Polyester film, method for producing same, and resin composition

Abstract

To provide a polyester film having good electrostatic adhesion, a method for producing the same, and a resin composition used in the production method. The polyester film contains 0.01-950 mass ppm of an ionic compound having an anion and a cation dissociation energy Q (kJ / mol) of 850 or less.

Description

[Technical Field]

[0001] This application claims priority based on Japanese Patent Application Nos. 2023-177741, 2024-031431, 2024-031434, 2024-055982, 2024-055985, 2024-055986, 2024-076078, 2024-094269, 2024-094270, 2024-113434, 2024-113436, and 2024-113437. The contents of these patent applications are incorporated herein by reference in their entirety.

[0002] The present invention relates to a polyester film, a method for producing the same, and a resin composition used in the production method. [Background technology]

[0003] BACKGROUND ART Polyester films, typified by polyethylene terephthalate, have been used for a variety of applications because of their excellent mechanical properties, heat resistance, electrical insulation, chemical resistance, and the like.

[0004] Polyester films are usually produced by melt-extruding a sheet from an extruder and then adhering it to the surface of a rotating cooling drum or the like to produce an unstretched film, which is then used as an unstretched film, or by further uniaxially or biaxially stretching the unstretched film to produce a stretched film.

[0005] In order to improve the uniformity of the thickness of these unstretched and stretched films and to increase the production speed, it is necessary to quickly and evenly adhere the melt-extruded sheet to the surface of a cooling drum or the like.

[0006] A widely known method for achieving adhesion is the electrostatic adhesion method, in which electrodes are provided between the extrusion die and the cooling rotating drum, a high voltage is applied to the electrodes, static electricity is deposited on the surface of the molten sheet, and the molten sheet is then adhered to the surface of the cooling rotating drum by electrostatic force.

[0007] In the electrostatic adhesion method, it is effective to increase the amount of charge on the surface of the molten sheet material, and it is known that an effective way to increase the amount of charge is to reduce the resistivity of the polyester raw material. Methods for reducing the resistivity include adding a compound of an alkali metal (Group 1) or an alkaline earth metal (Group 2).

[0008] However, these methods tend to cause the added metals to precipitate as foreign matter, which can cause defects in the film or reduce transparency. Therefore, methods have been proposed to reduce the amount of precipitated foreign matter by optimizing the amount and timing of addition of these metals (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-327053 Summary of the Invention [Problem to be solved by the invention]

[0010] In particular, in recent years, polyester films have become essential in fields requiring high precision, such as optical films, process films, and high-barrier films. There is a demand for polyesters that can be produced with high productivity using electrostatic adhesion methods, and in particular for polyester films with high clarity that have good electrostatic adhesion and few problems caused by precipitation of additives.

[0011] In view of the above circumstances, one of the objects of the present invention is to provide a polyester film having good electrostatic adhesion, particularly a polyester film that also has high clarity and can be used for various purposes.

[0012] In recent years, with an awareness of the Sustainable Development Goals (SDGs), polyester films have also become more popular, including polyesters made from biomass-derived materials, material-recycled polyesters made from recovered used polyester products such as bottles, and chemically recycled polyesters polymerized from monomers and oligomers obtained by decomposing used polyester. There is a demand for polyester films made from these raw materials that have similar resistivity and high clarity. While the resins used in polyester film often contain added electrostatic adhesives and lubricant particles, for reasons of economic efficiency and reducing the environmental impact, a method is also being adopted in which additive-free polyester is produced on a large scale, with the additives for the film being added separately.

[0013] In view of the above circumstances, one of the objects of the present invention is to provide a polyester film having good electrostatic adhesion, particularly a polyester film having high clarity and usable for various applications, a method for producing the same, and a resin composition used in the production method. [Means for solving the problem]

[0014] As a result of extensive investigations, the present inventors have found that a polyester film can be produced by blending an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 850 or less in an amount of 0.01 mass ppm or more and 950 mass ppm or less, a polyester resin composition A containing the ionic compound, and a polyester resin composition B having a melt resistivity greater than that of polyester resin composition A (or a melt resistivity of 1×10 8 The present inventors have found that the above-mentioned problems can be solved by producing a polyester film by a method comprising the steps of mixing a polyester resin composition A and a polyester resin B (having a resistivity of 0.1 Ω·cm or more) into a film, and molding a mixture containing polyester resin composition A and polyester resin B into a film. As a result of further investigation, the present inventors have completed the present invention.

[0015] The present invention encompasses the embodiments described in the following sections. [Section 1] A polyester film containing 0.01 mass ppm or more and 950 mass ppm or less of an ionic compound whose anion-cation dissociation energy Q (kJ / mol) is 850 or less. [Section 2] The melt resistivity of the resin constituting the polyester film is 20×10 8 Item 1. The polyester film according to item 1, having a resistivity of Ω·cm or less. [Section 3] The melt resistivity of the resin constituting the polyester film is 0.001×10 8 Item 3. The polyester film according to item 1 or 2, having a resistivity of Ω·cm or more. [Section 4] Item 4. The polyester film according to any one of items 1 to 3, wherein at least one of the anions and cations constituting the ionic compound has an ionic radius of 10 Å or less. [Section 5] The absolute value of the average charge density of at least one of the anions and cations constituting the ionic compound is 0.0025 e / Å 2 More than 0.075e / Å 2 5. The polyester film according to any one of items 1 to 4, wherein: [Section 6] Item 6. The polyester film according to any one of items 1 to 5, wherein the ionic compound has a cation having an ionic radius of 2 Å or more. [Section 7] The absolute value of the average charge density of the cations constituting the ionic compound is 0.015 e / Å 2 Item 7. The polyester film according to any one of items 1 to 6, wherein: [Section 8] Item 8. The polyester film according to any one of items 1 to 7, comprising the ionic compound in an amount of less than 100 ppm by mass. [Section 9] Item 9. The polyester film according to any one of items 1 to 8, wherein the resin constituting the polyester film is polyethylene terephthalate and / or polyethylene naphthalate. [Section 10] A method for producing a polyester film containing an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 850 or less, A step of mixing a polyester resin A, a polyester resin composition A containing an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 850 or less, and a polyester resin B having a melt resistivity greater than that of the polyester resin composition A; A step of molding a mixture containing a polyester resin composition A and a polyester resin B into a film; A method for producing a polyester film comprising the steps of: [Section 11] The melt resistivity of polyester resin composition A is 5 × 10 8 Item 11. The manufacturing method according to Item 10, wherein the electrical resistance is Ω·cm or less. [Section 12] A method for producing a polyester film containing an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 850 or less, A polyester resin composition A containing a polyester resin A and an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 850 or less, and a melt resistivity of 1×10 8 A step of mixing polyester resin B having a viscosity of Ω·cm or more; A step of molding a mixture containing a polyester resin composition A and a polyester resin B into a film; A method for producing a polyester film comprising the steps of: [Section 13] Item 10. A method for producing a polyester film according to any one of items 1 to 9, A step of mixing a polyester resin A, a polyester resin composition A containing an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 850 or less, and a polyester resin B having a melt resistivity greater than that of the polyester resin composition A; A step of molding a mixture containing a polyester resin composition A and a polyester resin B into a film; A method for producing a polyester film comprising the steps of: [Section 14] Item 10. A method for producing a polyester film according to any one of items 1 to 9, A polyester resin composition A containing a polyester resin A and an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 850 or less, and a melt resistivity of 1×10 8 A step of mixing polyester resin B having a viscosity of Ω·cm or more; A step of molding a mixture containing a polyester resin composition A and a polyester resin B into a film; A method for producing a polyester film comprising the steps of: [Section 15] The composition contains a polyester resin and an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 850 or less, and has a melt resistivity of 0.0001 x 10 8 Ω cm or more 0.1×10 8 A polyester resin composition having a resistivity of Ω·cm or less. [Section 16] Item 16. The polyester resin composition according to Item 15, wherein at least one of the anions and cations constituting the ionic compound has an ionic radius of 10 Å or less. [Section 17] The absolute value of the average charge density of at least one of the anions and cations constituting the ionic compound is 0.0025 e / Å 2 More than 0.075e / Å 2 Item 17. The polyester resin composition according to item 15 or 16, wherein: [Section 18] Item 18. The polyester resin composition according to any one of items 15 to 17, wherein the ionic radius of the cation constituting the ionic compound is 2 Å or more. [Section 19] The absolute value of the average charge density of the cations constituting the ionic compound is 0.015 e / Å 2 Item 19. The polyester resin composition according to any one of items 15 to 18, wherein: [Section 20] Item 13. The method according to any one of Items 10 to 12, wherein the polyester resin A and the polyester resin B are polyethylene terephthalate and / or polyethylene naphthalate. [Section 21] Item 20. The polyester resin composition according to any one of items 15 to 19, wherein the polyester resin is polyethylene terephthalate and / or polyethylene naphthalate. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a polyester film having good electrostatic adhesion, in particular a polyester film having high clarity and usable for various applications, a method for producing the same, and a resin composition used in the production method. DETAILED DESCRIPTION OF THE INVENTION

[0017] [Polyester film] In this specification, the term "polyester film" refers to a film in which the main component of the resin constituting the film (hereinafter sometimes referred to as the raw resin) is a polyester resin, and hereinafter may be referred to simply as "film." The term "main component" refers to the component present in the largest amount among the raw resins. The proportion of the polyester resin is preferably selected from a range of 50% by mass or more, for example, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, relative to 100% by mass of the raw resin. The raw resin of the film may be polyester resin alone, but when a resin other than polyester resin is combined with polyester resin, the proportion of the polyester resin is preferably selected from a range of 50% by mass or more but less than 100% by mass, for example, 70% by mass or more but less than 99% by mass, relative to 100% by mass of the raw resin.

[0018] (polyester resin) In this specification, the term "polyester resin" refers to a resin having a dicarboxylic acid component and a glycol component as repeating units, or a resin having a hydroxycarboxylic acid component as repeating units, and the repeating units may be a mixture of both.

[0019] Examples of dicarboxylic acid components include aromatic dicarboxylic acid components such as terephthalic acid, isophthalic acid, 1,6-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and sodium sulfoisophthalate; alicyclic dicarboxylic acid components such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid; aliphatic dicarboxylic acid components such as malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, and dimer acid; and heterocycle-containing dicarboxylic acid components such as furandicarboxylic acid. The dicarboxylic acid components may be used alone or in combination of two or more.

[0020] Examples of glycol components include aliphatic glycol components such as ethylene glycol, diethylene glycol (DEG), triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, neopentyl glycol, and 1,6-hexanediol; alicyclic glycol components such as 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, spiroglycol, and isosorbide; and aromatic glycol components such as p-xylylene glycol, m-xylylene glycol, and an ethylene oxide adduct of bisphenol A. The glycol components may be used alone or in combination of two or more.

[0021] Examples of the hydroxycarboxylic acid component include lactic acid (lactide), glycolic acid, 3-hydroxypropionic acid, 6-hydroxycaproic acid (ε-caprolactone), etc. The hydroxycarboxylic acid component may be used alone or in combination of two or more.

[0022] Specific polyester resins include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polycyclohexylene dimethylene terephthalate (PCT), polyethylene furanoate (PEF), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene succinate lactate (PBSL), polybutylene adipate terephthalate (PBAT), polyethylene succinate (PES), etc., and polyethylene terephthalate (PET) and / or polyethylene naphthalate (PEN) are particularly preferred. In this specification, when a polyester resin is specified by the above-mentioned name, the total of the polymerization components (dicarboxylic acid component and glycol component and / or hydroxycarboxylic acid component) of the polyester resin is 100 mol%, and the total of the polymerization components based on the name is preferably 60 mol% or more. For example, in the case of polyethylene terephthalate (PET), it refers to a polyester resin in which the total amount of terephthalic acid and ethylene glycol components is 60 mol% or more of the total polymerized components. The polyester resin preferably contains 70 mol% or more, more preferably 80 mol% or more, even more preferably 85 mol% or more, and particularly preferably 90 mol% or more of the polymerized components based on the name, and may even contain 95 mol% or more, 97 mol% or more, or 98 mol% or more of the polymerized components based on the name. Note that multimers such as dimers and trimers of glycol components, such as diethylene glycol, generated as by-products are not considered to be polymerized components based on the name. The upper limit of the polymerized components based on the name of the total polymerized components is 100 mol%, but when producing a polyester resin from a dicarboxylic acid component and a glycol component, a multimer of the glycol component may be copolymerized, and the upper limit may be 99.5 mol% or even 99 mol%.

[0023] Furthermore, the polyester resin may contain, as copolymerization components, trifunctional or higher polyfunctional carboxylic acid components such as trimellitic acid and pyromellitic acid; and trifunctional or higher polyfunctional alcohol components such as trimethylolpropane and pentaerythritol. The copolymerization components may be used alone or in combination of two or more. When the total acid components are 100 mol % and the total alcohol components are 100 mol %, the total amount of the polyfunctional carboxylic acid components and the polyfunctional alcohol components is preferably 5 mol % or less, more preferably 3 mol % or less. The lower limit of the total amount of the polyfunctional carboxylic acid components and the polyfunctional alcohol components is not particularly limited and may be 0 mol % or 0.1 mol %.

[0024] The dicarboxylic acid component, glycol component, and hydroxycarboxylic acid component may be derived from petroleum, but if biomass-derived components are industrially available, biomass-derived components are preferred.

[0025] As the terephthalic acid component (or ethylene terephthalate component), bis(2-hydroxyethyl) terephthalate (BHET) obtained by chemical recycling may be used.

[0026] The polyester resin may be a single type or a mixture of multiple types with different compositions, and the polyester film may contain the polyester resin as a single layer or multiple layers with different compositions.

[0027] In the case of polyester resins of the same composition, a biomass-derived polyester resin and a petroleum-derived polyester resin may be mixed and used, or a recycled polyester resin and a non-recycled polyester resin may be mixed and used.

[0028] In particular, it is preferable to use recycled PET obtained by collecting used PET bottles and the like.

[0029] The lower limit of the intrinsic viscosity (sometimes referred to as inherent viscosity or IV) of the polyester resin is preferably 0.45 dL / g, more preferably 0.5 dL / g, and even more preferably 0.55 dL / g. The upper limit of the intrinsic viscosity of the polyester resin is preferably 1.2 dL / g, more preferably 1 dL / g, even more preferably 0.9 dL / g, and particularly preferably 0.8 dL / g. In one embodiment, the intrinsic viscosity of the polyester resin is preferably 0.45 dL / g or more and 1.2 dL / g or less. By setting the intrinsic viscosity within the above range, the mechanical properties of the film are ensured, and stable production is facilitated while suppressing the generation of foreign matter and discoloration due to thermal degradation during film formation. The intrinsic viscosity of the polyester resin can be measured at 30°C using an Ostwald viscometer after dissolving the polyester resin in a mixed solvent of phenol (6 parts by mass) and 1,1,2,2-tetrachloroethane (4 parts by mass).

[0030] The lower limit of the acid value (sometimes abbreviated as AV) of the polyester resin is preferably 0 eq / ton, more preferably 1 eq / ton, even more preferably 3 eq / ton, and particularly preferably 5 eq / ton. The upper limit of the acid value of the polyester resin is preferably 50 eq / ton, more preferably 40 eq / ton, and even more preferably 30 eq / ton. In one embodiment, the acid value of the polyester resin is preferably selected from a range of 30 eq / ton or less, and may be, for example, a range of 1 eq / ton to 30 eq / ton. The acid value of the polyester resin can be measured by dissolving the polyester resin in benzyl alcohol and titrating it with an ethanolic potassium hydroxide solution using phenol red as an indicator.

[0031] The raw material resin, such as a polyester resin, preferably has a thermal stability parameter (TS), which indicates heat resistance, of 0.5 or less. Setting the TS within this range ensures high heat resistance. Furthermore, by suppressing the decrease in molecular weight due to the progression of thermal decomposition and the generation of low-molecular-weight oligomers, foreign matter and defects in the film can be reduced, preventing deterioration of processability. Furthermore, it also prevents breakage of the molded product caused by foreign matter, preventing deterioration of productivity. For example, the raw material resin composition (polyester resin composition) is placed in a glass ampoule, purged with nitrogen, and the glass ampoule is sealed under a reduced pressure of 13.3 kPa (nitrogen atmosphere). The raw material resin composition is then heat-treated for 2 hours at a temperature 40°C higher than the melting point of the raw material resin, and the intrinsic viscosity of the raw material resin composition is measured, and the TS can be calculated using the following formula: TS=0.245{[IV] f2 -1.47 -[IV] i -1.47} [IV] i and [IV] f2 indicate the intrinsic viscosity of the raw material resin composition before and after the heat treatment, respectively.

[0032] It is preferable that the polyester film contains as little foreign matter as possible. The total number of particles of 5 μm or larger in the polyester film (or polyester resin) is preferably 15 or less, more preferably 14 or less, even more preferably 13 or less, even more preferably 12 or less, particularly preferably 11 or less, and most preferably 10 or less; it may be less than 10 or even 5 or less. By keeping the number within this range, the film and molded product obtained by film formation have a high degree of clarity. The total number of particles can be determined, for example, by observing 20 fields of view with a field area of ​​718 μm × 583 μm using a 100x phase-contrast microscope and counting the number of particles of 5 μm or larger using an image analyzer.

[0033] When the polyester resin is PET, the polyester resin may contain cyclic trimers (CT). The CT content is usually 1.1% by mass or less, preferably 1% by mass or less. To prevent contamination of film production equipment by CT and to prevent an increase in haze due to heating of the film, the CT content is more preferably 0.7% by mass or less, particularly preferably 0.6% by mass or less, and most preferably 0.5% by mass or less. From the viewpoint of polyester resin productivity, the lower limit of the CT content is preferably 0.3% by mass, more preferably 0.33% by mass, and even more preferably 0.35% by mass. The CT content can be measured, for example, by precisely weighing 100 mg of a pulverized sample, dissolving it in 3 mL of a hexafluoroisopropanol / chloroform mixture (volume ratio = 2 / 3), diluting it with 20 mL of chloroform, adding 10 mL of methanol to precipitate the polymer, filtering it, evaporating the filtrate to dryness, and adjusting the volume to a constant volume with 10 mL of dimethylformamide, followed by quantification by high-performance liquid chromatography.

[0034] The polymerization catalyst for raw material resins such as polyester resins is not particularly limited, and examples thereof include antimony compounds such as diantimony trioxide, antimony pentoxide, antimony acetate, and antimony glycolate; germanium compounds such as germanium dioxide; aluminum compounds such as aluminum acetate; titanium compounds such as organic titanium compounds; manganese compounds such as manganese acetate; and mixtures of two or more of these. Among these, at least one selected from antimony compounds such as diantimony trioxide, germanium compounds such as germanium dioxide, aluminum compounds, and titanium compounds is preferred in terms of the transparency of the resulting polyester resin and availability.

[0035] The lower limit of the Sb content in a raw material resin such as a polyester resin is preferably 40 ppm by mass, more preferably 50 ppm by mass, even more preferably 60 ppm by mass, particularly preferably 70 ppm by mass, and most preferably 76 ppm by mass. The lower limit of the Sb content may be 78 ppm by mass or 80 ppm by mass. The upper limit of the Sb content is preferably 400 ppm by mass, more preferably 350 ppm by mass, even more preferably 300 ppm by mass, particularly preferably 250 ppm by mass, and may be less than 250 ppm by mass, and most preferably 200 ppm by mass. In one embodiment, the Sb content is preferably 40 ppm by mass or more and 400 ppm by mass or less.

[0036] The lower limit of the Ge content in a raw material resin such as a polyester resin is preferably 10 ppm by mass, more preferably 20 ppm by mass, and even more preferably 30 ppm by mass. The upper limit of the Ge content is preferably 200 ppm by mass, more preferably 150 ppm by mass, and even more preferably 100 ppm by mass. In one embodiment, the Ge content is preferably 10 ppm by mass or more and 200 ppm by mass or less.

[0037] The lower limit of the Ti content in a raw material resin such as a polyester resin is preferably 1 ppm by mass, more preferably 2 ppm by mass, even more preferably 3 ppm by mass, particularly preferably 4 ppm by mass, and most preferably 5 ppm by mass. The upper limit of the Ti content is preferably 50 ppm by mass, more preferably 40 ppm by mass, even more preferably 30 ppm by mass, particularly preferably 25 ppm by mass, and most preferably 20 ppm by mass. In one embodiment, the Ti content is preferably 1 ppm by mass or more and 50 ppm by mass or less.

[0038] The lower limit of the Mn content in a raw material resin such as a polyester resin is preferably 10 ppm by mass, more preferably 20 ppm by mass, and even more preferably 25 ppm by mass. The upper limit of the Mn content is preferably 100 ppm by mass, more preferably 80 ppm by mass, and even more preferably 70 ppm by mass. In one embodiment, the Mn content is preferably 10 ppm by mass or more and 100 ppm by mass or less.

