WO2022054669A1 - ポリエステル樹脂組成物の製造方法 - Google Patents

ポリエステル樹脂組成物の製造方法 Download PDF

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WO2022054669A1
WO2022054669A1 PCT/JP2021/032138 JP2021032138W WO2022054669A1 WO 2022054669 A1 WO2022054669 A1 WO 2022054669A1 JP 2021032138 W JP2021032138 W JP 2021032138W WO 2022054669 A1 WO2022054669 A1 WO 2022054669A1
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polyester resin
aluminum
phosphorus
resin composition
solution
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PCT/JP2021/032138
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English (en)
French (fr)
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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Priority to JP2022506778A priority Critical patent/JPWO2022054669A1/ja
Priority to CN202180062031.8A priority patent/CN116075543A/zh
Publication of WO2022054669A1 publication Critical patent/WO2022054669A1/ja

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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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • 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 method for producing a polyester resin composition.
  • Polyester resins typified by polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc. are excellent in mechanical properties and chemical properties, depending on the properties of each polyester 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.
  • metal antimony precipitates during polymerization, which causes darkening and foreign matter on the polyester resin, which may cause surface defects of the film.
  • 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 or containing no antimony compound as a catalyst 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 or 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.
  • Patent Documents 1 and 2 disclose a catalyst composed of an aluminum compound and a phosphorus compound as a novel polymerization catalyst.
  • Patent Documents 1 and 2 since the amount of catalyst added is large and the cost of the phosphorus compound used is also high, there is a problem that the catalyst cost required for polymerization is high and the polymerization activity is low.
  • a polyester film is manufactured using a polyester resin
  • the film has slipperiness, running property and abrasion resistance. , It is necessary to improve handling characteristics such as take-up performance.
  • Patent Document 3 describes a film containing a polyester resin containing no inorganic particles and a polyester composition for a masterbatch containing inorganic particles and produced by a catalyst composed of an aluminum compound and a phosphorus compound. Polyester compositions for use are disclosed. Also in this technique, there is a problem that the catalyst cost required for polymerization is high because the amount of the catalyst added, particularly the amount of the phosphorus compound added is large, and the cost of the phosphorus compound used is also high.
  • the present invention has been made to solve the problems of the prior art, and an object thereof is to use a base polyester resin as an aluminum compound and phosphorus in a method for producing a polyester resin composition using a base polyester resin.
  • a polymerization catalyst composed of a compound is used, the polyester resin has a high polymerization activity, a low catalyst cost, and a small amount of foreign matter.
  • the present inventors have made it possible to reduce the amount of aluminum element contained in the base polyester resin and to keep the molar ratio of phosphorus element to aluminum element in an appropriate range.
  • a polymerization catalyst such as an antimony compound or a germanium compound
  • 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 base polyester resin and keeping the molar ratio of phosphorus element to aluminum element in an appropriate range, the increase in the amount of aluminum-based foreign matter is suppressed while suppressing the catalyst cost. While doing so, they have found that the polymerization activity can be improved, and have completed the present invention.
  • the present invention has the following configuration.
  • [1] Having a step of mixing a base polyester resin (A) containing an aluminum compound and a phosphorus compound and satisfying the following (1) to (3) and a master batch (B) containing an antiblocking agent.
  • a method for producing a polyester resin composition (1) The content of aluminum element in the base polyester resin (A) is 9 to 19 mass ppm. (2) The content of phosphorus element in the base polyester resin (A) is 13 to 31 mass ppm. (3) The molar ratio of the phosphorus element to the aluminum element in the base polyester resin (A) is 1.32 or more and 1.80 or less [2]
  • the master batch (B) is insoluble in the base polyester resin (A).
  • a method for producing a polyester resin composition [3] The method for producing a polyester resin composition according to the above [1] or [2], wherein a masterbatch (C) containing an electrostatic adhesion imparting agent is further mixed.
  • the master batch (C) is a polyester resin containing a magnesium compound, an alkali metal compound and a phosphorus compound, and 400 to 2700 mass ppm of magnesium element and an alkali metal element are contained in the master batch (C).
  • the masterbatch (D) containing the antiblocking agent and the electrostatic adhesion imparting agent is mixed with the base polyester resin (A) in the above [1] or [2].
  • the master batch (D) contains insoluble particles which are insoluble particles in the base polyester resin (A), and the insoluble particles have a volume average particle diameter of 0.5 to 3.0 ⁇ m and are insoluble.
  • the particle content is 0.5 to 20% by mass
  • the master batch (D) contains 400 to 2700% by mass of magnesium element, 40 to 270% by mass of alkali metal element, and 200 to 200% by mass of phosphorus element.
  • the phosphorus compound contained in the master batch (C) or the master batch (D) is a phosphoric acid trialkyl ester, and at least one of the alkyl groups of the phosphoric acid trialkyl ester is an alkyl having 2 to 4 carbon atoms.
  • the master batch (C) or the master batch (D) is a polyester containing a dicarboxylic acid component and a glycol component, and the amount of the magnesium element with respect to the dicarboxylic acid component is m (mol%).
  • Method. The method for producing a polyester resin composition according to any one of the above [1] to [13], wherein the intrinsic viscosity (IV) of the base polyester resin (A) is 0.56 dl / g or more.
