WO2022054670A1 - Composition de résine polyester ainsi que procédé de fabrication de celle-ci, et film de polyester mettant en œuvre celle-ci - Google Patents

Composition de résine polyester ainsi que procédé de fabrication de celle-ci, et film de polyester mettant en œuvre celle-ci Download PDF

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WO2022054670A1
WO2022054670A1 PCT/JP2021/032139 JP2021032139W WO2022054670A1 WO 2022054670 A1 WO2022054670 A1 WO 2022054670A1 JP 2021032139 W JP2021032139 W JP 2021032139W WO 2022054670 A1 WO2022054670 A1 WO 2022054670A1
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polyester resin
resin composition
aluminum
solution
phosphorus
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PCT/JP2021/032139
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English (en)
Japanese (ja)
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悟 中川
耕輔 魚谷
慎也 金高
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東洋紡株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a polyester resin composition, a method for producing the same, and a polyester film using the same.
  • Polyester resins typified by polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc. are excellent in mechanical properties and chemical properties, and depending on the properties of each polyester resin, For example, 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 products such as bottles and engineering plastics.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PET polyethylene terephthalate
  • the polyester resin whose main constituent is a unit derived from aromatic dicarboxylic acid and alkylene glycol, which are typical polyester resins, is terephthalic acid or dimethyl terephthalate and ethylene glycol.
  • Bis (2-hydroxyethyl) terephthalate is produced by esterification or ester exchange, and is industrially produced by a polycondensation method or the like in which the bis (2-hydroxyethyl) terephthalate is polycondensed using a catalyst at high temperature and under vacuum.
  • an antimony compound or a germanium compound has been widely used as a polyester polymerization catalyst used in the polymerization of such a polyester resin.
  • Antimony trioxide which is an example of an antimony compound, is an inexpensive catalyst having excellent catalytic activity, but it is used as a main component, that is, in an amount added so as to exhibit a practical polymerization rate. Then, since metal antimony is precipitated during polymerization, darkening and foreign matter are generated in the polyester resin, which also causes surface defects of the film. Further, when it is used as a raw material for a hollow molded product or the like, it is difficult to obtain a hollow molded product having excellent transparency. For this reason, a polyester resin containing no antimony compound as a catalyst or containing no antimony compound as a main component is desired.
  • Germanium compounds have already been put into practical use as catalysts for giving polyester resins having excellent catalytic activity other than antimony compounds and not having the above-mentioned problems.
  • the germanium compound has a problem that it is very expensive and that it is easy to distill out of the reaction system during polymerization, so that the catalyst concentration of the reaction system changes and it becomes difficult to control the polymerization.
  • a polymerization catalyst that replaces the antimony-based catalyst or the germanium-based catalyst is also being studied. Titanium compounds typified by tetraalkoxy titanates have already been proposed, but polyester resins produced using titanium compounds are susceptible to thermal deterioration during melt molding, and the polyester resin has a problem of being significantly colored.
  • polymerization catalyst that uses metal components other than antimony, germanium, and titanium as the main metal components of the catalyst, and has excellent catalytic activity, excellent color tone and thermal stability, and transparency of molded products.
  • a polymerization catalyst that gives an excellent polyester resin is desired.
  • Patent Documents 1 and 2 disclose a catalyst composed of an aluminum compound and a phosphorus compound as a novel polymerization catalyst.
  • Patent Documents 3 and 4 disclose a polyester film made of a polyester resin produced by using a catalyst composed of an aluminum compound and a phosphorus compound. By using the above polymerization catalyst, it is possible to obtain a polyester resin or a polyester film having good color tone, transparency, and thermal stability.
  • Patent Documents 1 to 4 have a problem that the amount of catalyst added is large in order to obtain high polymerization activity, and the catalyst cost required for polymerization is high.
  • the present invention has been made to solve the problems of the prior art, and an object of the present invention is to reduce the catalyst cost and reduce the catalyst cost even when a polymerization catalyst composed of an aluminum compound and a phosphorus compound is used. It is to provide a polyester resin composition with few foreign substances. Another object of the present invention is to provide a polyester film formed by forming a film of the polyester resin composition.
  • the present inventors have reduced the amount of aluminum element contained in the polyester resin composition and set the molar ratio of phosphorus element to aluminum element to an appropriate range. We have found that the object can be achieved and have reached the present invention.
  • the polymerization activity is generally proportional to the amount of the catalyst added.
  • a polymerization catalyst composed of an aluminum compound and a phosphorus compound
  • the relationship between the polymerization activity and the amount of the catalyst added cannot be simplified because the complex formation reaction between the aluminum compound and the phosphorus compound affects the polymerization activity.
  • the present inventors analyzed the controlling factors of the catalytic activity of the polymerization catalyst composed of the aluminum compound and the phosphorus compound. As a result, by reducing the amount of aluminum element in the polyester resin composition and setting the molar ratio of phosphorus element to aluminum element in an appropriate range, the amount of aluminum-based foreign matter can be increased while suppressing the catalyst cost.
  • the present invention has been completed by finding that it is possible to improve the polymerization activity while suppressing it.
  • the present invention has the following configuration.
  • the polyester resin contains an aluminum compound and a phosphorus compound, and the polyester resin compositions are described in the following (1) to (1) to (1).
  • the content of aluminum element in the polyester resin composition is 9 to 19 mass ppm.
  • the content of phosphorus element in the polyester resin composition is 13 to 31 parts by mass ppm.
  • the molar ratio of phosphorus element to aluminum element in the polyester resin composition is 1.32 or more and 1.80 or less.
  • the content of the insoluble particles in the polyester resin composition is 500 to 2000 mass ppm. 2. 2.
  • the content of the aluminum element corresponding to the aluminum-based foreign substance in the polyester resin is 3000 mass ppm or less.
  • the intrinsic viscosity (IV) is 0.56 dl / g or more. Or 2.
  • the phosphorus compound has a phosphorus element and a phenol structure in the same molecule. ⁇ 3.
  • the volume average particle diameter of the insoluble particles is 0.5 to 3.0 ⁇ m. ⁇ 4.
  • the insoluble particles are silica. ⁇ 5.
  • the polyester resin composition according to any one of. 7. The above 1. ⁇ 6.
  • the first step of synthesizing a polyester which is a polycondensate or an oligomer thereof as an intermediate, and the intermediate are further weighted. It has a second step of condensation, and after the first step and before the second step, a solution A1 in which an aluminum compound is dissolved in the intermediate and a solution B1 in which a phosphorus compound is dissolved are added.
  • the addition amounts of the solution A1 and the solution B1 satisfy the following (5) to (7), the insoluble particles are added during the first step or after the completion of the first step, and the addition amount of the insoluble particles is as follows ( A method for producing a polyester resin composition, which is characterized by satisfying 8).
  • the amount of the aluminum element added to the produced polyester resin is 9 to 19 mass ppm.
  • the amount of phosphorus element added to the produced polyester resin is 18 to 38 mass ppm.
  • the molar ratio of the amount of phosphorus element added in (6) to the amount of aluminum element added in (5) is 1.50 or more and 2.30 or less.
  • the insoluble particles with respect to the polyester resin produced. Addition amount is 500-2000 mass ppm 8.
  • the polyester resin composition is produced by a batch polymerization method. The method for producing a polyester resin composition according to. 9.
  • 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 first polymerization reaction tank. ..
  • the method for producing a polyester resin composition according to. 10 The solution A1 is a glycol solution, and the maximum absorption wavelength of the solution A1 is 562.0 to 572.0 nm. ⁇ 9.
  • the solution B1 is a glycol solution, and the solution B1 has a maximum absorption wavelength of 460.0 to 463.0 nm.
  • the glycol solution B1 heat-treats a phosphorus compound at 170 to 196 ° C. for 125 to 240 minutes in the glycol solution.
  • the method for producing a polyester resin composition according to. 13 The solution A1 and the solution B1 are glycol solutions, and the maximum absorption wavelength of the mixed solution of the glycol solution A1 and the glycol solution B1 is 559.5 to 560.8 nm. ⁇ 12.
  • the method for producing a polyester resin composition according to any one of. 14. The above 1. ⁇ 6.
  • the electrostatic adhesion imparting agent is further added to the polyester resin composition.
  • the polyester resin composition of the present invention uses a polymerization catalyst composed of an aluminum compound and a phosphorus compound, the catalyst cost can be kept low and foreign substances derived from the catalyst contained in the polyester resin composition can be reduced. Therefore, the cost required for producing the polyester resin composition can be reduced and the quality can be improved. Further, the acidity and basicity of the solution in which the aluminum compound to be added as a catalyst is dissolved, the solution in which the phosphorus compound to be added as a catalyst is dissolved, and the mixed solution thereof are set within a preferable range (the maximum of the solution and the mixed solution). By setting the absorption wavelength in a preferable range), it is possible to further suppress an increase in the amount of aluminum-based foreign matter.
  • the polyester resin composition of the present invention can be obtained at low cost and has high quality, the production cost of the polyester film obtained by forming the polyester resin composition of the present invention can be reduced, and the polyester film can be produced. The quality can also be improved. Further, since the polyester film is excellent in running performance, 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 polyester resin composition of the present invention contains a polyester resin and insoluble particles which are particles insoluble in the polyester resin. Further, the polyester resin contains an aluminum compound and a phosphorus compound.