[0039] The lower limit of the Al content in a raw material resin such as a polyester resin is preferably 1 ppm by mass, more preferably 3 ppm by mass, even more preferably 5 ppm by mass, particularly preferably 7 ppm by mass, and most preferably 10 ppm by mass. The upper limit of the Al content is preferably 100 ppm by mass, more preferably 70 ppm by mass, even more preferably 50 ppm by mass, particularly preferably 40 ppm by mass, and most preferably 30 ppm by mass, and may even be 20 ppm by mass. By keeping the Al content at or below the above upper limit, foreign matter can be further suppressed. In one embodiment, the Al content is preferably 1 ppm by mass or more and 100 ppm by mass or less.

[0040] By setting the amount of polymerization catalyst within the above range, polymerization can be carried out within an appropriate time, ensuring resin productivity, preventing discoloration of the resin and generation of foreign matter due to deterioration, and preventing generation of foreign matter due to precipitation or aggregation of the catalyst metal.

[0041] It is also preferable to further add a phosphorus compound to raw material resins such as polyester resins. Adding a phosphorus compound makes it easier to suppress the precipitation of metals used as polymerization catalysts. In addition, using an aluminum compound and a phosphorus compound in combination as a polymerization catalyst is preferable because it can increase the activity of the polymerization catalyst.

[0042] The phosphorus compound is not particularly limited, but it is preferable to use a phosphonic acid compound, a phosphinic acid compound, etc., because they have a large effect of improving the catalytic activity. Among these, it is more preferable to use a phosphonic acid compound, because they have a particularly large effect of improving the catalytic activity.

[0043] Among the above phosphorus compounds, phosphorus compounds having a phosphorus element and a phenol structure in the same molecule are preferred. The phosphorus compound having a phosphorus element and a phenol structure in the same molecule is not particularly limited, but it is preferred to use one or more compounds selected from the group consisting of phosphonic acid compounds having a phosphorus element and a phenol structure in the same molecule and phosphinic acid compounds having a phosphorus element and a phenol structure in the same molecule, as this has a large effect of improving the catalytic activity, and it is more preferred to use one or more phosphonic acid compounds having a phosphorus element and a phenol structure in the same molecule, as this has a very large effect of improving the catalytic activity of aluminum.

[0044] Examples of phosphorus compounds that have phosphorus element and phenol structure in the same molecule include P(=O)R 1 (OR 2 )(OR 3 ), phosphonic acid compounds represented by P(=O)R 1 R 4 (OR 2 ) and phosphinic acid compounds represented by R 1 R represents a hydrocarbon group having 1 to 50 carbon atoms and containing a phenol structure, or a hydrocarbon group having 1 to 50 carbon atoms and containing a phenol structure and a substituent such as a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. 4 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a substituent such as a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. 2 and R 3 R each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a substituent such as a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may contain a branched chain structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl. 2 and R 4 The ends of may be bonded together.

[0045] Examples of phosphorus compounds 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, bis(p-hydroxyphenyl)phosphinic acid, methyl bis(p-hydroxyphenyl)phosphinate, phenyl bis(p-hydroxyphenyl)phosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, and phenyl p-hydroxyphenylphosphinate.

[0046] Examples of phosphorus compounds having a phosphorus element and a phenol structure in the same molecule include, in addition to the phosphorus compounds exemplified above, phosphorus compounds having a phosphorus element and a hindered phenol structure (such as a phenol structure in which an alkyl group having a tertiary carbon (preferably an alkyl group having a tertiary carbon at the benzylic position, such as a t-butyl group or a thexyl group; a neopentyl group, etc.) is bonded to one or two ortho-positions of a hydroxyl group) in the same molecule. Phosphorus compounds having a phosphorus element and a structure of the following formula A in the same molecule are preferred, and among these, dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate shown in the following formula B is more preferred.

[0047] [ka] (In Formula A, * represents a bond.)

[0048] [ka] (In formula B, X 1 and X 2 each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms.

[0049] In the above formula B, X 1 and X 2are preferably alkyl groups having 1 to 4 carbon atoms, more preferably alkyl groups having 1 to 3 carbon atoms, and even more preferably alkyl groups having 1 or 2 carbon atoms. In particular, diethyl esters having 2 carbon atoms are preferred because they are readily available commercially as Irganox 1222 (manufactured by BASF).

[0050] Furthermore, when an aluminum compound is used as the polymerization catalyst, it is also preferable to add a lithium compound such as lithium acetate. The lower limit of the Li content in the raw material resin such as a polyester resin is preferably 1 ppm by mass, more preferably 3 ppm by mass, and even more preferably 5 ppm by mass. The upper limit of the Li content in the raw material resin such as a polyester resin is preferably 50 ppm by mass, more preferably 30 ppm by mass, and even more preferably 20 ppm by mass. In one embodiment, the Li content in the raw material resin such as a polyester resin is preferably 1 ppm by mass or more and 50 ppm by mass or less.

[0051] The lower limit of the total content of Mg and Ca in a raw material resin such as a polyester resin is preferably 0 ppm by mass (below the detection limit), more preferably 0.01 ppm by mass, even more preferably 0.1 ppm by mass, and particularly preferably 0.5 ppm by mass. The upper limit of the total content of Mg and Ca is preferably 50 ppm by mass, more preferably 40 ppm by mass, even more preferably 30 ppm by mass, even more preferably 20 ppm by mass, particularly preferably 10 ppm by mass, and most preferably 5 ppm by mass. By keeping it below the above upper limit, the generation of foreign matter can be further suppressed.

[0052] The lower limit of the Mg content in a raw material resin such as a polyester resin is preferably 0 ppm by mass (below the detection limit), more preferably 0.01 ppm by mass, even more preferably 0.1 ppm by mass, and particularly preferably 0.5 ppm by mass. The upper limit of the Mg content is preferably 10 ppm by mass, more preferably 9 ppm by mass, even more preferably 8 ppm by mass, particularly preferably 7 ppm by mass, and most preferably 6 ppm by mass. By keeping the content below the above upper limit, the generation of foreign matter can be further suppressed.

[0053] The lower limit of the total alkali metal content in raw material resins such as polyester resins is preferably 0 ppm by mass (below the detection limit), more preferably 0.1 ppm by mass, and even more preferably 0.5 ppm by mass. The upper limit of the total alkali metal content is preferably 18 ppm by mass, more preferably 16 ppm by mass, even more preferably 15 ppm by mass, particularly preferably 14 ppm by mass, and most preferably 13 ppm by mass. By keeping the content below the above upper limit, coloration of the polyester film can be further suppressed.

[0054] The lower limit of the Na content in a raw material resin such as a polyester resin is preferably 0 ppm by mass (below the detection limit), more preferably 0.1 ppm by mass, and even more preferably 0.5 ppm by mass. The upper limit of the Na content is preferably 13 ppm by mass, more preferably 10 ppm by mass, even more preferably 7 ppm by mass, particularly preferably 5 ppm by mass, and most preferably 3 ppm by mass. By keeping the Na content below the above upper limit, coloration of the polyester film can be further suppressed.

[0055] In particular, by keeping the content of alkali metals such as Na in raw resins such as polyester resins below the above upper limit, discoloration can be suppressed even when the resin has a large thermal history, such as when the extrusion temperature during film production is high, when the piping is long and the residence time at high temperatures is long, or when recovered materials such as film edges are mixed as raw materials for the resin.

[0056] It is not necessary to exclude the above-mentioned Ca, Mg, and alkali metals. Even if these metals are present, stable electrostatic adhesion is possible using ionic compounds, and by keeping the content within the above ranges, foreign matter and coloration are suppressed, resulting in a film that can be stably produced.

[0057] The lower limit of the Mn content in a raw material resin such as a polyester resin is preferably 0 ppm by mass (below the detection limit). The upper limit of the Mn content is preferably 22 ppm by mass, more preferably 20 ppm by mass, even more preferably 18 ppm by mass, and particularly preferably 16 ppm by mass. By keeping the Mn content below the upper limit, the generation of foreign matter and coloration can be further suppressed.

[0058] The lower limit of the Cu content in a raw material resin such as a polyester resin is preferably 0 ppm by mass (below the detection limit). The upper limit of the Cu content is preferably 160 ppm by mass, more preferably 150 ppm by mass. By keeping the Cu content below the upper limit, the generation of foreign matter and coloration can be further suppressed.

[0059] In order to increase the productivity of the polyester resin while suppressing the generation of foreign matter, it is preferable to set the Sb content in the raw material resin such as a polyester resin to 76 ppm by mass or more and the Mg content to 10 ppm by mass or less. Also, in order to increase the productivity of the raw material resin while suppressing the generation of foreign matter, it is preferable to set the Sb content in the raw material resin such as a polyester resin to 76 ppm by mass or more and the Cu content to 160 ppm by mass or less.

[0060] The lower limit of the total metal content in a raw material resin such as a polyester resin is preferably 1 ppm by mass, more preferably 2 ppm by mass, even more preferably 3 ppm by mass, particularly preferably 4 ppm by mass, and most preferably 5 ppm by mass. The upper limit of the total metal content is preferably 500 ppm by mass, more preferably 450 ppm by mass, even more preferably 400 ppm by mass, particularly preferably 300 ppm by mass, and most preferably 250 ppm by mass. By keeping the content below the above upper limit, the generation of foreign matter and coloration can be further suppressed. In one embodiment, the total metal content is preferably 1 ppm by mass or more and 500 ppm by mass or less.

[0061] The metal content in the raw resin can be calculated by pretreating the sample (e.g., by pre-carbonization, ashing, acid treatment, and dissolution) to prepare a measurement solution, and measuring the element concentration in the resulting measurement solution using a high-frequency inductively coupled plasma (ICP) optical emission spectrometer (e.g., SPECTROBLUE, manufactured by Hitachi High-Tech Science Corp.). Note that if it is difficult to perform the measurement at the wavelengths described in the examples below, other wavelengths may be used with reference to literature.

[0062] (Biomass PET) Of the polyester resins, it is also preferable to use biomass-derived PET (bioPET) as the PET.

[0063] Bio-PET contains at least one of the polymerization components, ethylene glycol and terephthalic acid, derived from biomass. When the ethylene glycol contains biomass-derived ethylene glycol, the biomass-derived ethylene glycol accounts for preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, particularly preferably 80% by mass or more, and particularly preferably 90% by mass or more of the total ethylene glycol, and may be 100% by mass or more. When the terephthalic acid contains biomass-derived terephthalic acid, the biomass-derived ethylene glycol accounts for preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more of the total terephthalic acid, and may be 100% by mass or more of biomass-derived terephthalic acid.

[0064] Bio-PET may be used without being mixed with petroleum-derived PET, or may be mixed with petroleum-derived PET.

[0065] Of the raw material resins (especially PET) of polyester films, biomass PET is preferably 10% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, and 95% by mass or more, in that order; more preferably more than 95% by mass, even more preferably 96% by mass or more, particularly preferably 97% by mass or more, and most preferably 100% by mass.

[0066] The radiocarbon (C 14The content of biomass-derived carbon measured by the ethylene glycol / terephthalic acid (EPO) method is preferably 2% or more, 6% or more, 10% or more, 14% or more, 16% or more, 18% or more, or 19% or more, in that order, and most preferably exceeds 19%. When biomass-derived ethylene glycol is used as the only ethylene glycol, the theoretical upper limit of the biomass-derived carbon content is 20%. When biomass-derived terephthalic acid is also used, the biomass-derived carbon content may exceed 20%, with higher values ​​being preferable, and therefore the most preferred value is 100%, but it may also be 95% or less, 90% or less, 80% or less, or 70% or less.

[0067] The above is a percentage based on carbon, but if hydrogen and oxygen are added and the calculation is based on the mass of the biomass raw material, and all of the ethylene glycol is considered to be derived from biomass and all of the terephthalic acid is considered to be derived from petroleum, the calculated percentage is 31.25 mass%.

[0068] Atmospheric carbon dioxide contains C 14 Since carbon dioxide is contained in the atmosphere at a constant rate (105.5pMC), plants that grow by absorbing carbon dioxide from the atmosphere, such as corn, contain 14 The carbon content is known to be about 105.5 pMC. 14 It is also known that almost no carbon is contained in polyester resin. 14 The biomass ratio can be calculated by measuring the ratio of carbon derived from biomass (biomass ratio). The biomass ratio can be calculated, for example, by measuring the ratio of radiocarbon (C 14 ) measurement.

[0069] When producing polyester film from bio-PET, the addition of an ionic compound can be carried out in the same manner as for petroleum-derived PET, but the use of a masterbatch is preferred. The masterbatch PET can be petroleum-derived, biomass-derived, or a mixture of both.

[0070] The polyester film may have two or more layers, with at least one layer containing biomass-derived PET.

[0071] Bio-PET is preferably produced using an aluminum compound as a polymerization catalyst.

[0072] (chemically recycled PET) Among polyester resins, it is also preferable to use polyethylene terephthalate (chemically recycled PET or CR-PET) polymerized using bis-2-hydroxyethyl terephthalate (chemically recycled BHET or CR-BHET) obtained by chemical recycling as the PET.

[0073] Chemically recycled BHET is preferably obtained by heating PET in the presence of ethylene glycol to depolymerize it. The original PET is preferably post-consumer PET, and examples include PET bottles collected from the streets, containers such as trays, fibers and products, waste products before production, B-grade products not shipped to the market, edge portions held during film stretching, slit offcuts, and molded products returned due to complaints, etc. The original PET may be derived from petroleum-derived terephthalic acid and / or ethylene glycol, or may be derived from biomass. The original PET may be a mechanically recycled molded product. The original PET may be a single type or a mixture of two or more types.

[0074] The original PET is typically crushed, washed, and cleaned of foreign matter before being subjected to a depolymerization process.

[0075] Chemically recycled BHET may contain linear dimers and higher polymers, and may also contain mono-2-hydroxyethyl terephthalate, terephthalic acid, ethylene glycol, and the like.

[0076] The total acid value and hydroxyl value of the chemically recycled BHET is preferably 6,500 eq / ton or more, more preferably 7,000 eq / ton or more, and even more preferably 7,500 eq / ton or more. The upper limit of this total is preferably 9,500 eq / ton, more preferably 9,000 eq / ton, and even more preferably 8,500 eq / ton. In one embodiment, the total is preferably 6,500 eq / ton or more and 9,500 eq / ton or less. By setting the total within this range, productivity can be ensured while maintaining sufficient purity.

[0077] The chemically recycled BHET may contain a dicarboxylic acid component other than terephthalic acid and / or a glycol component other than ethylene glycol. Examples of dicarboxylic acid components other than terephthalic acid include naphthalenedicarboxylic acid and isophthalic acid. The dicarboxylic acid components other than terephthalic acid may be used alone or in combination of two or more. Examples of glycol components other than ethylene glycol include diethylene glycol, neopentyl glycol, cyclohexanedimethanol, trimethylene glycol, tetramethylene glycol, an ethylene glycol or propylene glycol adduct of bisphenol A, and an ethylene glycol or propylene glycol adduct of bisphenol S. The glycol components other than ethylene glycol may be used alone or in combination of two or more.

[0078] The amounts of dicarboxylic acid components of the terephthalic acid component and glycol components other than ethylene glycol in the chemically recycled BHET are each independently preferably 2 mol% or less, more preferably 1.5 mol% or less, even more preferably 1 mol% or less, particularly preferably 0.7 mol% or less, and most preferably 0.5 mol% or less, based on the dicarboxylic acid component and glycol component, respectively, being 100 mol%. As mentioned above, chemically recycled BHET is preferably obtained by depolymerizing PET, including recycled PET from the market. Although recycled PET may contain components other than PET for adjusting crystallinity and physical properties, from a cost perspective, it is preferable to use the BHET with components other than PET added as is, rather than selecting only pure PET from the recycled material or purifying the BHET to a level where components other than terephthalic acid and ethylene glycol are undetectable. Therefore, the amounts of dicarboxylic acid components other than terephthalic acid and glycol components other than ethylene glycol may each independently be preferably 0.01 mol% or more, more preferably 0.05 mol% or more, based on the dicarboxylic acid component and glycol component, respectively, being 100 mol%.

[0079] The lower limit of the amount of chemically recycled BHET relative to the amount of BHET used in producing CR-PET is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, particularly preferably 80% by mass, and most preferably 90% by mass, and may even be 100% by mass.

[0080] CR-PET may be mixed with PET resins other than chemically recycled PET resins. When PET is blended with polyester resins other than PET, CR-PET may be used as the PET.

[0081] The polyester film may be made of two or more layers, with at least one layer containing chemically recycled PET resin.

[0082] Of the raw resins (especially PET) of polyester films, CR-PET is preferably 10% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, in that order, and may be more than 95% by mass, 96% by mass or more, 97% by mass or more, or even 100% by mass. Note that even in masterbatches containing high concentrations of additives such as ionic compounds and lubricants, the CR-PET contained in the masterbatch is counted as chemically recycled resin.

[0083] When producing polyester film from CR-PET, the addition of an ionic compound can be carried out in the same manner as for non-chemically recycled PET, but a masterbatch method is preferred. The polyester resin in the masterbatch may be CR-PET, a material other than CR-PET, or a mixture of both.

[0084] CR-PET is preferably produced using an aluminum compound as a polymerization catalyst.

[0085] (Recycled polyester resin) It is also preferable to use a recycled polyester resin as the polyester resin. The recycled polyester resin is usually a recycled polyester resin molded product that has not been used or has been used.

[0086] Examples of recovered molded products include PET bottles collected from the streets, containers such as trays, fiber and film products, products discarded before being cut into products during manufacturing, products that were not shipped to the market as B-grade products, edge portions that are gripped during film stretching, offcuts from slits, and molded products that have been returned due to complaints, etc. These may be single items with known origins, such as recovered PET bottles or film edge portions, or may be a mixture of items from different origins. In particular, the recovered polyester resin is preferably derived from recovered PET bottles, and preferably contains 90% by mass or more, and even 95% by mass or more, of components derived from recovered PET bottles.

[0087] The recovered polyester resin may be in the form of, for example, chips, flakes, powder, etc., and may be obtained by pulverizing the recovered molded products described above. However, from the viewpoint of ease of handling, it is preferable to melt the recovered molded products and pelletize them.

[0088] When the total amount of the polymerization components (dicarboxylic acid components, glycol components, and / or hydroxycarboxylic acid components) of the polyester resin is taken as 100 mol%, the recycled polyester resin preferably contains a total of terephthalic acid components and ethylene glycol components of 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more. Optional copolymerization components include divalent or higher carboxylic acid components other than terephthalic acid, divalent or higher alcohol components other than ethylene glycol, and hydroxycarboxylic acid components, specific examples of which are as described above.

[0089] The recovered polyester resin preferably contains at least one selected from antimony, titanium, and germanium, i.e., the recovered polyester resin is preferably produced using at least one polymerization catalyst selected from antimony compounds, titanium compounds, and germanium compounds, and among these, recovered polyester resins containing antimony and germanium are preferred.

[0090] The total content of antimony, titanium, and germanium in the recovered polyester resin is preferably 2 ppm by mass or more, more preferably 5 ppm by mass or more, even more preferably 10 ppm by mass or more, still more preferably 30 ppm by mass or more, and particularly preferably 50 ppm by mass or more. The total content is preferably 500 ppm by mass or less, more preferably 400 ppm by mass or less, even more preferably 300 ppm by mass or less, and particularly preferably 250 ppm by mass or less. In one embodiment, the total content is preferably 2 ppm by mass or more and 500 ppm by mass or less, more preferably 5 ppm by mass or more and 400 ppm by mass or less, even more preferably 10 ppm by mass or more and 300 ppm by mass or less, and particularly preferably 50 ppm by mass or more and 250 ppm by mass or less.

[0091] The recycled polyester resin may contain additives such as colorants, lubricants (particularly lubricant particles), ultraviolet absorbers, melt resistivity adjusters, antistatic agents, antioxidants, heat stabilizers, etc. The additives may be used alone or in combination of two or more.

[0092] The intrinsic viscosity of the recovered polyester resin is preferably 0.5 dL / g or more, more preferably 0.55 dL / g or more, and even more preferably 0.57 dL / g or more. The intrinsic viscosity of the recovered polyester resin is preferably 0.8 dL / g or less, more preferably 0.75 dL / g or less, and even more preferably 0.73 dL / g or less. In one embodiment, the intrinsic viscosity of the recovered polyester resin is preferably 0.5 dL / g or more and 0.8 dL / g or less, more preferably 0.55 dL / g or more and 0.75 dL / g or less, and even more preferably 0.57 dL / g or more and 0.73 dL / g or less.

