WO2024252686A1 - Composition de résine de polyester et film de polyester - Google Patents

Composition de résine de polyester et film de polyester Download PDF

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Publication number
WO2024252686A1
WO2024252686A1 PCT/JP2023/027111 JP2023027111W WO2024252686A1 WO 2024252686 A1 WO2024252686 A1 WO 2024252686A1 JP 2023027111 W JP2023027111 W JP 2023027111W WO 2024252686 A1 WO2024252686 A1 WO 2024252686A1
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resin composition
polyester resin
weight
ppm
content
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Japanese (ja)
Inventor
凌土 林
泰広 稲川
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Toray Industries Inc
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Toray Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a polyester resin composition.
  • Polyesters have excellent mechanical properties, thermal properties, chemical resistance, electrical properties, and moldability, and are used in a variety of applications.
  • polyethylene terephthalate hereinafter referred to as PET
  • PET polyethylene terephthalate
  • various optical films such as prism sheets for liquid crystal display components, light diffusion sheets, reflectors, base films for touch panels, anti-reflection base films, explosion-proof base films for displays, PDP filter films, and films for dry film resist supports.
  • the required quality also improves.
  • the electrostatic casting method When making PET resin into a film, the electrostatic casting method is often used, in which a high voltage is applied to the top surface of an unsolidified sheet-like material, and the sheet-like material is adhered to a rotating cooling drum.
  • the electrostatic casting method if the speed of the rotating cooling drum is increased to increase the film production speed, the adhesion between the sheet-like material and the rotating cooling drum decreases, resulting in a decrease in the uniformity of the film thickness and transparency, and defects on the film surface due to uneven voltage application.
  • Patent Document 1 proposes a method of adding large amounts of alkali metal compounds, alkaline earth metal compounds, and phosphorus compounds to polyester as a method of improving electrostatic applicability.
  • this method can improve electrostatic applicability to a certain extent, it uses large amounts of metal compounds such as magnesium acetate, which generates metal foreign matter and causes the polyester film to fall short of the required quality.
  • Patent Document 2 proposes the addition of a quaternary phosphonium sulfonate salt as a method for improving electrostatic applicability, but because it contains a large amount of alkali metal or alkaline earth metal, it is insufficient in suppressing metallic foreign matter, and is also insufficient in suppressing gel-like foreign matter caused by thermal decomposition.
  • Patent Document 3 proposes a method for producing a polyester resin composition in which a sulfonic acid compound is added and no metal elements other than the polymerization catalyst are added, but the amount of phosphoric acid added is large and is insufficient to obtain the electrostatic applicability required for film molding.
  • JP 2006-249213 A International Publication No. WO 1990/8171 Japanese Patent Application Publication No. 10-36495
  • the object of the present invention is to provide a polyester resin composition that has little foreign matter, good color tone, excellent transparency, excellent heat resistance and hydrolysis resistance, and good electrostatic applicability during film molding.
  • the polyester resin composition according to (2) wherein the content of antimony element is 15 ppm by weight or less and the content of germanium element is 5 ppm by weight to 150 ppm by weight, based on the total weight of the polyester resin composition.
  • a polyester resin composition having an intrinsic viscosity of 0.55 dL/g or more, the content of a p-toluenesulfonic acid component being 0.07 to 0.65 mol/t, the content of a quaternary phosphonium component being 0.07 to 0.65 mol/t, and the content of an alkali metal element being 3 ppm by weight or less, relative to the total weight of the polyester resin composition, the heat resistance parameter X represented by formula 1 being 1.0 ⁇ X ⁇ 1.3, the number of foreign matter particles having a circle equivalent diameter of 0.2 ⁇ m or more being 630 pieces/0.1 mm2 or less, and the color tone b value measured by a color difference meter being 10.0 or less.
  • the present invention provides a polyester resin composition that has few foreign matter, good color tone, excellent transparency, excellent heat resistance and hydrolysis resistance, good electrostatic applicability during film molding, and few defects due to exposure damage when used as a film for a dry film resist support.
  • weight are synonymous with “mass”, “mass %”, and “parts by mass”, respectively.
  • element may also be used synonymously with “atom”.
  • the polyester resin composition used in the present invention refers to a polyester resin composition obtained by polycondensation of a dicarboxylic acid component and a diol component.
  • the dicarboxylic acid component of the present invention includes terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, malonic acid, dimer acid, and the like. More preferred embodiments of the dicarboxylic acid of the present invention are terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, or alkyl esters thereof, since they have a high melting point and can provide a polyester composition that is easily processed into films, fibers, and the like. Terephthalic acid or its alkyl esters are more preferred, since they have a high melting point and provide better processability.
  • the diol component of the present invention is aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,2-hexanediol, 1,6-hexanediol, and neopentyl glycol; saturated alicyclic primary diols such as cyclohexanedimethanol, cyclohexanediethanol, norbornanedimethanol, norbornanediethanol, tricyclodecane dimethanol, tricyclodecane diethanol, decalin dimethanol, and decalin diethanol; saturated heterocyclic primary diols containing cyclic ethers such as isosorbide; and other cycloaliphatic diols.
  • saturated alicyclic primary diols such as ethylene glycol, 1,2-propanediol, 1,3
  • diol examples include various alicyclic diols such as cyclohexanediol, bicyclohexyl-4,4'-diol, 2,2-bis(4-hydroxycyclohexylpropane), 2,2-bis(4-(2-hydroxyethoxy)cyclohexyl)propane, cyclopentanediol, 3-methyl-1,2-cyclopentadiol, 4-cyclopentene-1,3-diol, and adamantanediol, and aromatic diols such as paraxylene glycol, bisphenol A, bisphenol S, styrene glycol, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, and 9,9'-bis(4-hydroxyphenyl)fluorene.
  • aromatic diols such as paraxylene glycol, bisphenol A, bisphenol S, styrene glycol, 9,9-bis(4-(2-hydroxy
  • polyfunctional alcohols such as trimethylolpropane and pentaerythritol can also be used within the scope of the present invention, so long as the effects of the present invention are not impaired.
  • diols having a boiling point of 230°C or less are preferred because they can be easily distilled out of the reaction system, and aliphatic diols are more preferred because they are low cost and highly reactive.
  • ethylene glycol is particularly preferred from the viewpoint of the mechanical properties of the resulting polyester resin composition and its molded products.
  • the polyester in the present invention is not particularly limited, but is preferably one having at least one structural unit selected from ethylene terephthalate, ethylene-2,6-naphthalate, propylene terephthalate, butylene terephthalate, hexamethylene terephthalate, cyclohexanedimethylene terephthalate, propylene-2,6-naphthalate, butylene-2,6-naphthalate, hexamethylene-2,6-naphthalate, cyclohexanedimethylene-2,6-naphthalate units, etc. as a main constituent component.
  • polyesters having ethylene terephthalate as a main constituent unit are particularly preferred because of their excellent moldability.
  • two or more polyesters may be mixed, or a copolymerized polyester may be used.
  • 99 mol % or more of the polyester constituent units are ethylene terephthalate, and it is particularly preferable that the polyester is polyethylene terephthalate that does not substantially contain a copolymerization component.