  • the polyester resin composition of the present invention satisfies the following (1) to (4).
  • the content of aluminum element in the polyester resin composition is 9 to 19 mass ppm.
  • the content of phosphorus element in the polyester resin composition is 13 to 31 parts by mass ppm.
  • the molar ratio of phosphorus element to aluminum element in the polyester resin composition is 1.32 or more and 1.80 or less.
  • the content of the insoluble particles in the polyester resin composition is 500 to 2000 mass ppm. In this specification, mass ppm means 10-4 % by mass.
  • the polyester resin used in the present invention includes a polyester resin composed of at least one selected from a polyvalent carboxylic acid and an ester-forming derivative thereof and at least one selected from a polyhydric alcohol and an ester-forming derivative thereof.
  • the main polyvalent carboxylic acid component is a dicarboxylic acid.
  • the polyester resin in which the main polyvalent carboxylic acid component is a dicarboxylic acid is preferably a polyester resin containing 70 mol% or more of the dicarboxylic acid with respect to the total polyvalent carboxylic acid component, and more preferably 80 mol% or more. It is a polyester resin containing 90 mol% or more, more preferably 90 mol% or more. When two or more kinds of dicarboxylic acids are used, it is preferable that the total of them is within the above range.
  • dicarboxylic acid examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decandicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, and hexadecanedicarboxylic acid.
  • 3-Cyclobutanedicarboxylic acid 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornandicarboxylic acid, dimer acid, etc.
  • the main polyvalent carboxylic acid component is terephthalic acid or an ester-forming derivative thereof or naphthalene dicarboxylic acid or an ester-forming derivative thereof.
  • the naphthalenedicarboxylic acid or an ester-forming derivative thereof include 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. Acids, or ester-forming derivatives thereof, may be mentioned.
  • a polyester resin containing 70 mol% or more of naphthalenedicarboxylic acid or an ester-forming derivative thereof in total is preferable, and a polyester resin containing 80 mol% or more is more preferable, and 90 mol% or more is more preferably contained. It is a polyester resin.
  • terephthalic acid 2,6-naphthalenedicarboxylic acid or ester-forming derivatives thereof. If necessary, other dicarboxylic acids may be used as constituents.
  • polyvalent carboxylic acid other than these dicarboxylic acids a trivalent or higher polyvalent carboxylic acid or a hydroxycarboxylic acid may be used in combination as long as the amount is small, and a trivalent to tetravalent polyvalent carboxylic acid is preferable.
  • the polyvalent carboxylic acid include ethanetricarboxylic acid, propantricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3', 4'-biphenyltetracarboxylic acid, and these. Examples thereof include ester-forming derivatives.
  • the amount of trivalent or higher polyvalent carboxylic acid is preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, based on the total polyvalent carboxylic acid component.
  • the total of them is within the above range.
  • hydroxycarboxylic acid examples include lactic acid, citric acid, malic acid, tartrate acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or these. Examples thereof include ester-forming derivatives of the above.
  • the hydroxycarboxylic acid is preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, based on the total polyvalent carboxylic acid component. When two or more kinds of hydroxycarboxylic acids are used, it is preferable that the total of them is within the above range.
  • ester-forming derivative of polyvalent carboxylic acid or hydroxycarboxylic acid examples include these alkyl esters, acid chlorides, acid anhydrides and the like.
  • the main polyhydric alcohol component is glycol
  • the polyester resin (A) in which the main polyhydric alcohol component is glycol is preferably a polyester resin containing 70 mol% or more of glycol with respect to the total polyvalent alcohol component, and more preferably 80 mol% or more. It is a polyester resin, more preferably a polyester resin containing 90 mol% or more. When two or more kinds of glycols are used, it is preferable that the total of them is within the above range.
  • glycol examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, and 1, 4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedi Alkylene glycols exemplified for methanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, etc .; polyethylene glycol, Aliphatic glycols exemplified by
  • Ethoxyphenyl) sulfone bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C , 2,5-Naphthalenediol, glycols obtained by adding ethylene oxide to these glycols, and the like, examples of aromatic glycols;
  • alkylene glycol is preferable, and ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, or 1,4-cyclohexanedimethanol is more preferable.
  • the alkylene glycol may contain a substituent or an alicyclic structure in the molecular chain, and two or more kinds may be used at the same time.
  • a trihydric or higher polyhydric alcohol may be used in combination as long as it is a small amount, and a trivalent to tetravalent polyhydric alcohol is preferable.
  • examples of the trihydric or higher polyhydric alcohol include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, and hexanetriol.
  • the amount of trihydric or higher polyhydric alcohol is preferably 20 mol% or less, more preferably 10 mol% or less, and further preferably 5 mol% or less with respect to the total polyhydric alcohol component. When two or more kinds of trihydric or higher polyhydric alcohols are used, it is preferable that the total of them is within the above range.
  • cyclic ester examples include ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -methyl- ⁇ -propiolactone, ⁇ -valerolactone, glycolide, lactide and the like.
  • ester-forming derivative of the polyhydric alcohol examples include esters of the polyhydric alcohol with a lower aliphatic carboxylic acid such as acetic acid.
  • 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 polyhydric alcohol component.
  • 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 polyhydric alcohol component.
  • it is preferable that the total of them is within the above range.
  • the polyester resin used in the present invention comprises only one monomer selected from ethylene terephthalate, butylene terephthalate, propylene terephthalate, 1,4-cyclohexanedimethylene terephthalate, ethylene naphthalate, butylene naphthalate, or propylene naphthalate. It is preferably a polymer or a copolymer composed of two or more kinds of the above-mentioned monomers, and the polyester resin used in the present invention is polyethylene terephthalate or a copolymer composed of at least one of the above-mentioned monomers other than ethylene terephthalate and ethylene terephthalate.
  • the copolymer composed of ethylene terephthalate and at least one of the above monomers other than ethylene terephthalate preferably contains 70 mol% or more, more preferably 80 mol% or more, and 90 mol of the component derived from the ethylene terephthalate monomer. It is more preferable to contain% or more.
  • the polyester resin of the present invention contains a catalyst amount of an aluminum compound-derived component and a phosphorus compound-derived component. That is, the polyester resin of the present invention is produced by using a polymerization catalyst composed of an aluminum compound and a phosphorus compound.
  • the aluminum compound constituting the polymerization catalyst is not limited as long as it is soluble in a solvent, and known aluminum compounds can be used without limitation.
  • Examples of aluminum compounds include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, and citric acid.
  • Carboxylates such as aluminum, aluminum tartrate, aluminum salicylate; inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate, aluminum phosphonate; aluminum methoxide , Aluminum ethoxide, aluminum n-propoxyside, aluminum isopropoxiside, aluminum n-butoxiside, aluminum t-butoxiside, etc.
  • Chelate compounds organic aluminum compounds such as trimethylaluminum and triethylaluminum and their partial hydrolysates, reaction products consisting of aluminum alcoholides and aluminum chelate compounds and hydroxycarboxylic acids, aluminum oxide, ultrafine aluminum oxide, aluminum silicate, aluminum. And composite oxides of titanium, silicon, aluminum, alkali metal, alkaline earth metal, etc. can be mentioned.
  • carboxylates, inorganic acid salts, and chelate compounds is preferable, and among these, aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetate are preferable.
  • At least one selected from nate is more preferred, and at least one selected from aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum chloride and aluminum acetylacetonate is even more preferred, aluminum acetate and base. At least one selected from the sex aluminum acetate is particularly preferable, and the basic aluminum acetate is the most preferable.
  • the aluminum compound is preferably an aluminum compound that is solubilized in a solvent such as water or glycol.
  • the solvents that can be used in the present invention are water and alkylene glycols.
  • alkylene glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylene glycol, ditrimethylethylene glycol, tetramethylene glycol, ditetramethylene glycol, neopentyl glycol and the like. .. It is preferably at least one selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol, and more preferably ethylene glycol. It is preferable to use a solution of the aluminum compound in water or ethylene glycol because the effect of the present invention can be remarkably exhibited.
  • the content of the aluminum element in the polyester resin composition needs to 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.
  • the mass is ppm. If the amount of aluminum element is less than 9% by mass, the polymerization activity may not be sufficiently exhibited. On the other hand, if it exceeds 19 mass ppm, the amount of aluminum-based foreign matter may increase.
  • the phosphorus compound constituting the polymerization catalyst of the present invention is not particularly limited, but it is preferable to use a phosphonic acid-based compound or a phosphinic acid-based compound because the effect of improving the catalytic activity is large, and among these, a phosphonic acid-based compound is used. It is more preferable because the effect of improving the catalytic activity is particularly large.
  • a phosphorus compound having a phosphorus element and a phenol structure in the same molecule is 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 a phosphonic acid compound having a phosphorus element and a phenol structure in the same molecule, and a phosphine having a phosphorus element and a phenol structure in the same molecule. It is highly preferable to use one or more compounds selected from the group consisting of acid compounds to greatly improve the catalytic activity, and one or more phosphonic compounds having a phosphorus element and a phenol structure in the same molecule can be used. When used, the effect of improving the catalytic activity is very large, which is more preferable.
  • R 1 represents a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, a substituent such as a hydroxyl group or a halogen group or an alkoxyl group or an amino group, and a hydrocarbon group having 1 to 50 carbon atoms including a phenol structure.
