Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/183—Terephthalic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
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  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/001—Combinations of extrusion moulding with other shaping operations
  • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/07—Flat, e.g. panels
  • B29C48/08—Flat, e.g. panels flexible, e.g. films
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/30—Extrusion nozzles or dies
  • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
  • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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  • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
  • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
  • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
  • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
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  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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  • B32B27/00—Layered products comprising a layer of synthetic resin
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  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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  • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
• • C—CHEMISTRY; METALLURGY
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  • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
• • C—CHEMISTRY; METALLURGY
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• • C—CHEMISTRY; METALLURGY
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  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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Definitions

• the present invention relates to a biaxially stretched polyester film having excellent hygiene, printability, processability, and productivity.
• Polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), which are thermoplastic resins with excellent heat resistance and mechanical properties, are used in a wide variety of fields such as plastic films, electronics, energy, packaging materials, and automobiles. It's being used.
• PET polyethylene terephthalate
• PBT polybutylene terephthalate
• plastic films biaxially stretched PET film is widely used in industrial and packaging fields because it has a good balance of mechanical strength, heat resistance, dimensional stability, chemical resistance, optical characteristics, and other costs. There is.
• the PET film imparted with hydrolysis resistance is also used as a film for a solar cell backsheet, and is used for various purposes as a functional film and a base film.
• a film having an excellent gas barrier property is used as a packaging material required to be airtight for foods, pharmaceuticals, electronic parts, or the like, or a gas barrier material, and the demand for the film is increasing in recent years.
• the packaging film it is desirable for the packaging film to have a small amount of foreign matter in the polyester film as it comes into direct contact with food.
• the antimony catalyst used in the process of producing (polymerizing) the polyester raw material may be carcinogenic, it is desirable that the polyester film contains as little antimony as possible or no antimony.
• polyester raw materials that do not use an antimony catalyst, as described in Patent Documents 1 and 2, for example.
• it does not describe a method for reducing the number of foreign matters in the film or desired film characteristics.
• the present invention which solves the above problems, has the following configurations.
• the content of antimony in the film is 10 ppm or less
• the content of phosphorus in the film is 25 ppm or more and 75 ppm or less
• the intrinsic viscosity of the film is 0.51 dl/g or more and 0.70 dl/g or less (4 )
• the number of defects of 1 mm or more per 1,000 square meters of film is 1.0 or less.
• a polymerization catalyst a polyester raw material characterized in that at least one selected from an aluminum compound and at least one selected from a phosphorus compound are contained in a polyester resin was used.
• the haze of the film is 1% or more and 8% or less. Or 2.
• the thermal shrinkage in the vertical direction measured under the condition of 150° C. for 15 minutes is 0.8% or more and 3% or less. ⁇ 3.
• the thickness unevenness values in the vertical direction and the horizontal direction measured with a continuous contact type thickness meter over a length of 1 m are both 1% or more and 10% or less.
• a packaging bag comprising one or more layers of the biaxially stretched polyester film according to any one of 1. 7.
• a label comprising one or more layers of the biaxially stretched polyester film according to any one of 1. 8.
• the raw polyester resin is melt extruded and then cooled and solidified to obtain an unstretched film so that the difference between the intrinsic viscosity of the raw polyester resin and the intrinsic viscosity of the polyester film is 0.06 dl/g or less.
• the film is biaxially stretched and then heat set. ⁇ 5.
• a method of manufacturing a roll is provided.
• the biaxially stretched polyester film of the present invention contains a polyethylene terephthalate resin as a constituent component.
• the polyethylene terephthalate-based resin contains an ethylene glycol-derived component and a terephthalic acid-derived component as main constituent components.
• the “main constituent” means that terephthalic acid is 80 mol% or more in 100 mol% of all dicarboxylic acid components constituting the polyester, and ethylene glycol is 80 mol% or more in 100 mol% of all glycol components.