  • the method for producing the base polyester resin (A) includes a first step of synthesizing a polyester which is a polycondensate or an oligomer thereof as an intermediate, and a second step of further polycondensing the intermediate.
  • 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, and the amount of the solution A1 and the solution B1 added.
  • the amount of the aluminum element added to the produced base polyester resin (A) is 9 to 19 mass ppm.
  • the amount of the phosphorus element added to the produced base polyester resin (A) is 18 to 38 mass ppm.
  • the base polyester resin (A) is a batch type weight.
  • the base polyester resin (A) is produced by a continuous polymerization method, and the solution A1 and the solution B1 are transferred to a final esterification reaction tank or a final esterification reaction tank and the first polymerization reaction tank.
  • the polyester resin composition produced by the production method of the present invention uses a polymerization catalyst composed of an aluminum compound and a phosphorus compound, the catalyst cost is kept low and the foreign substance derived from the catalyst contained in the polyester resin is contained in the polyester resin.
  • the base polyester resin having a reduced amount of the above the cost required for producing the polyester resin composition can be reduced, and the quality of the polyester resin composition can be improved.
  • the polyester resin composition obtained by the production method 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 can be reduced. The quality of the polyester film 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 method for producing a polyester resin composition of the present invention includes a step of mixing a base polyester resin (A) and a master batch (B) containing an anti-blocking agent.
  • the base polyester resin (A) is simply referred to as "polyester resin (A)” below, and the master batch (B) containing the anti-blocking agent is referred to as "anti-blocking agent-containing master batch (B)” or "master batch (master batch). B) ”may be described.
  • polyester resin (A) contains an aluminum compound and a phosphorus compound. Further, the polyester resin (A) satisfies the following (1) to (3). (1) The content of aluminum element in the polyester resin (A) is 9 to 19 mass ppm. (2) The content of phosphorus element in the polyester resin (A) is 13 to 31 mass ppm. (3) The molar ratio of the phosphorus element to the aluminum element in the polyester resin (A) is 1.32 or more and 1.80 or less. In the present specification, mass ppm means 10-4 % by mass.
  • the polyester resin (A) contains 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. Further, it is preferable that the main polyhydric alcohol component is glycol.
  • the polyester resin (A) 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, more preferably 80 mol. % Or more of the polyester resin, more preferably 90 mol% or more of the polyester resin.
  • 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.
  • 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 (A) is a weight composed of only one monomer selected from ethylene terephthalate, butylene terephthalate, propylene terephthalate, 1,4-cyclohexanedimethylene terephthalate, ethylene naphthalate, butylene naphthalate, or propylene naphthalate. It is preferable that the polymer is a combination or a copolymer composed of two or more kinds of the above-mentioned monomers, and the polyester resin (A) is a polyethylene terephthalate or a copolymer composed of at least one kind of the above-mentioned monomers other than ethylene terephthalate and ethylene terephthalate.
  • polyethylene terephthalate is particularly preferable.
  • 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 (A) contains a catalyst amount of an aluminum compound-derived component and a phosphorus compound-derived component. That is, the polyester resin (A) 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 elemental aluminum in the polyester resin (A) 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 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 as a catalyst. It is more preferable because the effect of improving the 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 (A) is 13 to 31 mass ppm, preferably 15 to 29 mass 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 phosphorus element to aluminum element hereinafter referred to as "residual molar ratio of phosphorus element to aluminum element” to distinguish it from “additional molar ratio of phosphorus element to aluminum element” described later.
  • Control 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 (A) are derived from the aluminum compound and the phosphorus compound used as the polymerization catalyst of the polyester resin (A), respectively.
  • polycondensation catalysts such as antimony compound, germanium compound and titanium compound can be used for the characteristics, processability and color tone of the polyester resin composition obtained by the production method of the present invention. It may be used in combination as long as it does not cause any problem to the product.
  • 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 (A) is preferably 0.56 dl / g or more, more preferably 0.56 to 0.65 dl / g, and even more preferably 0.58 to 0. It is 64 dl / g. If the intrinsic viscosity of the polyester resin (A) 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 (A) exceeds the above range, the economic efficiency is lowered, which is not preferable.
  • polyester resin (A) As a method for producing the polyester resin (A), it is known except that a polyester polymerization catalyst composed of an aluminum compound and a phosphorus compound is used as a catalyst, and a polymerization catalyst is added so as to satisfy the following (5) to (7). It can be carried out by a method including the above steps. (5) The amount of the aluminum element added to the produced polyester resin (A) is 9 to 19 mass ppm. (6) The amount of the phosphorus element added to the produced polyester resin (A) is 18 to 38 mass ppm. (7) 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
  • 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 are performed. 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 above (5) to (7). It is preferable to add to.
  • the polyvalent carboxylic acid and its ester-forming derivative used for producing the polyester resin (A), the hydroxycarboxylic acid which may be added in a small amount and the ester-forming derivative thereof, and the cyclic ester which may be added in a small amount are being polymerized. Since almost 100% of the amount used initially added to the system as a catalyst remains in the polyester resin (A) produced by polymerization without distilling out of the reaction system, it is "generated” from these charged amounts. The mass of the polyester resin (A) to be obtained can be calculated.