  • R 4 represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group or a substituent such as an alkoxyl group or an amino group.
  • R 2 and R 3 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 alkoxyl group, respectively.
  • the hydrocarbon group may contain a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl. The ends of R 2 and R 4 may 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, diphenyl p-hydroxyphenylphosphonate, and bis.
  • (P-Hydroxyphenyl) Phosphonic Acid Methyl Bis (p-Hydroxyphenyl) Phosphonate, Bis (p-Hydroxyphenyl) Phosphonate Phosphonate, p-Hydroxyphenyl Phosphonate, Methyl p-Hydroxyphenyl Phosphonate, p-Hydroxyphenyl Examples thereof include phenyl phosphinate and dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate represented by the following (formula 1).
  • the phosphorus compound having a phosphorus element and a phenol structure in the same molecule is particularly preferably a phosphorus compound having a hindered phenol structure, and among them, 3,5-di-tert-butyl represented by the following (formulation formula 1). It is preferably dialkyl-4-hydroxybenzylphosphonate.
  • X 1 and X 2 represent hydrogen and an alkyl group having 1 to 4 carbon atoms, respectively.
  • the alkyl groups of X 1 and X 2 have preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms.
  • an ethyl ester compound having 2 carbon atoms is preferable because Irganox1222 (manufactured by BAS) is commercially available and easily available.
  • the phosphorus compound in the present invention is preferably 3,5-di-tert-butyl-4-hydroxybenzylphosphonate dialkyl represented by the above (formulation formula 1), but other than that, 3,5-di.
  • a modified version of -tert-butyl-4-hydroxybenzylphosphonate dialkyl may also be included. Details of the denatured product will be described later.
  • the content of the phosphorus element in the polyester resin composition is 13 to 31 mass ppm, preferably 15 to 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, if it exceeds 31 parts by mass, the polymerization activity may decrease and the amount of the phosphorus compound added increases, which is not preferable because the catalyst cost increases.
  • the molar ratio of the phosphorus element to the aluminum element (in order to distinguish it from the "molar ratio of the addition of the phosphorus element to the aluminum element" described later, the following is referred to as "the residual molar ratio of the phosphorus element to the aluminum element”. ) Is also important and needs to be 1.32 to 1.80, preferably 1.38 to 1.68.
  • the aluminum element and the phosphorus element in the polyester resin composition are derived from the aluminum compound and the phosphorus compound used as the polymerization catalyst of the polyester resin composition, respectively.
  • polycondensation catalysts such as antimony compound, germanium compound and titanium compound may cause problems in the product such as characteristics, processability and color tone of the polyester resin composition of the present invention. It may be used in combination as long as it does not occur.
  • the content of the antimonate element in the polyester resin composition is preferably 30 mass ppm or less, and the content of the germanium element in the polyester resin composition is preferably 10 mass ppm or less, and the polyester resin composition.
  • the content of the element titanium in the product is preferably 3% by mass or less.
  • the intrinsic viscosity (IV) of the polyester resin composition of the present invention is preferably 0.56 dl / g or more, preferably 0.56 to 0.65 dl / g, and more preferably 0.58 to 0. It is .64 dl / g. If the intrinsic viscosity of the polyester resin composition is less than the above, the mechanical strength and impact resistance of the molded product may be insufficient. On the other hand, if the intrinsic viscosity of the polyester resin composition exceeds the above range, the economic efficiency is lowered, which is not preferable.
  • a polyester polymerization catalyst composed of an aluminum compound and a phosphorus compound is used as a catalyst, a polymerization catalyst is added so as to satisfy the following (5) to (7), and the catalyst is added. Except for the point of adding the insoluble particles by the method described later, the method can be carried out by a method provided with a known step.
  • the method for producing the polyester resin composition of the present invention includes a first step of synthesizing a polyester or an oligomer thereof, which is a polycondensate (lower-order condensate) as an intermediate, and a second step of further polycondensing the intermediate. It is preferable to have.
  • the solution A1 in which the aluminum compound is dissolved in the intermediate and the solution B1 in which the phosphorus compound is dissolved are satisfied with the following (5) to (7). It is preferable to add to.
  • Polyvalent carboxylic acids and ester-forming derivatives thereof used in the production of polyester resins, hydroxycarboxylic acids and ester-forming derivatives thereof which may be added in a small amount, and cyclic esters which may be added in a small amount are reaction systems during polymerization. Since almost 100% of the amount used initially added to the system as a catalyst remains in the polyester resin produced by polymerization without distilling out of the system, the "polyester resin produced" from these charged amounts The mass can be calculated.
  • the amount of aluminum element added to the produced polyester resin is 9 to 19 mass ppm.
  • the amount of phosphorus element added to the produced polyester resin is 18 to 38 mass ppm.
  • the molar ratio of the amount of phosphorus element added in (6) to the amount of aluminum element added in (5) (hereinafter referred to as "the molar ratio of phosphorus element added to aluminum element") is 1.50 or more. 30 or less
  • the method for producing polyester or an oligomer thereof, which is a low-order condensate (low polymer) used in the present invention is not particularly limited.
  • the method for producing a polyester resin used in the present invention uses a polyester polymerization catalyst composed of an aluminum compound and a phosphorus compound as a catalyst, and the content of aluminum element in the polyester resin, the content of phosphorus element, and the phosphorus element with respect to the aluminum element. Except for adjusting the molar ratio of the above to a specific range, it can be carried out by a method provided with conventionally known steps. For example, in the case of producing polyethylene terephthalate, terephthalic acid, ethylene glycol and, if necessary, other copolymerization components are directly reacted to distill off water for transesterification, and then polycondensation is performed under normal pressure or reduced pressure.
  • Direct esterification method or transesterification by reacting dimethyl terephthalate with ethylene glycol and, if necessary, other copolymerization components to distill off methyl alcohol and transesterify, and then perform polycondensation under normal pressure or reduced pressure. Manufactured by law. Further, if necessary, solid phase polymerization may be performed to increase the intrinsic viscosity.
  • the polymerization may be a batch type polymerization method or a continuous polymerization method.
  • the amount (mass) of the polyester resin produced can be calculated from the amount (mass) of the polyvalent carboxylic acid containing the dicarboxylic acid or the like used as the raw material.
  • the esterification reaction or the transesterification reaction may be carried out in one step or may be carried out in multiple steps.
  • the number and size of the reactors, the production conditions of each step, etc. can be appropriately selected without limitation, and may be carried out in one step or may be carried out in multiple steps in 2 to 5 steps. It is preferably present, more preferably 3 to 4 steps, and even more preferably 3 steps.
  • the melt polymerization reaction is preferably carried out in a continuous reaction apparatus.
  • a continuous reaction device is a fusion polymerization reaction vessel in which a reaction vessel for an esterification reaction or an ester exchange reaction and a melt polymerization reaction vessel are connected by a pipe, and raw materials are continuously charged without emptying each reaction vessel.
  • polyester resin composition is produced by an esterification reaction or an ester exchange reaction in multiple steps and by a continuous polymerization method, a solution A1 in which an aluminum compound is dissolved and a solution B1 in which a phosphorus compound is dissolved are added in multiple steps. It is preferable to add it to the transfer line between the final reaction tank (final esterification reaction tank or final esterification reaction tank) and the first polymerization reaction tank.
  • 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 in a continuous apparatus in the same manner as the melt polycondensation reaction.
  • the first stage is the initial stage
  • the final stage is the late stage
  • the second stage It is preferable that the stage immediately before the final stage is the intermediate stage, and the reaction conditions for the polymerization reaction in the intermediate stage are between the reaction conditions in the initial stage and the reaction conditions in the final stage. It is preferable that the degree of increase in intrinsic viscosity reached in each of these polymerization reaction steps is smoothly distributed.
  • the acid terminal group concentration of the intermediate (low-order condensate) produced by the first step is preferably 400 to 1500 eq / ton. More preferably, it is 500 to 1200 eq / ton.
  • the ratio of the hydroxyl group ends (OH%) to the total terminal group concentration of the intermediate is preferably 45 to 70 mol%, more preferably 55 to 65 mol%. If the ratio of the hydroxyl group ends of the oligomer is less than 45 mol%, the polycondensation activity may become unstable and the amount of aluminum-based foreign matter may increase. On the other hand, if the ratio of the hydroxyl group ends of the oligomer exceeds 70 mol%, the polycondensation activity may decrease.
  • an aluminum compound and a phosphorus compound are used as catalysts, they are preferably added in the form of a slurry or a solution, more preferably a solution dissolved in a solvent such as water or glycol, and even more preferably water and / or glycol. , It is most preferable to use a solution dissolved in ethylene glycol.
  • the content (residual amount) of the aluminum element and the phosphorus element in the polyester resin composition is the solution A1 in which the aluminum compound is dissolved and the solution B1 in which the phosphorus compound is dissolved. It is preferable to add the mixture so as to satisfy the above (1) to (3).
  • the solution A1 in which the aluminum compound is dissolved and the solution B1 in which the phosphorus compound is dissolved are added so that the content (residual amount) of the aluminum element and the phosphorus element in the polyester resin composition satisfies the above (1) to (3).
  • a complex having catalytic activity is functionally formed in the polymerization system, and sufficient polymerization activity can be exhibited.
  • the generation of aluminum-based foreign matter can be suppressed.