[0093] The recycled polyester resin is preferably PET recycled from PET bottles for beverages, etc. PET recycled from PET bottles for beverages, etc. is sometimes called bottle-recycled PET. The recycled polyester resin preferably contains 70% by mass or more of bottle-recycled PET, more preferably 80% by mass or more, and even more preferably 90% by mass or more, and may contain 100% by mass.

[0094] Recycled polyester resin (particularly recycled bottle PET) may contain an isophthalic acid component as a copolymerization component. When the total acid components are taken as 100 mol%, the lower limit of the isophthalic acid component content is preferably 0.02 mol%, more preferably 0.05 mol%, even more preferably 0.1 mol%, particularly preferably 0.2 mol%, and most preferably 0.3 mol%. The upper limit of the isophthalic acid component content is preferably 5 mol%, more preferably 4 mol%, even more preferably 3 mol%, particularly preferably 2.5 mol%, and most preferably 2 mol%. In one embodiment, the content of the isophthalic acid component is preferably 0.02 mol% or more and 5 mol% or less.

[0095] Diethylene glycol is not only contained in polyester resins as a by-product of ethylene glycol during polyester polymerization, but may also be added during polymerization to adjust crystallization.

[0096] The lower limit of the diethylene glycol component content in recovered polyester resin (particularly recycled bottle PET) is preferably 0.5 mol%, more preferably 0.8 mol%, even more preferably 1 mol%, particularly preferably 1.2 mol%, and most preferably 1.4 mol%, when the total glycol components are taken as 100 mol%. The upper limit of the diethylene glycol component content is preferably 5 mol%, more preferably 4 mol%, even more preferably 3.5 mol%, and particularly preferably 3 mol%. In one embodiment, the diethylene glycol component content is preferably 0.5 mol% or more and 5 mol% or less.

[0097] The upper limit of the copolymerization components other than isophthalic acid and diethylene glycol in recovered polyester resin (particularly recycled bottle PET) is preferably 3 mol %, more preferably 2.5 mol %, and even more preferably 2 mol %, assuming that the total acid components are 100 mol % and the total glycol components are 100 mol %, respectively.

[0098] The total amount of copolymerization components of the recycled polyester resin (particularly recycled bottle PET) is preferably 0.5 mol% or more, more preferably 1 mol%, even more preferably 1.5 mol%, and particularly preferably 2 mol%, when the sum of all acid components and all glycol components is 200 mol%. The upper limit of the total amount is preferably 7 mol%, more preferably 6 mol%, even more preferably 5 mol%, and particularly preferably 4 mol%. When the total amount is equal to or less than the upper limit, the heat resistance and mechanical strength of the resulting polyester film can be prevented from decreasing, and there is no need to limit the amount of recycled polyester resin added. In one embodiment, the total amount is preferably 0.5 mol% or more and 7 mol% or less.

[0099] The recycled polyester resin may be mixed with virgin polyester resin. When PET is blended with polyester resin other than PET, recycled bottle PET may be used as the PET.

[0100] The polyester film may have two or more layers, and at least one of the layers may contain recycled polyester resin.

[0101] Of the raw material resins (particularly polyester resins) of polyester films, the recovered polyester resin may account for 10% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, or may be more than 95% by mass, 96% by mass or more, 97% by mass or more, or even 100% by mass. Note that even in masterbatches containing high concentrations of additives such as ionic compounds and lubricants, the recovered polyester resin contained in the masterbatch is counted as recovered polyester resin.

[0102] When producing polyester film using recycled polyester resin, the addition of an ionic compound can be carried out in the same manner as with virgin polyester resin, but a method using a masterbatch is preferred. The polyester resin in the masterbatch may be virgin polyester resin, recycled polyester resin, or a mixture of both. The polyester resin in the masterbatch may also contain CR-PET.

[0103] (Resins other than polyester resins) The resin other than the polyester resin may be a resin compatible with the polyester resin or a resin incompatible with the polyester resin. Examples of the resin other than the polyester resin include thermoplastic resins such as polystyrene, polycarbonate, polyolefins such as polypropylene, polymethylpentene, and polycyclic olefins, polyamides such as 6-nylon and 6,6-nylon, polyetheramide, polyamideimide, polyimide, polyetherimide, polysulfone, and polyethersulfone. These may be used alone or in combination of two or more.

[0104] (ionic compounds) Ionic compounds can, for example, control (e.g., reduce) melt resistivity. The mechanism by which melt resistivity is controlled is thought to be that when a voltage is applied, the cations and anions that make up the ionic compound migrate in the molten raw resin, causing a bias in the charge in the raw resin.

[0105] In this specification, an ionic compound refers to a salt composed of a cation and an anion. Examples of ionic compounds include metal salts containing alkali metals, alkaline earth metals, transition metals (metals of Groups 3 to 11), and metals of Groups 12 to 16; and ionic liquids obtained by combining organic or inorganic cations with organic or inorganic anions. Among these, ionic liquids are more preferred because of their excellent dispersibility in the raw resin and the ability to control the melt resistivity of the raw resin with the addition of a small amount. Any one of the ionic compounds may be used alone, or two or more may be used in combination. When two or more ionic compounds are used in combination, they may be used in combination with metal salts, with ionic liquids, or with a metal salt and an ionic liquid; however, a combination of ionic liquids or a combination of a metal salt and an ionic liquid is more preferred.

[0106] The amount of ionic compound added (which can be read as content) in the resin constituting the film is greater than 0 ppm by mass, preferably 0.01 ppm by mass or more, more preferably 0.1 ppm by mass or more, and even more preferably 0.5 ppm by mass or more, based on the mass of the raw material resin (particularly polyester resin). The amount of the ionic compound added is preferably 950 ppm by mass or less, more preferably 800 ppm by mass or less, and even more preferably 700 ppm by mass or less. In one embodiment, the amount of the ionic compound added is preferably 0.01 ppm by mass or more and 950 ppm by mass or less, more preferably 0.1 ppm by mass or more and 800 ppm by mass or less, and even more preferably 0.5 ppm by mass or more and 700 ppm by mass or less. By being within the above range, it is possible to achieve high moldability and processability while suppressing the generation of foreign matter, etc. The amount of the ionic compound added may be 500 ppm by mass or less, 250 ppm by mass or less, or 150 ppm by mass or less. The amount of the ionic compound added may be less than 100 ppm by mass, 99 ppm by mass or less, 95 ppm by mass or less, 90 ppm by mass or less, 70 ppm by mass or less, 50 ppm by mass or less, 40 ppm by mass or less, 30 ppm by mass or less, 20 ppm by mass or less, or 10 ppm by mass or less. It may also be less than 10 ppm by mass, 9 ppm by mass or less, 8 ppm by mass or less, or 7 ppm by mass or less. The amount of the ionic compound added can be appropriately set depending on the type of ionic compound and the melt resistivity of the resin constituting the film.

[0107] Reducing the amount of ionic compound added has the advantages of, for example, making it less likely for the ionic compound to bleed out onto the film surface, making it easier to suppress contamination of the film production line, and reducing changes over time in adhesion properties with adhesives, coating layers, printing inks, etc. Therefore, one method is to consider compatibility with the resin and select an ionic compound that can efficiently reduce melt resistivity even when added in a small amount.

[0108] The relationship between the amount R of the ionic compound added and the dissociation energy Q preferably satisfies the following formula (1) and / or the following formula (2). R≦0.15×Q+890 (1) R≦-20×Q+16000 (2) (In the formula, R is the amount (ppm by mass) of the ionic compound added to the raw material resin, and Q is the dissociation energy (kJ / mol) of the anion and cation that constitute the ionic compound.) When multiple types of ionic compounds are used in combination, R is the sum of the amounts of each ionic compound added (R = ΣR i ), and Q is the mass fraction (R i / R) and Q(Q i ) and the sum of the products (Q=Σ(R i / R)Q i )

[0109] Equation (1) shows that ionic compounds with low dissociation energy dissociate more efficiently into cations and anions, and therefore can exhibit electrostatic chargeability even in small amounts. When R satisfies equation (1), the raw resin's conductivity does not become too high, and sparks are prevented from occurring when a voltage is applied to the raw resin to impart a charge, enabling stable production. Furthermore, the raw resin is not subject to damage such as scratches, holes, or breakage, which could make it difficult to process the raw resin using a charge.

[0110] Equation (2) shows that ionic compounds with smaller dissociation energy can have a high degree of clarity even when present in large quantities. This is presumably because ionic compounds with larger dissociation energy have stronger bonds between cations and anions, and the ionic compounds themselves tend to aggregate and become foreign matter, reducing the clarity of the raw resin.

[0111] It is more preferable that the dissociation energy of the ionic compound and the amount added to the raw material resin satisfy both formulas (1) and (2). In this case, a film having high clarity and exhibiting high moldability and processability can be provided, and a method for producing the same can be provided.

[0112] The dissociation energy Q (kJ / mol) of the anion and cation constituting the ionic compound is preferably 850 or less, more preferably 800 or less, even more preferably 700 or less, even more preferably 600 or less, particularly preferably 500 or less, and most preferably 400 or less. The dissociation energy Q may be 0 or greater or greater than 0, and is not particularly limited. The lower limit is, for example, 10, preferably 50, or may be 100, 150, 200, or 250. By setting the dissociation energy Q within this range, the electrostatic applicability during melting of the raw material resin is improved, and high moldability and processability can be achieved. This is believed to be due to the fact that the inter-ionic interaction is appropriately weakened, making it easier for the ions to dissociate when a voltage is applied.

[0113] The average charge density (e / Å) of the anions and cations that make up an ionic compound 2 The absolute values ​​of the average charge densities (e / Å) of the anions and cations are preferably 0.0025 or more, more preferably 0.003 or more, and even more preferably 0.0035 or more, and may be 0.0038 or more. 2 ) are each independently preferably 0.075 or less, more preferably 0.07 or less, even more preferably 0.065 or less, and may be 0.06 or less, 0.05 or less, 0.04 or less, 0.03 or less, 0.02 or less, or 0.015 or less. In one embodiment, the average charge density (e / Å) of at least one ion selected from the anions and cations is 2The absolute values ​​of the average charge densities (e / Å) of both the anions and cations are preferably 0.0025 or more and 0.075 or less, more preferably 0.003 or more and 0.07 or less, and even more preferably 0.0035 or more and 0.065 or less. 2 ) is preferably 0.0025 or more and 0.075 or less, more preferably 0.003 or more and 0.07 or less, and even more preferably 0.0035 or more and 0.065 or less. By setting it within this range, the electrostatic applicability during melting of the raw material resin is improved, and high moldability and processability can be achieved. This is thought to be because the ionic interaction with counter ions is a factor affected by the average charge density of anions or cations, and by setting the absolute value of the average charge density within this range, it becomes easier to dissociate into ions when a voltage is applied.

[0114] Furthermore, the average charge density (e / Å) of the anions that make up the ionic compound 2 The lower limit of the absolute value of (a) may be 0.0038 or 0.004, and the upper limit may be 0.015, 0.01, 0.0095, 0.009, or 0.008. In one embodiment, the absolute value of the average charge density of the anions constituting the ionic compound is preferably 0.0038 or more and 0.015 or less.

[0115] Average charge density (e / Å) of cations that make up ionic compounds 2 The lower limit of the absolute value of (e / Å) may be 0.0038, 0.004, or 0.0045, and the upper limit may be 0.02, 0.015, 0.0145, 0.013, 0.01, or 0.008. In one embodiment, the average charge density (e / Å) of the cations constituting the ionic compound is 2 ) is preferably 0.0038 or more and 0.015 or less.

[0116] Either the ionic radius of the anion (hereinafter also referred to as anion radius) constituting the ionic compound or the ionic radius of the cation (hereinafter also referred to as cation radius) constituting the ionic compound is preferably 1 Å or more, more preferably 1.5 Å or more, and may be 2 Å or more. Either the anion radius or the cation radius is preferably 10 Å or less, more preferably 5 Å or less, and particularly preferably 4 Å or less. In one embodiment, the ionic radius (or either the anion radius or the cation radius) of at least one of the anions and cations constituting the ionic compound is preferably 10 Å or less, more preferably 1 Å or more and 10 Å or less, and even more preferably 1.5 Å or more and 5 Å or less. Furthermore, the ionic radius (or the anion radius or the cation radius) of at least one of the anions and cations constituting the ionic compound is preferably 2 Å or more. The ionic radius is a factor that affects the average charge density of the ions. By setting the ionic radius within this range, electrostatic applicability during melting is improved, and high moldability and processability can be achieved.

[0117] It is preferable that both the anion radius and the cation radius are within the above ranges. On the other hand, the lower limit of the anion radius may be 2.5 Å, 2.6 Å, 2.65 Å, 2.7 Å, 2.8 Å, 2.9 Å, or 3 Å. In one embodiment, the anion radius is preferably 2.5 Å or more and 10 Å or less. The lower limit of the cation radius may be 1.4 Å, 1.5 Å, 1.7 Å, 2 Å, or 2.2 Å. The upper limit of the cation radius may be 3.7 Å or more and 3.5 Å. In one embodiment, the cation radius is preferably 1.4 Å or more and 3.7 Å or less.

[0118] By selecting an ionic compound with low dissociation energy and by selecting an ionic compound with a large ionic radius for the cation and anion and a small absolute value of the average charge density, it becomes easier to maintain the melt resistivity within an appropriate range even when the amount added is reduced. The ions of the above-mentioned ionic compounds have good compatibility with the polyester resin without being excessively constrained, which is thought to lead to a stable effect of reducing the melt resistivity and suppressing aggregation. Among these, it is preferable to select an ionic compound with a large ionic radius and a small absolute value of the average charge density as the cation. Furthermore, by using an anion with a large ionic radius and a small absolute value of the average charge density, it becomes easier to suppress foreign matter, even when a metal such as magnesium or calcium is used as the cation.

[0119] The anion radius, cation radius, average charge density of the anion, and average charge density of the cation can be calculated using, for example, quantum chemistry calculation software "Gaussian16" by the COSMO method according to the following procedure.

[0120] First, the anion and cation are optimized in vacuum. The density functional (DFT) method is used for the optimization. The functional is BVP86, the basis set is TZVP, and the fitting basis set is DGA1. The keyword opt is set. Next, based on the structure optimized in vacuum, a structural optimization is performed under conditions where the molecular surface is shielded with a conductor. The same DFT method, functionals, basis functions, and fitting basis functions as in vacuum are used for structural optimization. Specify opt scrf=(cpcm,read) as a keyword. Additionally, specify radii=klamt as an additional option. Next, the COSMO method is used based on the structure optimized under conductor shielding conditions. The COSMO method uses the same DFT methods, functionals, basis functions, and fitting basis functions as in vacuum. By specifying the keyword scrf=cosmors, a file containing charge information when the molecular surface is shielded with a conductor is output.

[0121] The anion radius and cation radius are calculated by approximating the molecular shape to a sphere based on the volume described in the file output by the COSMO method.

[0122] The average charge density of anions and cations can be calculated by dividing the charge of anions and cations by the surface area listed in the file output by the COSMO method. If necessary, unit conversion was performed using 1 Bohr = 0.529117 Å.

[0123] The dissociation energy can be calculated as the difference between the sum of the energy of the anion and the energy of the cation that constitute the ionic compound and the energy of the ionic compound itself. (Dissociation energy) = (Energy of anion) + (Energy of cation) - (Energy of ionic compound) For the energies of anions, cations, and ionic compounds, the total energy calculated by geometry optimization in vacuum is used. The density functional (DFT) method is used for geometry optimization. The functional used is BVP86, the basis set is TZVP, and the fitting basis set is DGA1. The keyword opt is set. The dissociation energy is calculated using the energy when geometry optimization is completed.

[0124] In one embodiment, the ionic compound is a metal salt. The metal salt preferably contains an alkali metal and / or an alkaline earth metal. Examples of alkali metals include lithium, sodium, and potassium, and examples of alkaline earth metals include magnesium, calcium, and barium. These may be used alone or in combination of two or more.

[0125] When a metal salt is used as the ionic compound, the total amount of metals (particularly alkali metals and alkaline earth metals) in a raw material resin such as a polyester resin is preferably 80 mass ppm or less, more preferably 70 mass ppm or less, 60 mass ppm or less, 50 mass ppm or less, 40 mass ppm or less, 30 mass ppm or less, 20 mass ppm or less, 10 mass ppm or less, and 5 mass ppm or less in that order. The total amount may also be 0 mass% (below the detection limit).

[0126] Examples of the form of the metal salt include hydroxides, aliphatic carboxylates (acetates, butyrates, etc., preferably acetates), aromatic carboxylates, salts with compounds having a hydroxyl group (salts with phenols, etc.), etc. Any of these may be used alone or in combination of two or more.

[0127] In one embodiment, the ionic compound preferably includes at least one compound that is liquid at a temperature of 100°C and a pressure of 1 atmosphere, particularly an ionic liquid. In this specification, an ionic liquid refers to a salt that becomes liquid at a relatively low temperature compared to common inorganic salts and has a melting point of 100°C or lower. In addition to being non-volatile and having a low viscosity, ionic liquids are characterized by their excellent ability to dissolve organic and inorganic compounds due to their high polarity based on their aprotic ionic structure. Methods that can be used to synthesize ionic liquids include, for example, an anion exchange method, an acid ester method, and a neutralization method.

[0128] The anion constituting the ionic compound may be either an inorganic anion or an organic anion, and is not particularly limited. Specific anion species include, for example, Cl - , Br - , I - , AlCl4 - , Al2Cl7 - , BF4 - , PF6 - , ClO4 - , NO3 - , CH3COO - (Abbreviation: AA), CF3COO - , CH3SO3 -, CF3SO3 - , C4F9SO3 - , (CF3SO2)2N - , (C2F5SO2)2N - , (C3F7SO2)2N - , (C4F9SO2)2N - , (CF3SO2)3C - , AsF6 - , SbF6 - , NbF6 - , TaF6 - , F(HF) n - (n is an integer of 1 or more, for example, an integer of 1 to 5), (CN)2N - (abbreviation: DCA), C4F9SO3 - , (C2F5SO2)2N - , C3F7COO - , (CF3SO2)(CF3CO)N - , C9H 19 COO - , (CH3)2PO4 - (Abbreviation: DMP), (C2H5)2PO4 - , C2H5OSO3 - , C6H 13 OSO3 - , C8H 17 OSO3 - , CH3(OC2H4)2OSO3 - , C6H4(CH3)SO3 - , (C2F5)3PF3 - , CH3CH(OH)COO - , and (FSO2)2N - Among them, (CF3SO2)2N is preferred because of its large ionic radius, small absolute value of average charge density, and excellent electrostatic applicability. - (Abbreviation: TFSI), (FSO2)2N - (abbreviation: FSI) is preferred.