  • 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 the polyester resin (A) uses a polyester polymerization catalyst composed of an aluminum compound and a phosphorus compound as a catalyst, and the content of the aluminum element in the polyester resin (A), the content of the phosphorus element, and phosphorus with respect to the aluminum element. Except for adjusting the molar ratio of the elements 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 in order to increase the ultimate viscosity.
  • the polymerization may be a batch type polymerization method or a continuous polymerization method.
  • the amount (mass) of the polyester resin (A) 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 (A) is produced by an esterification reaction or an ester exchange reaction in multiple steps and 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 mixed 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 (A) 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 is the stage immediately before the final stage
  • 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 the ultimate 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 further a solution dissolved in water and / or glycol. Most preferably, a solution dissolved in ethylene glycol is used.
  • the solution A1 in which the aluminum compound is dissolved and the solution B1 in which the phosphorus compound is dissolved are contained in the polyester resin (A) as the content (residual amount) of the aluminum element and the phosphorus element. Is preferably added so as to satisfy the above (1) to (3).
  • a solution A1 in which an aluminum compound is dissolved and a solution B1 in which a phosphorus compound is dissolved are added so that the content (residual amount) of the aluminum element and the phosphorus element in the polyester resin (A) 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 phosphorus compound that functions as a catalyst together with the aluminum compound is a part (about 10 to 40%) of the amount initially added to the system as a catalyst when the polyester resin (A) is placed in a reduced pressure environment during polymerization. Is removed from the system, but 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 aluminum-containing solution or phosphorus-containing solution. It varies depending on the addition method (whether it is added in one 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 (A) as 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 (A) is composed of 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, the aluminum compound is dissolved.
  • the prepared solution A1 is preferably a glycol solution in which an aluminum compound is dissolved (hereinafter, referred to as an aluminum-containing glycol solution A1), and the solution B1 in which a phosphorus compound is dissolved is a glycol solution in which a phosphorus compound is dissolved (hereinafter, phosphorus).
  • the contained glycol solution (referred to as 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 component of the polyester resin (A).
  • 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 polyester resin (A) preferably has an aluminum element content corresponding to an aluminum-based foreign substance in the polyester resin (A) of 3000 mass ppm or less, more preferably 2800 mass 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 (A). If the content of the aluminum-based foreign matter exceeds the above, fine foreign matter insoluble in the polyester resin (A) 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 is for relatively evaluating the amount of aluminum-based foreign matter, and is a polyester resin.
  • (A) does not indicate the absolute value of the amount of aluminum-based foreign matter contained in (A).
  • the type of polyester resin constituting the masterbatch (B) is not limited, but it is preferably the same polyester resin as the base polyester resin (A).
  • the volume average particle size of the antiblocking agent contained in the masterbatch (B) is preferably 0.5 to 3.0 ⁇ m, more preferably 0.8 to 2.5 ⁇ m, and even more preferably 2.0 to 2.0. It is 2.5 ⁇ m. If the volume average particle size of the anti-blocking agent is less than 0.5 ⁇ m, the effect of imparting handleability such as slipperiness and runnability to the film may be reduced. On the other hand, if the volume average particle size of the antiblocking agent 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 anti-blocking agent 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 content of the antiblocking agent in the masterbatch (B) is preferably in the range of 0.5 to 20% by mass, more preferably in the range of 0.6 to 15% by mass. If it is less than 0.5% by mass, it is necessary to increase the blending amount of the masterbatch (B), which is economically disadvantageous. On the contrary, if it exceeds 20% by mass, the anti-blocking agent aggregates and coarse particles increase, and the filter for clarifying the polymer is clogged in the film forming process, or the surface defect when the film is formed is a defect. There is a risk of problems such as increase.
  • the masterbatch (B) preferably contains insoluble particles which are insoluble particles in the polyester resin (A). That is, it is preferable that the antiblocking agent contains insoluble particles which are insoluble particles in the polyester resin (A).
  • the volume average particle diameter of the insoluble particles is 0.5 to 3.0 ⁇ m, and the content of the insoluble particles is more preferably 0.5 to 20% by mass.
  • the insoluble particles used in the present invention are not particularly limited as long as they are insoluble in the polyester resin (A), 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 type of the organic particles is not particularly limited, and examples thereof include silicone type, crosslinked polyacrylic acid type, and benzoguanamine resin type.
  • the insoluble particles are silica particles because a highly transparent polyester film can be obtained.
  • the method for producing the masterbatch (B) is not particularly limited, and may be, for example, a polymerization step addition method in which a slurry of an antiblocking agent is added in the polyester resin polymerization step, or in a state where the polyester resin is melted.
  • a so-called melt-kneading method in which an anti-blocking agent is mixed may be used.
  • the timing of adding the anti-blocking agent slurry in the polymerization step addition method is not limited. 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 the initial polymerization. It may be added directly to the reaction tank, or it may be added to the transfer line between each reaction tank with a mixer or the like. Moreover, you may add by installing an addition tank.
  • a medium stirring type disperser such as a sand grinder, attritor, ultrasonic wave, and addition of an alkali metal compound, an ammonium compound, and a phosphorus compound. It is more preferable to add the mixture after improving the dispersion efficiency.