  • the polyester resin composition of the present invention must contain a p-toluenesulfonic acid component and a quaternary phosphonium component.
  • a p-toluenesulfonic acid component and a quaternary phosphonium component in the polyester resin composition, good electrostatic applicability can be obtained during film formation.
  • the content of the p-toluenesulfonic acid component in the polyester resin composition of the present invention must be 0.07 to 0.65 mol/t relative to the total weight of the polyester resin composition. It is preferably 0.20 to 0.60 mol/t, and more preferably 0.25 to 0.50 mol/t. If the content of the p-toluenesulfonic acid component is less than 0.07 mol/t, the melt resistivity of the polyester resin composition when melted increases, which may result in poor electrostatic applicability during film molding.
  • the p-toluenesulfonic acid component refers to a compound having a p-toluenesulfonic acid anion, such as p-toluenesulfonic acid and its alkali metal salts.
  • p-toluenesulfonic acid sodium p-toluenesulfonate, potassium p-toluenesulfonate, and methyl p-toluenesulfonate.
  • the p-toluenesulfonic acid component does not contain an alkali metal, and p-toluenesulfonic acid is preferable. Since the p-toluenesulfonic acid component does not have an ester-forming functional group, it is dispersed in the resin without being copolymerized with the polyester resin, and therefore good electrostatic applicability can be imparted during film molding without impairing the thermal properties of the polyester resin composition, such as the melting point and glass transition point. In addition, since it does not have an ester-forming functional group, it is possible to suppress the coarsening of foreign matter derived from the sulfonic acid compound when it is formed.
  • the polyester resin composition of the present invention must have a quaternary phosphonium component content of 0.07 to 0.65 mol/t relative to the total weight of the polyester resin composition. This is preferably 0.10 to 0.49 mol/t, and more preferably 0.15 to 0.33 mol/t. If the quaternary phosphonium component content is less than 0.07 mol/t, the melt resistivity of the polyester resin composition when melted may increase, resulting in poor electrostatic applicability during film molding. If the quaternary phosphonium component content exceeds 0.65 mol/t, foreign matter may be generated and the solution haze of the polyester resin composition may worsen.
  • the quaternary phosphonium component refers to a compound having a quaternary phosphonium cation.
  • Specific examples of quaternary phosphonium include tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, methyltributylphosphonium, ethyltributylphosphonium, octyltributylphosphonium, hexadecyltributylphosphonium, benzyltrimethylphosphonium, benzyltriethylphosphonium, and 3-(trifluoromethyl)phenyltrimethylphosphonium.
  • Examples of the quaternary phosphonium component include hydroxides of these compounds, and halides such as chlorides and bromides. Of these, tetrabutylphosphonium hydroxide is preferred.
  • the method of incorporating the p-toluenesulfonic acid component and the quaternary phosphonium component into the polyester resin composition is not particularly limited. They can be implemented by known methods, such as a method of adding them during the polycondensation reaction of the polyester resin composition, or a method of kneading them with the polyester resin composition after the polycondensation reaction using a twin-screw kneading extruder.
  • a method of incorporating them by neutralizing the p-toluenesulfonic acid component and the quaternary phosphonium component to prepare a diol solution of p-toluenesulfonic acid quaternary phosphonium, passing it through a filtration filter, and then adding it to the reaction system before the start of the polycondensation reaction is also suitable.
  • the intrinsic viscosity of the polyester resin composition of the present invention is 0.55 dL/g or more. There is no upper limit, but it is preferably 0.75 dL/g or less. If it is less than 0.55 dL/g, the mechanical properties during film molding may be inadequate. From the viewpoint of reducing the temperature rise due to shear heat during melt extrusion in film molding, suppressing the regeneration of cyclic trimers when the resin is melted, and preventing deterioration of mechanical properties during film molding due to thermal degradation of the resin, it is preferable that the intrinsic viscosity of the polyester resin composition is 0.60 dL/g or more.
  • the polyester resin composition of the present invention must have a heat resistance parameter X, represented by formula 1, of 1.0 ⁇ X ⁇ 1.3. Preferably, 1.0 ⁇ X ⁇ 1.2, and more preferably, 1.0 ⁇ X ⁇ 1.1.
  • 1610 cm -1 is an IR absorption peak characteristic of thermally modified polyesters (gelled products formed by repeated hydrolysis, thermal decomposition and crosslinking reactions of polyesters), and 1580 cm -1 is an IR absorption peak of the polyester main chain.
  • the range is set to ⁇ 10 cm -1 in consideration of measurement error, and the peaks with the highest absorption intensity within this range are defined as the absorption of the thermally modified polyester and the polyester main chain, respectively.
  • the ratio of the absorption near 1610 cm -1 to the absorption near 1580 cm -1 in the numerator and denominator, respectively indicates the proportion of the thermally modified polyester to the polyester main chain.
  • the polyester resin composition of the present invention must have a number of foreign matter particles having a circle equivalent diameter of 0.2 ⁇ m or more of 650/0.1 mm2 or less . It is preferably 630/0.1 mm2 or less, more preferably 600/0.1 mm2 or less, and even more preferably 500/0.1 mm2 or less . If the polyester resin composition has more than 650 foreign matter particles having a circle equivalent diameter of 0.2 ⁇ m or more , the transparency of the polyester resin composition may be impaired. Details of the method for measuring the number of foreign matter particles in the polyester resin composition will be described in the examples.
  • the first polyester resin composition of the present invention must have a melt resistivity of 4.0 ⁇ 10 6 ⁇ cm or less, and the second polyester resin composition preferably has a melt resistivity of 4.0 ⁇ 10 6 ⁇ cm or less. It is preferably 3.5 ⁇ 10 6 ⁇ cm or less, and more preferably 3.0 ⁇ 10 6 ⁇ cm or less. If the melt resistivity of the polyester resin composition is greater than 4.0 ⁇ 10 6 ⁇ cm, the electrostatic applicability may be poor when the polyester resin composition is used to form a film. Details of the method for measuring the melt resistivity of the polyester resin composition will be described in the examples.
  • the polyester resin composition of the present invention must have a color tone b value of 10.0 or less in a color difference meter.
  • the larger the color tone b value the more yellowish the polyester resin composition is. If the color tone b value exceeds 10.0, the polyester resin composition is perceived to be too yellowish, which is unsuitable.
  • the color tone b value is preferably 9.0 or less.
  • the polycondensation reaction catalyst may be a known compound. For example, oxides, carboxylates, acetates, hydroxides, chelate complexes, alkoxides, etc.
  • the form of these polycondensation reaction catalysts when added may be any of powder, slurry, and solution, and it is preferable to add them as a solution or slurry from the viewpoint of dispersibility.
  • the solvent used in this case is preferably the same as the diol component of the polyester resin composition.