[0129] The cation constituting the ionic compound is not particularly limited, but is preferably an organic compound cation, since it can increase the ionic radius and reduce the absolute value of the average charge density. By using an organic compound as the cation, the cation radius can be increased (for example, 2 Å or more) and the absolute value of the average charge density can be reduced (for example, 0.015 e / Å). 2 Among the cations of organic compounds, cations of nitrogen-containing compounds are preferred. The cation of the nitrogen-containing compound is preferably at least one selected from the group consisting of the following (1) to (16):

[0130] (1) Pyridinium cations such as 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, and 1-butyl-3,4-dimethylpyridinium cation;

[0131] (2) Pyrrolidinium cations such as 1,1-dimethylpyrrolidinium cation, 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1-dipropylpyrrolidinium cation, 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation, and pyrrolidinium-2-one cation;

[0132] (3) piperidinium cations such as 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, and 1,1-dibutylpiperidinium cation;

[0133] (4) pyrrolium cations such as 2-methyl-1-pyrrolium cation;

[0134] (5) Indolium cations such as 1-ethyl-2-phenylindolium cation and 1,2-dimethylindolium cation;

[0135] (6) Carbazolium cations such as 1-ethylcarbazolium cation;

[0136] (7) Morpholinium cations such as N-ethyl-N-methylmorpholinium cation;

[0137] (8) imidazolium cations such as 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, 1-(2-methoxyethyl)-3-methylimidazolium cation, and 1-allyl-3-methylimidazolium cation;

[0138] (9) Tetrahydropyrimidinium cations such as 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, and 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation;

[0139] (10) Dihydropyrimidinium cations such as 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, and 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation;

[0140] (11) Pyrazolium cations such as 1-methylpyrazolium cation, 2-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolium cation, 1-ethyl-2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, and 1-butyl-2,3,5-trimethylpyrazolium cation;

[0141] (12) Pyrazolinium cations such as 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, and 1-butyl-2,3,5-trimethylpyrazolinium cation;

[0142] (13) Tetraalkylammonium cations such as tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, and tetraheptylammonium cation;

[0143] (14) Trialkylsulfonium cations such as trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, and dimethyldecylsulfonium cation;

[0144] (15) Tetraalkylphosphonium cations such as tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, diallyldimethylammonium cation, and tributyl-(2-methoxyethyl)phosphonium cation;

[0145] (16) N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N,N-dimethyl-N-ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-N-butylammonium cation, N,N-dimethyl-N-ethyl-N-pentylammonium cation, N,N-dimethyl-N-ethyl-N-hexylammonium cation, N,N-dimethyl-N-ethyl-N-heptylammonium cation, N,N-dimethyl-N-ethyl-N-heptylammonium cation, N,N-dimethyl-N-ethyl-N-pentylammonium cation, N,N-dimethyl-N-ethyl-N-hex ...pentylammonium cation, N,N-dimethyl-N-ethyl-N-pentylammonium cation, N,N-dimethyl-N-ethyl-N-pentylammonium cation, N,N-dimethyl-N-ethyl-N-hexylammonium cation, N,N-dimethyl-N-ethyl-N-heptylammonium cation, N,N-dimethyl-N-ethyl-N-pentylammonium cation, N,N-dimethyl-N-ethyl-N-pentylammonium cation, N,N-dimethyl-N-ethyl-N- N,N-ethyl-N-nonylammonium cation, N,N-dimethyl-N,N-dipropylammonium cation, N,N-dimethyl-N-propyl-N-butylammonium cation, N,N-diethyl-N-propyl-N-butylammonium cation, N,N-dimethyl-N-propyl-N-pentylammonium cation, N,N-dimethyl-N-propyl-N-hexylammonium cation, N,N-dimethyl-N-propyl-N-heptylammonium cation, N,N-dimethyl-N-butyl-N-hexylammonium cation, N,N-dimethyl-N-butyl-N-heptylammonium, N,N-diethyl-N-butyl-N-heptylammonium cation, N,N-dimethyl-N-pentyl-N-hexylammonium cation, N,N-dimethyl-N,N-dihexylammonium cation, trimethylheptylammonium cation, N,N-diethyl-N-methyl-N-propylammonium cation, N,N-diethyl-N-methyl-N-pentylammonium cation, N,N-diethyl-N-methyl-N-heptylammonium cation, N,N-diethyl-N- Propyl-N-pentylammonium cation, trimethyldecylammonium cation, triethylmethylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, tributylethylammonium cation, N,N-dipropyl-N-methyl-N-ethylammonium cation, N,N-dipropyl-N-methyl-N-pentylammonium cation, N,N-dipropyl-N-butyl-N-hexylammonium cation, N,N-dipropyl-N,Examples of tetraalkylammonium cations include N-dihexylammonium cation, N,N-dibutyl-N-methyl-N-pentylammonium cation, N,N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, and N-methyl-N-ethyl-N-propyl-N-pentylammonium cation.

[0146] In the above, the alkyl is preferably an alkyl having 1 to 10 carbon atoms, and may be an alkyl having 1 to 8 carbon atoms, an alkyl having 1 to 6 carbon atoms, an alkyl having 1 to 4 carbon atoms, an alkyl having 1 to 3 carbon atoms, or an alkyl having 1 or 2 carbon atoms. Of the above, from the viewpoint of high thermal stability, imidazolium cations such as 1-ethyl-3-methylimidazolium cation (abbreviation: EMIM), 1,3-dimethylimidazolium cation (abbreviation: MMIM), and 1-allyl-3-methylimidazolium cation (abbreviation: AMIM) are preferred, and pyrrolidinium cations such as 1-(2-methoxyethyl)-1-methylpyrrolidinium cation (abbreviation: MEMP) are particularly preferred.

[0147] Specific examples of the ionic compound are appropriately selected from the combinations of the cations and anions described above, and include, for example, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylpyridinium bis(pentafluoroethanesulfonyl) ) imide, 1-hexylpyridinium tetrafluoroborate, 1,1-dimethylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl- 1-Hexylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl) )imide, 1-ethyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1,1-dipropylpyrrolidinium bis(triple oromethanesulfonyl)imide, 1-propyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1,1-dibutylpyrrolidinium bis(triple oromethanesulfonyl)imide, 1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-pentylpiperidinium bis(trifluoromethanesulfonyl)imide, 1,1-Dimethylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-ethylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-butylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl)imide, 1-ethyl-1-butylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl)imide, 1,1-dipropylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-propyl-1-butylpiperidinium bis(trifluoromethanesulfonyl)imide, 1,1-dibutylpiperidinium bis(trifluoromethanesulfonyl)imide,1-Dimethylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-ethylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-heptylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-propylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-butylpyrrolidinium 1-ethyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-heptylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1,1-dipropylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-propyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1,1-dibutylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-propylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-pentylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1,1-dimethylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-ethylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1 -butylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1,1-dipropylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-propyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1,1-dibutylpiperidinium bis(pentafluoroethanesulfonyl)imide, 2-methyl-1-pyrrolium tetrafluoroborate, 1-ethyl-2-phenylindolium tetrafluoroborate, 1,2-Dimethylindolium tetrafluoroborate, 1-ethylcarbazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolium difluoromethanesulfonate Cyanamide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-3-methylimidazolium tris(trifluoromethanesulfonyl)methide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate , 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethane Sulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide, 1-methylpyrazolium tetrafluoroborate, 2-methylpyrazolium tetrafluoroborate, 1-ethyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)imide, 1-propyl-2,3,5-Trimethylpyrazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl)imide, 1-butyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-ethyl-2,3, 5-Trimethylpyrazolinium bis(trifluoromethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazolinium bis(trifluoromethanesulfonyl)imide, 1-butyl-2,3,5-trimethylpyrazolinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazolinium bis(pentafluoroethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazolinium bis(pentafluoroethanesulfonyl)imide, 1-butyl-2,3,5-trimethylpyrazolinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazolinium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolinium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3,5-Trimethylpyrazolinium bis(trifluoromethanesulfonyl)trifluoroacetamide, tetrapentylammonium trifluoromethanesulfonate, tetrapentylammonium bis(trifluoromethanesulfonyl)imide, tetrahexylammonium trifluoromethanesulfonate, tetrahexylammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium tetrafluoroborate, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium bis(pentafluoroethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate, N,N-diethyl -N-methyl-N-(2-methoxyethyl)ammonium trifluoromethanesulfonate, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonyl)imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis(trifluoromethanesulfonyl)imide, glycidyltrimethylammonium bi bis(pentafluoroethanesulfonyl)imide, tetraoctylphosphonium trifluoromethanesulfonate, tetraoctylphosphonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-butylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl- N-ethyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-nonylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N,N-dipropylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-butylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl- N-propyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-butyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-butyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide,N-dimethyl-N-pentyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N,N-dihexylammonium bis(trifluoromethanesulfonyl)imide, trimethylheptylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-propylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-propyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, triethylpropylammonium Bis(trifluoromethanesulfonyl)imide, triethylpentylammonium bis(trifluoromethanesulfonyl)imide, triethylheptylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-methyl-N-ethylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-butyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N,N-dihexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dibutyl-N-methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imideExamples of such compounds include N-dibutyl-N-methyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, trioctylmethylammonium bis(trifluoromethanesulfonyl)imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, 1-butylpyridinium(trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-3-methylpyridinium(trifluoromethanesulfonyl)trifluoroacetamide, 1-ethyl-3-methylimidazolium(trifluoromethanesulfonyl)trifluoroacetamide, N-ethyl-N-methylmorpholinium thiocyanate, and 4-ethyl-4-methylmorpholinium methylcarbonate. These compounds may be used alone or in combination of two or more. Among these, from the viewpoint of exhibiting excellent melt resistivity, a combination of an imidazolium cation and a bis(trifluoromethanesulfonyl)imide anion (abbreviation: TFSI) or a bis(fluorosulfonyl)imide anion (abbreviation: FSI), or a combination of a pyrrolidinium cation and TFSI or FSI is preferred, a combination of an imidazolium cation and TFSI or FSI is more preferred, a combination of a 1,3-dialkylimidazolium cation and TFSI or FSI is particularly preferred, and a combination of a 1-ethyl-3-methylimidazolium cation (abbreviation: EMIM) and bis(trifluoromethanesulfonyl)imide (abbreviation: TFSI) is most preferred.

[0148] The content of the ionic compound in the polyester film and the content of the ionic compound in the masterbatch described below can be measured, for example, by liquid chromatography mass spectrometry. Since the ease of decomposition and volatility of the cation and anion of the ionic compound may differ, the content of the ionic compound in the polyester film can be the total amount of the detected cation and anion. The preferred content of the ionic compound in the polyester film is the same as above.

[0149] Examples of methods for adding an ionic compound include the following methods (A) to (C).

[0150] (A) A method of adding an ionic compound to a raw material resin (especially a polyester resin) in advance Method (A) is, for example, a method of adding an ionic compound during polymerization of a polyester resin. The timing of addition may be any stage before the start of the esterification reaction, during the reaction, or after the completion of the reaction. When adding during the esterification reaction, it is preferable to add the ionic compound after the esterification reaction rate has reached preferably 95% or more, more preferably 97% or more, from the viewpoint of ensuring uniformity.

[0151] When adding an ionic compound, it may be dissolved in a solvent (for example, water, an organic solvent such as ethylene glycol, etc.) and added in order to ensure accurate supply. The organic solvent to be used is not particularly limited, and can be selected from aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, heptane, and octane; alcohol solvents such as methanol, ethanol, propanol, butanol, and benzyl alcohol; glycol solvents such as ethylene glycol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, 1,3-dimethylimidazolidinone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone; lactone solvents such as γ-butyrolactone; and phenolic solvents such as phenol, taking into consideration the solubility of the ionic compound, miscibility with the raw material resin, and reactivity with the raw material resin. Among these, ketone solvents such as methyl ethyl ketone and acetone, alcohol solvents such as methanol and ethanol, and glycol solvents such as ethylene glycol are preferred from the viewpoint of solubility of the ionic compound, and are also preferred from the viewpoint of not interfering with the polycondensation reaction when the polycondensation step is carried out in the coexistence of an ionic compound. These solvents can be used alone or in combination of two or more.

[0152] The ionic compound may be added after the raw resin (particularly polyester resin) is produced and chipped, but before melt-kneading to form a polyester film. For example, the ionic compound may be added after the raw resin (particularly polyester resin) is chipped and dried (particularly just before drying). In this case, it is preferable to add the ionic compound dissolved in a solvent (e.g., water, organic solvent, etc.) as described above, and the solvent preferably has a boiling point below the drying temperature (e.g., 135°C or below).

[0153] (B) A method in which raw resin (especially polyester resin) is melt-kneaded and an ionic compound is added In method (B), it is also preferable to add the ionic compound after dissolving it in a solvent (e.g., water, an organic solvent, etc.) as in method (A). Note that method (B) also includes a method in which an ionic compound is added to a raw material resin that has been melt-kneaded during film formation.

[0154] (C) A first raw material resin composition (such as a polyester resin composition) containing an ionic compound (particularly at a high concentration) is converted into a resin composition that does not contain an ionic compound, or that contains an ionic compound at a lower concentration than the first raw material resin composition, or that has a melt resistivity higher than that of the first raw material resin composition, or that has a melt resistivity of 1×10 8 A method of blending with a second raw material resin (such as a polyester resin) or a second raw material resin composition (such as a polyester resin composition) containing the second raw material resin (such as a polyester resin composition) having a resistivity of Ω·cm or more.

[0155] The above method (C) will now be explained in more detail. In the following description, a polyester resin composition that is an example of a first raw material resin composition and contains a polyester resin and an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 850 or less is referred to as polyester resin composition A, a polyester resin used in polyester resin composition A is referred to as polyester resin A, and a polyester resin that is an example of a second raw material resin and has a melt resistivity greater than that of polyester resin composition A (or a melt resistivity of 1×10 8The polyester resin with a resistivity of Ω·cm or more will be referred to as polyester resin B.

[0156] In one embodiment, the above method (C) is a method for producing a polyester resin composition A containing a polyester resin A and an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 850 or less, and a polyester resin composition B containing an ionic compound having a melt resistivity greater than that of the polyester resin composition A (or a melt resistivity of 1×10 8 Preferably, the method includes a step of mixing (particularly melt-mixing) a polyester resin B (having a resistivity of Ω·cm or more). In this method, it is preferable that the polyester resin B has a high melt resistivity and poor electrostatic adhesion. By mixing the polyester resin B with a polyester resin composition A containing an ionic compound, the melt resistivity can be reduced and good electrostatic adhesion can be obtained.

[0157] (Polyester resin composition A) The polyester resin composition A may be referred to as an ionic compound masterbatch or an electrostatic adhesion agent masterbatch, or simply as a masterbatch (MB).

[0158] The polyester resin A is preferably selected from the polyester resins described above, specifically PET, PEN, PTT, PBT, PCT, PEF, PLA, PBS, PBSA, PBSL, PBAT, and PES. Furthermore, polyester resin A and polyester resin B are preferably polyester resins having the same main polymerization components (dicarboxylic acid component, glycol component, and / or hydroxycarboxylic acid component), but they do not necessarily have to be strictly identical. When the total amount of the polymerization components (dicarboxylic acid component, glycol component, and / or hydroxycarboxylic acid component) of the polyester resin is taken as 100 mol%, the total amount of the polymerization components that differ between polyester resin A and polyester resin B is preferably 7 mol% or less, more preferably 5 mol% or less, even more preferably 3 mol% or less, and particularly preferably 2 mol% or less. It may be 0 mol% or more. (Example) In the above specific example, the difference in terephthalic acid component among all dicarboxylic acid components is 1 mol %, and the difference in ethylene glycol component among all glycol components is 0.4 mol %, for a total difference of 1.4 mol %.

[0159] When there are a plurality of polyester resins A and B, the composition is calculated as an average.

[0160] Furthermore, when the polyester resin used as the raw material for the polyester film is a copolymer polyester resin or when a plurality of polyester resins with different compositions are blended, the above is not limitative. When the polyester resin used as the raw material for the polyester film is a copolymer polyester resin, the polyester resin A may not be the PET or the like listed above, but may be a polyester resin B used to produce a masterbatch to form the polyester resin composition A. Furthermore, when a plurality of polyester resins with different compositions are blended, it is also a preferred embodiment to form the polyester resin composition A by adding an ionic compound to one or more of the polyester resins.

[0161] The amount of the ionic compound added to the polyester resin composition A is preferably 1% by mass (10,000 ppm by mass) or less, more preferably 5,000 ppm by mass or less, even more preferably 2,000 ppm by mass or less, and particularly preferably 1,000 ppm by mass or less. The amount of the ionic compound added can be appropriately optimized depending on the melt resistivity of the resin constituting the film to be obtained and the dissociation energy of the ionic compound. If the ionic compound has a small dissociation energy, the melt resistivity can be reduced with a smaller amount, and the amount of the ionic compound added to the polyester resin composition A can also be reduced.

[0162] The amount of the ionic compound added to the polyester resin composition A may be 950 ppm by mass or less, 900 ppm by mass or less, 850 ppm by mass or less, 700 ppm by mass or less, 500 ppm by mass or less, 400 ppm by mass or less, 250 ppm by mass or less, 150 ppm by mass or less, 90 ppm by mass or less, 40 ppm by mass or less, 20 ppm by mass or less, 10 ppm by mass or less, or 9 ppm by mass or less.

[0163] The amount of the ionic compound added to the polyester resin composition A is preferably 1 ppm by mass or more, more preferably 2 ppm by mass or more, even more preferably 3 ppm by mass or more, particularly preferably 4 ppm by mass or more, and particularly preferably 5 ppm by mass or more. In one embodiment, the amount of the ionic compound added to the polyester resin composition A is preferably 1 ppm by mass or more and 10,000 ppm by mass or less.

[0164] The amount added can be read as the content.

[0165] It is preferable that the polyester resin composition A satisfies the above formulas 1 and 2.

[0166] As a method for adding an ionic compound to polyester resin A, for example, the above-mentioned methods (A) to (C) can be mentioned.

[0167] The concentration C1 of the ionic compound contained in the polyester resin composition A is preferably at least 3 times, more preferably at least 5 times, even more preferably at least 8 times, and particularly preferably at least 10 times the concentration C2 of the ionic compound contained in the polyester film (or raw material resin such as polyester resin). Furthermore, the concentration C1 is preferably no more than 10,000 times, more preferably no more than 1,000 times, even more preferably no more than 500 times, particularly preferably no more than 200 times, and most preferably no more than 100 times. In one embodiment, the concentration C1 is preferably at least 3 times and no more than 10,000 times the concentration C2.

[0168] The upper limit of the melt resistivity of the polyester resin composition A is preferably 5×10 8 Ω·cm, and more preferably 2×10 8 Ω·cm, and more preferably 1×10 8 Ω·cm, and particularly preferably 0.5×10 8 Ω·cm, and most preferably 0.1×10 8 The lower limit of the melt resistivity of the polyester resin composition A is preferably 0.0001×10 8 Ω·cm, and more preferably 0.0005×10 8 Ω·cm, and more preferably 0.001×10 8 Ω·cm, and particularly preferably 0.005×10 8 Ω cm, and most preferably 0.01×10 8 In one embodiment, the melt resistivity of polyester resin composition A is 0.0001×10 8 Ω cm or more 0.1×10 8 By setting the viscosity within this range, economical production becomes easier, and the mixture becomes easier to mix uniformly, which makes stable production easier.

[0169] The polyester resin composition A may contain components other than the polyester resin A and the ionic compound. Specific examples of such components include colorants such as pigments, lubricants (particularly lubricant particles), ultraviolet absorbers, antistatic agents, antioxidants, heat stabilizers, and resins other than the polyester resin A. The components other than the polyester resin A and the ionic compound may be used alone or in combination of two or more.

[0170] Lubricants (particularly lubricant particles) are often added to films to ensure smoothness and enable winding. Such films can usually be produced by a method including a step of blending a polyester resin that does not contain (or contains at a low concentration of) lubricants (particularly lubricant particles) with a polyester resin composition (lubricant masterbatch) in which lubricants (particularly lubricant particles) have been added (or added at a high concentration) to the polyester resin. It is also a preferred method to add an ionic compound to this lubricant masterbatch to form polyester resin composition A.

[0171] (lubricant masterbatch) The lubricant masterbatch will now be described. Examples of lubricants include oxides, carbonates, silicates, sulfates, and aluminates of metals such as titanium, aluminum, silicon, calcium, magnesium, and barium. More specific examples include titanium dioxide, alumina, aluminosilicate, silicon dioxide (silica), calcium oxide, calcium carbonate, and barium sulfate, as well as particles of naturally occurring talc, mica, kaolinite, and zeolite, but are not limited to these. Lubricants may be used alone or in combination of two or more.

[0172] The lower limit of the average particle size of the lubricant is preferably 0.1 μm, more preferably 0.2 μm, even more preferably 0.3 μm, particularly preferably 0.4 μm, and most preferably 0.5 μm. The upper limit of the average particle size of the lubricant is preferably 5 μm, more preferably 4 μm, even more preferably 3 μm, particularly preferably 2.7 μm, and most preferably 2.5 μm. In one embodiment, the average particle size of the lubricant is preferably 0.1 μm or more and 5 μm or less. By setting the particle size within the above range, unevenness is efficiently formed on the film surface, imparting the effect of improving handleability such as slipperiness and runnability, while suppressing an increase in haze and the formation of coarse protrusions. The average particle size of the lubricant can be determined, for example, by photographing the particles using an electron microscope, randomly selecting and observing 100 unagglomerated particles, and averaging their equivalent-circle diameters to determine the average particle size. The particles may be measured before addition, or the lubricant masterbatch or film may be dissolved in a solvent that dissolves polyester resin, filtered through a membrane filter such as PTFE, and the particles captured on the filter may be measured.

[0173] The lower limit of the amount of lubricant relative to the lubricant masterbatch is preferably 1000 ppm by mass, more preferably 2000 ppm by mass, even more preferably 3000 ppm by mass, particularly preferably 4000 ppm by mass, and most preferably 5000 ppm by mass. The upper limit of the amount of lubricant relative to the lubricant masterbatch is preferably 70000 ppm by mass, more preferably 50000 ppm by mass, even more preferably 40000 ppm by mass, particularly preferably 30000 ppm by mass, and most preferably 20000 ppm by mass. In one embodiment, the amount of lubricant relative to the lubricant masterbatch is preferably 1000 ppm by mass or more and 70000 ppm by mass or less.

[0174] When polyester resin composition A is produced as a lubricant masterbatch, it is preferable to add a lubricant to polyester resin A so that the amount of lubricant is a preferred amount. When the amount of lubricant relative to the lubricant masterbatch is within the above range, there is no need to add a large amount of lubricant masterbatch, and there is no risk of deterioration in color tone and heat resistance or increased production costs. In addition, there is no risk of lubricant aggregation occurring, which would lead to an increase in the number of coarse defects (coarse particles) after blending and dilution.