  • the amount of the antiblocking agent added in the above polymerization step addition method is preferably 0.5 to 2.0% by mass, more preferably 0.6 to 1.8% by mass. If it is less than 0.5% by mass, the production of coarse particles due to the aggregation of the antiblocking agent after the blend dilution may increase. On the other hand, if it exceeds 2.0% by mass, the effect of preventing coarse particles is not sufficient, and foreign matter may be generated when the film is formed.
  • the method of the melt-kneading method is also not limited.
  • a single-screw or multi-screw kneader may be used, or a kneader may be used.
  • the amount of the anti-blocking agent added in the above melt-kneading method is preferably 2.0 to 20% by mass, preferably 3.0 to 15% by mass, based on the polyester resin used in the masterbatch (B). Is more preferable. If the amount of the anti-blocking agent added is less than 2.0% by mass or more than 20% by mass, the dispersibility of the anti-blocking agent with respect to the polyester resin is inferior, and coarse particles which are aggregates of the anti-blocking agent may increase. ..
  • the above melt-kneading method may be carried out by melting the polyester resin, or may be carried out by attaching a kneading device to the outlet of the polyester resin polymerization step.
  • the polymerization catalyst of the polyester resin used in the masterbatch (B) is not limited, but it is preferably the same as the catalyst used in the production of the polyester resin (A). That is, the polyester resin used in the masterbatch (B) is preferably produced by using a polymerization catalyst composed of an aluminum compound and a phosphorus compound.
  • Masterbatch containing electrostatic adhesion imparting agent (C) When a polyester resin composition containing a masterbatch (C) containing an electrostatic adhesion imparting agent (hereinafter, may be referred to as "masterbatch (C)") is formed into a film, a sheet-like product is obtained in the electrostatic adhesion casting method. Since the electrostatic adhesion to the cooling drum can be improved, effects such as improvement of film productivity and reduction of film thickness unevenness can be exhibited. This can improve the productivity and quality of the polyester film.
  • the type of polyester resin constituting the masterbatch (C) is not limited, but it is preferably the same polyester resin as the polyester resin (A).
  • the melting specific resistance of the masterbatch (C) is preferably 0.005 ⁇ 10 8 to 0.05 ⁇ 10 8 ⁇ ⁇ cm, preferably 0.005 ⁇ 10 8 to 0.025 ⁇ 10 8 ⁇ ⁇ cm. It is more preferable to have.
  • the melt resistivity of the masterbatch is higher than 0.05 ⁇ 108 ⁇ ⁇ cm, it is necessary to add a large amount of the masterbatch (C) in order to improve the film forming property of the polyester resin composition. Problems such as increased manufacturing costs arise. It is technically difficult to make the melt resistivity of the masterbatch (C) less than 0.005 ⁇ 10 8 ⁇ ⁇ cm.
  • the melt specific resistance of the polyester film formed from the polyester resin composition containing the masterbatch (C) 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 melt resistivity can be measured by the method described in the section of Examples described later.
  • a magnesium compound or an alkali metal compound is added to the master batch (C) 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 master batch (C) preferably contains 400 to 2700 mass ppm of magnesium element, 40 to 270 mass ppm of alkali metal element, and 200 to 1700 mass ppm of phosphorus element.
  • 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.
  • the masterbatch (C) preferably contains 400 to 2700 mass ppm of magnesium element.
  • 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 (C) in order to improve the film forming property of the polyester resin composition, and as a masterbatch. There is a risk that problems such as increased manufacturing costs will occur due to its low efficacy.
  • the amount of the magnesium element exceeds 2700 mass ppm, the amount of insoluble foreign matter (magnesium salt) produced increases, the heat resistance is lowered, and the coloring of the film may be severe.
  • the amount of the magnesium element is more preferably 450 to 2500 mass ppm, further preferably 450 to 2000 mass ppm.
  • Examples of the alkali metal of the alkali metal compound included in the master batch (C) 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 masterbatch (C) preferably contains 40 to 270 mass ppm of alkali metal element.
  • 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 (C) in order to improve the film-forming property of the polyester resin composition.
  • the efficacy of (C) is low, and problems such as an increase in manufacturing cost may occur.
  • 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 45 to 250 mass ppm, further preferably 45 to 200 mass ppm.
  • Examples of the phosphorus compound to be included in the master batch (C) 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 (C) having a low melt resistivity, a small amount of foreign matter, and an excellent color tone can be obtained.
  • the masterbatch (C) preferably contains 200 to 1700 mass ppm of phosphorus element.
  • the amount of phosphorus element is less than 200 mass ppm, the effect of stabilizing magnesium ion and alkali metal ion and dispersing them in the polyester resin composition is reduced, so that the amount of insoluble magnesium-based foreign matter may be increased. be. 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 220 to 1000 mass ppm.
  • the content of magnesium element, alkali metal element, and phosphorus element in the masterbatch (C) can be quantified by the method described in the following Examples.
  • the timing of adding the magnesium compound, alkali metal compound, and phosphorus compound to the polyester resin used in the master batch (C) is not particularly limited, but during polyester polymerization, especially during the esterification (or transesterification) step, or By adding it between the time when the esterification (or transesterification) process is completed and the time when the polycondensation process is started, it is possible to prevent the acid component of polyester and magnesium ions and alkali metal ions from forming salts and becoming foreign substances. It is preferable because it can be formed and can be uniformly dispersed in the oligomer.