  • the aluminum element in the aluminum compound that functions as a catalyst was placed in a reduced pressure environment during the polymerization of the polyester resin, almost 100% of the amount used initially added to the system as a catalyst was produced by the polymerization. It remains in the polyester resin. That is, since the amount of the aluminum compound hardly changes before and after polycondensation, if the amount of the aluminum element added to the intermediate is 9 to 19 parts by mass, the content of the aluminum element in the polyester resin composition also increases. It will be 9 to 19 mass ppm.
  • the phosphorus compound that functions as a catalyst together with the aluminum compound is placed in a reduced pressure environment during the polymerization of the polyester resin, a part (about 10 to 40%) of the amount initially added to the system as a catalyst is out of the system.
  • the removal ratio is the molar ratio of phosphorus element added to aluminum element, the basicity and acidity of the aluminum-containing glycol solution or phosphorus-containing glycol solution to be added, and the method of adding the aluminum-containing solution or phosphorus-containing solution ( It changes depending on whether it is added in a single solution or added separately). Therefore, it is preferable to appropriately set the addition amount of the phosphorus compound so that the content of the phosphorus element in the polyester resin composition to be the final product satisfies the above (2).
  • the solution A1 in which the aluminum compound is dissolved and the solution B1 in which the phosphorus compound is dissolved are previously added to the intermediate. It is a more preferable embodiment to prepare a mixed solution by mixing at a ratio of addition to the above, and to add the liquefied mixed solution to the intermediate. By carrying out in this embodiment, the effect of the present invention can be more stably expressed.
  • the method of pre-condensing each solution include a method of mixing each solution in a tank, a method of merging and mixing pipes to which a catalyst is added in the middle, and the like.
  • 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 esterification reaction or the ester exchange reaction is completed, and are after the first step and before the second step.
  • the solution A1 in which the aluminum compound is dissolved and the solution B1 in which the phosphorus compound is dissolved 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 to the intermediate. If added before the end of the esterification reaction or transesterification reaction, the amount of aluminum-based foreign matter may increase.
  • the polyester resin used in the present invention comprises at least one selected from a polyhydric carboxylic acid and an ester-forming derivative thereof and at least one selected from a polyhydric alcohol and an ester-forming derivative thereof, an aluminum compound.
  • the solution A1 in which the ester is dissolved is preferably a glycol solution in which an aluminum compound is dissolved (hereinafter referred to as an aluminum-containing glycol solution A1)
  • the solution B1 in which a phosphorus compound is dissolved is a glycol solution in which a phosphorus compound is dissolved (hereinafter referred to as a glycol solution).
  • Phosphorus-containing glycol solution B1) is preferable.
  • the maximum absorption wavelengths of the aluminum-containing glycol solution A1 and the phosphorus-containing glycol solution B1 will be described.
  • a polyester resin having stable polymerization activity and stable quality can be obtained.
  • the Lewis acid / base characteristics of the aluminum-containing glycol solution A1 and the phosphorus-containing glycol solution B1 can be controlled in a specific range. It is presumed that the Lewis acid / base property affects the complex formation reaction between the aluminum compound and the phosphorus compound, and the complex formation reaction affects the polymerization activity.
  • the aluminum-containing glycol solution A1 preferably has a maximum absorption wavelength of 562.0 to 572.0 nm, more preferably 567.0 to 572.0 nm.
  • the maximum absorption wavelength of the aluminum-containing glycol solution A1 is obtained by adding the acid dye Modant Blue 13 to the aluminum-containing glycol solution A1 and then measuring the absorption spectrum of the sample solution using an ultraviolet-visible spectrophotometer. The details of the measurement method will be described later.
  • the aluminum compound In order for the aluminum compound to functionally form a complex having catalytic activity with the phosphorus compound and exhibit polymerization activity, it is preferable to set the basicity of the aluminum compound contained in the aluminum-containing glycol solution A1 within a specific range. ..
  • the maximum absorption wavelength of the aluminum-containing glycol solution A1 is affected by the type and amount of the aluminum compound used, the type of glycol, the temperature, pressure, time, etc. at the time of preparing the glycol solution.
  • the maximum absorption wavelength of the aluminum-containing glycol solution A1 is less than the above range, the basicity of the aluminum compound in the solution is low and the complex with the phosphorus compound is not sufficiently formed, so that the polymerization activity is lowered or aluminum is used. The amount of foreign matter may increase. On the other hand, it is technically difficult for the maximum absorption wavelength to exceed the above range.
  • the phosphorus-containing glycol solution B1 preferably has a maximum absorption wavelength of 458.0 to 465.0 nm, more preferably 460.0 to 463.0 nm, and even more preferably 461.0 to 462.0 nm.
  • the maximum absorption wavelength of the phosphorus-containing glycol solution B1 is obtained by adding an aqueous solution of Bismarck Brown, which is a basic dye, to the phosphorus-containing glycol solution B1 and then measuring the absorption spectrum of the sample solution using an ultraviolet-visible spectrophotometer. The details of the measurement method will be described later.
  • the acidity of the phosphorus compound contained in the phosphorus-containing glycol solution B1 is preferable to set the acidity of the phosphorus compound contained in the phosphorus-containing glycol solution B1 within a specific range.
  • the maximum absorption wavelength of the phosphorus-containing glycol solution B1 is affected by the type and amount of the phosphorus compound used, the type of glycol, the temperature, pressure, time, etc. at the time of preparing the glycol solution.
  • the maximum absorption wavelength of the phosphorus-containing glycol solution B1 exceeds the above range, the acidity of the phosphorus compound is low and the complex is not sufficiently formed with the aluminum compound. Therefore, the phosphorus compound is distilled off from the polymerization system to form aluminum. It is not preferable because the amount of foreign matter increases.
  • the maximum absorption wavelength is less than the above 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 significantly lowered.
  • the phosphorus compound used in the present invention is preferably 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 alkylene glycol, but as the alkylene glycol, it is preferable to use a solvent that dissolves a phosphorus compound, and the purpose is ethylene glycol or the like. It is more preferable to use glycol, which is a constituent of the polyester resin.
  • the heat treatment in the solvent is preferably carried out after dissolving the phosphorus compound, but it does not have to be completely dissolved.
  • the heat treatment conditions are preferably such that the heat treatment temperature is 170 to 196 ° C, more preferably 175 to 185 ° C, and even 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 heat treatment is preferably 3 to 10% by mass.
  • the acidity of the phosphorus compound contained in the glycol solution can be made constant, the polymerization activity is improved when used in combination with the aluminum compound, and the amount of aluminum-based foreign matter caused by the polymerization catalyst is generated. Can be reduced.
  • 3,5-di-tert-butyl-4-hydroxybenzylphosphonate dialkyl which is the phosphorus compound represented by the above (formula 1)
  • the phosphorus compound it is represented by (formula 1) in the above heat treatment.
  • a part of the phosphorus compound 3,5-di-tert-butyl-4-hydroxybenzylphosphonate dialkyl is structurally changed. For example, it changes to desorption of t-butyl group, hydrolysis of ethyl ester group and transesterification structure (ester exchange structure with ethylene glycol).
  • the phosphorus compound includes a phosphorus compound having a structural change in addition to the 3,5-di-tert-butyl-4-hydroxybenzylphosphonate dialkyl represented by (Formula 1). Desorption of the t-butyl group occurs remarkably at a high temperature in the polymerization step.
  • the phosphorus compounds are shown as nine phosphorus compounds having a structural change in a part of diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.
  • the amount of each phosphorus compound whose structure has changed in the glycol solution can be quantified by the P-NMR spectrum measurement method of the solution.
  • the phosphorus compound in the present invention in addition to 3,5-di-tert-butyl-4-hydroxybenzylphosphonate dialkyl, nine 3,5-di-tert-butyl-4-hydroxy represented by the above chemical formulas are used. Also included are variants of dialkyl benzyl phosphonate.
  • a mixture of an aluminum-containing glycol solution A1 and a phosphorus-containing glycol solution B1 (hereinafter, simply referred to as “mixture”) preferably has a maximum absorption wavelength of 559.0 to 560.9 nm, and is preferably 559.5 to 560. It is more preferably 8.8 nm, and even more preferably 559.7 to 560.6 nm.
  • the maximum absorption wavelength of the mixed solution is a value obtained by adding the acidic dye Modant Blue 13 to the mixed solution and then measuring the absorption spectrum of the sample solution using an ultraviolet-visible spectrophotometer. The details of the measurement method will be described later.
  • the complex formation reaction of the aluminum compound and the phosphorus compound can be maintained in a preferable state for achieving both the improvement of the polymerization activity and the suppression of aluminum-based foreign substances. preferable.
  • the maximum absorption wavelength exceeds the above range, the basicity of the mixed solution is high and the polymerization system of the polyester resin is acidic. Therefore, when the mixed solution is added to the polymerization system, the aluminum compound becomes the polyester resin. There is a risk that the amount of aluminum-based foreign matter will increase due to neutralization with the carboxyl group terminal of the resin and formation of foreign matter.
  • the maximum absorption wavelength is less than the above 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.
  • the content 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.