  • the content of antimony element is preferably in the range of 50 ppm by weight to 150 ppm by weight based on the total weight of the polyester resin composition from the viewpoint of polymerization reactivity and activity for decomposition reaction. If the content of antimony element exceeds 150 ppm by weight, the amount of metal antimony in the polyester resin composition increases, which is not preferable because it becomes a foreign matter during film processing. If the content of antimony element is less than 50 ppm by weight, the polymerization activity may be insufficient, and the polyester resin composition may not reach the target intrinsic viscosity.
  • the content of antimony element is preferably in the range of 50 ppm by weight to 120 ppm by weight, and more preferably in the range of 50 ppm by weight to 100 ppm by weight.
  • the content of antimony element is preferably 15 ppm by weight or less, more preferably 10 ppm by weight or less, based on the total weight of the polyester resin composition. Furthermore, the content of titanium element is preferably 0.1 ppm by weight to 20 ppm by weight, more preferably 2 ppm by weight to 15 ppm by weight.
  • the content of antimony element is 15 ppm by weight or less, foreign matter originating from metallic antimony in the polyester resin composition can be reduced.
  • Metallic antimony is generated by the reduction of antimony compounds such as antimony trioxide, and is known to become foreign matter in the polyester resin composition, causing a decrease in transparency and defects during film molding.
  • the content of titanium element exceeds 20 ppm by weight, the color tone b value and heat resistance of the polyester resin composition deteriorate, which is not preferable.
  • the content of titanium element is less than 0.1 ppm by weight, the polymerization activity is insufficient, and the polyester resin composition may not reach the target intrinsic viscosity.
  • the content of antimony element is preferably 15 ppm by weight or less, more preferably 10 ppm by weight or less, based on the total weight of the polyester resin composition. Furthermore, the content of germanium element is preferably 5 ppm by weight to 150 ppm by weight. When the content of antimony element is 15 ppm by weight or less, foreign matter originating from metallic antimony in the polyester resin composition can be reduced, and defects during film molding can be suppressed. When the content of germanium element exceeds 150 ppm by weight, foreign matter is likely to be generated, and the solution haze of the polyester resin composition may worsen. When the content of germanium element is less than 5 ppm by weight, the polymerization activity is insufficient, and the polyester resin composition may not reach the target intrinsic viscosity.
  • the content of antimony element is preferably 15 ppm by weight or less, more preferably 10 ppm by weight or less, based on the total weight of the polyester resin composition. Furthermore, the content of aluminum element is preferably 0.1 ppm by weight to 100 ppm by weight, and the upper limit of the content of aluminum element is more preferably 50 ppm by weight, and even more preferably 30 ppm by weight. Furthermore, the lower limit of the content of aluminum element is more preferably 3 ppm by weight.
  • the content of antimony element is 15 ppm by weight or less, foreign matter originating from metallic antimony in the polyester resin composition can be reduced, and defects during film molding can be suppressed.
  • the content of aluminum element exceeds 100 ppm by weight, foreign matter is likely to be generated, and the solution haze of the polyester resin composition deteriorates, as well as the color tone b value and heat resistance deteriorate, which is not preferable.
  • the content of aluminum element is less than 0.1 ppm by weight, the polymerization activity is insufficient, and the polyester resin composition may not reach the target intrinsic viscosity.
  • the polyester resin composition of the present invention may contain elemental manganese.
  • the content of elemental manganese is preferably 5 to 40 ppm by weight, more preferably 5 to 30 ppm by weight, relative to the total weight of the polyester resin composition.
  • elemental manganese By including elemental manganese, gel-like foreign matter can be reduced, but if the content of elemental manganese exceeds 40 ppm by weight, the amount of foreign matter increases and the solution haze of the polyester resin composition worsens, which is not preferred. Also, if the content of elemental manganese is less than 5 ppm by weight, the amount of gel-like foreign matter produced increases, which is not preferred.
  • the polyester resin composition of the present invention may contain a phosphorus compound other than the quaternary phosphonium component.
  • the phosphorus compound other than the quaternary phosphonium component may be one or more selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonoacetic acid, or their methyl esters, ethyl esters, phenyl esters, and half esters. Two or more of these may be mixed and used, and phosphoric acid is more preferred.
  • the polyester resin composition of the present invention preferably has a phosphorus content of 3 to 50 ppm by weight, more preferably 5 to 40 ppm by weight, based on the total weight of the polyester resin composition.
  • the phosphorus content represents the total amount of the quaternary phosphonium component and other phosphorus compounds. If the phosphorus content exceeds 50 ppm by weight, foreign matter increases and the solution haze of the polyester resin composition deteriorates, which is not preferred. If the phosphorus content is less than 3 ppm by weight, the melt resistivity of the polyester resin composition when melted increases, which is not preferred, and also results in poor electrostatic applicability during film molding.
  • the polyester resin composition of the present invention may contain an alkali metal element within a range that does not impair the effects of the present invention. From the viewpoint of suppressing foreign matter having a circular equivalent diameter of 0.2 ⁇ m or more and suppressing an increase in solution haze of the polyester resin composition, it is preferable that the content of alkali metal is 3 ppm by weight or less relative to the total weight of the polyester resin composition, and it is more preferable that the alkali metal is not substantially contained. In order to make the polyester resin composition of the present invention contain an alkali metal element, an alkali metal compound is used.
  • alkali metal compound examples include lithium acetate, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, alkali metal phosphate salts such as sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, and tripotassium phosphate, and alkali metal salts of sulfonic acid compounds such as sodium methanesulfonate, potassium methanesulfonate, sodium butylsulfonate, potassium butylsulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, sodium tetrafluoroethanesulfonate, and tetrafluoroethanesulfonic acid.
  • alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide
  • alkali metal phosphate salts such
  • alkali metal compounds include potassium, sodium nonafluorobutanesulfonate, potassium nonafluorobutanesulfonate, sodium benzenesulfonate, potassium benzenesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, sodium 2,4,6-trimethylbenzenesulfonate, potassium 2,4,6-trimethylbenzenesulfonate, sodium styrenesulfonate, potassium styrenesulfonate, sodium perfluorooctane sulfonate, potassium perfluorooctane sulfonate, sodium heptadecafluorooctane sulfonate, and potassium heptadecafluorooctane sulfonate.
  • alkali metal compounds can be added to the polyester resin composition by known methods, such as adding the compounds during the polycondensation reaction of the polyester resin composition or kneading the compounds with the polyester resin composition after the polycondensation reaction using a twin-screw kneading extruder or the like.
  • the polyester resin composition of the present invention may contain particles.
  • the particles contained in the polyester resin composition of the present invention include inorganic particles such as silica, alumina, barium sulfate, barium carbonate, magnesium oxide, magnesium sulfate, magnesium carbonate, zinc oxide, zinc sulfide, zinc carbonate, titanium dioxide, cerium oxide, zirconium oxide, iron oxide, kaolin, talc, mica, carbon black, and silicon, and organic particles such as crosslinked polystyrene, crosslinked silicon, crosslinked acrylic, crosslinked styrene-acrylic, crosslinked polyester, polyimide, and melamine resin particles, but the type of particles is not particularly limited. From the viewpoints of economy, thermal stability, and particle dispersibility, it is preferable to use silica particles, alumina particles, and crosslinked polystyrene particles.