  • the polyester resin used in the master batch (C) is a polyester resin containing a dicarboxylic acid component and a glycol component as constituent components
  • the amount of magnesium element with respect to the dicarboxylic acid component is m mol%
  • the amount of alkali metal element is k mol. %
  • the effect of the present invention can be obtained by satisfying the following formula (4). (4) 2 ⁇ (m + k / 2) / p ⁇ 3.5 It is considered that the phosphorus atom stabilizes the magnesium ion and the alkali metal ion without making them foreign substances.
  • 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 3.5, the amount of phosphorus element is relatively small with respect to the magnesium element and the alkali metal element, the magnesium ion and the alkali metal ion are stabilized, and the polyester resin composition is formed.
  • (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. That is, the effect of lowering the melt resistivity and the color tone are antinomy events. Therefore, by satisfying the equation (4), it is possible to achieve both the effect of lowering the melt resistivity and the color tone.
  • the polymerization catalyst of the polyester resin used in the masterbatch (C) is not limited, but it is preferably the same as the catalyst used in the production of the polyester resin (A). Since the compound used as the electrostatic adhesion imparting agent also acts as a co-catalyst, it is not necessary to use the phosphorus compound among the catalysts used in the production of the polyester resin (A), that is, even only the aluminum compound. good.
  • the anti-blocking agent / electrostatic adhesion imparting agent composite masterbatch (D) (hereinafter referred to as “composite masterbatch (D)” or “masterbatch (D)”) in the present invention is the anti-blocking agent masterbatch (hereinafter referred to as “masterbatch (D)”). It has the respective compositions and characteristics of B) and the electrostatic adhesion imparting agent masterbatch (C). Therefore, instead of the masterbatch (B), the masterbatch (D) can be mixed with the base polyester resin (A).
  • the polyester resin composition in which the composite masterbatch (D) and the polyester resin (A) are blended is used.
  • the polyester resin composition in which the polyester resin (A), the masterbatch (B) and the masterbatch (C) are blended is used.
  • the electrostatic adhesion can be improved, and thereby the productivity of the polyester film can be improved.
  • surface protrusions on the surface of the obtained polyester film with an anti-blocking agent handling characteristics such as slipperiness, running property, abrasion resistance and winding property of the film can be improved.
  • the composite masterbatch (D) contains insoluble particles which are insoluble particles in the polyester resin (A), the volume average particle diameter of the insoluble particles is 0.5 to 3.0 ⁇ m, and the content of the insoluble particles is high. It is preferably 0.5 to 20% by mass. Further, the composite master batch (D) preferably contains 400 to 2700 mass ppm of magnesium element, 40 to 270 mass ppm of alkali metal element, and 200 to 1700 mass ppm of phosphorus element.
  • the volume average particle size and content of the antiblocking agent contained in the composite masterbatch (D) are preferably in the same range as the volume average particle size and content of the antiblocking agent in the masterbatch (B).
  • the reason is the same as the reason described in the item of masterbatch (B).
  • the content of magnesium element, alkali metal element, and phosphorus element in the composite master batch (D) is preferably in the same range as the content of magnesium element, alkali metal element, and phosphorus element in the master batch (C).
  • the reason is the same as the reason described in the item of master batch (C).
  • the content of magnesium element, alkali metal element, and phosphorus element in the composite masterbatch (D) is quantified by the method described in the following Examples, similarly to the content of the above elements in the masterbatch (C). It is possible.
  • the timing of adding the magnesium compound, the alkali metal compound, and the phosphorus compound to the polyester resin used in the composite master batch (D) is not particularly limited, but during the polymerization of the polyester, especially in the middle of the esterification (or transesterification) step. Alternatively, by adding it between the time when the esterification (or transesterification) process is completed and the time when the polycondensation process is started, the acid component of polyester and magnesium ions or alkali metal ions form salts and become foreign substances.
  • the polyester resin used in the composite master batch (D) is a polyester resin containing a dicarboxylic acid component and a glycol component
  • the amount of magnesium atoms with respect to the dicarboxylic acid component is m (mol%), and the amount of alkali metal atoms.
  • k (mol%) and the amount of phosphorus atom are p (mol%)
  • the molar ratio of magnesium atom, alkali metal atom and phosphorus atom satisfies the above-mentioned formula (4), so that the effect of the present invention can be obtained. can get.
  • the reason is the same as the reason described in the item of masterbatch (C).
  • the polymerization catalyst of the polyester resin used in the composite masterbatch (D) is not limited, but it is preferably the same as the catalyst used in the production of the polyester resin (A). Since the compound used as the electrostatic adhesion imparting agent also acts as a co-catalyst, it is not necessary to use the phosphorus compound among the catalysts used in the production of the polyester resin (A), that is, even only the aluminum compound. good.
  • the manufacturing method of the composite masterbatch (D) is not particularly limited.
  • a slurry solution of an antiblocking agent and the components constituting the above-mentioned masterbatch (C) may be added, and the masterbatch (B) and the masterbatch (B) may be added.
  • the batch (C) and the batch (C) may be melt-kneaded for production.