  • protrusions are formed on the surface of the obtained polyester film by insoluble particles, so that the film has slipperiness, running property, abrasion resistance, winding property, etc. It is possible to develop a function of improving the handling characteristics of the film. If the content of the insoluble particles is less than 500 mass ppm, the effect of improving the handling characteristics such as slipperiness, running property, abrasion resistance, and winding property of the film is insufficient, which is not preferable. On the other hand, if it exceeds 2000 mass ppm, film defects due to coarse particles and the like may increase, and the transparency of the film may decrease. In addition, the polymerization activity may decrease during 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 inorganic particles or organic particles. Further, it may be an inorganic / organic composite particle.
  • the type of the inorganic particles is not particularly limited, and examples thereof include metal oxides such as titanium, aluminum, silicon, calcium, magnesium, and barium, carbonates, silicates, sulfates, and aluminates.
  • the types of the inorganic particles include titanium dioxide, alumina, aluminosilicate, silicon dioxide, calcium oxide, calcium carbonate, barium sulfate, and the like, as well as naturally occurring talc, mica, kaolinite, and zeolite. However, it is not limited to these.
  • the insoluble particles are 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 ⁇ m, more preferably 0.8 to 2.5 ⁇ m, and even more preferably 2.0 to 2.5 ⁇ m. If the volume average particle diameter of the insoluble particles is less than 0.5 ⁇ m, the effect of imparting handling characteristics such as slipperiness and runnability to the film may be reduced. On the other hand, when the volume average particle diameter of the insoluble particles exceeds 3.0 ⁇ m, the quality of the film may be impaired due to the formation of coarse protrusions.
  • the volume average particle size 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.
  • the insoluble particles are preferably added as a slurry dispersed in ethylene glycol.
  • the time of addition is not particularly limited, but it is preferable that the insoluble particles are added during the first step or after the completion of the first step. Specifically, it may be added at any time 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 vessel, or may be added to the piping between the reaction vessels by an in-line mixer or the like. Moreover, you may add by installing an addition container.
  • the insoluble particles added to the intermediate remain in the polyester resin composition as they are without distilling out of the polymerization system. That is, the addition amount (addition rate) of the insoluble particles to the produced polyester resin is the same as the content rate of the insoluble particles in the polyester resin composition. Therefore, the amount of the insoluble particles added to the intermediate is 500 to 2000 mass ppm, preferably 700 to 1800 mass ppm.
  • the method for quantifying insoluble particles contained in the polyester resin composition is not limited.
  • the polyester resin used in the present invention preferably has an aluminum element content corresponding to an aluminum-based foreign substance in the polyester resin (polyester resin composition excluding insoluble particles) of 3000 mass ppm or less, more preferably 2800.
  • the mass is ppm or less.
  • the aluminum-based foreign matter is caused by the aluminum compound used as the polymerization catalyst, and is a foreign matter insoluble in the polyester resin. If the content of the aluminum-based foreign matter exceeds the above, fine foreign matter insoluble in the polyester resin may be the cause, and the quality of the film may be deteriorated. In addition, it leads to a problem that the filter is often clogged during polyester filtration in the polycondensation process and the film forming process.
  • the preferable lower limit of the content of the aluminum element corresponding to the aluminum-based foreign substance is preferably 0 mass ppm, but it is about 300 mass ppm due to technical difficulty.
  • this index relatively evaluates the amount of aluminum-based foreign matter based on the amount of aluminum element. It does not indicate the absolute value of the amount of aluminum-based foreign matter contained in the polyester resin.
  • the polyester resin can be obtained by producing it by the same method as the polyester resin composition described above, except that it does not contain insoluble particles.
  • 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 excluding the insoluble particles which are the constituent components of the polyester resin composition.
  • the insoluble particles are clogged in the membrane filter, so that the insoluble particles cannot be separated from the aluminum-based foreign matter. Therefore, by evaluating the amount of aluminum-based foreign matter in the polyester resin containing no insoluble particles instead of the polyester resin composition, it can be regarded as the amount of aluminum-based foreign matter in the polyester resin composition.
  • the polyester resin composition of the present invention preferably does not contain a resin other than the polyester resin, but may contain a resin other than the polyester resin as long as it does not impair the object of the present invention.
  • the resin other than the polyester resin is not particularly limited, and examples thereof include a polyolefin resin, a polyamide resin, and a polyacetal resin.
  • the 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, further preferably 5% by mass or less, and preferably 3% by mass or less. It is particularly preferable, and most preferably 1% by mass or less.
  • the method of blending the above resin with the polyester resin is not particularly limited, and examples thereof include methods that can be uniformly mixed, such as addition in the polyester resin manufacturing process and dry blending with the polyester resin after production.
  • the polyester film of the present invention is preferably a polyester film formed from a polyester resin composition, and an electrostatic adhesion imparting agent is further added to the polyester resin composition (electrostatic adhesion with the polyester resin composition). It is more preferably a polyester film formed from an imparting agent), and even more preferably a polyester film formed from the polyester resin composition and a master batch containing an electrostatic adhesion imparting agent.
  • a method of adding the electrostatic adhesion imparting agent to the polyester resin composition of the present invention it is preferable to add a masterbatch having the electrostatic adhesion 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 the polyester resin used in the present invention.
  • a masterbatch having an electrostatic adhesion imparting agent may be referred to as a masterbatch containing an electrostatic adhesion imparting agent or simply a "masterbatch".
  • the melting specific resistance of the masterbatch is preferably 0.005 ⁇ 10 8 to 0.05 ⁇ 10 8 ⁇ ⁇ cm, preferably 0.005 ⁇ 10 8 to 0.025 ⁇ 10 8 ⁇ ⁇ cm. Is more preferable.
  • the melt resistivity of the masterbatch is higher than 0.05 ⁇ 108 ⁇ ⁇ cm, it is necessary to add a large amount of the masterbatch in order to improve the film forming property of the polyester resin composition, and the manufacturing cost. Problems such as an increase in the number of plastics occur. It is technically difficult to make the melt resistivity of the masterbatch less than 0.005 ⁇ 108 ⁇ ⁇ cm.
  • the melt specific resistance of the polyester film formed from the composition obtained by blending the masterbatch with the polyester resin composition is 0.1 ⁇ 10 8 to 0.3. It is preferably ⁇ 10 8 ⁇ ⁇ cm, and more preferably 0.15 ⁇ 10 8 to 0.25 ⁇ 10 8 ⁇ ⁇ cm.
  • the electrostatic adhesion imparting agent is preferably a magnesium compound or an alkali metal compound in order to reduce the melt resistivity. Further, it is preferable to add a phosphorus compound in order to disperse these metal ion components in the polyester resin composition without making them foreign substances and further improve the thermal stability.
  • the magnesium compound preferably has a magnesium element content of 15 to 150 mass ppm in the polyester film, and more preferably 30 to 100 mass ppm. If the content of the magnesium element is less than the above range, the melt resistivity becomes high, the electrostatic adhesion is deteriorated, and the film forming property may be deteriorated.
  • the alkali metal compound preferably has an alkali metal element content of 1.5 to 15 mass ppm in the polyester film, and more preferably 3 to 10 mass ppm. If the content of the alkali metal element is less than the above range, the melt resistivity may be high, the electrostatic adhesion may be deteriorated, and the film forming property may be deteriorated. On the other hand, if the content of the alkali metal element exceeds the above range, the thermal stability may be lowered and the coloring of the film may be severe.
  • the phosphorus compound preferably has a phosphorus element content of 7 to 80 mass ppm in the polyester film, and more preferably 20 to 50 mass ppm. If the content of the phosphorus element is less than the above range, the amount of insoluble foreign matter produced increases, the melt resistivity becomes high, the electrostatic adhesion deteriorates, and the film forming property may deteriorate. Further, the thermal stability may be deteriorated and the coloring of the film may be severe. On the other hand, if the content of the phosphorus element exceeds the above range, the melt resistivity becomes high, the electrostatic adhesion is deteriorated, and the film forming property may be deteriorated.
  • magnesium compound used in the present invention a known magnesium compound can be used.
  • a lower fatty acid salt such as magnesium acetate, an alcokiside such as magnesium methoxide, and the like may be mentioned, and any one of these may be used alone or two or more thereof may be used in combination.
  • magnesium acetate is preferable.
  • magnesium element it is preferable to add magnesium element to the polyester resin constituting the masterbatch so as to be 400 to 2700 mass ppm.
  • the amount of magnesium element is less than 400 mass ppm, the melt specific resistance becomes high, and it is necessary to add a large amount of masterbatch in order to improve the film-forming property of the polyester resin composition, and the effect as a masterbatch is high. It is low and may cause problems such as an increase in manufacturing cost.
  • the amount of the magnesium element exceeds 2700 mass ppm, the effect of improving the melt resistivity is saturated, the heat resistance is lowered, and the coloring of the film may be severe.
  • the amount of the magnesium element is more preferably 600 to 2500 mass ppm, still more preferably 800 to 2000 mass ppm.
  • Examples of the alkali metal of the alkali metal compound included in the master batch include lithium, sodium and potassium.
  • Examples of the alkali metal compound include lower fatty acid salts having 2 to 4 carbon atoms such as lithium acetate and potassium acetate, and alcoholides such as potassium methoxide, and any one of them is used alone. Or two or more of them may be used in combination.
  • As the alkali metal potassium has a large effect of lowering the melt resistivity and is preferable.
  • the alkali metal compound is preferably a lower fatty acid salt having 2 to 4 carbon atoms, more preferably an alkali metal acetate, and even more preferably potassium acetate.