  • the method of incorporating particles into the polyester resin composition of the present invention is not particularly limited, but from the viewpoint of improving particle dispersibility, it is preferable to incorporate particles into the polyester resin composition by adding the particles during the polycondensation reaction of the polyester resin composition, or by kneading the particles with the polyester resin composition after the polycondensation reaction using a twin-screw kneading extruder or the like.
  • the number of particle types incorporated into the polyester resin composition of the present invention is not particularly limited as long as it is within a range that does not impair the effects of the present invention, and one or more types of particles can be incorporated.
  • the particles When the particles are added to the polyester resin composition of the present invention, they may be in the form of either a powder or a slurry, but it is preferable to add them as a slurry from the viewpoint of dispersibility.
  • the slurry may be either a water slurry or a slurry of the diol component of the polyester composition, but it is preferable that the slurry is the same as the diol component of the polyester from the viewpoint of particle dispersibility of the polyester resin composition.
  • the method for producing the polyester resin composition of the present invention is specifically described below.
  • the polyester in the present invention is polyethylene terephthalate (hereinafter referred to as PET), it is usually manufactured by a process in which terephthalic acid or dimethyl terephthalate and ethylene glycol are used as raw materials, and a low polymer such as bishydroxyethyl terephthalate (hereinafter referred to as BHET) is obtained by a reaction such as esterification or transesterification, and then a high molecular weight PET is obtained by a polycondensation reaction.
  • PET polyethylene terephthalate
  • BHET bishydroxyethyl terephthalate
  • the reaction for obtaining low polymer BHET is not particularly limited, and can be carried out by known reactions.
  • BHET can be obtained by an ester exchange reaction that proceeds by adding an ester exchange reaction catalyst to dimethyl terephthalate and ethylene glycol as raw materials, or an esterification reaction that proceeds without a catalyst due to the self-catalytic action of carboxylic acid using terephthalic acid and ethylene glycol as raw materials.
  • BHET can also be obtained by depolymerizing recovered PET products.
  • An esterification reaction is preferable because the reaction proceeds sufficiently without a catalyst due to the self-catalytic action of carboxylic acid, and there is no need to add a reaction catalyst such as a calcium compound, magnesium compound, or manganese compound.
  • the obtained BHET is transferred to a polymerization tank, where additives such as a p-toluenesulfonic acid component and a quaternary phosphonium component, as well as a polycondensation reaction catalyst, are added, after which the temperature inside the apparatus is slowly heated to 279°C and the pressure is reduced from normal pressure to 133 Pa or less. As the polymerization reaction progresses, the viscosity of the reactants increases. When a predetermined stirring torque is reached, the reaction is terminated and molten PET is obtained. The obtained molten PET is then extruded in the form of strands from a nozzle, cooled, and pelletized using a cutter to produce a polyester resin composition.
  • additives such as a p-toluenesulfonic acid component and a quaternary phosphonium component, as well as a polycondensation reaction catalyst
  • the obtained polyester resin composition is preferably pre-crystallized before the drying step.
  • Pre-crystallization can be performed by applying a mechanical shock to the polyester resin composition to perform a shear treatment, or by performing a heat treatment under a hot air flow.
  • the polyester composition of the present invention may be subjected to solid-phase polymerization in order to obtain a polyester resin composition having a high molecular weight.
  • the solid-phase polymerization is carried out by heating the polyester composition in an inert gas atmosphere or under reduced pressure at a temperature below the melting point of the polyester resin composition, although the apparatus and method are not particularly limited.
  • Any inert gas may be used as long as it is inert to the polyester resin composition, and examples of such gas include nitrogen, helium, and carbon dioxide gas, although nitrogen is preferably used from an economical standpoint.
  • a higher vacuum is advantageous because it shortens the time required for the solid-phase polymerization reaction, and specifically, it is preferable to maintain the pressure at 110 Pa or less.
  • the polyester resin composition of the present invention can be suitably used for various applications such as films, fibers, and molded articles, and is particularly suitable for use in films due to its good electrostatic applicability and transparency.
  • the film can be molded by a known molding method.
  • one or more types of additives such as colorants including pigments and dyes, lubricants, antistatic agents, flame retardants, ultraviolet absorbers, antibacterial agents, nucleating agents, plasticizers, and release agents, can also be added within a range that does not impair the effects of the present invention.
  • the film made of the polyester resin composition of the present invention may be an unstretched film produced by melt extrusion, or a stretched film produced by uniaxial or biaxial stretching.
  • the film may be a sequentially biaxially stretched film or a simultaneous biaxially stretched film.
  • the pellets of the obtained polyester resin composition are vacuum dried at 180°C for 3 hours or more, and then fed to an extruder heated to 280-320°C under a nitrogen stream or vacuum so as not to reduce the intrinsic viscosity.
  • the pellets are then passed through a fiber-sintered stainless steel metal filter, extruded from a slit-shaped die, and cooled while applying a static charge to the cast drum to obtain an unstretched film.
  • the unstretched film is then guided to an infrared heater device and stretched between rolls in the longitudinal direction, which is the running direction of the film, to obtain a uniaxially stretched film.
  • the uniaxially stretched film is then held by a clip and stretched in the width direction perpendicular to the longitudinal direction while being heated, and then cooled to complete the crystal orientation to obtain a sequentially biaxially stretched film.
  • an unstretched film can be stretched in both the longitudinal and transverse directions at the same time to obtain a simultaneously biaxially stretched film.
  • the film made of the polyester resin composition of the present invention may be a single-layer film in which the entire film is made of the same resin, or may be a single-layer film made by blending the polyester resin composition of the present invention with another polyester resin composition. It may also be a laminated film containing at least one film layer containing the polyester resin composition of the present invention. When a film layer containing the polyester resin composition of the present invention is laminated, the blending amount of the polyester resin composition of the present invention is not particularly limited. In addition, from the viewpoint of imparting easy slipperiness to the obtained polyester film, a polyester resin composition containing particles may be blended.
  • the polyester resin composition of the present invention has few foreign matters, good color tone, excellent transparency (haze), heat resistance, and good electrostatic applicability, and can therefore be suitably used for films for release applications such as substrates for green sheet molding of multilayer ceramic capacitors, separators for liquid crystal polarizing plates, and substrates for dry film resists, as well as high-quality films for optical applications.
  • a polyester film made from the polyester resin composition of the present invention has the characteristics of good electrostatic applicability during molding, little unevenness in film thickness, few metal foreign matters, and excellent transparency.
  • alkali metal elements lithium (atom), sodium (atom), potassium (atom)
  • atomic absorption spectrometry polarized Zeeman atomic absorption spectrophotometer 180-80 manufactured by Hitachi, Ltd., flame: acetylene air.
  • the Daruma flask was heated to 80°C and slowly sprayed with nitrogen gas, concentrated, and then diluted with dimethyl sulfoxide to obtain a sample for liquid chromatography (hereinafter referred to as HPLC).