  • an antiblocking agent and an electrostatic adhesion imparting agent may be added in the manufacturing process of the polyester resin used in the composite masterbatch (D).
  • the polyester resin composition used in 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.
  • a diethylene glycol inhibitor In the polyester resin composition used in the present invention, depending on the purpose of use, a diethylene glycol inhibitor, a fluorescent whitening agent, a color tone adjusting agent such as a dye or a pigment, an ultraviolet inhibitor, an infrared absorbing dye, a heat stabilizer, and a surface activity.
  • various additives such as agents and antioxidants can be contained in one or more of the polyester resin (A) and the master batches (B) to (D).
  • a basic compound such as an alkylamine compound or an ammonium salt compound can be used, and as an antioxidant, an antioxidant such as an aromatic amine type or a phenol type can be used, and as a stabilizer.
  • stabilizers such as sulfur-based and amine-based stabilizers.
  • These additives can be added to the polyester resin composition in a proportion of preferably 10% by mass or less, more preferably 5% by mass or less.
  • a polyester film can be obtained by forming a film of the polyester resin composition obtained by the production method of the present invention.
  • the polyester film may have a single-layer structure or a multi-layer structure having two or more layers.
  • the single-layer structure polyester film is preferably formed by forming a polyester resin composition containing the polyester resin (A) and the masterbatch (B). More preferably, the polyester resin (A) has a content of insoluble particles in the film of 500 to 2000 mass ppm and a melt ratio resistance of the film of 0.15 to 0.6 ⁇ 108 ⁇ ⁇ cm. ), A single-layer polyester film formed by forming a film of a polyester resin composition containing the master batch (B) and the master batch (C), or a polyester resin (A) and a composite master batch (D). It is a single-layer polyester film formed by forming a film of the blended polyester resin composition. The content of the insoluble particles in the single-layer polyester film is more preferably 600 to 1800 mass ppm. Further, the melt resistivity of the single-layer polyester film is more preferably 0.15 to 0.4 ⁇ 108 ⁇ ⁇ cm.
  • the composition of each layer may be changed so as to have the above-mentioned characteristics, or all the layers may be layers having the same composition.
  • an antiblocking agent is blended in at least one (preferably both) of the polyester composition forming the surface layer A and the surface layer B, and the intermediate layer is formed. It is preferable not to blend it in the polyester composition forming the above. If the anti-blocking agent is present on the surface layer of the polyester film, it forms surface protrusions on the surface of the polyester film, and as a result, improves handling properties such as slipperiness, running property, wear resistance, and take-up property of the film.
  • a master batch (C) containing an electrostatic adhesion imparting agent or a composite master batch (D) in all layers from the viewpoint of improving electrostatic adhesion.
  • the number of layers and the thickness ratio in the case of the multi-layer structure are not limited, but the three-layer structure and the thickness ratio of the surface layer / intermediate layer / surface layer are 0.05 / 0.9 / 0.05 to 0.2 / 0. It is preferably .6 / 0.2.
  • the recovered polyester resin recovered from the film manufacturing scraps such as cut parts and poor quality parts at both ends of the film generated in the film manufacturing process
  • it is generated in the process of manufacturing the film in the intermediate layer in the above three-layer structure film.
  • the polyester resin (A) and the masterbatch (B) are blended so that the content of insoluble particles in the surface layer of one side (preferably both sides) is 500 to 2000 mass ppm. It is preferable to melt-extrude the polyester resin composition to form a film. The content of the insoluble particles in the surface layer is more preferably 600 to 1800 mass ppm.
  • the composite masterbatch (D) may be used instead of the masterbatch (B). By using the composite masterbatch (D), the transparency of the polyester film can be improved and the economy can be improved.
  • the melt resistivity of the film satisfies 0.15 to 0.6 ⁇ 108 ⁇ ⁇ cm. It is preferable to add the masterbatch (C) to the polyester resin composition forming any layer so that the melt resistivity of the film is within the above range.
  • the composite masterbatch (D) may be used instead of the masterbatch (C).
  • the melt resistivity of the film is more preferably 0.15 to 0.4 ⁇ 10 8 ⁇ ⁇ cm.
  • 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 (A) Content of phosphorus element in polyester resin (A)
  • the polyester resin (A) 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 concentration of the phosphorus element in the polyester resin (A) 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 (A) and 250 mL of p-chlorophenol / tetrachloroethane (3/1: mass ratio) mixed solution are put into a 500 mL Erlenmeyer flask containing a stirrer, and a hot stirrer is used. Then, it was heated and dissolved at 100 to 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.
  • Co-b Color tone (Co-b) Using a colorimeter (ZE-6000 manufactured by Nippon Denshoku Kogyo Co., Ltd.), Co-b was measured from the tristimulatory value XYZ expressing the basic amount of color stimulation. The higher the Co-b value, the stronger the yellowness.
  • the central part of the sample thickness was observed using a phase-contrast microscope (manufactured by Nikon Corporation, OPTIPHOT) and an objective lens (manufactured by Nikon Corporation, magnification 10 times, aperture 0.5).