  • the alkali metal element it is preferable to add the alkali metal element to the polyester resin constituting the masterbatch so as to be 40 to 270 mass ppm.
  • the amount of the alkali metal element is less than 40 mass ppm, the melt specific resistance becomes high, and it is necessary to add a large amount of masterbatch in order to improve the film-forming property of the polyester resin composition, and the effect as a masterbatch. There is a risk of problems such as increased manufacturing costs.
  • the amount of the alkali metal element exceeds 270 mass ppm, the effect of improving the melt resistivity is saturated, the heat resistance is lowered, and the coloring of the film may be severe.
  • the amount of the alkali metal element is more preferably 60 to 250 mass ppm, further preferably 80 to 200 mass ppm.
  • Examples of the phosphorus compound to be included in the master batch include phosphoric acid, phosphoric acid, hypophosphorous acid, phosphonic acid, phosphinic acid and ester compounds thereof.
  • phosphoric acid trimethyl phosphate, tributyl phosphate, triphenyl phosphate, monomethyl phosphate, dimethyl phosphate, monobutyl phosphate, dibutyl phosphate, phosphite, trimethyl phosphite, tributyl phosphite, methylphosphonic acid.
  • it is preferably at least one selected from the group consisting of a phosphoric acid trialkyl ester and an ethyl diethylphosphonoacetate, and more preferably a phosphoric acid trialkyl ester.
  • a phosphoric acid trialkyl ester it is more preferable that at least one of the alkyl groups of the alkyl ester is an alkyl group having 2 to 4 carbon atoms, and all the alkyl groups of the alkyl ester are alkyl groups having 2 to 4 carbon atoms. Is particularly preferred.
  • the particularly preferable phosphorus compound include triethyl phosphate, tripropyl phosphate, tributyl phosphate and the like, and any one of these may be used alone or in combination of two or more. good.
  • triethyl phosphate is considered to form a complex having an appropriate strong interaction with magnesium ions, and is most preferable because a masterbatch having a low melt resistivity, a small amount of foreign matter, and an excellent color tone can be obtained.
  • the phosphorus element it is preferable to add the phosphorus element to the polyester resin constituting the masterbatch so as to have a phosphorus element of 200 to 1700 mass ppm.
  • the amount of the phosphorus element is less than 200 mass ppm, the effect of stabilizing magnesium ions and alkali metal ions and dispersing them in the polyester resin is reduced, so that the amount of insoluble magnesium-based foreign substances produced may increase. Further, magnesium that has become a foreign substance loses the effect of lowering the melt resistivity, so that the melt resistivity may increase. In addition, the heat resistance may be lowered and the coloring of the film may be severe.
  • the amount of phosphorus element exceeds 1700 mass ppm, the excess phosphorus compound interacts with magnesium ions, so the charge of magnesium ions does not contribute to the effect of lowering the melt resistivity, and despite the large amount of magnesium added.
  • the melt resistivity may increase.
  • a more preferable amount of phosphorus element is 400 to 1000 mass ppm.
  • the content of magnesium atom, alkali metal atom, and phosphorus atom in the masterbatch can be quantified by the method described in the following examples.
  • the timing of addition of the master batch containing the magnesium compound, the alkali metal compound, and the phosphorus compound to the polyester resin is not particularly limited, but is not particularly limited, but during the polymerization of the polyester, particularly during the esterification (or transesterification) step, or during the esterification (or esterification) step.
  • the addition amounts of magnesium atoms and alkali metal atoms remain in the polyester resin composition as they are, but the phosphorus atoms are distilled off from the polymerization system under a reduced pressure environment. 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.
  • the polyester is a polyester composed of a dicarboxylic acid component and a glycol component
  • the amount of the magnesium element with respect to the dicarboxylic acid component is mmol%
  • the amount of the alkali metal element is kmol%
  • the amount of the phosphorus element is pmol%.
  • magnesium ion is divalent and alkali metal ion is monovalent
  • the sum of the amounts of magnesium ion and alkali metal ion is expressed as (m + k / 2), which is the ratio divided by p.
  • (M + k / 2) / p is the relative amount of magnesium ion and alkali metal ion with respect to the phosphorus atom.
  • the value of (m + k / 2) / p exceeds 3
  • the amount of phosphorus element is relatively small compared to magnesium element and alkali metal element, and magnesium ion and alkali metal ion are stabilized and dispersed in the polyester resin. The effect is reduced and the amount of insoluble foreign substances (magnesium salt, alkali metal salt) produced is increased.
  • the melt resistivity becomes higher with respect to the amount of magnesium added.
  • the heat resistance is lowered and the color tone of the masterbatch containing the electrostatic adhesion imparting agent or the film is deteriorated.
  • the value of "(m + k / 2) / p" is less than 2, the amount of phosphorus element becomes relatively excessive with respect to magnesium element and alkali metal element, and the excess phosphorus compound interacts with magnesium ion. Therefore, the deterioration of the color tone is improved, but the charge of the magnesium ion does not contribute to the effect of lowering the melt specific resistance, and the melt specific resistance becomes high with respect to the amount of magnesium added.
  • (M + k / 2) / p is more preferably 2.3 or more and 3 or less, and further preferably 2.5 or more and 3 or less.
  • the room temperature is 15 to 30 ° C., and a series of operations are performed indoors in this temperature range.
  • Equipment UV-1800 UV-Visible spectrophotometer manufactured by Shimadzu Corporation Spectral bandwidth: 1 nm
  • Sample cell Square cell (Material: Polymethyl methacrylate (PMMA), Optical path length: 10 mm)
  • Control liquid Ethylene glycol Scan range: 400-700 nm
  • the room temperature is 15 to 30 ° C., and a series of operations are performed indoors in this temperature range.
  • Equipment UV-1800 UV-Visible spectrophotometer manufactured by Shimadzu Corporation Spectral bandwidth: 1 nm
  • Sample cell Square cell (Material: PMMA, Optical path length: 10 mm)
  • Control liquid Ethylene glycol Scan range: 400-700 nm
  • 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'.
  • the mixing ratio of the aluminum-containing ethylene glycol solution a1 and the phosphorus-containing ethylene glycol solution b1 or b1'in the above mixed solution is the mixing ratio of the aluminum-containing ethylene glycol solution a1 and the phosphorus-containing ethylene glycol solution b1 or b1'in each example. Is the same as. In this measurement, the room temperature is 15 to 30 ° C., and a series of operations are performed indoors in this temperature range.
  • volume average particle size of silica particles Using a laser light scattering type particle size distribution meter (Microtrac HRA model: 9320-X100, manufactured by Leeds & Northrup), the ethylene glycol slurry of silica particles is substantially diluted with water. Measured in an aqueous system. The volume cumulative 50% diameter of the measurement result was defined as the volume average particle diameter.
  • polyester resin composition was weighed in a platinum crucible, carbonized on an electric stove, and then incinerated in a muffle furnace at 550 ° C. for 8 hours. The incinerated 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 emission spectrometry of the prepared sample solution.
  • Nebulizer Cross flow Nebulizer Chamber: Cyclone chamber Measurement wavelength: 167.078 nm
  • polyester resin composition was wet-decomposed with sulfuric acid, nitric acid and perchloric acid, and then neutralized with aqueous ammonia. 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 absorbance meter (UV-1700, manufactured by Shimadzu Corporation). The phosphorus element concentration in the polyester resin composition was determined from the calibration curve prepared in advance.
  • UV-1700 ultraviolet visible absorbance meter
  • Amount of aluminum-based foreign matter 30 g of polyester resin and 250 mL of p-chlorophenol / tetrachloroethane (3/1: mass ratio) mixed solution were put into a 500 mL Erlenmeyer flask containing a stirrer, and 100 using a hot stirrer. It was melted by heating at ⁇ 105 ° C. for 1.5 hours. Foreign matter was filtered off from the solution using a membrane filter made of polytetrafluoroethylene having a diameter of 47 mm and a pore size of 1.0 ⁇ m (PTFE membrane filter manufactured by Advantec, product name: T100A047A). The effective filtration diameter was 37.5 mm.
  • the cells were subsequently washed with 50 mL of chloroform and then the filter was dried.
  • the amount of aluminum element was quantified on the filtration surface of the membrane filter with a scanning fluorescent X-ray analyzer (ZSX100e, Rh line sphere 4.0 kW, manufactured by RIGAKU). The quantification was performed on the central portion of the membrane filter having a diameter of 30 mm.
  • the calibration curve of the fluorescent X-ray analysis method was obtained using a polyethylene terephthalate resin having a known aluminum element content, and the apparent aluminum element content was expressed in ppm.
  • the measurement was carried out by measuring the Al-K ⁇ ray intensity under the conditions of PHA (pulse height analyzer) 100-300 using pentaerythritol as a spectroscopic crystal and PC (proportion counter) as a detector at an X-ray output of 50 kV-70 mA. ..
  • PHA pulse height analyzer
  • PC proportion counter
  • the spinning nozzle a nozzle having 12 orifices having a hole diameter of 0.23 mm ⁇ and a length of 0.3 mm was used.
  • the filter a 100-mesh wire mesh, a 10 ⁇ m Naslon filter, a 100-mesh wire mesh, and a 50-mesh wire mesh were used in order from the extruder outlet side.
  • the back pressure increase coefficient k was calculated by the following equation from the back pressure increase amount ⁇ P (MPa / hour) per unit time, the flow rate Q (kg / hour), and the filtration area S (cm 2 ).