  • HPLC liquid chromatography
  • the content (mol/t) of the p-toluenesulfonic acid component in the sample was determined from a calibration curve of p-toluenesulfonic acid prepared in advance, and the content (mol/t) of the quaternary phosphonium component was determined from a calibration curve of each substance (tetrabutylphosphonium hydroxide, tetraethylphosphonium hydroxide, and other quaternary phosphonium compounds were added in the same manner) prepared in advance using an HPLC device.
  • the components separated by HPLC were identified by liquid chromatography-mass spectrometry (LC-MS).
  • Amount of COOH terminal groups in polyester resin composition (unit: eq/t) The measurement was performed by the method of M. J. Maurice, F. Huizinga, Anal. Chem. Acta, 22, 363 (1960). That is, 0.5 g of the polyester resin composition is weighed out to within 0.001 g accuracy. 50 ml of a solvent made by mixing o-cresol/chloroform in a mass ratio of 7/3 is added to the sample, and the mixture is heated until the internal temperature reaches 90°C, after which it is heated and stirred for 20 minutes to dissolve. The mixed solvent alone is also heated separately as a blank solution.
  • the solution is cooled to room temperature, and titration is performed with a 1/50N solution of potassium hydroxide in methanol using a potentiometric titrator. Titration is also performed similarly on the blank solution of the mixed solvent alone.
  • the amount of COOH terminal groups in the polyester resin composition was calculated according to the following formula.
  • COOH terminal group amount (eq/t) ⁇ (V1-V0) x N x f ⁇ x 1000/S
  • V1 is the titration volume (mL) of the sample solution
  • V0 is the titration volume (mL) of the blank solution
  • N is the normality (N) of the titration solution
  • f is the factor of the titration solution
  • S is the mass (g) of the polyester resin composition.
  • Heat resistance parameter X (measurement of FT-IR absorption peak before and after heat treatment) Sampling was performed from inside each sample, and the FT-IR of the polymer was measured using a micro infrared spectrometer (FT-IR MICROSCOPE: Nicolet Continuum II (Micro FT-IR manufactured by ThermoFisher scientific)) before heat treatment and after heat treatment for 5 hours at 285°C in a nitrogen atmosphere, and the absorption intensities at 1610 cm -1 and 1580 cm -1 ⁇ 10 cm -1 were obtained. In order to minimize measurement variation, the same sample was measured five times and the arithmetic mean was used. The heat resistance parameter X was calculated from the obtained absorption intensities according to Equation 1.
  • Measurements are performed at different observation points over 0.1 square mm, and the number of white matter observed with a circle equivalent diameter of 0.2 ⁇ m or more is counted as metallic antimony in the filtered matter, and is used as an index of the number of metallic antimony in the polyester resin composition.
  • the white matter observed in the backscattered electron image was confirmed to be antimony by observation with SEM-EDX (energy dispersive X-ray spectroscopy). The fewer the number of metallic antimony particles in the filtered matter, the better. 100 particles/0.1 mm2 or less was considered good, 101 particles/0.1 mm2 to 500 particles/0.1 mm2 was considered pass, and 501 particles/0.1 mm2 or more was considered fail.
  • a photomask patterned with chromium metal was placed on top of the polyester film, and exposure was performed from above the photomask using an I-line stepper.
  • the resist layer was placed in a container containing the developer N-A5 and developed for about 1 minute. Then, the resist layer was taken out of the developer and washed with water for about 1 minute.
  • the occurrence rate of open defects or short defects was evaluated as ⁇ (good) when it was less than 5%, ⁇ (pass) when it was 5% or more but less than 10%, and ⁇ (fail) when it was 10% or more. Note that an evaluation of ⁇ or higher is a practical level.
  • Example 1 A slurry consisting of 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1.15 times the molar amount relative to terephthalic acid) was gradually added to an esterification reactor charged with 105 parts by weight of BHET dissolved at 250° C., and the esterification reaction was allowed to proceed while distilling off water. The temperature in the reaction system was controlled to 245 to 250° C., and the esterification reaction was terminated when the reaction rate reached 95%, and 105 parts by weight of the resulting esterification reaction product (corresponding to 100 parts by weight of PET) was charged in a molten state into a polymerization apparatus equipped with a distillation device.
  • tetrabutylphosphonium hydroxide 0.0112 parts by weight of tetrabutylphosphonium hydroxide was added as an ethylene glycol solution, and then 0.0077 parts by weight of p-toluenesulfonic acid was added as an ethylene glycol solution. Then, 0.0090 parts by weight of manganese acetate tetrahydrate was added as an ethylene glycol solution, and then 0.0084 parts by weight of diantimony trioxide was added as an ethylene glycol slurry.
  • the pressure inside the polymerization reaction tank was gradually reduced to 0.13 kPa or less in 35 minutes, and at the same time, the temperature was gradually increased to 279°C, and the polymerization reaction was carried out until the intrinsic viscosity of the polyester resin composition reached 0.62 dL/g.
  • the polycondensation reaction tank was then returned to normal pressure with nitrogen gas, the mixture was discharged in the form of strands from the nozzle into cold water, and then pelletized into cylindrical pellets using an extrusion cutter to obtain a polyester resin composition having a number of foreign matter particles with a circular equivalent diameter of 0.2 ⁇ m or more of 490/0.1 mm2 , a melt resistivity of 2.2 x 106 ⁇ cm, and a heat resistance parameter X of 1.1.
  • the obtained polyester resin composition contained the p-toluenesulfonic acid component, the quaternary phosphonium component, elemental antimony, elemental phosphorus, and elemental manganese in the amounts shown in Table 1.
  • the color tone b value was 6.8, the main chain scission rate (% BB) as a heat resistance index was 0.38%, the increase in the amount of COOH terminal groups ( ⁇ COOH) as a hydrolysis resistance index was 72.9 eq/t, and the solution haze was 0.9%, all of which were good values.
  • the number of metallic antimonies in the filtered matter was 270 pieces/0.1 mm2 , which was within the acceptable range.
  • the resin pellets of the obtained polyester resin composition were dried under reduced pressure at 160°C for 8 hours, fed to an extruder, melt extruded at a temperature of 285°C, and cast onto a statically charged cast drum at 20°C to obtain an unstretched sheet.
  • This unstretched sheet was stretched 3.5 times in the longitudinal direction using a stretching roll heated to 90°C, then stretched 4.0 times in the transverse direction at 120°C using a tenter-type stretching machine, and then heat-set at 230°C for 10 seconds. After uniformly cooling in the cooling zone, the sheet was wound up on a roll to obtain a polyester film with a thickness of 16 ⁇ m.
  • the film-forming property of this polyester film was evaluated to have good static electricity applicability. Furthermore, the yield of conductor circuits using the obtained polyester film was evaluated to be good.
  • Examples 2 to 7, Comparative Examples 1 to 3 A polyester resin composition and a polyester film were obtained in the same manner as in Example 1, except that the amount of p-toluenesulfonic acid added was changed to the contents shown in Tables 1 and 2. The results are shown in Table 2.