[0175] The lubricant masterbatch can be produced, for example, by adding a lubricant during polymerization of the polyester resin, or by melt-kneading the lubricant after producing the polyester resin.

[0176] When a lubricant is added during polymerization of a polyester resin, the timing of adding the lubricant to the polyester resin is not particularly limited, but it is preferable to add it during the esterification (or transesterification) step or between the end of the esterification (or transesterification) step and the start of the polycondensation step, since this allows the lubricant to be uniformly dispersed in the polyester resin. The lubricant is preferably added as a slurry of ethylene glycol.

[0177] Examples of methods for adding an ionic compound to a lubricant masterbatch include a method of adding an ionic compound to a polyester resin composition for a lubricant masterbatch, a method of adding an ionic compound or an ionic compound masterbatch when melt-kneading a polyester resin and a lubricant, a method of melt-kneading a polyester resin composition for an ionic compound masterbatch with a lubricant masterbatch, and a method of melt-kneading a lubricant masterbatch with an ionic compound masterbatch.

[0178] The film can also be produced by a method including a step of blending a polyester resin that does not contain (or contains at a low concentration) an ultraviolet absorber with a polyester resin composition (ultraviolet absorber masterbatch) in which an ultraviolet absorber has been added (or added at a high concentration) to the polyester resin. A preferred method is to add an ionic compound to this ultraviolet absorber masterbatch to form polyester resin composition A. Examples of ultraviolet absorbers include organic and inorganic ultraviolet absorbers, with organic ultraviolet absorbers being preferred from the viewpoint of transparency. Examples of organic ultraviolet absorbers include benzophenones, benzotriazoles, acrylonitriles, cyclic iminoesters, and combinations thereof.

[0179] Examples of the benzophenone-based ultraviolet absorber, benzotriazole-based ultraviolet absorber, and acrylonitrile-based ultraviolet absorber include 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxypropyl)phenyl]-2H-benzotriazole, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2' ,4,4'-tetrahydroxybenzophenone, 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(5-chloro(2H)-benzotriazol-2-yl)-4-methyl-6-(tert-butyl)phenol, 2,2'-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol, and the like.

[0180] Examples of cyclic iminoester-based ultraviolet absorbers include 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one), 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, and 2-phenyl-3,1-benzoxazin-4-one.

[0181] From the viewpoint of durability, benzothazole-based ultraviolet absorbers and / or cyclic iminoester-based ultraviolet absorbers are particularly preferred.

[0182] Another preferred method is to incorporate an ionic compound into the UV absorber masterbatch to produce polyester resin composition A. The UV absorber concentration in the UV absorber masterbatch is preferably 5 to 30% by mass to uniformly disperse the UV absorber and economically compound it. The UV absorber masterbatch is preferably prepared using a kneading extruder at an extrusion temperature of from the melting point of the polyester resin to 290°C for 1 to 15 minutes. This extrusion temperature and extrusion time range can suppress both weight loss of the UV absorber and a decrease in the viscosity of the UV absorber masterbatch. This extrusion time range also enables more uniform mixing of the UV absorber. At this time, additives such as stabilizers, color adjusters, and antistatic agents may be added as needed. An ionic compound or an ionic compound masterbatch may be added to the polyester resin composition for the UV absorber masterbatch, a UV absorber may be added to the polyester resin composition for the ionic compound masterbatch, or the UV absorber masterbatch and the ionic compound masterbatch may be melt-kneaded.

[0183] (Polyester resin B) The melt resistivity of polyester resin B is higher than that of polyester resin composition A, and is 1×10 8 The melt resistivity of polyester resin B is preferably 5×10 8 It is more preferable that the resistance is Ω·cm or more, and 10×10 8The upper limit of the melt resistivity of polyester resin B is not particularly limited, but is preferably 10,000×10 8 Ω·cm, and more preferably 1000×10 8 In one embodiment, the melt resistivity of polyester resin B is 1×10 8 Ω cm or more 10000×10 8 It is preferable that the resistivity is Ω·cm or less.

[0184] In one preferred embodiment, polyester resin B includes one selected from biomass PET, chemically recycled PET, and recycled polyester resin.

[0185] The polyester resin B may contain a colorant such as a pigment, a lubricant (particularly lubricant particles), an ultraviolet absorber, an antistatic agent, an antioxidant, a heat stabilizer, a resin other than polyester resin, and the like.

[0186] The polyester resin composition A and the polyester resin B are preferably in the form of chips, and the shape may be any shape, such as a sphere, an oval sphere (rugby ball shape), a cylinder, or a bale (hamburger steak shape). The mass of the chips is preferably 10 to 100 mg, more preferably 15 to 70 mg, and even more preferably 20 to 50 mg. When the polyester resin composition A and the polyester resin B are dry-blended, it is preferable to make the chip shapes and masses of the two similar to reduce segregation during feeding. When the larger mass of the polyester resin composition A and the smaller mass of the polyester resin B (including when the masses are the same) is defined as 1, the smaller mass is preferably 0.5 or more, more preferably 0.6 or more, more preferably 0.7 or more, and particularly preferably 0.75 or more. The upper limit is preferably 1.

[0187] The polyester resin composition A and the polyester resin B can be mixed, for example, by the following method: - Premixing chips and adding them through the same inlet of the extruder; Adding chips through separate ports in the extruder; A method in which polyester resin composition A is melted in a separate extruder and then merged with an extruder for polyester resin B; A method in which polyester resin composition A and polyester resin B are melted in separate extruders and then mixed in yet another extruder is also exemplified.

[0188] When mixing the polyester resin composition A and the polyester resin B, a lubricant masterbatch may be used in combination, or an ultraviolet absorber masterbatch may be used in combination, or other additives may be added directly or as a masterbatch.

[0189] The amount of polyester resin A relative to the total amount of polyester resin composition A and polyester resin B is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, particularly preferably 0.5% by mass or more, and most preferably 1% by mass or more. The amount of polyester resin A is preferably 33% by mass or less, more preferably 20% by mass or less, even more preferably 12.5% ​​by mass or less, and particularly preferably 10% by mass or less. In one embodiment, the amount of polyester resin A is preferably 0.01% by mass or more and 33% by mass or less. By setting the amount within the above range, the ionic compound can be added stably, enabling high-speed and stable film formation, which is advantageous in terms of cost, and a polyester film with few defects and coloration can be obtained.

[0190] In order to keep the amount of ionic compound added small and thereby reduce film discoloration and contamination of the film manufacturing equipment, it is preferable to add an ionic compound having an ionic dissociation energy within the above range. However, the dissociation energy of the ionic compound itself to be added may be outside the above range, as long as ion exchange or the like occurs within the film and an ionic compound whose ionic dissociation energy is substantially within the above range is produced.

[0191] Specifically, multiple ionic compounds with dissociation energies outside the above range may be added to the film, causing ion exchange or the like in the film to produce a combination of anions and cations that substantially results in a dissociation energy within the above range. In this case, polyester resin composition A may be added to produce a combination of anions and cations that results in a dissociation energy within the above range, or polyester resin compositions A may be separately prepared to produce a combination of anions and cations that results in a dissociation energy within the above range when mixed, and then these may be mixed. The content of ionic compounds in the film can be the total amount of the combination of anions and cations that corresponds to the ionic compounds among the detected cations and anions.

[0192] The polyester film may be a multilayer film containing two or more polyester layers. The multilayer film may be, for example, a coextruded film (CCF). In the case of a multilayer film, it is preferable that at least one layer contains an ionic compound, and a layer that does not contain an ionic compound may also be present.

[0193] In the case of a multilayer film having three or more layers, the outermost layers on both sides may be layers that do not contain an ionic compound, and the inner layers may be layers that contain an ionic compound. By using such a configuration, bleeding out of the ionic compound can be suppressed.

[0194] When the film has layers that do not contain an ionic compound, the layers containing the ionic compound preferably account for 30% or more of the total thickness of the film, more preferably 50% or more, even more preferably 60% or more, particularly preferably 70% or more, and most preferably 90% or more. The layers containing the ionic compound preferably account for 99% or less of the total thickness of the film, more preferably 96% or less, even more preferably 94% or less, and particularly preferably 92% or less. In one embodiment, the layers containing the ionic compound preferably account for 30% or more and 99% or less of the total thickness of the film.

[0195] It is preferable to adjust the amount of the ionic compound added to the layer containing the ionic compound so that the melt resistivity of all layers falls within an appropriate range.

[0196] Other typical configurations of multilayer films include, for example, a configuration of two or more layers in which one outermost layer contains a lubricant (particularly lubricant particles) and the other outermost layer does not contain a lubricant (particularly lubricant particles); a configuration in which the outermost layers on both sides contain a lubricant (particularly lubricant particles) and at least one of the inner layers does not contain a lubricant (particularly lubricant particles); a configuration in which the outermost layers on both sides do not contain a lubricant (particularly lubricant particles) and at least one of the inner layers contains a lubricant (particularly lubricant particles); and a configuration in which the outermost layers on both sides do not contain an ultraviolet absorber and at least one of the inner layers contains an ultraviolet absorber. Any combination or composite (for example, a layer containing an ionic compound and an ultraviolet absorber, a layer containing an ionic compound and a lubricant (particularly lubricant particles), etc.) is possible.

[0197] [Polyester film manufacturing method] The method for producing a polyester film preferably includes the steps of feeding raw materials such as a polyester resin into an extruder, melt-kneading the materials, and then extruding the materials through a die having a long, narrow slit onto a cooling roll to obtain an unstretched film. In one embodiment, the raw materials may include a polyester resin composition A and a polyester resin B.

[0198] The lower limit of the melting temperature (melting point) is preferably the melting point of the raw resin of the film + 5°C, more preferably the melting point + 10°C, even more preferably the melting point + 15°C, and particularly preferably the melting point + 20°C. The upper limit of the melting temperature (melting point) is preferably the melting point + 50°C, more preferably the melting point + 45°C, even more preferably the melting point + 40°C, and particularly preferably the melting point + 35°C. In one embodiment, the melting temperature is preferably the melting point + 5°C or more and the melting point + 50°C or less. By setting the melting temperature within the above range, it becomes easier to form a film of uniform thickness and also suppress the generation of foreign matter and discoloration due to decomposition of the raw resin. For example, in the case of PET, the lower limit of the melting temperature is preferably 265°C, more preferably 270°C, and even more preferably 275°C. The upper limit of the melting temperature is preferably 310°C, more preferably 305°C, and even more preferably 300°C. In one embodiment, the melting temperature is preferably 265°C or more and 310°C or less. When the film is made of multiple raw material resins, the melting point of the resin with the highest melting point is used. The melting point can be evaluated by the endothermic peak value from the results obtained using a differential scanning calorimeter (e.g., DSC7020 manufactured by Hitachi High-Tech Science Corporation) under the following conditions: Sample: 5mg Measurement conditions: 1st RUN (heating): Heating rate 10°C / min, rt → 250°C (hold for 3 minutes) 1stRUN (temperature fall): Temperature fall rate -50℃ / min, 250℃→25℃ 2nd RUN (heating): Heating rate 10℃ / min, rt→250℃

[0199] The electrostatic adhesion method is preferred as a method for adhering the molten raw material resin to the chill roll. The electrostatic adhesion method is a method in which an electrode is usually provided before (particularly immediately before) the molten raw material resin comes into contact with the chill roll, and the molten resin is charged by applying a voltage to the electrode, thereby adhering the molten resin to the chill roll by electrostatic force.

[0200] Examples of the electrode include wire-shaped and ribbon-shaped electrodes. The diameter Φ of the wire-shaped electrode is preferably 0.05 to 1 mm, particularly preferably 0.08 to 0.5 mm. The thickness of the ribbon-shaped electrode is preferably 0.05 to 1 mm, particularly preferably 0.08 to 0.5 mm, and the width of the ribbon-shaped electrode is preferably 3 to 50 mm, particularly preferably 5 to 40 mm. The electrodes may be used in combination with a plurality of types and sizes, such as a wire and a tape, or a small-diameter wire and a large-diameter wire. It is preferable that the electrodes be unwound from one side and wound up on the other side.

[0201] Examples of materials for the electrodes include tungsten, iron, nickel, cobalt, molybdenum, titanium, tantalum, aluminum, copper, stainless steel, etc., and alloys of these may also be used. The surfaces of the electrodes may also be plated with gold, platinum, etc.

[0202] The electrode is provided on the opposite side of the molten resin film from the cooling roll, and the distance from the molten resin film is preferably 2 to 50 mm, more preferably 3 to 30 mm, and even more preferably 4 to 20 mm. The electrode is preferably provided between the die exit and the point where the cooling roll and molten resin contact each other, and is provided preferably 1 to 50 mm upstream, and more preferably 2 to 30 mm upstream, of the point where the cooling roll and molten resin contact each other.

[0203] The voltage is preferably 1 to 100 KV, more preferably 3 to 50 KV.

[0204] The electrostatic adhesion method may be used in combination with a mechanical adhesion method such as a vacuum box or an air knife, and it is particularly preferable to use it in combination with a method of blowing air onto both ends.

[0205] Because the melt resistivity of the raw resin can be optimized, high adhesion can be achieved even when the film is formed at a high speed. For example, an unstretched film can be produced at a speed of 60 m / min or more, 80 m / min or more, 100 m / min or more, or 120 m / min or more. The upper limit of the speed is not limited because it depends on the overall capacity and cooling capacity of the extruder and film-forming machine, but is approximately 500 m / min, 400 m / min, or 300 m / min. In one embodiment, the speed is preferably 60 m / min or more and 500 m / min or less.

[0206] The cooled film may be used as an unstretched film, or may be subsequently stretched to form a stretched film. Stretching may be either uniaxial or biaxial. Uniaxial stretching may be in either the MD (longitudinal) or TD (transverse) direction, or may be in an oblique direction. Biaxial stretching may be any method, such as sequential stretching, simultaneous biaxial stretching, or a combination of these. Biaxial stretching may be either MD stretching followed by TD stretching, or TD stretching followed by MD stretching, and further MD stretching or TD stretching may be added and alternately repeated, or MD stretching and TD stretching may be performed in multiple stages.

[0207] The lower limit of the stretching ratio in uniaxial stretching is preferably 2, more preferably 2.5, even more preferably 2.8, particularly preferably 3, and most preferably 3.2. The upper limit of the stretching ratio in uniaxial stretching is preferably 8, more preferably 7, even more preferably 6, particularly preferably 5.5, and most preferably 5. In one embodiment, the stretching ratio in uniaxial stretching is preferably 2 to 8 times.

[0208] The lower limit of the stretching ratio in at least one of the biaxial stretching directions (main directions) is preferably 2, more preferably 2.5, even more preferably 2.8, particularly preferably 3, and most preferably 3.2. The upper limit of the stretching ratio in at least one of the biaxial stretching directions (main directions) is preferably 8, more preferably 7, even more preferably 6, particularly preferably 5.5, and most preferably 5. In one embodiment, the stretching ratio in at least one of the biaxial stretching directions (main directions) is preferably 2 to 8.

[0209] The lower limit of the stretching ratio in the other direction of biaxial stretching is preferably 1.05, more preferably 1.1, even more preferably 1.2, particularly preferably 1.3, and most preferably 1.5. The upper limit of the stretching ratio in the other direction of biaxial stretching is preferably 8, more preferably 7, even more preferably 6, particularly preferably 5.5, and most preferably 5. In one embodiment, the stretching ratio in the other direction of biaxial stretching is preferably 1.05 to 8.

[0210] The lower limit of the area ratio of biaxial stretching is preferably 4 times, more preferably 5 times, even more preferably 6 times, particularly preferably 7 times, and most preferably 8 times. The upper limit of the area ratio of biaxial stretching is preferably 25 times, more preferably 22 times, even more preferably 20 times, particularly preferably 18 times, and most preferably 16 times. In one embodiment, the area ratio of biaxial stretching is preferably 4 times or more and 25 times or less.

[0211] In the case of a typical biaxial stretching method in which MD stretching is followed by TD stretching, the lower limit of the MD stretching ratio is preferably 2.3 times, more preferably 2.6 times, and even more preferably 2.8 times. The upper limit of the MD stretching ratio is preferably 4.2 times, more preferably 3.8 times, and even more preferably 3.5 times. In one embodiment, the MD stretching ratio is preferably 2.3 times or more and 4.2 times or less.

[0212] The lower limit of the TD stretching ratio is preferably 2.8, more preferably 3, even more preferably 3.2, and particularly preferably 3.4. The upper limit of the TD stretching ratio is preferably 6, more preferably 5, even more preferably 4.5, particularly preferably 4.3, and most preferably 4. In one embodiment, the TD stretching ratio is preferably 2.8 to 6.

[0213] The lower limit of the stretching temperature is preferably Tg + 0°C, more preferably Tg + 3°C, even more preferably Tg + 5°C, and particularly preferably Tg + 10°C. The upper limit of the stretching temperature is preferably Tg + 50°C, more preferably Tg + 40°C, even more preferably Tg + 35°C, and particularly preferably Tg + 30°C. In one embodiment, the stretching temperature is preferably Tg or higher and Tg + 50°C or lower. In this specification, Tg refers to the midpoint glass transition temperature defined in JIS K7121 (1987). In addition, in the case of a film containing a mixture of multiple resins, it is the Tg of the molten mixture (the resin composition extruded onto the cooling roll).

[0214] For PET, the lower limit of the stretching temperature is preferably 80° C., more preferably 83° C., and even more preferably 85° C. For PET, the upper limit of the stretching temperature is preferably 130° C., more preferably 125° C., and even more preferably 120° C. In one embodiment, the stretching temperature for PET is preferably 80° C. or higher and 130° C. or lower.

[0215] For PET, the lower limit of the MD stretching temperature is preferably 80° C., more preferably 83° C., and even more preferably 85° C. For PET, the upper limit of the MD stretching temperature is preferably 110° C., more preferably 105° C., and even more preferably 100° C. In one embodiment, the MD stretching temperature for PET is preferably 80° C. or higher and 110° C. or lower.

[0216] For PET, the lower limit of the TD stretching temperature is preferably 85° C., more preferably 90° C., and even more preferably 95° C. For PET, the upper limit of the TD stretching temperature is preferably 130° C., more preferably 125° C., and even more preferably 120° C. In one embodiment, the TD stretching temperature for PET is preferably 85° C. or higher and 130° C. or lower. The above temperatures are merely guidelines for the film temperature, and it is preferable to adjust the temperatures of the heating rollers, infrared heater, tenter, etc. so that the film reaches the above temperatures during stretching.

[0217] The lower limit of the stretching speed (tenter) is preferably 10% / s, more preferably 15% / s, even more preferably 20% / s, and particularly preferably 25% / s. By setting the speed to equal to or higher than the above lower limit, productivity can be increased. The upper limit of the stretching speed (tenter) is preferably 100% / s, more preferably 90% / s, even more preferably 80% / s, and particularly preferably 75% / s. By setting the speed to equal to or lower than the above upper limit, breakage can be suppressed and uniform stretching can be achieved. In one embodiment, the stretching speed (tenter) is preferably 10% / s or more and 100% / s or less. The standard for the stretching speed is that the length before stretching is taken as 100%.

[0218] The lower limit of the heat treatment temperature is preferably 120°C, more preferably 150°C, even more preferably 170°C, and particularly preferably 190°C. By setting the temperature at or above the lower limit, the thermal shrinkage rate of the film can be suppressed. The upper limit of the heat treatment temperature is preferably 250°C, more preferably 245°C, even more preferably 240°C, and particularly preferably 235°C. By setting the temperature at or below the upper limit, good flatness can be achieved. In one embodiment, the heat treatment temperature is preferably 120°C or higher and 250°C or lower.

[0219] The lower limit of the heat treatment time is preferably 2 seconds, more preferably 3 seconds, and even more preferably 5 seconds. The upper limit of the heat treatment time is preferably 120 seconds, more preferably 60 seconds, even more preferably 30 seconds, and particularly preferably 20 seconds. In one embodiment, the heat treatment time is preferably 2 seconds or more and 120 seconds or less.

[0220] The lower limit of the relaxation treatment temperature is preferably 100°C, more preferably 120°C, even more preferably 140°C, and particularly preferably 150°C. The upper limit of the relaxation treatment temperature is preferably the heat treatment temperature, more preferably the heat treatment temperature minus 5°C, even more preferably the heat treatment temperature minus 10°C, and may be, for example, 250°C or lower. In one embodiment, the relaxation treatment temperature is preferably 100°C or higher and the heat treatment temperature or lower, and may be 100°C or higher and 250°C or lower.

[0221] The lower limit of the relaxation rate is preferably 0.5%, more preferably 1%, and even more preferably 1.5%. By setting it to the above lower limit or higher, the thermal shrinkage rate can be effectively suppressed. The upper limit of the relaxation rate is preferably 5%, more preferably 4.5%, and even more preferably 4%. By setting it to the above upper limit or lower, the flatness can be improved. In one embodiment, the relaxation rate is preferably 0.5% or more and 5% or less.

