of static friction (μs) in case of ester film bonding.

(11) Melting specific resistance (ρi) Two electrodes (diameter 0.6 mm) were placed on both ends of the composition for film production (hereinafter referred to as film production composition) of Example 11 which was melted at 275°C stainless steel wire), in the form of sandwiching the above-mentioned composition and 2 electrodes with 2 pieces of quartz plates with a width of 2cm, to form a layer of the composition for film production with a uniform thickness of 2cm and a thickness of 0.6mm, at a temperature of 280 ° C Under the conditions, the current (io) when a DC voltage of 120 V was applied was measured, and the melting resistance value ρi (Ω·cm) was obtained by substituting it into the following formula. Moreover, about the composition for thin film production of Example 12, the melting resistivity was calculated|required similarly. ρi(Ω・cm)=(A/L)×(V/io) [A: electrode area (cm ² ), L: distance between electrodes (cm), V: voltage (V), io: current (A) ] A (cm ² )=[width of the melted film-forming composition layer]×[thickness]=2(cm)×0.06(cm), V=120(V). L is a value measured excluding the diameter of the electrode, and is 1.3 cm.

(12) Electrostatic Adhesion of the Film Production Compositions of Examples 11 and 12 An electrode made of tungsten wire is set between the blowing nozzle of the extruder and the cooling cylinder, and a voltage of 10-15KV is applied between the electrode and the casting cylinder for casting. Casting speed evaluation for Pinner Bubble generation. The higher the casting speed, the better the electrostatic adhesion.

The preparation of the ethylene glycol solution containing aluminum, the ethylene glycol solution containing phosphorus, the ethylene glycol slurry containing silica particles, and the preparation of the master batch containing the electrostatic adhesion imparting agent will be described below. (1) Preparation of ethylene glycol solution a1 containing aluminum The same amount (volume ratio) of ethylene glycol with respect to the 20 g/L aqueous solution of basic aluminum acetate was put into the mixing tank, stirred at room temperature (23°C) for several hours, and then reduced under reduced pressure (3 kPa). . Water was distilled off from the system while stirring for several hours at 50 to 90° C. to prepare an aluminum-containing ethylene glycol solution a1 containing 20 g/L of the aluminum compound. The maximum absorption wavelength of the ethylene glycol solution a1 containing aluminum is 571.6 nm.

(2) Preparation of ethylene glycol solutions b1 and b1' containing phosphorus <Phosphorus-containing ethylene glycol solution b1> Irganox 1222 (manufactured by BASF Corporation) as a phosphorus compound was put into a mixing tank together with ethylene glycol, and heat-treated at 175°C for 150 minutes with stirring under nitrogen substitution to prepare a phosphorus-containing ethylene glycol solution containing 50 g/L of the phosphorus compound. b1. The maximum absorption wavelength of the ethylene glycol solution b1 containing phosphorus is 461.2 nm. <Phosphorus-containing ethylene glycol solution b1'> A phosphorus-containing ethylene glycol solution b1' was prepared in the same manner as the phosphorus-containing ethylene glycol solution b1, except that the heat treatment conditions were changed to 80°C for 60 minutes. The maximum absorption wavelength of the phosphorous-containing ethylene glycol solution b1' is 470.8 nm. Phosphorus-containing ethylene glycol solution b1' was used in Comparative Example 8, and phosphorus-containing ethylene glycol solution b1 was used in all Examples and Comparative Examples other than Comparative Example 8.

(3) Preparation of ethylene glycol slurry containing silica particles 5 liters of ethylene glycol and 600 g of silica particles (manufactured by FUJI SILYSIA CHEMICAL, SYLYSIA 310) with an average particle size of 2.4 μm were put into a dispersing tank with a homogenizer, and dispersed and stirred at 8000 rpm for 2 hours to prepare a slurry of 120 g/L.