  • the image was taken into an image analysis device (LUZEX AP, manufactured by Nireco Co., Ltd.) via a CCD camera, and image analysis was performed to measure the number of particles having a particle size of 10 ⁇ m or more. The same measurement was performed 20 times while changing the field of view, the total number of particles was obtained, and the number of particles having a particle size of 10 ⁇ m or more per 1 mm 2 of the field of view was calculated and used as the number of coarse particles. Also, in the composite masterbatch (D), the number of coarse particles was determined by the above method in the same manner as in the masterbatch (B).
  • melt resistivity was similarly determined for the film-making compositions, master batches (C), and composite master batches (D) of Examples 12 to 14 and Comparative Example 11.
  • ⁇ i ( ⁇ ⁇ cm) (A / L) ⁇ (V / io) [A: Electrode area (cm 2 ), L: Distance between electrodes (cm), V: Voltage (V), io: Current (A)]
  • L is a value measured without including the diameter of the electrode, and is 1.3 cm.
  • Electrostatic Adhesion of Film-making Composition Using the film-making compositions of Examples 11 to 14 and Comparative Example 11, an electrode made of tungsten wire is provided between the base of the extruder and the cooling drum. Casting was performed by applying a voltage of 10 to 15 KV between the electrode and the casting drum, and the surface of the obtained casting film was visually observed and evaluated at the casting speed at which 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 6, and the phosphorus-containing ethylene glycol solution b1 was used in all Examples and Comparative Examples other than Comparative Example 6.
  • polyester resin (A) [Example of batch polymerization method] (Example 1) A 10 L stainless steel autoclave equipped with a stirrer is charged with a polyester oligomer having a pre-prepared high-purity terephthalic acid and ethylene glycol having an esterification rate of about 95% and high-purity terephthalic acid, and an esterification reaction is carried out at 260 ° C. , An oligomer mixture was obtained. The obtained oligomer mixture had an acid end group concentration of 750 eq / ton and a hydroxide end group 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.
  • 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 (A) produced can be calculated from the amount of terephthalic acid to be added. In this example, 10 mass ppm and 20 as aluminum element and phosphorus element with respect to the produced polyester resin.
  • the mixed solution is added so as to have a mass of ppm. 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 (A) was obtained.
  • Examples 2 to 5, Comparative Examples 1 to 5 The same method as in Example 1 except that the aluminum-containing ethylene glycol solution a1 and the phosphorus-containing ethylene glycol solution b1 were added to the obtained polyester resin (A) so as to have the amount of the catalyst element added as shown in Table 1. A polyester resin (A) was obtained.
  • Table 1 shows the physical characteristics of the polyester resin (A) obtained in Examples 1 to 5 and Comparative Examples 1 to 6.
  • 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 polymerization time is short and the amount of aluminum-based foreign matter is small even though the addition amounts of the aluminum element and the phosphorus element are small, so that the back pressure increase coefficient is small and high. Quality. 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 low.
  • 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 (A) increases and the back pressure increase coefficient is large, and the quality of the polyester resin (A) is large. Is inferior.
  • Comparative Example 6 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 is low. Further, since the amount of aluminum-based foreign matter in the polyester resin (A) increases and the coefficient of increase in back pressure increases, the quality of the polyester resin (A) is inferior.
  • 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 and liquefied, and the mixed solution is transferred from the third esterification tank to the first polycondensation reactor.
  • the aluminum-containing ethylene glycol solution a1 and the phosphorus-containing ethylene glycol solution b1 prepared by the above method were added to the obtained oligomers as 13 mass ppm and 36 mass ppm as aluminum element and phosphorus element, respectively.
  • the mixture was mixed so as to be, and a liquefied solution was added.
  • the amount of the polyester resin (A) produced can be calculated from the amount of terephthalic acid to be added, and in this example, 13 parts by mass of the aluminum element and the phosphorus element with respect to the produced polyester resin (A).
  • the mixed solution is added so as to be ppm and 36 mass ppm.
  • the above oligomer containing the mixed solution 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 polycondensation reactor was of the second.
  • Polycondensation was performed at a reaction temperature of 270 ° C., a pressure of 0.930 kPa, a reaction temperature of a third polycondensation reactor of 274 ° C., and a pressure of 0.162 kPa to obtain a polyester resin (A) having an IV of 0.59 dl / g.
  • the polyester resin (A) was extruded into a strand shape, cooled in water, cut, and pelletized.
  • Example 7 and 8 Comparative Examples 7 and 8
  • An aluminum-containing ethylene glycol solution a1 and a phosphorus-containing ethylene glycol solution b1 were added to the obtained oligomer in the same manner as in Example 6 except that the amount of the catalyst element added was as shown in Table 2. A) was obtained.
  • Table 2 shows the physical characteristics of the polyester resin (A) obtained in Examples 6 to 8 and Comparative Examples 7 and 8.
  • the production amount ratio shown in Table 2 is based on the production amount per hour of Comparative Example 7 (with the production amount per hour of Comparative Example 7 being 1.00), Examples 6 to 8 and Comparative Example.
  • the production amount per hour of 8 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.
  • the polyester resins (A) of Examples 6 to 8 have a higher production amount ratio than Comparative Examples 7 and 8, and the polymerization activity is improved even though the addition amounts of the aluminum element and the phosphorus element are small.