  • k ⁇ P / (Q / S)
  • the area S was calculated from the filter diameter, and the flow rate Q was calculated from the discharge amount.
  • melt resistivity was similarly determined for the film-forming composition of Example 12.
  • ⁇ i ( ⁇ ⁇ 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 composition layer for producing a molten film]
  • ⁇ [thickness] 2 (cm) ⁇ 0.06 (cm)
  • V 120 (V).
  • L is a value measured without including the diameter of the electrode, and is 1.3 cm.
  • Electrostatic Adhesion of Film Fabrication Compositions of Examples 11 and 12 A tungsten wire electrode is provided between the base of the extruder and the cooling drum, and a voltage of 10 to 15 KV is applied between the electrode and the casting drum. Casting was performed by applying the cast material, and the surface of the obtained cast material was observed with the naked eye and evaluated at the casting speed at which the occurrence of pinner bubbles began to occur. The higher the casting speed, the better the electrostatic adhesion.
  • ⁇ 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 phosphorus-containing ethylene glycol solution b1'was 470.8 nm. The phosphorus-containing ethylene glycol solution b1'was used in Comparative Example 8, and the phosphorus-containing ethylene glycol solution b1 was used in all Examples and Comparative Examples other than Comparative Example 8.
  • Example 1 In a 10 L stainless steel autoclave with a stirrer, a polyester oligomer consisting of high-purity terephthalic acid and ethylene glycol prepared in advance and having an esterification rate of about 95%, high-purity terephthalic acid and an ethylene glycol slurry containing silica particles prepared by the above method. It was charged so as to have 1200 mass ppm as silica particles with respect to the mass of the obtained oligomer mixture, and an esterification reaction was carried out at 260 ° C. to obtain an oligomer mixture.
  • the obtained oligomer mixture had an acid terminal group concentration of 750 eq / ton and a hydroxyl group terminal ratio (OH%) of 59 mol%.
  • a mixed solution prepared by mixing the aluminum-containing ethylene glycol solution a1 and the phosphorus-containing ethylene glycol solution b1 prepared by the above method was added to the obtained oligomer mixture.
  • the mixed solution was prepared so as to be 10 mass ppm and 20 mass ppm as the aluminum element and the phosphorus element with respect to the mass of the oligomer mixture, respectively.
  • the amount of the polyester resin produced can be calculated from the amount of terephthalic acid to be added, and in this embodiment, the aluminum element and the phosphorus element are 10 mass ppm and 20 mass ppm with respect to the produced polyester resin.
  • the mixed solution is added so as to be. After that, the temperature of the system was raised to 280 ° C. in 1 hour, and the pressure of the system was gradually reduced to 0.15 kPa during this period, and the polycondensation reaction was carried out under these conditions, and the IV was 0.60 dl / g. A polyester resin composition was obtained.
  • Examples 2 to 5 Comparative Examples 1 to 5
  • An aluminum-containing ethylene glycol solution a1 and a phosphorus-containing ethylene glycol solution b1 were added to the obtained polyester resin composition in the same manner as in Example 1 except that the amount of the catalyst element added was as shown in Table 1.
  • a polyester resin composition was obtained.
  • Example 6 A polyester resin composition was obtained in the same manner as in Example 2 except that the amount of the ethylene glycol slurry containing silica particles was changed.
  • Example 7 A polyester resin was obtained in the same manner as in Example 2 except that the ethylene glycol slurry containing silica particles was not added.
  • Polyester resins were prepared in the same manner as in Examples 1 to 5 and Comparative Examples 1 to 6 and 8 except that the ethylene glycol slurry containing silica particles was not added, and used as a polyester resin for measuring the amount of aluminum-based foreign matter.
  • Comparative Example 7 since the ethylene glycol slurry containing silica particles was not added, the polyester resin of Comparative Example 7 was used as it was as the polyester resin for measuring the amount of aluminum-based foreign matter.
  • Table 1 shows the physical characteristics 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.
  • the addition amount / residual amount of the aluminum element is described as Al
  • the addition amount / residual amount of the phosphorus element is described as P
  • the addition molar ratio / residual molar ratio of the phosphorus element to the aluminum element is described as P / Al. did.
  • the polyester resin compositions of Examples 1 to 5 have a short polymerization time and a small amount of aluminum-based foreign matter, so that the back pressure increase coefficient is small and high quality, even though the addition amounts of the aluminum element and the phosphorus element are small. Is. Moreover, since the amount of catalyst added is small, the cost of the catalyst can be reduced. Comparative Examples 1 and 2 are preferable in that the catalyst cost is high because the amount of the phosphorus compound added is large and the molar ratio of the phosphorus element added to the aluminum element is high, so that aluminum-based foreign substances are suppressed, but the polymerization activity is lowered. Therefore, it is not preferable. In addition, the catalyst cost becomes high.
  • Comparative Example 3 Although the residual molar ratio of the phosphorus element to the aluminum element is within the range of the present invention, the polymerization activity is insufficient due to the addition amount of the aluminum element being too small, and the polymerization time is long.
  • Comparative Examples 4 and 5 since the residual molar ratio of the phosphorus element to the aluminum element is too low, the amount of aluminum-based foreign matter in the polyester resin composition increases and the back pressure increase coefficient increases, so that the quality of the polyester resin composition increases. Is inferior.
  • Comparative Example 6 the residual molar ratio of the phosphorus element to the aluminum element is within the range of the present invention, but the polymerization activity is lowered and the polymerization time is long because the addition amount of the silica particles is too large.
  • Comparative Example 7 will be described later in the section of Comparative Example 12 (a film produced by using the polyester resin of Comparative Example 7).
  • the molar ratio of the phosphorus element added to the aluminum element is within the range of the present invention, the polymerization time is short, and the catalyst cost is low.
  • the maximum absorption wavelength of the phosphorus-containing ethylene glycol solution b1' is too large as compared with Examples 1 to 5, the residual molar ratio of the phosphorus element to the aluminum element becomes low, and the amount of aluminum-based foreign matter in the polyester resin composition increases.
  • the quality of the polyester resin composition is inferior because it increases and the back pressure increase coefficient increases.
  • Example of continuous polymerization method (Example 6) An in-line mixer consisting of three continuous esterification reactors and three continuous polycondensation reactors and equipped with a high-speed stirrer is installed on the transfer line from the third esterification reactor to the first polycondensation reactor. A slurry prepared by mixing 0.75 parts by mass of ethylene glycol with 1 part by mass of high-purity terephthalic acid was continuously supplied to the continuous production apparatus for the polyester resin, and the reaction of the first esterification reactor was performed.
  • the reaction was carried out at a temperature of 255 ° C., a pressure of 203 kPa, a reaction temperature of the second esterification reactor of 261 ° C., a pressure of 102 kPa, a reaction temperature of the third esterification reactor of 261-263 ° C., and a pressure of 126 kPa to obtain an oligomer.
  • the oligomer at the outlet of the third esterification reactor had an acid terminal group concentration of 550 eq / ton and a hydroxyl group terminal ratio (OH%) of 60 mol%.
  • the obtained oligomer is mixed with the aluminum-containing ethylene glycol solution a1 and the phosphorus-containing ethylene glycol solution b1 prepared by the above method to form a one-component mixture, and the silica particle-containing ethylene glycol slurry prepared by the above method is used as a third ester. It was added to the transfer line from the conversion tank to the first polycondensation reactor using an in-line mixer. As a catalyst, the aluminum-containing ethylene glycol solution a1 and the phosphorus-containing ethylene glycol solution b1 prepared by the above method are adjusted to 13 mass ppm and 36 mass ppm as the aluminum element and the phosphorus element with respect to the obtained oligomers, respectively.
  • the mixed solution and the ethylene glycol slurry containing silica particles are added so as to be 1200 mass ppm with respect to the obtained oligomer as silica particles.
  • the amount of the polyester resin produced can be calculated from the amount of terephthalic acid to be added, and in this embodiment, the aluminum element and the phosphorus element are 13 mass ppm and 36 mass ppm with respect to the produced polyester resin.
  • the mixed solution is added so as to be.
  • the above oligomer containing the mixed solution and silica particles was continuously transferred to a continuous polycondensation device consisting of three reactors, and the reaction temperature of the first polycondensation reactor was 268 ° C, the pressure was 5.3 kPa, and the second polycondensation was performed.
  • Polycondensation was performed at a reaction temperature of the reactor of 270 ° C. and a pressure of 0.930 kPa, a reaction temperature of the third polycondensation reactor of 274 ° C. and a pressure of 0.162 kPa to obtain a polyester resin composition having an IV of 0.59 dl / g. rice field.
  • the polyester resin composition was extruded into strands, cooled in water, cut and pelletized.
  • Example 7 and 8 Comparative Examples 9 and 10.
  • the polyester resin composition was the same as in Example 6 except that the aluminum-containing ethylene glycol solution a1 and the phosphorus-containing ethylene glycol solution b1 were added to the obtained oligomer so as to be the amount of the catalyst element added as shown in Table 2. I got something.
  • Table 2 shows the physical characteristics of the polyester resin compositions obtained in Examples 6 to 8 and Comparative Examples 9 and 10.
  • the production amount ratio shown in Table 2 is based on the production amount per hour of Comparative Example 9 (with the production amount per hour of Comparative Example 9 being 1.00), Examples 6 to 8 and Comparative Example.