(4) Preparation of master batch containing electrostatic adhesion imparting agent Put terephthalic acid, ethylene glycol, and triethylamine in a polymerization equipment equipped with a stirrer, a distillation column, and a pressure regulator, and carry out an esterification reaction according to the routine, An intermediate polyester oligomer is produced. Next, in the polyester oligomer, relative to the produced polyester resin (theoretical amount of the produced polyester resin), the amount of aluminum element was 60 mass ppm, and the magnesium element was 1000 mass ppm, respectively. Basic aluminum acetate, magnesium acetate dihydrate, potassium acetate, and triethyl phosphate were added so that the potassium element would be 100 mass ppm and the phosphorus element would be 660 mass ppm. After that, the temperature of the system was raised to 280° C. for 1 hour, and the pressure of the system was gradually reduced to 150 Pa during this period, and a polycondensation reaction was carried out under this condition for 80 minutes to obtain a mother containing an electrostatic adhesion imparting agent. material. The IV of the obtained master batch was 0.5 dl/g, and the ρi value was 0.011×10 ⁸ Ω·cm.

[Example of batch polymerization method] (Example 1) In a 10L stainless steel autoclave with a stirrer, the pre-blended high-purity terephthalic acid and ethyl acetate were put in so that the mass of the obtained oligomer mixture was 1200 mass ppm in terms of silica particles. Polyester oligomers with an esterification rate of about 95% composed of diols, and high-purity terephthalic acid and the ethylene glycol slurry containing silica particles prepared by the above method, were subjected to an esterification reaction at 260 °C, An oligomer mixture is obtained. The concentration of acid end groups in the obtained oligomer mixture was 750 eq/ton, and the ratio of hydroxyl end groups (OH%) was 59 mol%. To the obtained oligomer mixture, a mixed solution obtained by mixing and liquefying the aluminum-containing ethylene glycol solution a1 and the phosphorus-containing ethylene glycol solution b1 prepared by the above method was added. This mixed liquid was prepared so that it might become 10 mass ppm and 20 mass ppm of aluminum element and phosphorus element respectively with respect to the mass of an oligomer mixture. In addition, the amount of the produced polyester resin can be calculated from the amount of terephthalic acid added. In this example, the aluminum element and the phosphorus element are 10 mass ppm and 20 mass ppm relative to the produced polyester resin. The mixture was added in mass ppm. Thereafter, the temperature of the system was raised to 280° C. for 1 hour, and the pressure of the system was gradually reduced to 0.15 kPa during this period, and a polycondensation reaction was carried out under these conditions to obtain a polyester resin with an IV of 0.60 dl/g. composition.

(Examples 2 to 5, Comparative Examples 1 to 5) Except that the ethylene glycol solution a1 containing aluminum and the ethylene glycol solution b1 containing phosphorus were added so as to be the catalyst element addition amounts described in Table 1 with respect to the obtained polyester resin composition, the use and Example 1 The polyester resin composition was obtained by the same method.

(Comparative Example 6) A polyester resin composition was obtained by the same method as in Example 2 except that the addition amount of the ethylene glycol slurry containing the silica particles was changed.

(Comparative Example 7) A polyester resin was obtained in the same manner as in Example 2, except that the silica particle-containing ethylene glycol slurry was not added.

(Comparative Example 8) A polyester resin composition was obtained in the same manner as in Example 2, except that the aforementioned solution b1' was used instead of the aforementioned solution b1 as the phosphorus-containing ethylene glycol solution.

(Manufacturing method of polyester resin for measuring the amount of aluminum-based foreign matter) A polyester resin was produced in the same manner as in Examples 1 to 5 and Comparative Examples 1 to 6 and 8, except that the silica particle-containing ethylene glycol slurry was not added, to prepare a polyester resin for measuring the amount of aluminum-based foreign matter. In addition, in Comparative Example 7, since the silica particle-containing ethylene glycol slurry was not added, the polyester resin of Comparative Example 7 was used as the polyester resin for measuring the amount of aluminum-based foreign matter.

The physical properties of the polyester resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 6 and 8 and the polyester resin obtained in Comparative Example 7 are shown in Table 1. In Table 1 and Table 2 to be described later, the added amount and the remaining amount of the aluminum element are described as Al, the added amount and the remaining amount of the phosphorus element are described as P, and the added molar ratio of the phosphorus element with respect to the aluminum element, The residual molar ratio was recorded as P/Al.