[0222] Relaxation in the TD direction can be achieved, for example, by narrowing the clip width in the tenter. Relaxation in the MD direction can be achieved, for example, by cutting off or releasing the edge portions held by the clips in the tenter and slowing the film take-up speed below the film running speed in the tenter, by narrowing the clip spacing using a simultaneous biaxial stretching machine, or by transferring the film between a first-stage clip chain and a second-stage clip chain running slower than the first-stage clip chain.

[0223] Typically, the film is then cooled and wound up. The lower limit of the cooling temperature (at the tenter outlet) is preferably 40°C, more preferably 50°C, and even more preferably 60°C. The upper limit of the cooling temperature (at the tenter outlet) is preferably 140°C, more preferably 120°C, and even more preferably 100°C. In one embodiment, the cooling temperature (at the tenter outlet) is preferably 40°C or higher and 140°C or lower.

[0224] The lower limit of the film temperature during winding is preferably 10°C, more preferably 15°C, and even more preferably 18°C. The upper limit of the film temperature during winding is preferably 50°C, more preferably 40°C, and even more preferably 35°C. By keeping the temperature at or below the above upper limit, charging and scratches due to tight winding can be reduced. In one embodiment, the film temperature during winding is preferably 10°C or higher and 50°C or lower.

[0225] It is preferable that an easy-adhesion layer is provided on at least one side of the polyester film. When easy-adhesion layers are provided on both sides, both sides may have the same composition or different compositions. The easy-adhesion layer may be provided in-line during film production or may be provided offline after film production, but it is preferable that it is provided in-line during film production. In this specification, the term polyester film may refer to a film including the above-mentioned easy-adhesion layer.

[0226] Preferred examples of the resin used in the easy-adhesion layer include polyester, acrylic, polyurethane (such as polyester polyurethane, polycarbonate polyurethane, and polyether polyurethane), ethylene-vinyl acetate copolymer, polyamide, styrene-acrylic copolymer, polyvinyl alcohol, etc. These resins may be used alone or in combination of two or more.

[0227] The adhesive layer is preferably crosslinked. Preferred examples of the crosslinking agent used include an isocyanate group-containing compound, an oxazoline group-containing compound, an epoxy group-containing compound, an amino resin such as melamine, and a carbodiimide compound. In the case of a photocurable resin, it may be a monomer or oligomer of a compound containing multiple double bonds, such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, an acrylic-modified polyurethane, or an acrylic-modified epoxy resin. The crosslinking agent may be used alone or in combination of two or more.

[0228] The adhesive layer may contain additives such as particles, surfactants, leveling agents, antistatic agents, catalysts, etc. The additives may be used alone or in combination of two or more.

[0229] The lower limit of the thickness of the easy-adhesion layer after drying is preferably 0.001 μm, more preferably 0.005 μm, even more preferably 0.01 μm, and particularly preferably 0.02 μm. The upper limit of the thickness of the easy-adhesion layer after drying is preferably 1 μm or less, more preferably 0.5 μm or less, even more preferably 0.3 μm or less, and particularly preferably 0.2 μm. In one embodiment, the thickness of the easy-adhesion layer after drying is preferably 0.001 μm or more and 1 μm or less.

[0230] The melt resistivity of polyester resin to which no ionic compounds are added varies depending on the polyester composition, the type and amount of catalyst, etc., and is 100 x 10 8Although the resistivity may be as high as Ω·cm, the use of an ionic compound (or polyester resin composition A) can lower the melt resistivity and provide electrostatic adhesion. In particular, for insulation applications, germanium, titanium, manganese, etc. are used as catalysts, and the amount of metal catalyst is kept as low as possible to ensure high insulating properties. However, if the amount of catalyst is increased to achieve electrostatic adhesion, the catalyst may precipitate, making that area more susceptible to short circuits and preventing sufficient insulating properties from being achieved. However, the use of an ionic compound (or polyester resin composition A) can lower the melt resistivity while suppressing short circuits caused by foreign matter and ensuring insulating properties.

[0231] The melt resistivity of the raw material resin (especially polyester resin) after adding the ionic compound is preferably 20 x 10 8 Ω·cm or less, and more preferably 15×10 8 Ω·cm or less, and more preferably 10×10 8 Ω·cm or less, and particularly preferably 5×10 8 Ω·cm or less, most preferably 2×10 8 By keeping the resistivity below the above upper limit, electrostatic adhesion can be maintained even in raw resins (especially polyester resins) that have high melt resistivity before the ionic compound is added.

[0232] In order to achieve faster film formation, the melt resistivity of the raw material resin (especially polyester resin) after adding the ionic compound is preferably 1×10 8 Ω·cm or less, and more preferably 0.8×10 8 Ω·cm or less, and more preferably 0.7×10 8 Ω·cm or less, and particularly preferably 0.6×10 8 Ω·cm or less, most preferably 0.5×10 8 The lower limit of the melt resistivity is preferably 0.001×10 8 Ω·cm, and more preferably 0.005×10 8 Ω·cm, and more preferably 0.01×10 8Ω·cm, and particularly preferably 0.05×10 8 Ω·cm, and most preferably 0.1×10 8 Ω·cm. By making the resistivity equal to or greater than the lower limit, the charge of the film can be maintained and high electrostatic adhesion can be ensured. In addition, scratches, holes, breaks, etc. in the film due to sparks between the electrode and the molten resin can be suppressed. In one embodiment, the melt resistivity is 0.001×10 8 Ω cm or more 1×10 8 It is preferable that the resistivity is Ω·cm or less.

[0233] When the purpose is to reduce the amount of foreign matter, or when high insulation properties are required, the melting resistivity should be 0.5 x 10 8 It may be 0.6×10 Ω·cm or more. 8 It may be 0.7×10 Ω·cm or more. 8 It may be 0.8×10 Ω·cm or more. 8 It may be 1×10 Ω·cm or more. 8 The melt resistivity may be Ω·cm or more. The melt resistivity may be the melt resistivity after the polyester resin composition A and the polyester resin B are mixed.

[0234] In this specification, melt resistivity refers to the resistivity value (unit: Ω cm) calculated from the amount of current that flows when a raw material resin such as polyester resin is heated to a temperature 20°C higher than its melting point and a predetermined voltage is applied to the raw material resin in a molten state, and is a numerical value that serves as an index of the electrical conductivity of the raw material resin.

[0235] It is preferable that the melt resistivity of the raw material resin (particularly polyester resin) of the polyester film is within the above range.

[0236] When the polyester film is formed from a mixture (composition) of a plurality of polyester resins, the melt resistivity of the mixture is preferably within the above range.

[0237] When the raw resin of the polyester film contains resins other than polyester resins or other additives, it is preferable that the melt resistivity of the entire raw resin composition is within the above range.

[0238] The melt resistivity of a film is measured by melting it at a temperature 20°C higher than the melting point of the raw resin, such as polyester resin, used in the film. When multiple raw resins, such as polyester resins, are used in the film, the melting point measured by melt-kneading the film can be used. Furthermore, if the melting point cannot be clearly detected, the melting point of the polymer of the largest amount of dicarboxylic acid component and the largest amount of glycol component among the main polymer components of the film can be used if the film has dicarboxylic acid component and glycol component as its main polymer components. When the film has hydroxycarboxylic acid component as its main polymer component, the melting point of the polymer of the largest amount of hydroxycarboxylic acid component alone can be used. The same applies to multilayer films in which the polyester resin composition in each layer is different. For example, if the repeating structural unit is mainly ethylene terephthalate (terephthalic acid components are 50 mol % or more of the total acid components, and ethylene glycol components are 50 mol % or more of the total glycol components), measurement can be performed at 280°C.

[0239] [Film characteristics] The lower limit of the film thickness is preferably 1 μm, more preferably 2 μm, even more preferably 3 μm, particularly preferably 5 μm, and most preferably 10 μm. The upper limit of the film thickness is preferably 300 μm, more preferably 250 μm, even more preferably 200 μm, particularly preferably 150 μm, and most preferably 100 μm. In one embodiment, the film thickness is preferably 1 μm or more and 300 μm or less. The film thickness can be measured, for example, in accordance with JIS K 7130-1999 Method A.

[0240] The lower limit of the intrinsic viscosity (IVf) of the film is preferably 0.4 dl / g, more preferably 0.45 dl / g, even more preferably 0.5 dl / g, particularly preferably 0.55 dl / g, and most preferably 0.6 dl / g. By setting it to the above lower limit or higher, the mechanical strength of the film can be ensured. The upper limit of the intrinsic viscosity (IVf) of the film is preferably 1.2 dl / g, more preferably 1 dl / g, even more preferably 0.9 dl / g, particularly preferably 0.8 dl / g, and most preferably 0.7 dl / g. By setting it to the above upper limit or lower, shear heat generation during melt extrusion can be suppressed, foreign matter and coloration can be reduced, and film formability can be improved. In one embodiment, the intrinsic viscosity (IVf) of the film is preferably 0.4 dl / g or higher and 1.2 dl / g or lower.

[0241] The lower limit of the acid value (AVf) of the film is preferably 3 eq / ton, more preferably 5 eq / ton, and even more preferably 7 eq / ton. The upper limit of the acid value (AVf) of the film is preferably 100 eq / ton, more preferably 80 eq / ton, even more preferably 75 eq / ton, particularly preferably 70 eq / ton, and most preferably 60 eq / ton. By keeping it below the above upper limit, foreign matter can be suppressed. In one embodiment, the acid value (AVf) of the film is preferably 3 eq / ton or more and 100 eq / ton or less.

[0242] The lower limit of the haze is preferably 0.1%, more preferably 0.2%. The upper limit of the haze is preferably 10%, more preferably 5%, even more preferably 3%, particularly preferably 2%, and most preferably 1%. In one embodiment, the haze is preferably 0.1% or more and 10% or less. By keeping the haze within the above range, the film can be preferably used in applications where transparency is required. The haze can be measured in accordance with JIS K 7136 using, for example, a haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.

[0243] The lower limit of the total light transmittance is preferably 80%, more preferably 85%, even more preferably 88%, particularly preferably 89%, and most preferably 90%. The upper limit of the total light transmittance is preferably 99%, more preferably 97%, even more preferably 95%, and particularly preferably 94%. In one embodiment, the total light transmittance is preferably 80% or more and 99% or less. By setting it within the above range, it can be preferably used in applications where transparency is required. Note that the total light transmittance may include an inline coating (IC) layer such as an easy-adhesion layer, but is a value measured on a film that does not include a layer provided by post-processing such as an anti-reflection layer. The total light transmittance can be measured, for example, using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0244] The lower limit of the breaking elongation in at least one of the MD and TD directions is preferably 30%, more preferably 40%, and even more preferably 50%. The upper limit of the breaking elongation is preferably 400%, more preferably 300%, and even more preferably 200%. In one embodiment, the breaking elongation is preferably 30% or more and 400% or less. Furthermore, the breaking elongation in both the MD and TD directions may be within the above ranges.

[0245] The lower limit of the breaking strength in at least one of the MD and TD directions is preferably 30 MPa, more preferably 50 MPa, even more preferably 100 MPa, particularly preferably 150 MPa, and most preferably 180 MPa. The upper limit of the breaking strength is preferably 500 MPa, more preferably 450 MPa, even more preferably 400 MPa, and particularly preferably 350 MPa. In one embodiment, the breaking strength is preferably 30 MPa or more and 500 MPa or less. Furthermore, the breaking strength in both the MD and TD directions may be within the above range.

[0246] The lower limit of the elastic modulus in at least one of the MD and TD directions is preferably 0.1 GPa, more preferably 0.5 GPa, even more preferably 1 GPa, even more preferably 1.5 GPa, particularly preferably 2 GPa, and most preferably 2.5 GPa. The upper limit of the elastic modulus is preferably 10 GPa, more preferably 8 GPa, even more preferably 7 GPa, and particularly preferably 6 GPa. In one embodiment, the elastic modulus is preferably 0.1 GPa or more and 10 GPa or less. Furthermore, the elastic modulus in both the MD and TD directions may be within the above range.

[0247] The breaking elongation and breaking strength can be determined, for example, according to JIS K 7127, by cutting a test sample 15 mm wide and 100 mm long in the longitudinal direction of the film and subjecting it to a tensile test using a tensile tester (Autograph AG-I manufactured by Shimadzu Corporation) under conditions of a gauge length of 50 mm and a pulling speed of 200 mm / min, and then determining the breaking elongation and breaking strength from the resulting stress-strain curve. The elastic modulus can be determined from the tangent to the rising portion of the stress-strain curve.

[0248] The lower limit of the tear propagation resistance in at least one of the MD and TD directions is preferably 1 N / mm, more preferably 3 N / mm, and even more preferably 5 N / mm. The upper limit of the tear propagation resistance is preferably 30 N / mm, more preferably 25 N / mm, and even more preferably 20 N / mm. In one embodiment, the tear propagation resistance is preferably 1 N / mm or more and 30 N / mm or less. The tear propagation resistance in both the MD and TD directions may be within the above range. The tear propagation resistance is a value measured in accordance with the Elmendorf method of JIS P8116 (2000).

[0249] The lower limit of the impact strength is preferably 0.005 J / μm, more preferably 0.01 J / μm, even more preferably 0.02 J / μm, and particularly preferably 0.03 J / μm. The upper limit of the impact strength is preferably 0.2 J / μm, more preferably 0.15 J / μm, even more preferably 0.1 J / μm, and particularly preferably 0.08 J / μm. In one embodiment, the impact strength is preferably 0.005 J / μm or more and 0.2 J / μm or less. By setting the impact strength within the above range, the strength of the polyester film is ensured, stable film production is achieved, problems such as breakage during post-processing are suppressed, and the film can be used in accordance with the properties required for various applications. The impact strength can be measured in an atmosphere of 23°C using an impact sphere with a diameter of 1 / 2 inch using an impact strength measuring device (e.g., a film impact tester manufactured by Toyo Seiki Seisakusho, Ltd.).

[0250] The lower limit of the heat shrinkage rate in the maximum direction is preferably 0%, more preferably 0.1%, even more preferably 0.2%, and particularly preferably 0.3%. The upper limit of the heat shrinkage rate in the maximum direction is preferably 5%, more preferably 4%, even more preferably 3%, and particularly preferably 2%. In one embodiment, the heat shrinkage rate in the maximum direction is preferably 0% or more and 5% or less. The heat shrinkage rate in the maximum direction can be measured, for example, by the following method. (Measurement method) After leaving the polyester film at 25°C and 50% RH for 168 hours, a circle with a diameter of 80 mm and a line D approximately 50 mm long, passing through the center of the circle and parallel to the TD direction of the film, are drawn. The diameter of the circle is measured continuously using an image dimension measuring device (KEYENCE Image Measure IM6500), with the direction of line D set to 0° and set to 1° increments, to determine the diameter of the circle at each angle before heat treatment. Next, the film is heat treated at 150°C for 30 minutes, and then cooled for 10 minutes in an environment set to room temperature (25°C). The diameter of the circle at each angle after heat treatment is determined in the same manner as before heat treatment. The above heat treatment is performed on the polyester film alone. Use the following formula to calculate the thermal shrinkage rate at each angle. Heat shrinkage rate = (length before heat treatment - length after heat treatment) / length before heat treatment x 100 In this way, the heat shrinkage of the polyester film can be measured in the direction in which the heat shrinkage is greatest.

[0251] The lower limit of the dynamic friction coefficient of at least one surface is preferably 0.2, more preferably 0.3. By making it equal to or greater than the above lower limit, it is possible to prevent slippage during transport, etc. The upper limit of the dynamic friction coefficient of at least one surface is preferably 0.8, more preferably 0.7, and even more preferably 0.6. By making it equal to or less than the above upper limit, it is possible to facilitate winding. In one embodiment, the dynamic friction coefficient of at least one surface is preferably 0.2 or more and 0.8 or less. Furthermore, the dynamic friction coefficients of both surfaces may be within the above range.

[0252] The lower limit of the static friction coefficient of at least one surface is preferably 0.2, more preferably 0.25, and even more preferably 0.3. By making it equal to or greater than the above lower limit, it is possible to prevent slippage during transport, etc. The upper limit of the static friction coefficient of at least one surface is preferably 0.8, more preferably 0.7, and even more preferably 0.6. By making it equal to or less than the above upper limit, it is possible to facilitate winding. In one embodiment, the static friction coefficient of at least one surface is preferably 0.2 or more and 0.8 or less. Furthermore, the static friction coefficients of both surfaces may be within the above range.

[0253] The dynamic friction coefficient and static friction coefficient can be measured, for example, using Tensilon (RTG-1210) manufactured by AND Co., Ltd. under conditions of a metal load of 3.5 kg, a pulling speed of 200 mm / min, 23° C., and 65% RH.

[0254] The lower limit of the water vapor permeability converted to a thickness of 50 μm is preferably 1 g / m 2 24h, more preferably 2g / m 2 24h, more preferably 3g / m 2 24h, and particularly preferably 5g / m2 24h, most preferably 8g / m 2 The upper limit of the water vapor permeability converted to a thickness of 50 μm is preferably 100 g / m 2 24h, more preferably 50g / m 2 24h, and more preferably 30g / m 2 24h, and particularly preferably 20g / m 2 24h, most preferably 15g / m 2 In one embodiment, the water vapor transmission rate converted to a thickness of 50 μm is 1 g / m 2 ·100g / m for 24 hours or more 2 The water vapor transmission rate can be measured in accordance with JIS-K7129-B method using a water vapor transmission rate measuring device (for example, "PERMATRAN-W 3 / 33MG" manufactured by MOCON).

[0255] The lower limit of the oxygen permeability converted to a thickness of 50 μm is preferably 10 cm 3 / m 2 ·24h·MPa, more preferably 50cm 3 / m 2 ·24h·MPa, and more preferably 100cm 3 / m 2 ·24h·MPa, and particularly preferably 150cm 3 / m 2 ·24h·MPa, and particularly preferably 200cm 3 / m 2 ·24h·MPa, most preferably 250cm 3 / m 2 The upper limit of the oxygen permeability converted to a thickness of 50 μm is preferably 1000 cm 3 / m 2 ·24h·MPa, and more preferably 700cm 3 / m 2 ·24h·MPa, and more preferably 500cm 3 / m 2 ·24h·MPa, and particularly preferably 400cm 3 / m 2·24h·MPa, and particularly preferably 350cm 3 / m 2 ·24h·MPa, most preferably 320cm 3 / m 2 In one embodiment, the oxygen permeability converted to a thickness of 50 μm is 10 cm 3 / m 2 ·24h · MPa or more 1000cm 3 / m 2 The oxygen permeability can be measured using an oxygen permeability measuring device (for example, "OX-TRAN2 / 20" manufactured by MOCON) in accordance with the electrolytic sensor method (Appendix A) of JIS-K7126-2.

[0256] The lower limit of the surface roughness (Ra) of at least one surface is preferably 0.1 nm, more preferably 0.5 nm, even more preferably 0.8 nm, and particularly preferably 1 nm. The upper limit of the surface roughness (Ra) of at least one surface is preferably 100 nm, more preferably 50 nm, even more preferably 30 nm, particularly preferably 20 nm, and most preferably 10 nm. In one embodiment, the surface roughness (Ra) of at least one surface is preferably 0.1 nm or more and 100 nm or less. The surface roughness (Ra) of both surfaces may also be within the above range.

[0257] The lower limit of the ten-point average surface roughness (Rzjis) of at least one surface is preferably 5 nm, more preferably 10 nm, even more preferably 15 nm, and particularly preferably 20 nm. The upper limit of the ten-point average surface roughness of at least one surface is preferably 500 nm, more preferably 400 nm, even more preferably 300 nm, and particularly preferably 250 nm. In one embodiment, the ten-point average surface roughness of at least one surface is preferably 5 nm or more and 500 nm or less. Furthermore, the ten-point average surface roughness of both surfaces may be within the above range. By ensuring the above range, smoothness, transparency, and clarity (low haze) can be ensured.

[0258] The surface roughness (Ra and Rzjis) can be measured in accordance with ISO 25178 using a non-contact surface shape measuring system (for example, VertScan R550H-M100 manufactured by Ryoka Systems Co., Ltd.).

[0259] The above film properties are typically preferred for PET or PEN films, but are also preferred for other polyester films. It is not necessary for a film to satisfy all of the above properties, and properties can be selected appropriately depending on the application, type of polyester, etc.