  • Table 2 to 4 and Comparative Example 1 As the p-toluenesulfonic acid component content increased, the amount of foreign matter with a circular equivalent diameter of 0.2 ⁇ m or more increased, causing an increase in the solution haze of the polyester resin composition, and ⁇ COOH also increased. These indices were within the acceptable range in Examples 2 to 4, but were unacceptable in Comparative Example 1.
  • Comparative Example 3 since no p-toluenesulfonic acid component was added, the melt resistivity increased significantly and the film formability of the polyester film was unacceptable. The number of metallic antimony particles in the filtered matter of the polyester resin composition was also unacceptable, and the yield of the conductor circuit in Comparative Example 3 could not be evaluated because a film could not be obtained.
  • Examples 8 to 14, Comparative Examples 4 to 6 A polyester resin composition and a polyester film were obtained in the same manner as in Example 1, except that the amount of tetrabutylphosphonium hydroxide added was changed to the contents shown in Tables 1 and 2. The results are shown in Table 2.
  • Example 8 to 11 and Comparative Example 4 as the content of the quaternary phosphonium component increased, the amount of foreign matter having a circle equivalent diameter of 0.2 ⁇ m or more increased, and the solution haze of the polyester resin composition increased. In addition, the number of metallic antimony particles in the filtered matter of the polyester resin composition also increased. In addition, the yield evaluation of the conductor circuit using the obtained polyester film tended to deteriorate.
  • Example 15 A slurry consisting of 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1.15 times the molar amount relative to terephthalic acid) was gradually added to an esterification reactor charged with 105 parts by weight of BHET dissolved at 250° C., and the esterification reaction was allowed to proceed while distilling off water. The temperature in the reaction system was controlled to 245 to 250° C., and the esterification reaction was terminated when the reaction rate reached 95%, and 105 parts by weight of the resulting esterification reaction product (corresponding to 100 parts by weight of PET) was charged in a molten state into a polymerization apparatus equipped with a distillation device.
  • tetrabutylphosphonium p-toluenesulfonate which had been previously prepared by neutralizing equimolar amounts of p-toluenesulfonic acid and tetrabutylphosphonium hydroxide, was added as an ethylene glycol solution, followed by 0.0090 parts by weight of manganese acetate tetrahydrate as an ethylene glycol solution, and then 0.0050 parts by weight of tetra-n-butyl titanate as an ethylene glycol solution.
  • the pressure in the polymerization reaction tank was gradually reduced to 0.13 kPa or less in 35 minutes, and at the same time the temperature was gradually increased to 279° C., and the polymerization reaction was carried out until the intrinsic viscosity of the polyester resin composition reached 0.62 dL/g.
  • the polycondensation reaction tank was then returned to normal pressure with nitrogen gas, the mixture was discharged from the die into cold water in the form of strands, and pelletized into cylindrical shapes using an extrusion cutter to obtain a polyester resin composition having a number of foreign objects with a circle equivalent diameter of 0.2 ⁇ m or more of 380/0.1 mm 2 , a melt resistivity of 2.2 ⁇ 10 6 ⁇ cm, and a heat resistance parameter X of 1.1.
  • a polyester film was also obtained in the same manner as in Example 1.
  • the results are shown in Table 4.
  • the obtained polyester resin composition had a color tone b value of 8.2, which was high, but within a good range.
  • the electrostatic applicability was good.
  • the yield evaluation of the conductor circuit using the obtained polyester film was good.
  • Examples 16 to 19, Comparative Examples 7 and 8 A polyester resin composition and a polyester film were obtained in the same manner as in Example 15, except that the amount of tetra-n-butyl titanate added was changed to the titanium element content shown in Table 3. The results are shown in Table 4.
  • the color tone b value, % BB, and ⁇ COOH tended to increase with increasing titanium element content, but these indices were within the acceptable range in Examples 16 and 17.
  • the color tone b value and % BB were unacceptable.
  • the polymerization time tended to become longer as the titanium element content decreased, but Examples 18 and 19 were within the acceptable range.
  • Example 20 A polyester resin composition and a polyester film were obtained in the same manner as in Example 15, except that 0.0072 parts by weight of germanium dioxide was added as an ethylene glycol solution instead of adding tetra-n-butyl titanate as a polycondensation reaction catalyst.
  • the color tone b value was 6.8, % BB was 0.34%, ⁇ COOH was 68.5 eq/t, and the solution haze was 0.5%, all of which were good values. Since no antimony catalyst was used, metallic antimony was not observed in the filtered matter of the polyester resin composition. In the film-forming property evaluation of the polyester film, the electrostatic applicability was good, and the yield evaluation of the conductor circuit using the obtained polyester film was good.
  • Example 21 and 22 Comparative Examples 9 and 10.
  • a polyester resin composition and a polyester film were obtained in the same manner as in Example 20, except that the amount of germanium dioxide added was changed to the germanium element content shown in Table 3.
  • the number of foreign matter particles having a circle equivalent diameter of 0.2 ⁇ m or more was as high as 610 pieces/0.1 mm2, and the solution haze of the polyester resin composition was 1.1%, but was within the acceptable range.
  • the electrostatic applicability was good, and the yield evaluation of the conductor circuit using the obtained polyester film tended to deteriorate, but was within the acceptable range.
  • Comparative Example 9 the number of foreign matter particles having a circular equivalent diameter of 0.2 ⁇ m or more was even higher at 680 particles/0.1 mm2 , and the solution haze of the polyester resin composition was 1.4%, which was unacceptable.
  • Example 22 the amount of germanium element was smaller and the polymerization time was longer than in Example 20, but the evaluation of the properties of the polyester resin composition was all within the acceptable range. In addition, the yield evaluation of the conductor circuit using the obtained polyester film tended to deteriorate, but was still within the acceptable range.
  • the amount of germanium element was even less than that in Example 22, and the activity of the polycondensation reaction was insufficient, so that the target intrinsic viscosity was not reached even after the polymerization time exceeded 5 hours. Therefore, the characteristics of the polyester resin composition and the polyester film were not evaluated.
  • Example 23 A polyester resin composition and a polyester film were obtained in the same manner as in Example 15, except that instead of adding tetra-n-butyl titanate as a polycondensation reaction catalyst, an ethylene glycol solution of aluminum acetate was added, and the aluminum element content was set as shown in Table 3.
  • the color tone b value was 6.9
  • % BB was 0.38%
  • ⁇ COOH was 70.6 eq/t
  • the solution haze was 0.9%, all of which were good values. Since no antimony catalyst was used, metallic antimony was not observed in the filtration capture of the polyester resin composition.
  • the electrostatic applicability was good, and the yield evaluation of the conductor circuit using the obtained polyester film was good.
  • Examples 24 to 28, Comparative Examples 11 and 12 A polyester resin composition and a polyester film were obtained in the same manner as in Example 23, except that the amount of aluminum acetate added was changed to the aluminum element content shown in Table 3.
  • the solution haze of the polyester resin composition increased due to an increase in foreign matter with a circle equivalent diameter of 0.2 ⁇ m or more, and the color tone b value, % BB, and ⁇ COOH tended to increase, but these indices were within the acceptable range in Examples 24 to 26.