[Table 1] project Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 The amount of catalyst element added Al (mass ppm) 10 14 13 12 17 twenty one 18 8 twenty one 14 14 14 14 P (mass ppm) 20 30 32 twenty four 36 58 58 20 20 20 30 30 30 P/Al (Morby) 1.74 1.87 2.14 1.74 1.84 2.41 2.81 2.18 0.83 1.24 1.87 1.87 1.87 Amount of silica particles added (mass ppm) 1200 1200 1200 1200 1200 1200 1200 1200 1200 1200 2400 0 1200 Maximum absorption wavelength (nm) Aluminum Compound Glycol Solution 571.6 571.6 571.6 571.6 571.6 571.6 571.6 571.6 571.6 571.6 571.6 571.6 571.6 Phosphorus Compound Glycol Solution 461.2 461.2 461.2 461.2 461.2 461.2 461.2 461.2 461.2 461.2 461.2 461.2 470.8 mixture 560.4 560.2 560.0 560.2 560.4 559.6 559.2 560.0 562.4 561.6 560.2 560.2 561.0 Polycondensation time (min) 51 51 57 50 50 75 75 69 44 47 64 46 46 IV(dl/g) 0.60 0.60 0.60 0.61 0.60 0.59 0.59 0.61 0.61 0.60 0.60 0.60 0.60 Catalyst element remaining amount Al (mass ppm) 10 14 13 12 17 twenty one 18 8 20 13 14 14 13 P (mass ppm) 16 twenty three twenty four 19 28 44 39 14 18 17 twenty three twenty three 18 P/Al (Morby) 1.39 1.43 1.61 1.38 1.43 1.83 1.89 1.52 0.78 1.14 1.43 1.43 1.21 Amount of aluminum foreign matter (mass ppm) 2300 2200 1500 2000 2500 710 710 1200 14000 6100 2400 2200 5000 Back pressure rise coefficient k 0.27 0.27 0.19 0.25 0.29 0.19 0.19 0.21 4.25 0.67 0.30 0.20 0.60

In the polyester resin compositions of Examples 1 to 5, although the addition amount of aluminum and phosphorus elements was small, the polymerization time was shortened, and the amount of aluminum-based foreign matter was also small, so that the back pressure increase coefficient was also small and high quality. In addition, since the amount of catalyst added is also small, the cost of the catalyst can be reduced. In Comparative Examples 1 and 2, the catalyst cost was high due to the large amount of phosphorus compound added, and although the molar ratio of the phosphorus element to the aluminum element was high, the suppression of aluminum-based foreign matter was better, but the polymerization activity was reduced. and not good. Also, the catalyst cost becomes high. In Comparative Example 3, although the residual molar ratio of phosphorus element to aluminum element was within the range of the present invention, since the addition amount of aluminum element was too small, the polymerization activity was insufficient, and the polymerization time was prolonged. In Comparative Examples 4 and 5, since the residual molar ratio of phosphorus element to aluminum element was too low, the amount of aluminum-based foreign matter in the polyester resin composition increased, and the back pressure increase coefficient increased, so the grade of the polyester resin composition was high. inferior. In Comparative Example 6, although the residual molar ratio of phosphorus element to aluminum element was within the range of the present invention, the polymerization activity was lowered due to the excessive addition of silica particles, and the polymerization time was prolonged. The comparative example 7 is mentioned later in the part of the comparative example 12 (the film manufactured using the polyester resin of the comparative example 7). In Comparative Example 8, the molar ratio of phosphorus added to aluminum was within the scope of the present invention, the polymerization time was short, and the catalyst cost was also low. However, since the maximum absorption wavelength of the phosphorous-containing ethylene glycol solution b1' was too large compared to Examples 1 to 5, the residual molar ratio of phosphorous to aluminum was low, and the polyester resin composition The amount of aluminum-based foreign matter increases and the back pressure increase coefficient increases, so the quality of the polyester resin composition is inferior.