[0260] [Uses of polyester film] The polyester film of the present invention can be used in a variety of applications, including, but not limited to, the following: Optical films such as polarizer protection films, prism and lens sheets, and anti-reflection films Surface protection film for image display devices and polarizing plates -Base film for transparent conductive films used in touch sensors, etc. · Ceramic green sheet manufacturing, process release films for dry film resists, functional thin film transfer films for liquid crystal compound thin films, etc. Insulating films for solar cell backsheets, motor insulation, film capacitors, etc. Circuit substrate film Barrier film substrate Light-reflecting film, light-blocking film ·Paper replacement hollow film ·Various packaging films Heat shrink film · Heat-molded film ·Metal plate lamination film

[0261] The resin composition and production conditions of the polyester film can be adjusted to suit these applications, thereby optimizing the film properties. For example, when used in the optical system of an image display device, such as a polarizer protective film, the lower limit of the thickness is preferably 10 μm, more preferably 20 μm, and the upper limit is preferably 150 μm, more preferably 100 μm.

[0262] In addition, the uniaxiality may be enhanced by increasing the orientation in one direction (stretching ratio), thereby increasing the retardation, thereby suppressing iridescence when used in an image display device. In this case, the retardation is preferably 1500 nm or more, more preferably 3000 nm or more, and can be 15000 nm or less, or 10000 nm or less. The lower limit of the difference between the refractive index in the slow axis direction of the film and the refractive index in the direction perpendicular thereto (the fast axis direction) is preferably 0.05, more preferably 0.07, and even more preferably 0.08, and the upper limit is preferably 0.2, more preferably 0.15, and even more preferably 0.1. The lower limit of the NZ coefficient is preferably 1.3, more preferably 1.4, and even more preferably 1.5. The upper limit of the NZ coefficient is preferably 3, more preferably 2.7, and even more preferably 2.5.

[0263] Furthermore, when used in an optical system, it is also preferable to adjust the TD magnification and MD magnification by biaxial stretching to enhance isotropy. The thickness can be selected from the same range as above. The retardation is preferably 3500 nm or less, more preferably 3000 nm or less, even more preferably 2500 nm or less, particularly preferably 2000 nm or less, and most preferably 1500 nm or less. Furthermore, the retardation may be preferably less than 1500 nm, more preferably 1000 nm or less, even more preferably 500 nm or less, and particularly preferably 300 nm or less to form a non-retardation (low retardation) film. The lower limit of the retardation is 0 nm, but it may be practically 10 nm or more, preferably 50 nm or more. The lower limit of the NZ coefficient is preferably 3, more preferably 4, and even more preferably 5. The upper limit of the NZ coefficient is theoretically infinite, but in practice it is preferably 300, more preferably 200, and even more preferably 100. [Example]

[0264] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples, and it is possible to carry out the invention by making appropriate modifications within the scope that is compatible with the spirit of the invention, and all of these modifications are included in the technical scope of the present invention.

[0265] [Melting resistivity] After vacuum drying at 40°C for 16 hours, the raw resin composition was heated to a temperature 20°C higher than the melting point of the raw resin to melt it, and two electrodes (stainless steel wires with a diameter of 0.6 mm) were placed in the raw resin composition, and the current (io) was measured when a voltage of 120 V was applied. This was applied to the following equation to calculate the resistivity Si (Ω·cm). Si(Ω·cm)=(A / L)×(V / io) [A: Area between electrodes (cm 2 ), L: distance between electrodes (cm), V: voltage (V), io: current (A)]

[0266] [Number of coarse particles] The raw resin composition was sandwiched between two cover glasses and melt-pressed to a thickness of 50 μm at a temperature 20°C higher than the melting point of the raw resin. After rapid cooling, 20 fields of view with a field area of ​​718 μm × 583 μm were observed using a 100x phase contrast microscope, and the number of particles of 5 μm or larger was counted using an image analyzer.

[0267] [Oligomer amount] 100 mg of the pulverized sample was precisely weighed and dissolved in 3 mL of a hexafluoroisopropanol / chloroform mixture (volume ratio = 2 / 3), and then diluted with 20 mL of chloroform. 10 mL of methanol was added to this to precipitate the polymer, which was then filtered. The filtrate was evaporated to dryness and made up to a constant volume with 10 mL of dimethylformamide. The cyclic trimer was then quantified using the following high-performance liquid chromatography method. Equipment: L-7000 (Hitachi) Column: μ-Bondasphere C18 5μ 100 Å 3.9mm x 15cm (Waters) Solvent: Eluent A: 2% acetic acid / water (v / v) Eluent B: Acetonitrile Gradient B%: 10 → 100% (0 → 55 min) Flow rate: 0.8mL / min Temperature: 30℃ Detector: UV-259nm

[0268] Thermal Stability Parameter (TS) The raw resin composition was placed in a glass ampoule, and after replacing the atmosphere with nitrogen, the glass ampoule was sealed under a reduced pressure of 13.3 kPa (nitrogen atmosphere). The raw resin composition was then heat-treated for 2 hours at a temperature 40°C higher than the melting point of the raw resin. The intrinsic viscosity of the raw resin composition was measured and calculated using the following formula. TS=0.245{[IV] f2 -1.47 -[IV] i -1.47} [IV] i and [IV] f2 indicate the intrinsic viscosity of the raw material resin composition before and after the heat treatment, respectively.

[0269] [Film formation stability] (Electrostatic casting ability) Raw material resin composition No. A-1 was dried at 135°C for 6 hours under a reduced pressure of 33 Pa. It was then melted and filtered twice, using 100 μm and 50 μm filters. A DC voltage of 6 kV was applied between the electrode and the cooling roller placed above the melt-extruded film to rapidly cool the sheet to adhere and solidify it. The casting speed was gradually increased, and the casting speed (m / min) at which unevenness in the voltage application occurred was determined and rated according to the following criteria. 〇:50m / min or more △: 30m / min or more and less than 50m / min ×: Less than 30 m / min

[0270] [Melting point] Using a DSC7020 manufactured by Hitachi High-Tech Science Corporation under the following conditions, the endothermic peak value was used for evaluation. Sample: 5mg Measurement conditions: 1st RUN (heating): Heating rate 10°C / min, rt → 250°C (hold for 3 minutes) 1stRUN (temperature fall): Temperature fall rate -50℃ / min, 250℃→25℃ 2nd RUN (heating): Heating rate 10℃ / min, rt→250℃

[0271] [Amount of metals and other elements] The sample was pretreated to prepare a measurement solution, and the element concentration in the resulting measurement solution was measured using a high-frequency inductively coupled plasma (ICP) optical emission spectrometer (SPECTROBLUE, manufactured by Hitachi High-Tech Science Corporation) to calculate the element content in the sample. (Pretreatment) Sb, P, Ge The sample was weighed into a platinum crucible, 5 mL of a 5% yttrium nitrate ethanol solution was added, and the sample was pre-carbonized on a hot plate to 400°C. The sample was then ashed at 550°C for 8 hours using a Yamato Scientific FO610 electric furnace. After ashing, 20 mL of 1.2 N hydrochloric acid was added to dissolve the nitrate, resulting in a measurement solution. Ti, Mn, Al, Mg, Ca, K, Na, Li, Cu The sample was weighed into a platinum crucible and pre-carbonized on a hot plate up to 400°C. It was then incinerated for 8 hours at 550°C using a Yamato Scientific FO610 electric furnace. After incineration, small amounts of 6.0N hydrochloric acid and hydrofluoric acid were added, and the sample was decomposed on a hot plate and heated until the acid had completely evaporated. After completion of the acid decomposition, the sample was diluted to volume with 20 mL of 1.2N hydrochloric acid, and the resulting solution was used as the measurement solution. (ICP emission analysis conditions) Plasma power: 1400W Plasma gas: 13.0 L / min Auxiliary gas: 1.0L / min Nebulizer: Crossflow nebulizer Chamber: Scott Chamber Measurement wavelength: See table below TIFF0007800778000004.tif87145

[0272] [Glass transition temperature (Tg)] The midpoint glass transition temperature is measured by DSC as specified in JIS K 7121 (1987).

[0273] [Film thickness] The measurement was carried out in accordance with JIS K7130-1999 Method A using an electric micrometer (Militron 1245D, manufactured by Fine Rufu Co., Ltd.) after leaving the material to stand for 168 hours in an environment of 25°C and 50% RH.

[0274] [Intrinsic viscosity IV] The polyester resin (or film) was dissolved in a mixed solvent of phenol (6 parts by mass) and 1,1,2,2-tetrachloroethane (4 parts by mass), and the viscosity was measured at 30°C using an Ostwald viscometer.

[0275] [Acid value] Polyester chips or films were freeze-pulverized and dried, and 0.2 g of the dried material was dissolved by heating in 10 mL of benzyl alcohol. The concentration was determined by titration with a 0.04 mol / L potassium hydroxide ethanol solution (80 mL of 0.5 mol / L potassium hydroxide aqueous solution diluted with ethanol to 1 L) using phenol red as an indicator.

[0276] [Hayes] Measurement was carried out in accordance with JIS K 7136. The haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. was used as the measuring instrument.

[0277] [Total light transmittance] The measurement was carried out using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0278] [Breaking elongation, breaking strength, and elastic modulus] In accordance with JIS K 7127, test samples 15 mm wide and 100 mm long were cut out in the longitudinal direction of the film. The test samples were subjected to tensile testing using a tensile tester (Shimadzu Corporation, Autograph AG-I) with a gauge length of 50 mm and a tensile speed of 200 mm / min. The breaking elongation and breaking strength of the test samples were calculated from the obtained stress-strain curve. The elastic modulus was determined from the tangent to the rising portion of the stress-strain curve.

[0279] [Tear propagation resistance] This was done according to the Elmendorf method of JIS P8116 (2000). The obtained value was divided by the film thickness (μm) and then multiplied by 10 to obtain the value per 10 μm thickness.

[0280] [Impact Strength] Measurement was performed using an impact strength measuring device (product name: Film Impact Tester, serial number T-84-3) manufactured by Toyo Seiki Seisakusho, Ltd. A rectangular sample measuring 100 mm in the width direction of the film and 100 mm in the length direction of the film was cut out. Next, the sample was placed in the apparatus, and the strength of the film against impact punching was measured using an impact sphere with a diameter of 1 / 2 inch in an atmosphere of 23°C. The strength converted into strength per 1 μm of thickness was taken as the impact strength, expressed in units of J / μm. The method for correcting the impact strength for thickness is as follows. (Impact strength) = (measured value) ÷ (thickness of measurement sample)

[0281] [150℃ heat shrinkage rate in the maximum direction] After leaving the polyester film to stand for 168 hours in an environment of 25°C and 50% RH, a circle with a diameter of 80 mm and a straight line D with a length of approximately 50 mm, passing through the center of the circle and parallel to the TD direction of the film, were drawn. The circle and straight line D were drawn using a fine-tip pen capable of drawing lines of 0.5 mm or less in thickness with black oil-based ink, with constant pen pressure to ensure that the line was as uniform in thickness as possible. A template or compass can be used to draw the circle. The diameter of the circle was measured continuously using an image dimension measuring device (IMAGE MEASURE IM6500 manufactured by KEYENCE Corporation) at 1° intervals, with the direction of line D set to 0°, and the diameter of the circle was determined at each angle before heat treatment. Next, heat treatment was performed for 30 minutes using a gear oven set to 150°C, and then cooled for 10 minutes in an environment set to room temperature of 25°C. After that, the diameter of the circle was determined at each angle after heat treatment in the same manner as before heat treatment. Note that the above heat treatment was performed on the polyester film alone. The heat shrinkage rate was evaluated at each angle using the following calculation formula. Heat shrinkage rate = (length before heat treatment - length after heat treatment) / length before heat treatment x 100 In this way, the heat shrinkage of the polyester film was measured in the direction in which the heat shrinkage was maximum.

[0282] [Dynamic and static friction coefficients] The obtained film was cut into a piece measuring 400 mm in the longitudinal direction and 100 mm in the width direction to prepare a sample film. This was aged for 12 hours in an atmosphere of 23°C and 65% RH. The sample was divided into a piece measuring 300 mm in the longitudinal direction and 100 mm in the width direction for the slide platform and a piece measuring 100 mm in the longitudinal direction and 100 mm in the width direction for the load. The slide platform sample was set on the slide platform, and the load sample was subjected to a metal load of 3.5 kg (the size of the base area was 39.7 mm). 2 The slide sample and the load sample were attached to the surface with tape so that they were in contact with each other. The static and dynamic friction coefficients of the metal load were measured using a Tensilon (RTG-1210) manufactured by AND Co., Ltd., at a pulling speed of 200 mm / min, 23°C, and 65% RH, and the average of three measurements was calculated. Friction between the same surfaces was measured.

[0283] [Water vapor permeability] In accordance with JIS-K7129-B method, the water vapor permeability was measured under normal conditions using a water vapor permeability measuring device ("PERMATRAN-W 3 / 33MG" manufactured by MOCON) in an atmosphere where the temperature and humidity on the high humidity side around the sample during measurement were 40°C and 90% RH, respectively.

[0284] [Oxygen permeability] In accordance with the electrolytic sensor method (Appendix A) of JIS-K7126-2, oxygen permeability was measured under normal conditions using an oxygen permeability measuring device (MOCON "OX-TRAN2 / 20") in an atmosphere where the temperature and humidity on the high humidity side around the sample during measurement were 23°C and 65% RH, respectively.

[0285] [Surface roughness (Ra and Rzjis)] Each surface roughness parameter was measured in accordance with ISO 25178 using a non-contact surface shape measurement system (VertScan R550H-M100, manufactured by Ryoka Systems Co., Ltd.) under the following conditions: (Measurement conditions) Measurement mode: WAVE mode Objective lens: 10x 0.5x Tube Lens Measurement area: 936μm x 702μm (Analysis conditions) Surface correction: 4th order correction Interpolation process: Full interpolation ISO parameter processing: S-Filter 10μm specified Measurements were taken at five points and the average value was calculated.

[0286] [Particle size] The IC particle size was determined by measuring the dispersion of the added particles using a laser diffraction method. The particle size of the particles added to the polyester was measured by photographing them with a scanning electron microscope. 100 non-aggregated inorganic particles were randomly selected and observed, and the average value was taken as the average particle size. The particle size was calculated as the equivalent circle diameter. The equivalent circle diameter was calculated by dividing the area of ​​the observed inorganic particle by π, calculating the square root, and then multiplying it by two. The area and equivalent circle diameter were calculated using an image analyzer (Shimadzu Corporation, particle image analyzer iSpect-DIA-10).

[0287] [Polyester composition] 20 mg of polyester resin was dissolved in 0.6 ml of a mixed solvent of deuterated hexafluoroisopropanol and deuterated chloroform in a volume ratio of 1:9, and the solution was centrifuged. Thereafter, the supernatant was collected and subjected to H-NMR measurement under the following conditions. Equipment: Fourier transform nuclear magnetic resonance spectrometer (BRUKER, AVANCE NEO600) 1H resonance frequency: 600.13MHz Lock solvent: deuterated chloroform Flip angle: 30° Data acquisition time: 4 seconds Delay time: 1 second Measurement temperature: 30℃ Number of times accumulated: 128

[0288] The content of EMIM-TFSI in the film was measured by the following analytical method. (Analysis method) Approximately 50 mg of the film was cut into small pieces and dissolved in 1.5 mL of a 2:3 HFIP / chloroform solvent. 10 mL of chloroform was added to the solution, followed by 5 mL of methanol to precipitate the resin. The filtrate was then concentrated and dried. 5 mL of DMF was added to the filtrate, and the filtrate was then diluted appropriately and subjected to HPLC analysis. The HPLC conditions were as follows: Equipment: Waters ACQUITY UPLC H Class Flow rate: 0.2mL / min Column temperature: 40℃ Injection volume: 5μL The conditions for TFSI are as follows: Column: Waters BEH C18 2.1mm x 150mm Mobile phase: A 0.1% formic acid, B ACN 0min(5%B)-25(98)-30(98) The conditions for EMIM are as follows: Column: TSKgel Amide 80 3μm 2.1mm x 150mm Mobile phase: A 0.1% formic acid, B ACN 0min(90%B)-10(50)-15(50) It was decided. MS was performed using a Waters Xevo G2-XS QTof as the instrument, with electrospray ionization (ESI) as the ionization method, with ESI negative for TFSI and ESI positive for EMIM.

[0289] [Polyester resin manufacturing example] [Polyester resin SbA-1] The esterification reactor was heated to 80°C, and terephthalic acid and 2 moles of ethylene glycol per mole of terephthalic acid were added. While stirring, diantimony trioxide was added as a catalyst so that the Sb atom concentration was 70 ppm relative to the PET produced, and 0.33 mole % of triethylamine relative to the terephthalic acid was further added. The reactor was then heated and the pressurized esterification reaction was carried out under conditions of a gauge pressure of 0.34 MPa and 240°C. The pressure inside the esterification reactor was then returned to normal, and 3 ppm of EMIM-TFSI was added as an ethylene glycol solution to the PET. The temperature was then raised to 260°C over 15 minutes, after which the resulting esterification reaction product was transferred to a polycondensation reactor, where it was gradually heated from 260°C to 280°C under reduced pressure, and then polycondensation was carried out at 285°C. After the polycondensation reaction was completed, the product was pelletized to obtain polyester resin SbA-1. The evaluation results are shown in Table 1.

[0290] [Polyester resin SbA-2] The esterification reactor was heated to 200°C, and a slurry of 2 mol of ethylene glycol per 1 mol of terephthalic acid was added at a rate of 2 tons / hr. While stirring, diantimony trioxide was added as a catalyst so that the Sb atom concentration was 70 ppm relative to the PET produced. Furthermore, 0.33 mol% of triethylamine relative to the terephthalic acid was added. The reactor was then heated and subjected to a pressure esterification reaction at a gauge pressure of 0.34 MPa and 240°C. The temperature was then raised to 260°C over 15 minutes, and the resulting esterification reaction product was transferred to a polycondensation reactor. The temperature was gradually raised from 260°C to 280°C under reduced pressure, and then the polycondensation reaction was carried out at 285°C. After the polycondensation reaction was completed, the product was pelletized. The resulting polyester resin pellets were then dried at 135°C for 6 hours under reduced pressure of 33 Pa and added in fixed amounts to a kneading extruder KZW15TW-45 / 60MG-NH(-2200) (manufactured by Technovel Co., Ltd.). While simultaneously feeding a predetermined amount of EMIM-TFSI from a separate feed port using an automatic feeder, the mixture was melted and kneaded at an actual temperature of 270°C, a screw rotation speed of 200 rpm, and a throughput of 1.6 to 2.0 kg / h. The mixture was then granulated and pelletized to obtain polyester resin SbA-2. The evaluation results are shown in Table 1.

[0291] [Polyester resins SbA-3 to SbA-8, Sb-0, and SbB-1 to SbB-5] Polyester resins SbA-3 to SbA-8, Sb-0, and SbB-1 to SbB-5 were produced in the same manner as polyester resin SbA-1, except that the type and amount of ionic compound added were changed as shown in Table 1. The evaluation results are shown in Table 1. Note that polyester resin SbA-8 is an example in which two types of ionic compounds were used in combination, with the amount of ionic compound added R (ppm) being 8 + 2 = 10, and the dissociation energy Q (kJ / mol) being (8 / 10) × 315 + (2 / 19) × 857 = 423.

[0292] [Polyester resin SbA-9] The same procedure as for polyester resin SbA-1 was carried out except that the amount of Sb was adjusted to 100 ppm.

[0293] [Polyester resin TiA-1 (Ti catalyst PET)] The esterification reactor was heated to 80°C, and terephthalic acid and 2 moles of ethylene glycol per mole of terephthalic acid were charged, and 0.33 mole % of triethylamine per mole of terephthalic acid was added while stirring. The temperature was then increased by heating, and a pressurized esterification reaction was carried out under conditions of a gauge pressure of 0.34 MPa and 240°C. The esterification reactor was then returned to atmospheric pressure, and EMIM-TFSI (3 ppm of ethylene glycol solution) and tetra-n-butoxytitanium (7 ppm of elemental Ti) were added to the resulting PET. The temperature was then raised to 260°C over 15 minutes, after which the resulting esterification reaction product was transferred to a polycondensation reactor. The temperature was gradually increased from 260°C to 280°C under reduced pressure, and then the polycondensation reaction was carried out at 285°C. After the polycondensation reaction was completed, the product was pelletized to obtain polyester resin TiA-1. The evaluation results are shown in Table 1.

[0294] [Polyester resin Ti-0 (Ti catalyst PET)] Polyester resin Ti-0 was produced in the same manner as polyester resin TiA-1, except that EMIM-TFSI was not added.

[0295] [Polyester resin GeA-1 (Ge catalyst PET)] Polyester resin GeA-1 was produced in the same manner as polyester resin TiA-1, except that germanium dioxide was added as a water / ethylene glycol aqueous solution instead of tetra-n-butoxytitanium, so that the Ge element content was 65 ppm relative to the produced PET.