  • the yield evaluation of the conductor circuit using the polyester film obtained in Example 26 tended to deteriorate, but was within the acceptable range.
  • Example 29 A polyester resin composition and a polyester film were obtained in the same manner as in Example 1, except that the polycondensation reaction catalyst was changed from diantimony trioxide to tetra-n-butyl titanate, and the titanium element and p-toluenesulfonic acid component were changed to the contents shown in Table 5. The results are shown in Table 6.
  • Example 29 has the same contents of p-toluenesulfonic acid component, quaternary phosphonium component, titanium element, and phosphorus element as Example 15, but the method of adding the p-toluenesulfonic acid component and the quaternary phosphonium component was changed.
  • Examples 36 to 42, Comparative Examples 15 and 16 A polyester resin composition and a polyester film were obtained in the same manner as in Example 1, except that the polycondensation reaction catalyst was changed from diantimony trioxide to tetra-n-butyl titanate, and the contents of titanium element, phosphorus element, and quaternary phosphonium component were changed to those shown in Table 5. The results are shown in Table 6. In Examples 36 to 39 and Comparative Example 15, as the quaternary phosphonium component content increases, the solution haze of the polyester resin composition increases due to an increase in foreign matter with a circle equivalent diameter of 0.2 ⁇ m or more, and the results were within the acceptable range in Examples 36 to 39, but were unsuccessful in Comparative Example 15.
  • Example 43 and 44, Comparative Examples 17 and 18 polyester resin compositions and polyester films were obtained in the same manner as in Example 29, except that after the addition of tetra-n-butyl titanate, an ethylene glycol solution of manganese acetate was then added to obtain the manganese element content shown in Table 7. The results are shown in Table 8.
  • Example 43 the manganese element was reduced from the polyester resin composition of Example 29, and as a result, the heat resistance parameter X was slightly increased, and the yield evaluation of the conductor circuit using the obtained polyester film tended to deteriorate, but was within the acceptable range. In addition, in the film-forming property evaluation of the polyester film, the electrostatic applicability was good.
  • Example 44 the manganese content was increased from that in Example 29, and the number of foreign matter particles having a circle equivalent diameter of 0.2 ⁇ m or more further increased, and the solution haze increased, but was within the acceptable range.
  • the electrostatic applicability was good, and the yield of the conductor circuit using the obtained polyester film was evaluated as good.
  • Comparative Example 17 the manganese element content was further increased from that of Example 44. The number of foreign matter particles having a circular equivalent diameter of 0.2 ⁇ m or more further increased, the solution haze increased, and the result was unacceptable, and the yield evaluation of the conductor circuit using the obtained polyester film was unacceptable.
  • Comparative Example 18 the same procedure as in Example 29 was followed except that manganese acetate was not added. Since the heat resistance parameter X exceeded the prescribed range, the yield of the conductor circuit using the obtained polyester film was unsatisfactory.
  • Comparative Example 19 A polyester resin composition and a polyester film were obtained in the same manner as in Example 29, except that an ethylene glycol solution of magnesium acetate was added instead of manganese acetate to give the magnesium element content shown in Table 7. The results are shown in Table 8. The use of magnesium acetate caused the heat resistance parameter X to exceed the prescribed range, and therefore the yield evaluation of the conductor circuit using the obtained polyester film was unacceptable.
  • Example 45 A polyester resin composition and a polyester film were obtained in the same manner as in Example 29, except that phosphoric acid was added as an ethylene glycol solution between the addition of tetrabutylphosphonium hydroxide and p-toluenesulfonic acid and the addition of tetra-n-butyl titanate to obtain the phosphorus element content shown in Table 7. The results are shown in Table 8.
  • Example 45 all of the properties of the polyester resin composition were within the acceptable range as compared with the polyester resin composition of Example 29 in which the amount of manganese element was reduced and no phosphoric acid was added.
  • the amount of phosphoric acid added was increased from that in Example 45, and the phosphorus element content was increased.
  • the polyester resin compositions were all within the acceptable range in the property evaluation.
  • Example 48 A polyester resin composition and a polyester film were obtained in the same manner as in Example 29, except that the quaternary phosphonium component was changed from tetrabutylphosphonium hydroxide to an ethylene glycol solution of tetraethylphosphonium hydroxide. The results are shown in Table 8. The obtained polyester resin composition had properties equivalent to those of the polyester resin composition of Example 29, and all of the indices were within the acceptable range. In addition, in the evaluation of the film-forming properties of the polyester film, the electrostatic applicability was good, and the yield of the conductor circuit using the obtained polyester film was evaluated as good.
  • the melt resistivity was high, and the electrostatic applicability was unsatisfactory in the film-forming evaluation of the polyester film, and the yield evaluation of the conductor circuit was not able to be performed because a film could not be obtained.
  • Comparative Example 21 3,5-dicarboxybenzenesulfonic acid having two ester-forming functional groups was used, and therefore the number of foreign matters having a circle equivalent diameter of 0.2 ⁇ m or more was greater than that of the polyester resin composition of Example 45, and the solution haze was high and unacceptable, so that the yield evaluation of the conductor circuit using the obtained polyester film was unacceptable.
  • the melt resistivity was high, the electrostatic applicability was within the acceptable range in the film-forming property evaluation of the polyester film.
  • the reaction product BHET was filtered through a pleated filter with an opening of 10 ⁇ m, and then 105 parts by weight (corresponding to 100 parts by weight of PET) was charged in a molten state into a polymerization reactor equipped with a distillation device.
  • 0.0112 parts by weight of tetrabutylphosphonium hydroxide, then 0.0077 parts by weight of p-toluenesulfonic acid were added as ethylene glycol solutions, then 0.0090 parts by weight of manganese acetate tetrahydrate was added as an ethylene glycol solution, then 0.0050 parts by weight of tetra-n-butyl titanate was added as an ethylene glycol solution.
  • the pressure in the polymerization reaction tank was gradually reduced to 0.13 kPa or less in 35 minutes, and at the same time the temperature was gradually increased to 279° C., and the polymerization reaction was carried out until the intrinsic viscosity of the polyester resin composition reached 0.62 dL/g.
  • the polycondensation reaction tank was then returned to normal pressure with nitrogen gas, the mixture was discharged in the form of strands from the nozzle into cold water, and then pelletized into cylindrical pellets using an extrusion cutter to obtain a polyester resin composition having a number of foreign matter particles with a circular equivalent diameter of 0.2 ⁇ m or more of 400/0.1 mm2 , a melt resistivity of 2.2 x 106 ⁇ cm, and a heat resistance parameter X of 1.1.
  • the obtained polyester resin composition contained the p-toluenesulfonic acid component, the quaternary phosphonium component, the titanium element, and the phosphorus element in the amounts shown in Table 7.
  • the color tone b value was 8.2
  • the % BB was 0.41%
  • the ⁇ COOH was 77.2 eq/t
  • the solution haze was 0.7%, all of which were good values.
  • metallic antimony was not observed in the filtration capture of the polyester resin composition.
  • a polyester film was obtained in the same manner as in Example 1. In the film-forming evaluation of this polyester film, the electrostatic applicability was good, and the yield evaluation of the conductor circuit using the obtained polyester film was good.