[Example of continuous polymerization method] (Example 6) The polyester resin is composed of 3 continuous esterification reactors and 3 continuous polycondensation reactors, and the transfer line from the third esterification reactor to the first polycondensation reactor is equipped with an in-pipe mixer with a high-speed agitator. The continuous production device continuously supplied a slurry prepared by mixing 0.75 parts by mass of ethylene glycol with respect to 1 part by mass of high-purity terephthalic acid, and the reaction temperature in the first esterification reactor was 255°C, pressure 203kPa, The reaction temperature of the second esterification reactor was 261°C, the pressure was 102 kPa, and the reaction temperature of the third esterification reactor was 261-263°C and the pressure was 126 kPa, and the reaction was carried out to obtain an oligomer. The concentration of oligomers at the outlet of the third esterification reactor was 550 eq/ton of acid end groups, and the ratio of hydroxyl end groups (OH%) was 60 mol%. To the obtained oligomer, the aluminum-containing ethylene glycol solution a1 prepared by the above method and phosphorus-containing ethylene glycol were added to the transfer line from the third esterification tank to the first polycondensation reactor using an in-pipe mixer. The alcohol solution b1 is mixed and a liquefied mixed solution and the ethylene glycol slurry containing silica particles prepared by the above method. In addition, the aluminum-containing ethylene glycol solution a1 prepared by the above method and phosphorus-containing ethylene glycol solution a1 prepared by the above method were mixed so that the aluminum element and the phosphorus element were 13 mass ppm and 36 mass ppm, respectively, with respect to the obtained oligomer. The glycol solution b1 was used as a catalyst, and the above-mentioned mixed liquid and the above-mentioned silica particle-containing ethylene glycol slurry were added so that the silica particle became 1200 mass ppm with respect to the obtained oligomer. In addition, the amount of the generated polyester resin can be calculated from the amount of terephthalic acid added, and in this example, the aluminum element and the phosphorus element are 13 mass ppm and 36 mass ppm relative to the generated polyester resin. way to add the mixture. The mixed solution and the above-mentioned oligomers containing silica particles were continuously transported to a continuous polycondensation device consisting of three reactors. The reaction temperature was 270° C., the pressure was 0.930 kPa, the reaction temperature of the third polycondensation reactor was 274° C., and the pressure was 0.162 kPa. Polycondensation was performed to obtain a polyester resin composition with an IV of 0.59 dl/g. The polyester resin composition is extruded into strands, cooled in water, and then cut and pelletized.

(Examples 7, 8, Comparative Examples 9, 10) The same procedure as in Example 6 was carried out, except that the aluminum-containing ethylene glycol solution a1 and the phosphorus-containing ethylene glycol solution b1 were added so as to be the catalyst element addition amounts described in Table 2 with respect to the obtained oligomer method to obtain a polyester resin composition.

Table 2 shows the physical properties and the like of the polyester resin compositions obtained in Examples 6 to 8 and Comparative Examples 9 and 10.

[Table 2] project Example 6 Example 7 Example 8 Comparative Example 9 Comparative Example 10 The amount of catalyst element added Al (mass ppm) 13 12 17 twenty one twenty one P (mass ppm) 36 twenty four 36 58 20 P/Al (Morby) 2.41 1.74 1.84 2.41 0.83 Amount of silica particles added (mass ppm) 1200 1200 1200 1200 1200 Maximum absorption wavelength (nm) Aluminum Compound Glycol Solution 571.6 571.6 571.6 571.6 571.6 Phosphorus Compound Glycol Solution 461.2 461.2 461.2 461.2 461.2 mixture 559.6 560.2 560.4 559.6 562.4 production volume ratio 1.02 1.05 1.06 1.00 0.95 IV(dl/g) 0.59 0.59 0.59 0.59 0.59 Catalyst element remaining amount Al (mass ppm) 13 12 17 twenty one 20 P (mass ppm) 25 19 28 45 18 P/Al (Morby) 1.68 1.38 1.43 1.87 0.78 Amount of aluminum foreign matter (mass ppm) 550 1800 2500 450 10000 Back pressure rise coefficient k 0.18 0.24 0.29 0.18 2.00