[0296] [Polyester resin AlA-1 (GS catalyst PET)] (Preparation of Aluminum-Containing Ethylene Glycol Solution) A 20 g / L aqueous solution of basic aluminum acetate and an equal amount (volume ratio) of ethylene glycol were charged into a blending tank and stirred at room temperature (23°C) for several hours. After that, the system was stirred under reduced pressure (3 kPa) at 50-90°C for several hours while distilling off water, to prepare an aluminum-containing ethylene glycol solution containing 20 g / L of aluminum compounds.

[0297] (Preparation of phosphorus-containing ethylene glycol solution) Irganox 1222 (manufactured by BASF) as a phosphorus compound was charged into a blending tank together with ethylene glycol, and the mixture was heat-treated at 175°C for 150 minutes while stirring under nitrogen substitution to prepare a phosphorus-containing ethylene glycol solution containing 50 g / L of the phosphorus compound.

[0298] (PET polymerization) Polyester resin AlA-1 was produced in the same manner as polyester resin TiA-1, except that instead of tetra-n-butoxytitanium, an aluminum-containing ethylene glycol solution and a phosphorus-containing ethylene glycol solution were added to the resulting PET so that the aluminum element amount was 21 ppm and the phosphorus element amount was 45 ppm. The aluminum-containing ethylene glycol solution and the phosphorus-containing ethylene glycol solution were mixed in advance before addition.

[0299] [Polyester resin CRA-1Sb (chemically recycled PET)] Chemically recycled BHET was charged into a reactor equipped with a stirrer, and diantimony trioxide was added to the resulting PET so that the Sb atom concentration was 70 ppm. Furthermore, EMIM-TFSI was added as an ethylene glycol solution at 3 ppm relative to the resulting PET. The temperature of the system was then raised to 280°C over 1 hour, during which the system pressure was gradually reduced to 0.15 kPa. Under these conditions, a polycondensation reaction was carried out to obtain a polyester resin. The chemically recycled BHET used was obtained by alkaline hydrolysis of collected PET bottles and polyester fibers in ethylene glycol, followed by purification processes such as filtration and distillation. The isophthalic acid content of the chemically recycled BHET was 1.0 mol% (relative to the total acid components), and the diethylene glycol content was 1.2 mol% (relative to the total acid components).

[0300] [Polyester resin CRA-1Al (chemically recycled PET)] Chemically recycled BHET was charged into a reaction vessel equipped with a stirrer, and an aluminum-containing ethylene glycol solution and a phosphorus-containing ethylene glycol solution were added so that the Al element amount was 21 ppm and the P element amount was 45 ppm relative to the produced PET. Polyester resin CRA-1Al was produced in the same manner as polyester resin AlA-1.

[0301] [Polyester resin CR-0Al (chemically recycled PET)] Polyester resin CR-0Al was produced in the same manner as CRA-1Al, except that EMIM-TFSI was not added.

[0302] [Polyester resin BIA-1Sb (bio-PET)] Polyester resin BIA-1Sb was produced in the same manner as polyester resin SbA-1, except that biomass-derived ethylene glycol was used instead of ethylene glycol.

[0303] [Polyester resin BI-0Al (bio-PET)] Esterification was carried out in the same manner as for polyester resin TiA-1, except that biomass-derived ethylene glycol was used instead. The pressure inside the esterification reactor was then returned to normal, and an aluminum-containing ethylene glycol solution and a phosphorus-containing ethylene glycol solution were added to the resulting PET so that the aluminum content was 21 ppm and the phosphorus content was 45 ppm. The temperature was then raised to 260°C over 15 minutes, after which the resulting esterification reaction product was transferred to a polycondensation reactor, where the temperature was gradually raised from 260°C to 280°C under reduced pressure, and then the polycondensation reaction was carried out at 285°C. After the polycondensation reaction was completed, the product was pelletized to obtain polyester resin BI-0Al.

[0304] [Polyester resin BIA-1Al] Polyester resin BIA-1Al was obtained in the same manner as polyester resin BI-0, except that 3 ppm of EMIM-TFSI was added to the produced PET.

[0305] [Polyester resin PEN] A reaction vessel was charged with 100 parts by mass of ethylene glycol and 100 parts by mass of dimethyl 2,6-naphthalenedicarboxylate, and to this was added antimony acetate so that the Sb atom content was 120 ppm relative to the PEN produced. Furthermore, 0.33 mol % of triethylamine relative to the dimethyl 2,6-naphthalenedicarboxylate and 150 ppm of trimethyl phosphate were added, and then the mixture was heated to increase the temperature, and a pressurized esterification reaction was carried out under conditions of a gauge pressure of 0.34 MPa and 245°C. Thereafter, the temperature was gradually increased to 285°C while reducing the pressure to 133 Pa, and then a polycondensation reaction was carried out at 285°C. Immediately before the end of the reaction, EMIM-TFSI was added to give a concentration of 5 ppm. After stirring for 5 minutes, the reaction was terminated and the mixture was pelletized.

[0306] [Polyester Resin MR (Material Recycled PET)] The collected PET beverage bottles were washed, crushed, and then pelletized. The isophthalic acid content was 1.5 mol% (relative to the total acid components), and the diethylene glycol content was 1.8 mol% (relative to the total acid components). The Sb content was 175 ppm, and the Ge content was 2.0 ppm. The IV was 0.64.

[0307] [Polyester resin MB-1Sb] Polyester resin MB-1Sb was produced in the same manner as polyester resin SbA-1, except that the amount of EMIM-TFSI was 80 ppm relative to the amount of PET produced.

[0308] [Polyester resin MB-1BI] Polyester resin MB-1BI was produced in the same manner as polyester resin BI-0Al, except that 80 ppm of EMIM-TFSI was added to the produced PET.

[0309] [Polyester resin MB-1CR] Polyester resin MB-1CR was produced in the same manner as polyester resin CRA-1Al, except that 80 ppm of EMIM-TFSI was added to the produced PET.

[0310] [Polyester resin MB-2Si1] Dried polyester resin Sb-0 and silica particles with an average particle size of 2.5 μm were added to a twin-screw extruder and kneaded at 285°C to produce pellets of polyester resin MB-2Si1 containing 6000 ppm of silica particles.

[0311] [Polyester resin MB-2Ca] The same procedure as for polyester resin MB-2Si1 was carried out except that calcium carbonate particles with an average particle size of 0.6 μm were used and the content was changed to 30,000 ppm.

[0312] [Polyester resin MB-2Si2] The same procedure as for polyester resin MB-2Si1 was carried out except that porous colloidal silica with an average particle size of 0.06 μm was used and the content was changed to 10,000 ppm.

[0313] [Polyester resin MB-2St] The same procedure as for polyester resin MB-2Si1 was carried out, except that porous colloidal silica with an average particle size of 0.2 μm and cross-linked polystyrene particles with an average particle size of 0.30 μm were used and the contents were 20,000 ppm and 15,000 ppm, respectively.

[0314] [Polyester resin composition MB-1Sia] Pellets of polyester resin composition MB-1Sia were produced in the same manner as MB-2Si1, except that a dry blend of polyester resin Sb-0 and polyester resin composition SbA-2 in a mass ratio of 9 / 1 was used instead of polyester resin Sb-0.

[0315] [Polyester resin composition MB-1Sib] The same procedure was followed as for the production of MB-2Si1, except that EMIM-TFSI was simultaneously fed from a separate feed port using an automatic feeder so that the concentration of EMIM-TFSI was 80 ppm relative to the polyester resin.

[0316] [Polyester resin MB-3] 10 parts by mass of the dried ultraviolet absorber (2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) and 90 parts by mass of the polyester resin SbA-1 were mixed, and pellets of the ultraviolet absorber-containing polyester resin MB-3 were obtained using a kneading extruder.

[0317] [Polyester resin composition MB-1UV] The same procedure was carried out as for polyester resin MB-3, except that polyester resin MB-1Sb was used instead of polyester resin SbA-1.

[0318] In the above preparation, all pellets were approximately 2.5 mm x 3.0 mm x 3.6 mm as measured by calipers.

[0319] The properties of the obtained resin are shown in Table 1. The abbreviations for the anions and cations constituting the ionic compounds in Table 1 have the following meanings. (anion) AA: acetic acid DCA: dicyanamide DMP: dimethyl phosphate FSI: Bis(fluorosulfonyl)imide TFSI: Bis(trifluoromethanesulfonyl)imide OA: Oleic acid (cation) AMIM: 1-allyl-3-methylimidazolium EMIM: 1-ethyl-3-methylimidazolium MEMP: 1-(2-methoxyethyl)-1-methylpyrrolidinium MMIM: 1,3-dimethylimidazolium

[0320] [Table 1-1]

[0321] [Table 1-2]

[0322] [Table 1-3]

[0323] [Preparation of easy-adhesion layer coating solution] The following raw materials were mixed to create a coating solution for forming a coating layer with excellent adhesion to the functional layer. The coating solution was filtered through a 10 μm filter medium (nominal filtration accuracy: 95% cutoff of 10 μm particles). Water 55.62% by mass Isopropanol 30.00% by mass Aliphatic polycarbonate polyurethane resin aqueous solution (solid content 35%) 11.29 mass% Oxazoline group-containing acrylic crosslinker aqueous solution (solid content 40%) 2.26 mass% Particles (silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass) 0.71% by mass Particles (silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) 0.07% by mass Surfactant (silicone-based, solid content 100% by mass) 0.05% by mass

[0324] [Example 1] The polyester resin was dried under reduced pressure (33 Pa) at 135°C for 6 hours, then fed into a single-screw extruder and melted at 285°C. The molten polymer was filtered through a sintered stainless steel filter (nominal filtration accuracy: 95% cut of 20 μm particles) and extruded into a sheet from a T-die. After that, it was wrapped around a casting drum with a surface temperature of 30°C using an electrostatic casting method, cooled, and solidified to produce an unstretched film.

[0325] Casting was carried out at a speed of 60 m / min by providing a tungsten wire electrode between the nozzle of the extruder and the cooling drum and applying a voltage of 5 to 15 KV between the electrode and the casting drum.

[0326] Subsequently, this unstretched film was stretched in the machine direction by 3.3 times at 95°C using rolls with different peripheral speeds.

[0327] The adhesive layer coating solution was applied to both sides of this uniaxially stretched PET film in an amount of 0.12 g / m after drying. 2 After coating so that the coating was uniform, the coating was introduced into a dryer and dried at 80°C for 20 seconds.

[0328] The uniaxially stretched film with the coating layer formed was introduced into a tenter stretching machine, and while the edges of the film were held with clips, it was introduced into a hot air zone at 125°C and stretched 3.5 times in the width direction. Next, while maintaining the stretched width in the width direction, it was treated at 225°C for 30 seconds, and then subjected to a 3% relaxation treatment in the TD direction. After cooling, both edges of the film were cut and taken up to obtain a biaxially stretched PET film with a film thickness of 50 μm.

[0329] [Examples 2 to 32 and Comparative Examples 1 to 10] The resins shown in Table 1 were charged into an extruder in the same manner as in Example 1 to obtain biaxially stretched polyester films. In Example 10, the casting speed was 30 m / min. In Examples 18 to 32 and Comparative Examples 8 to 9, which used two or more resins, the resins were dry-blended in advance and then dried. In Examples 24, 25, 31, and 32, no easy-adhesion layer was provided. In the case of PEN (Example 17), the melting temperature was 290°C, the roll temperature during longitudinal stretching was 110°C, and the tenter temperature was 135°C.

[0330] In all Examples except Example 10, the casting speed was 50 m / min or more, and stable film formation was possible at high speed. In addition, there were no sparks. Example 10 corresponds to a case where the amount of metal such as a catalyst was reduced for insulating purposes, etc., but the film was able to effectively reduce the melt resistivity and was less likely to cause short circuits. On the other hand, Comparative Examples 1 and 5 had good electrostatic adhesion and no sparks, but the amount of foreign matter in the film was large. Comparative Examples 2 and 7 had no problems with foreign matter, but had poor electrostatic adhesion. Comparative Example 6 had slightly poor electrostatic adhesion and a large amount of foreign matter. Comparative Examples 3 and 4 had sparks, and film formation was unstable.

[0331] [Examples 33, 40, 41, and 44] The resins for the surface layer and the intermediate layer were dry-blended and dried, then fed into extruders for the surface layer and the intermediate layer, filtered through the same filter material, and then introduced into a two-type, three-layer T-die to similarly obtain a biaxially stretched film.

[0332] [Examples 34 and 42] The resins for the surface layer and the intermediate layer were dry-blended and dried, then fed into the extruders for the surface layer and the intermediate layer, filtered through the same filter material, and then fed into a two-type, three-layer T-die to obtain an unstretched sheet. An easy-adhesion layer was provided on both sides of the obtained unstretched sheet, and the sheet was stretched 4.0 times in the width direction using a tenter at 125 ° C. The heat setting temperature was 190 ° C, and the sheet was subjected to a 2% relaxation treatment in the TD direction. The thickness of the obtained film was 80 μm.

[0333] [Examples 35 and 43] The unstretched sheet having the adhesive layer obtained above was stretched 2.2 times in the width direction and 6.5 times in the machine direction using a simultaneous biaxial stretching machine. It was then heat-set at 225°C. The thickness of the obtained film was 40 µm.

[0334] [Examples 36 to 39 and 44] Using a two-type, two-layer T-die, biaxially oriented polyester films were obtained by varying the thickness of the lubricant-containing layer and the lubricant-free layer.

[0335] The resins used, the film configuration, and the film properties are shown in Tables 2 to 4. The content of ionic compounds in the film obtained in Example 1 was measured and found to be 2.2 ppm by mass.

[0336] [Table 2-1]

[0337] [Table 2-2]

[0338] [Table 3-1]

[0339] [Table 3-2]

[0340] [Table 4-1]

[0341] [Table 4-2]

[0342] The physical properties of the obtained film are shown in Table 5.

[0343] [Table 5-1] (*1) The films of Examples 1 to 16 and 18 to 21 had almost the same properties, so the properties of the film of Example 1 are shown as a representative example. (*2) Value of particle-containing layer

[0344] [Table 5-2] (*3) The films of Examples 26 to 30 had almost the same properties, so the properties of the film of Example 26 are shown as a representative example.

[0345] The optical properties of the films of Examples 34, 35, 42, and 43 are shown in Table 6.

[0346] [Table 6]

Claims

1. Condition 1, Condition 2, Equation 1, and Equation 2 below: Condition 1: The dissociation energy Q (kJ / mol) of the anion and cation of the ionic compound is 800 or less. Condition 2: The polyester film contains an ionic compound in an amount of 0.01 ppm by mass or more and 950 ppm by mass or less. Formula 1: R≦0.15×Q+890 Formula 2: R≦-20×Q+16000 (In the formula, R is the amount (ppm by mass) of the ionic compound added to the resin constituting the polyester film, and Q is the dissociation energy (kJ / mol) of the anion and cation constituting the ionic compound.) A method for producing a polyester film containing an ionic compound, A step of melt-mixing a polyester resin composition A containing a polyester resin A and an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 800 or less, and a polyester resin B having a melt resistivity greater than that of the polyester resin composition A; a step of extruding a molten mixture containing the polyester resin composition A and the polyester resin B onto a cooling roll to form a film; A method for producing a polyester film comprising:

2. The melt resistivity of polyester resin composition A is 5×10 ８ The method according to claim 1, wherein the resistivity is Ω·cm or less.

3. Condition 1, Condition 2, Equation 1, and Equation 2 below: Condition 1: The dissociation energy Q (kJ / mol) of the anion and cation of the ionic compound is 800 or less. Condition 2: The polyester film contains an ionic compound in an amount of 0.01 ppm by mass or more and 950 ppm by mass or less. Formula 1: R≦0.15×Q+890 Formula 2: R≦-20×Q+16000 (In the formula, R is the amount (ppm by mass) of the ionic compound added to the resin constituting the polyester film, and Q is the dissociation energy (kJ / mol) of the anion and cation constituting the ionic compound.) A method for producing a polyester film containing an ionic compound, A polyester resin composition A containing a polyester resin A and an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 800 or less, and a melt resistivity of 1×10 ８ A step of melt-mixing polyester resin B having a viscosity of Ω cm or more; a step of extruding a molten mixture containing the polyester resin composition A and the polyester resin B onto a cooling roll to form a film; A method for producing a polyester film comprising:

4. The melt resistivity of polyester resin composition A is 0.0001×10 ８ Ω・cm or more 0.1×10 ８ The method for producing a polyester film according to any one of claims 1 to 3, wherein the elastic modulus is Ω·cm or less.

5. The method for producing a polyester film according to any one of claims 1 to 3, wherein a resin constituting the polyester film contains 0.01 mass ppm to 90 mass ppm of an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 800 or less.

6. The method for producing a polyester film according to any one of claims 1 to 3, wherein a resin constituting the polyester film contains 0.01 mass ppm to 40 mass ppm of an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 800 or less.

7. The method for producing a polyester film according to any one of claims 1 to 3, wherein a resin constituting the polyester film contains 0.01 mass ppm to 9 mass ppm of an ionic compound having an anion-cation dissociation energy Q (kJ / mol) of 800 or less.

8. The method for producing a polyester film according to any one of claims 1 to 3, wherein the ionic compound has a dissociation energy Q (kJ / mol) of 400 or less.

9. The method for producing a polyester film according to any one of claims 1 to 3, wherein the manganese content in the resin constituting the polyester film is 22 ppm by mass or less.

10. The method for producing a polyester film according to any one of claims 1 to 3, wherein the sodium content in the resin constituting the polyester film is 13 ppm by mass or less.

11. The method for producing a polyester film according to any one of claims 1 to 3, wherein the magnesium content in the resin constituting the polyester film is 10 ppm by mass or less.

12. The method for producing a polyester film according to any one of claims 1 to 3, wherein the resin constituting the polyester film has a copper content of 160 ppm by mass or less.

13. The method for producing a polyester film according to any one of claims 1 to 3, wherein the content of antimony in a resin constituting the polyester film is 76 ppm by mass or more and 250 ppm by mass or less.

14. The method for producing a polyester film according to any one of claims 1 to 3, wherein the content of aluminum in a resin constituting the polyester film is 1 ppm by mass or more and 100 ppm by mass or less.

15. The melt resistivity of the resin constituting the polyester film is 20×10 ８ The method for producing a polyester film according to any one of claims 1 to 3, wherein the elastic modulus is Ω·cm or less.

16. The melt resistivity of the resin constituting the polyester film is 1×10 ８ The method for producing a polyester film according to any one of claims 1 to 3, wherein the elastic modulus is Ω·cm or less.

17. The melt resistivity of the resin constituting the polyester film is 0.001×10 ８ The method for producing a polyester film according to any one of claims 1 to 3, wherein the elastic modulus is Ω·cm or more.

18. The method for producing a polyester film according to any one of claims 1 to 3, wherein at least one of the anions and cations constituting the ionic compound has an ionic radius of 1 Å or more and 10 Å or less.

19. The method for producing a polyester film according to claim 18, wherein the ionic radius of the cation constituting the ionic compound is 2 Å or more and 5 Å or less.

20. The method for producing a polyester film according to claim 18, wherein the anion constituting the ionic compound has an ionic radius of 2.7 Å or more and 5 Å or less.

21. The absolute value of the average charge density of at least one of the anions and cations constituting the ionic compound is 0.0025 e / Å ２ 0.075e / Å or more ２ The method for producing a polyester film according to any one of claims 1 to 3, wherein the polyester film is:

22. The absolute value of the average charge density of the cations constituting the ionic compound is 0.015 e / Å ２ The method for producing a polyester film according to claim 21, wherein:

23. The method for producing a polyester film according to any one of claims 1 to 3, wherein the cation constituting the ionic compound is a cation of an organic compound.

24. The method for producing a polyester film according to any one of claims 1 to 3, wherein the cation constituting the ionic compound is selected from the group consisting of pyridinium cation, pyrrolidinium cation, piperidinium cation, pyrrolium cation, indolium cation, carbazolium cation, morpholinium cation, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyrazolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation, and tetraalkylammonium cation.

25. The method for producing a polyester film according to any one of claims 1 to 3, wherein the ionic compound is selected from the group consisting of a combination of an imidazolium cation and a bis(trifluoromethanesulfonyl)imide anion, a combination of an imidazolium cation and a bis(fluorosulfonyl)imide anion, a combination of a pyrrolidinium cation and a bis(trifluoromethanesulfonyl)imide anion, and a combination of a pyrrolidinium cation and a bis(fluorosulfonyl)imide anion.

26. The method for producing a polyester film according to claim 25, wherein the imidazolium cation is a 1,3-dialkylimidazolium cation.

27. The method for producing a polyester film according to any one of claims 1 to 3, wherein the polyester film contains the ionic compound in an amount of 0.1 ppm by mass or more.

28. The method for producing a polyester film according to any one of claims 1 to 3, wherein the resin constituting the polyester film is polyethylene terephthalate and / or polyethylene naphthalate.

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