  • Examples 50 to 53 A polyester resin composition and a polyester film were obtained in the same manner as in Example 1, except that the amount of diantimony trioxide added was changed to the contents shown in Table 9. The results are shown in Table 10.
  • the polyester resin composition obtained showed an increasing tendency in the %BB and the number of metal antimony in the filtered matter of the polyester resin composition as the antimony element content increased, but all the indices were within the acceptable range.
  • the electrostatic applicability was good, and the yield of the conductor circuit using the obtained polyester film was good.
  • Examples 54 and 55 A polyester resin composition and a polyester film were obtained in the same manner as in Example 1, except that the p-toluenesulfonic acid component was changed to a mixture of p-toluenesulfonic acid and sodium p-toluenesulfonate to have the alkali metal content shown in Table 9. The results are shown in Table 10. As the content of alkali metal elements in the obtained polyester resin composition increased, the amount of foreign matter having a circle equivalent diameter of 0.2 ⁇ m or more increased, and the solution haze of the polyester resin composition increased, but was within the acceptable range. On the other hand, in the film-forming evaluation of the obtained polyester film, the electrostatic applicability was good. In addition, the yield evaluation of the conductor circuit using the obtained polyester film was good in Example 54, and tended to deteriorate in Example 55, but was within the acceptable range.
  • Example 23 A polyester resin composition and a polyester film were obtained in the same manner as in Example 1, except that the p-toluenesulfonic acid component was changed to sodium p-toluenesulfonate and the alkali metal content was set as shown in Table 9. The results are shown in Table 10.
  • the obtained polyester resin composition had a higher alkali metal element content than the polyester resin composition of Example 55, and had an inappropriate number of foreign matter particles having a circular equivalent diameter of 0.2 ⁇ m or more at 760 pieces/0.1 mm2 . Therefore, the solution haze of the polyester resin composition was 1.4%, which was unacceptable, and the yield evaluation of the conductor circuit using the obtained polyester film was unacceptable.
  • Examples 56 and 57 A polyester resin composition and a polyester film were obtained in the same manner as in Example 1, except that phosphoric acid was added as an ethylene glycol solution between the addition of tetrabutylphosphonium hydroxide and p-toluenesulfonic acid and the addition of diantimony trioxide, and furthermore, an ethylene glycol solution of manganese acetate was added after the addition of diantimony trioxide to achieve the contents shown in Table 9. The results are shown in Table 10.
  • the color tone b value of the polyester resin composition obtained in Example 58 was 7.0, % BB was 0.29%, and ⁇ COOH was 78.7 eq/t, all of which were good values.
  • the solution haze was 1.1%, and the number of metallic antimony particles in the filtered matter was 270/0.1 mm2 , all of which were within the acceptable range.
  • the color tone b value of the polyester resin composition obtained in Example 57 was 7.3, % BB was 0.30%, and ⁇ COOH was 66.9 eq/t, all of which were good values.
  • the solution haze was 1.1%, and the number of metallic antimony particles in the filtered matter was 270/0.1 mm2 , all of which were within the acceptable range.
  • the film-forming properties of the polyester films obtained in Examples 56 and 57 were evaluated to be good in terms of electrostatic applicability.
  • the yield of conductor circuits using the obtained polyester films was evaluated to be good in Example 56, and tended to deteriorate in Example 57, but was within the acceptable range.
  • Example 58 and 59 A polyester resin composition and a polyester film were obtained in the same manner as in Examples 56 and 57, except that the polycondensation reaction catalyst was changed from diantimony trioxide to an ethylene glycol solution of germanium dioxide and the germanium element content was set as shown in Table 9. The results are shown in Table 10.
  • the polyester resin compositions obtained in Examples 58 and 59 were all within the acceptable range in terms of all properties, and furthermore, no metallic antimony was observed in the filtered matter of the polyester resin composition, which was a good result.
  • the electrostatic applicability was good in all cases.
  • the yield evaluation of the conductor circuit using the obtained polyester film was good in Example 58, and tended to deteriorate in Example 59, but was within the acceptable range.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Le problème décrit par la présente invention consiste à fournir une composition de résine de polyester qui présente peu de matières étrangères, une bonne tonalité de couleur, une excellente transparence, une excellente résistance à la chaleur et une excellente résistance à l'hydrolyse et de bonnes propriétés d'application d'électricité statique pendant la formation de film et qui, lorsqu'elle est utilisée en tant que film pour un support de résine photosensible de film sec, présente peu de défauts dus à des défauts d'exposition à la lumière. La solution selon l'invention porte sur une composition de résine de polyester présentant une viscosité inhérente d'au moins 0,55 dl/g, ladite composition de résine de polyester étant caractérisée en ce que : par rapport à la quantité totale de la composition de résine de polyester, la teneur en constituant d'acide p-toluènesulfonique est de 0,07 à 0,65 mole/t et la teneur en constituant de phosphonium quaternaire est de 0,07 à 0,65 mole/t ; un paramètre de résistance à la chaleur X représenté par l'expression 1 est de 1,0≤X≤1,3 ; le nombre de morceaux de matière étrangère présentant un diamètre de cercle équivalent de 0,2 µm ou plus est inférieur ou égal à 650 morceaux/0,1 mm2 ; la résistance spécifique à l'état fondu est inférieure ou égale à 4,0×106Ω･cm ; et une valeur de tonalité de couleur b dans un compteur de différence de couleur est inférieure ou égale à 10,0.
PCT/JP2023/027111 2023-06-08 2023-07-25 Composition de résine de polyester et film de polyester Ceased WO2024252686A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000211009A (ja) * 1999-01-25 2000-08-02 Teijin Ltd 多層フイルムの製造方法
JP2018062574A (ja) * 2016-10-13 2018-04-19 東レ株式会社 ポリエチレンテレフタレート樹脂組成物およびそれからなるフィルム
JP2020007542A (ja) * 2018-06-27 2020-01-16 東レ株式会社 ポリエステル樹脂組成物およびその製造方法
JP2022089784A (ja) * 2020-12-04 2022-06-16 東レ株式会社 ポリエステル樹脂組成物及びそれを用いてなるポリエステルフィルム
JP2023015002A (ja) * 2021-07-19 2023-01-31 東レ株式会社 二軸配向ポリエステルフィルム、および積層体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000211009A (ja) * 1999-01-25 2000-08-02 Teijin Ltd 多層フイルムの製造方法
JP2018062574A (ja) * 2016-10-13 2018-04-19 東レ株式会社 ポリエチレンテレフタレート樹脂組成物およびそれからなるフィルム
JP2020007542A (ja) * 2018-06-27 2020-01-16 東レ株式会社 ポリエステル樹脂組成物およびその製造方法
JP2022089784A (ja) * 2020-12-04 2022-06-16 東レ株式会社 ポリエステル樹脂組成物及びそれを用いてなるポリエステルフィルム
JP2023015002A (ja) * 2021-07-19 2023-01-31 東レ株式会社 二軸配向ポリエステルフィルム、および積層体

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