The throughput ratios described in Table 2 are based on the throughput per hour of Comparative Example 9 (the throughput per hour of Comparative Example 9 is set to 1.00), When the throughput per hour is expressed as a ratio, if the throughput ratio is higher than 1, the catalyst has high polymerization activity, and conversely, if the throughput ratio is 1 or less, the catalyst has low polymerization activity. Compared with Comparative Example 9, the polyester resin compositions of Examples 6 to 8 have a larger production ratio and less additions of aluminum and phosphorus elements, which can reduce the cost of catalysts and improve the polymerization activity. In addition, since the amount of aluminum-based foreign substances in the polyester resin composition is also small, the back pressure increase coefficient is also small, and a high-quality polyester resin composition can be obtained. In Comparative Example 10, since the residual molar ratio of phosphorus element to aluminum element was too low, the amount of aluminum-based foreign matter in the polyester resin composition increased, the back pressure increase coefficient increased, and the polyester resin composition was inferior in quality. Moreover, the throughput ratio is also low.

Using the results of Examples 1 to 5 and Comparative Examples 1, 2, 4, and 5 in Table 1, the relationship between the residual molar ratio of phosphorus element to aluminum element, the amount of aluminum-based foreign matter, and the polymerization time is shown in FIG. 1 . Fig. 2 shows the relationship between the maximum absorption wavelength of the mixed solution of the aluminum-containing ethylene glycol solution a1 and the phosphorus-containing ethylene glycol solution b1, the amount of aluminum-based foreign matter, and the polymerization time. The values of Comparative Example 3 are removed from these figures. The reason for this is that in Comparative Example 3, although the residual molar ratio of phosphorus element to aluminum element was within the scope of the present invention, the catalyst activity was not sufficiently exhibited because the residual aluminum content was too small, and the polymerization activity was insufficient compared with other cases.

From these figures, it is clear that the scope of the present invention is a critical value. In addition, it can be clearly seen that the amount of aluminum-based foreign matter and the polymerization time are an antinomy phenomenon.

[Manufacture of polyester film] (Example 9) The polyester resin composition obtained in Example 1 was vacuum-dried at 135° C. for 10 hours. Next, it was quantitatively supplied to a biaxial extruder, extruded into a thin sheet at 280°C, rapidly cooled and solidified on a metal roll maintained at a surface temperature of 20°C, and a cast film with a thickness of 1400 μm was obtained. When the metal roll is rapidly cooled and solidified, the adhesiveness to the metal roll is improved by using an electrostatic bonding device composed of a saw-shaped electrode. Next, the cast film was heated to 100° C. by a heated roll group and an infrared heater, and then extended 3.5 times in the longitudinal direction by a roll group having a peripheral speed difference to obtain a uniaxially oriented film. Next, the film was stretched 4.0 times in the width direction at 120° C. with a tenter, heated with an infrared heater at 260° C. for 0.5 seconds with the film width and length fixed, and further heated at 200° C. for 23 seconds for 3% relaxation treatment to obtain a biaxially oriented polyester film with a thickness of 100 μm. The static friction coefficient (μs) of the obtained polyester film was 0.50, and it could be said that it was a film having good sliding properties and excellent handling properties such as running properties, abrasion resistance, and winding properties.

(Example 10) A biaxially oriented polyester film was produced in the same manner as in Example 9 except that the polyester resin composition obtained in Example 6 was used. The static friction coefficient (μs) of the obtained polyester film was 0.50, and it could be said that it was a film having good sliding properties and excellent handling properties such as running properties, abrasion resistance, and winding properties.

(Comparative Example 11) A biaxially oriented polyester film was produced in the same manner as in Example 9 except that the polyester resin obtained in Comparative Example 6 was used. The static friction coefficient (μs) of the obtained polyester film is 0.45, which can be said to be a film with good sliding properties and excellent handling properties such as running properties, abrasion resistance, and winding properties. The films of Examples 9 and 10 had poor transparency.

(Comparative Example 12) A biaxially oriented polyester film was produced in the same manner as in Example 9 except that the polyester resin composition obtained in Comparative Example 7 was used. The static friction coefficient (μs) of the obtained polyester film is 1 or more, and it can be said that it is inferior in sliding property and inferior in handling properties such as running property, abrasion resistance, and winding property.