  • the production amount per hour of 10 is expressed as a ratio. If the production amount ratio is higher than 1, the polymerization activity of the catalyst is high, and conversely, if the production amount ratio is 1 or less, the polymerization activity of the catalyst is low. Is shown. In the polyester resin compositions of Examples 6 to 8, the production amount ratio is larger than that of Comparative Example 9, the addition amount of the aluminum element and the phosphorus element is small, the catalyst cost can be reduced, and the polymerization activity is improved.
  • FIG. 2 shows the relationship between the maximum absorption wavelength of the mixed solution of the ethylene glycol solution a1 containing ethylene glycol and the ethylene glycol solution b1 containing phosphorus, the amount of aluminum-based foreign matter, and the polymerization time.
  • the values of Comparative Example 3 are excluded.
  • Comparative Example 3 the residual molar ratio of the phosphorus element to the aluminum element is within the range of the present invention, but the residual amount of aluminum is too small, so that the catalytic activity is not sufficiently exhibited, and the catalytic activity is not sufficiently exhibited, as compared with other cases. This is because the polymerization activity is insufficient.
  • Example 9 The polyester resin composition obtained in Example 1 was vacuum dried at 135 ° C. for 10 hours. Then, it was quantitatively supplied to a twin-screw extruder, extruded into a sheet at 280 ° C., and rapidly cooled and solidified on a metal roll maintained at a surface temperature of 20 ° C. to obtain a cast film having a thickness of 1400 ⁇ m. When quenching and solidifying on the metal roll, the adhesion to the metal roll was improved by an electrostatic adhesion device composed of saw-shaped electrodes. Next, this cast film was heated to 100 ° C.
  • the relaxation treatment was carried out to obtain a biaxially oriented polyester film having a thickness of 100 ⁇ m.
  • the obtained polyester film has a coefficient of static friction ( ⁇ s) of 0.50, has good slipperiness, and can be said to be a film having excellent handling characteristics such as running performance, wear resistance, and winding property.
  • 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 obtained polyester film has a coefficient of static friction ( ⁇ s) of 0.50, has good slipperiness, and can be said to be a film having excellent handling characteristics such as running performance, wear resistance, and winding property.
  • 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 obtained polyester film has a coefficient of static friction ( ⁇ s) of 0.45, has good slipperiness, and can be said to have excellent handling characteristics such as running performance, wear resistance, and take-up property. , The transparency was inferior to that of the films of Examples 9 and 10.
  • 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 obtained polyester film has a coefficient of static friction ( ⁇ s) of 1 or more, and can be said to be a film having poor slipperiness and poor handling characteristics such as running performance, wear resistance, and winding property.
  • Example 11 The polyester resin composition of Example 6 was vacuum dried at 135 ° C. for 10 hours. Then, it was quantitatively supplied to a twin-screw extruder, extruded into a sheet at 280 ° C., and rapidly cooled and solidified on a metal roll maintained at a surface temperature of 20 ° C. to obtain a cast film having a thickness of 1680 ⁇ m. When quenching and solidifying on the metal roll, the adhesion to the metal roll was improved by an electrostatic contact device made of a wire-shaped electrode which is widely used. Next, this cast film was heated to 100 ° C.
  • 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 fixed, and further heated at 200 ° C. for 23 seconds at 3%.
  • the relaxation treatment was carried out to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m.
  • the characteristics of the obtained polyester film are shown in Table 3.
  • Example 12 Same as Example 11 except that the polyester resin composition of Example 6 and the masterbatch containing the electrostatic adhesion imparting agent prepared by the above method were mixed at the ratios shown in Table 3 and then vacuum dried at 135 ° C. for 10 hours. A biaxially oriented polyester film was produced by the above method. The characteristics of the obtained polyester film are shown in Table 3. The polyester film of Example 12 has better electrostatic adhesion than the polyester film of Example 11, and the film can be produced by increasing the film forming speed.
  • the polyester film of Example 11 Since the polyester film of Example 11 has few aluminum-based foreign substances, the quality of the film is high.
  • the polyester film of Example 12 is thin in that the quality of the film is high, the film productivity is excellent, and the obtained film has excellent slipperiness and other characteristics, and there is a strong demand for improvement in film productivity. Suitable for the production of films such as, for example, packaging films.
  • the polyester resin composition of the present invention can improve the productivity of the polyester resin composition while keeping the catalyst cost low, which has been a problem of the polyester resin composition obtained by the polymerization catalyst composed of an aluminum compound and a phosphorus compound. It is possible to reduce foreign substances derived from the catalyst contained in the polyester resin composition. This makes it possible to provide a clean and high-quality polyester resin composition. Further, the polyester film produced by using the polyester resin composition of the present invention has slipperiness. Further, by adding an electrostatic adhesion imparting agent to the polyester resin composition of the present invention to form a film, the melt resistivity can be sufficiently lowered, the film forming property is improved, and the quality is also excellent. Polyester films can be manufactured.
  • the polyester film produced by using the polyester resin composition of the present invention is, for example, an antistatic film, an easily adhesive film, a card, a dummy can, an agricultural film, a building material, a decorative material, and a wallpaper.
  • OHP film for printing, for inkjet recording, for sublimation transfer recording, for laser beam printer recording, for electrophotographic recording, for thermal transfer recording, for thermal transfer recording, for printed board wiring, for membrane switch, for plasma display Infrared absorbing film, transparent conductive film for touch panel and electroluminescence, masking film, photoengraving, roentgen film, photographic negative film, retardation film, polarizing film, polarizing film protection (TAC), deflection Protective film and / or separator film for inspection of plates and retardation plates, photosensitive resin film, field enlargement film, diffusion sheet, reflective film, antireflection film, UV protection, back grind tape, etc. It can be used for a wide range of purposes.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention fournit une composition de résine polyester qui réduit le coût de catalyseur, y compris dans le cas où un catalyseur de polymérisation constitué d'un composé aluminium et d'un composé phosphore, est mis en œuvre, et qui présente peu de substances étrangères. Plus précisément, l'invention concerne une composition de résine polyester qui contient une résine polyester, et des particules insolubles consistant en des particules non solubles dans la résine polyester. Cette composition de résine polyester est caractéristique en ce qu'elle satisfait les points (1) à (4) suivants, et en ce que ladite résine polyester contient un composé aluminium et un composé phosphore.　(1) La teneur en élément aluminium dans ladite composition de résine polyester, est comprise entre ９ et １９ppm en masse ; (2) la teneur en élément phosphore dans ladite composition de résine polyester, est comprise entre 13 et 31ppm en masse ; (3) le rapport molaire de l'élément phosphore vis-à-vis de l'élément aluminium dans ladite composition de résine polyester, est supérieur ou égal à １,３２ et inférieur ou égal à １,８０ ; et (4) la teneur en particules insolubles dans ladite composition de résine polyester, est comprise entre ５００ et ２０００ppm en masse.
PCT/JP2021/032139 2020-09-11 2021-09-01 Composition de résine polyester ainsi que procédé de fabrication de celle-ci, et film de polyester mettant en œuvre celle-ci WO2022054670A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002057335A1 (fr) * 2001-01-18 2002-07-25 Toyo Boseki Kabushiki Kaisha Catalyseur de polymerisation de polyester, polyester et procede de fabrication de celui-ci
JP2003212982A (ja) * 2002-01-24 2003-07-30 Toyobo Co Ltd ポリエステルの製造方法
CN101029126A (zh) * 2001-02-23 2007-09-05 东洋纺织株式会社 聚酯聚合催化剂、利用其制得的聚酯和聚酯的制造方法
JP2009503177A (ja) * 2005-07-25 2009-01-29 テルガル フィブレ 重縮合によってポリエステルを製造するための触媒系及びポリエステルの製造方法
JP2012076457A (ja) * 2010-09-08 2012-04-19 Toyobo Co Ltd ブロー成形による中空容器の成形方法
WO2017183550A1 (fr) * 2016-04-20 2017-10-26 東洋紡株式会社 Résine à base de poly(téréphtalate de butylène)
WO2021125137A1 (fr) * 2019-12-18 2021-06-24 東洋紡株式会社 Résine polyester, et procédé de fabrication de celle-ci

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002057335A1 (fr) * 2001-01-18 2002-07-25 Toyo Boseki Kabushiki Kaisha Catalyseur de polymerisation de polyester, polyester et procede de fabrication de celui-ci
CN101029126A (zh) * 2001-02-23 2007-09-05 东洋纺织株式会社 聚酯聚合催化剂、利用其制得的聚酯和聚酯的制造方法
JP2003212982A (ja) * 2002-01-24 2003-07-30 Toyobo Co Ltd ポリエステルの製造方法
JP2009503177A (ja) * 2005-07-25 2009-01-29 テルガル フィブレ 重縮合によってポリエステルを製造するための触媒系及びポリエステルの製造方法
JP2012076457A (ja) * 2010-09-08 2012-04-19 Toyobo Co Ltd ブロー成形による中空容器の成形方法
WO2017183550A1 (fr) * 2016-04-20 2017-10-26 東洋紡株式会社 Résine à base de poly(téréphtalate de butylène)
WO2021125137A1 (fr) * 2019-12-18 2021-06-24 東洋紡株式会社 Résine polyester, et procédé de fabrication de celle-ci

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