  • FIG. . shows the relationship between the maximum absorption wavelength of the mixed solution of the aluminum-containing ethylene glycol solution a1 and the phosphorus-containing ethylene glycol solution b1, the amount of aluminum-based foreign matter, and the polymerization time.
  • FIG. 3 shows the relationship between the maximum absorption wavelength of the mixed solution of the aluminum-containing ethylene glycol solution a1 and the phosphorus-containing ethylene glycol solution b1 and the back pressure increase coefficient k.
  • Comparative Example 3 the values of Comparative Example 3 are excluded. The reason is that in 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.
  • polyester resin (A) obtained in Examples 1 and 6 is also used below, the polyester resin (A) obtained in Example 1 can be obtained in the polyester resin (A-1) and Example 6.
  • the polyester resin (A) is called a polyester resin (A-2).
  • Example of melt kneading method (Manufacturing Example 1-2) After blending the polyester resin (A-2) and silica particles having a volume average particle diameter of 2.4 ⁇ m (manufactured by Fuji Silysia Chemical Ltd., Silicia 310) as an anti-blocking agent at a ratio of 90 parts by mass and 10 parts by mass, respectively, two.
  • a master batch (B-2) containing silica was obtained by melt-kneading at a cylinder temperature of 300 ° C. using a shaft extruder (manufactured by Japan Steel Works, TEX30 ⁇ ).
  • the obtained silica-containing masterbatch (B-2) had 120 coarse particles, and the silica-containing masterbatch (B-2) had a small number of coarse particles and was of high quality.
  • the adhesion to the metal roll was improved by an electrostatic adhesion device composed of saw-shaped electrodes.
  • this cast film was heated to 100 ° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a peripheral speed difference to obtain a uniaxially oriented film.
  • 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 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 (A-2) was used instead of the polyester resin (A-1).
  • 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 9 A biaxially oriented polyester film was prepared in the same manner as in Example 9 except that the silica-containing masterbatch (B-2) was not mixed and only the polyester resin (A-1) was vacuum dried.
  • 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 10 A biaxially oriented polyester film was prepared in the same manner as in Example 10 except that the silica-containing masterbatch (B-2) was not mixed and only the polyester resin (A-2) was vacuum dried.
  • 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.
  • a containing masterbatch (C) was obtained.
  • Table 3 shows the physical characteristics of the obtained masterbatch (C) containing an electrostatic adhesion imparting agent.
  • the electrostatic adhesion-imparting agent-containing masterbatch (C) produced in Production Example 2-1 will be referred to as an electrostatic adhesion-imparting agent-containing masterbatch (C-1), and Production Example 2-2.
  • the masterbatch containing an electrostatic adhesion-imparting agent (C) produced in the above is referred to as a masterbatch containing an electrostatic adhesion-imparting agent (C-2).
  • the electrostatic adhesion imparting agent-containing master batch (C-1) and (C-) In 2) By keeping the content of magnesium element, alkali metal element, and phosphorus element in the master batch (C) within the above-mentioned suitable range, the electrostatic adhesion imparting agent-containing master batch (C-1) and (C-) In 2), it was possible to suppress the degree of coloring (Co-b) and enhance the electrostatic adhesion (reduce the melt ratio resistance ⁇ i).
  • Example 12 A silica-containing masterbatch (B-2) was used instead of the silica-containing masterbatch (B-1), and the biaxially oriented polyester was used in the same manner as in Example 11 except that the mixing ratio was changed to the ratio shown in Table 4. A film was made.
  • Example 11 A biaxially oriented polyester film was prepared in the same manner as in Example 11 except that the silica-containing masterbatch (B-1) was not mixed and only the polyester resin (A-2) was used.
  • Table 4 shows the physical characteristics of the polyester films obtained in Examples 11 to 12 and Comparative Example 11.
  • the polyester films of Examples 11 and 12 have excellent electrostatic adhesion, and the film can be produced by increasing the film forming speed.
  • the obtained polyester films of Examples 11 and 12 have excellent slipperiness.
  • the polyester film obtained in Comparative Example 11 was inferior in both electrostatic adhesion and slipperiness, and was of low quality.
  • Example 13 Production of a polyester film having a three-layer structure (Example 13)
  • the melt extrusion method is changed to a three-layer method having three extruders, the thickness ratio of the surface layer / intermediate layer / surface layer is set to 0.11 / 0.78 / 0.11, and the polyester of the surface layer is used.
  • a biaxially oriented polyester film having a total thickness of 12 ⁇ m was produced by the same method as in Example 11.
  • the obtained polyester film had the same productivity and slipperiness as the polyester film obtained in Example 11, and was excellent in transparency by visual evaluation.
  • Table 5 shows the physical characteristics of the polyester films obtained in Examples 13 to 14.
  • the polyester resin composition obtained by the production method of the present invention has a problem of the polyester resin composition obtained by the polymerization catalyst composed of an aluminum compound and a phosphorus compound, while keeping the catalyst cost low, and the productivity of the polyester resin composition. Can be improved, and foreign substances derived from the catalyst contained in the polyester resin composition can be reduced. 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 has slipperiness. Further, the melt resistivity can be sufficiently lowered by forming a film of the polyester resin composition to which the electrostatic adhesion imparting agent is added.
  • 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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