(Example 11) The polyester resin composition of Example 6 was vacuum dried at 135°C for 10 hours. Next, it was quantitatively supplied to a biaxial extruder, extruded into a thin sheet at 280°C, rapidly cooled and solidified on a metal roll maintained at a surface temperature of 20°C, and a cast film with a thickness of 1680 μm was obtained. When the metal roll is rapidly cooled and solidified, the adhesion to the metal roll is improved by using a commonly used electrostatic bonding device composed of linear electrodes. Next, the cast film was heated to 100° C. by a heated roll group and an infrared heater, and then extended 3.5 times in the longitudinal direction by a roll group having a peripheral speed difference to obtain a uniaxially oriented film. Next, the film was stretched 4.0 times in the width direction at 120° C. with a tenter, heated with an infrared heater at 260° C. for 0.5 seconds with the film width and length fixed, and further heated at 200° C. for 23 seconds for 3% relaxation treatment to obtain a biaxially oriented polyester film with a thickness of 12 μm. The properties of the obtained polyester film are shown in Table 3.

(Example 12) Except that after mixing the polyester resin composition of Example 6 and the masterbatch containing the electrostatic adhesion imparting agent prepared by the above method at the ratio shown in Table 3, vacuum drying at 135° C. for 10 hours, use and implementation A biaxially oriented polyester film was produced in the same manner as in Example 11. The properties of the obtained polyester film are shown in Table 3. The polyester film of Example 12 is more excellent in electrostatic adhesion than the polyester film of Example 11, and the film-forming speed can be increased to manufacture a film.

[table 3] project Example 11 Example 12 Resin mixing ratio (mass %) Polyester resin (Example 6) 100 95 Masterbatch containing electrostatic adhesion imparting agent - 5 Film properties ρi(×10 ⁸ Ω・cm) 3.50 0.22 Static friction coefficient (μs) 0.43 0.45 Electrostatic Adhesion (m/min) 20 54

Since the polyester film of Example 11 has few aluminum-based foreign substances, it is of high quality in terms of film quality. The polyester film of Example 12 is not only of high quality in terms of film quality, but also excellent in film productivity, and the obtained film has excellent properties such as slipperiness, and is suitable for thin films (such as packaging films) that strongly require improved film productivity. etc.) production. [Industrial Availability]

The polyester resin composition of the present invention can improve the productivity of the polyester resin composition while suppressing the catalyst cost, which is the problem of the polyester resin composition obtained by the polymerization catalyst composed of an aluminum compound and a phosphorus compound. It improves and reduces foreign matter originating from the catalyst contained in the polyester resin composition. Thereby, a pure and high-quality polyester resin composition can be provided. Furthermore, the polyester film produced using the polyester resin composition of the present invention has sliding properties. Furthermore, by adding an electrostatic adhesiveness imparting agent to the polyester resin composition of the present invention to form a film, the melting specific resistance can be sufficiently reduced, the film forming property can be improved, and a polyester film having excellent quality can be produced. Therefore, the polyester film produced using the polyester resin composition of the present invention can be used, for example, for antistatic films, adhesive films, cards, fake cans, agriculture, building materials, cosmetic materials, For wallpaper, for OHP film, for printing, for inkjet recording, for sublimation transfer recording, for laser printer recording, for electrophotographic recording, for thermal transfer recording, for thermal transfer recording, for printed circuit board wiring , Membrane switch, near-infrared absorption film for plasma display, transparent conductive film for touch panel and electroluminescence, masking film, photoplate, X-ray film, photographic film, retardation film , polarizing film, polarizing film protection (TAC), protective film and/or separation film for deflection plate and retardation plate inspection, photosensitive resin film, visual field enlargement film, diffuser sheet, reflective film, anti- Widely used for reflective films, anti-ultraviolet rays, and back grinding tapes.

none.

FIG. 1 is a graph showing the correlation between the residual molar ratio of phosphorus element with respect to the aluminum element, the amount of aluminum-based foreign matter, and the polymerization time, which were obtained from the results of Examples and Comparative Examples. 2 is a graph showing the correlation between the maximum absorption wavelength, the amount of aluminum-based foreign matter, and the polymerization time of the mixed solution of the phosphorus-containing ethylene glycol solution and the aluminum-containing ethylene glycol solution obtained from the results of Examples and Comparative Examples.

Claims (15)

A polyester resin composition, comprising polyester resin and insoluble particles of particles insoluble in the polyester resin, characterized by: The polyester resin contains an aluminum compound and a phosphorus compound, and the polyester resin composition satisfies the following (1) to (4); (1) The content rate of aluminum element in the polyester resin composition is 9 to 19 mass ppm (2) The content rate of phosphorus element in the polyester resin composition is 13 to 31 mass ppm (3) The molar ratio of phosphorus element to aluminum element in the polyester resin composition is 1.32 or more and 1.80 or less (4) The content rate of the insoluble particles in the polyester resin composition is 500 to 2000 mass ppm. The polyester resin composition according to claim 1, wherein the content rate of the aluminum element corresponding to the aluminum-based foreign matter in the polyester resin is 3000 mass ppm or less. As claimed in claim 1 or 2, the polyester resin composition has an intrinsic viscosity (IV) of 0.56 dl/g or more. The polyester resin composition according to any one of claims 1 to 3, wherein the phosphorus compound has a phosphorus element and a phenol structure in the same molecule. The polyester resin composition according to any one of claims 1 to 4, wherein the volume average particle diameter of the insoluble particles is 0.5-3.0 μm. The polyester resin composition according to any one of claims 1 to 5, wherein the insoluble particles are silica. A method for producing a polyester resin composition, which is a method for producing a polyester resin composition such as the polyester resin composition according to any one of claims 1 to 6, characterized in that: The first step in which the polyester or its oligomer of synthetic polycondensate is used as an intermediate, and the second step in which the intermediate is further polycondensed, After the first step and before the second step, add the solution A1 in which the aluminum compound is dissolved and the solution B1 in which the phosphorus compound is dissolved, to the intermediate, The addition amounts of the solution A1 and the solution B1 satisfy the following (5) to (7), The insoluble particles are added in the first step or after the first step, and the added amount of the insoluble particles satisfies the following (8); (5) The amount of aluminum added to the polyester resin produced is 9 to 19 ppm by mass (6) The amount of phosphorus added relative to the polyester resin produced is 18 to 38 ppm by mass (7) The molar ratio of the addition amount of the phosphorus element in the (6) to the addition amount of the aluminum element in the (5) is 1.50 or more and 2.30 or less (8) The addition amount of the insoluble particles with respect to the produced polyester resin is 500 to 2000 mass ppm. The method for producing a polyester resin composition according to claim 7, wherein the polyester resin composition is produced by a batch polymerization method. The method for producing a polyester resin composition according to claim 7, wherein the polyester resin composition is produced by a continuous polymerization method, and the solution A1 and the solution B1 are added to the final esterification reaction tank or the final esterification reaction The transfer line between the tank and the initial polymerization tank. The method for producing a polyester resin composition according to any one of claims 7 to 9, wherein the solution A1 is a diol solution, and the maximum absorption wavelength of the solution A1 is 562.0-572.0 nm. The method for producing a polyester resin composition according to claim 10, wherein the solution B1 is a glycol solution, and the solution B1 is a maximum absorption wavelength of 460.0 to 463.0 nm. The method for producing a polyester resin composition according to claim 11, wherein the diol solution B1 is a heat treatment of the phosphorus compound at 170-196° C. for 125-240 minutes in the diol solution. The method for producing a polyester resin composition according to any one of claims 7 to 12, wherein the solution A1 and the solution B1 are glycol solutions, and the mixed solution of the glycol solution A1 and the glycol solution B1 The maximum absorption wavelength is 559.5 ~ 560.8nm. A polyester film formed from the polyester resin composition according to any one of claims 1 to 6. The polyester film of claim 14, wherein an electrostatic adhesion imparting agent is further added to the polyester resin composition.

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