• the copolymerization amount of the other dicarboxylic acid component and the glycol component is less than 20 mol %, preferably 10 mol% or less, and preferably 5 mol% or less with respect to the total dicarboxylic acid component or the total glycol component. Is particularly preferable.
• dicarboxylic acid components include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl and 5-sodium sulfoisophthalic acid, 1,4-cyclohexanedicarboxylic acid, Alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid and tetrahydrophthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid And aliphatic dicarboxylic acids such as sebacic acid, undecanedioic acid, dodecanedioic acid, octadecanedioic acid, fumaric acid, maleic acid, itaconic acid,
• aromatic dicarboxylic acids
• glycols examples include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 1,10-decanediol, dimethyloltricyclodecane, diethylene glycol, Aliphatic glycols such as triethylene glycol, bisphenol A, bisphenol S, bisphenol C, bisphenol Z, bisphenol AP, 4,4'-biphenol ethylene oxide adduct or propylene oxide adduct, 1,2-cyclohexanedimethanol, 1 And alicyclic glycols such as 3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, polyethylene glycol, Aliphatic glycol
• Such a polyethylene terephthalate-based resin can be polymerized by directly reacting terephthalic acid with ethylene glycol, and optionally other dicarboxylic acid component and glycol component, and dimethyl ester of terephthalic acid (if necessary. (Including methyl ester of other dicarboxylic acid) and ethylene glycol (including other glycol component if necessary) are subjected to transesterification reaction and then polycondensation reaction is used. Can be done.
• recycled resins made from recycled PET bottles as polyester resins, and polyester resins containing biomass-derived monomer components.
• polyamide, polystyrene, polyolefin may contain other resins such as polyesters other than the above, in the mechanical properties of the biaxially stretched polyester film, in terms of heat resistance
• the content of other resins is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on the total resin components of the polyester film, and 0% by mass.
• % All resin components constituting the polyester film are substantially polyethylene terephthalate resin) are most preferable.
• the intrinsic viscosity of the polyethylene terephthalate resin is preferably in the range of 0.57 to 0.76 dl/g, more preferably 0.60 to 0.73 dl/g, and further preferably 0.63 to 0. It is 7 dl/g. If the intrinsic viscosity is lower than 0.57 dl/g, the polyester film is likely to tear during production (so-called breakage), and if higher than 0.76 dl/g, the filtration pressure rises significantly and high precision filtration is possible. It is difficult to extrude the resin through the filter.
• the intrinsic viscosity of the resin of the polyester film is preferably in the range of 0.51 to 0.70 dl/g, more preferably 0.56 to 0.68 dl/g, and further preferably 0.59 to 0. It is 65 dl/g.
• the polyester film is easy to tear in the processing such as printing, and when the intrinsic viscosity is higher than 0.76 dl/g, the effect of improving the mechanical properties is saturated. Prone.
• the polymerization catalyst used in the present invention is a polymerization catalyst characterized by having the ability to promote esterification.
• a polymerization catalyst of an antimony compound such as antimony trioxide, which has been conventionally used, as described below.
• a polymerization catalyst containing at least one selected from aluminum compounds and at least one selected from phosphorus compounds is preferable.
• a publicly known aluminum compound can be used without limitation as the aluminum compound constituting the polymerization catalyst used when synthesizing the raw material polyester resin used in the present invention.
• the aluminum compound examples include aluminum acetate, basic aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate, and aluminum oxalate and other organoaluminum compounds and portions thereof. Hydrolyzate etc. are mentioned.
• carboxylates, inorganic acid salts and chelate compounds are preferable, and among these, aluminum acetate, basic aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are more preferable, Aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide and aluminum hydroxide chloride are more preferable, and aluminum acetate and basic aluminum acetate are most preferable.
• the amount of the aluminum compound used in the polymerization catalyst according to the present invention is preferably 1 to 80 ppm, more preferably 2 to 60 ppm, as aluminum atoms based on the total mass of the obtained polyester resin. , More preferably 3 to 50 ppm, particularly preferably 5 to 40 ppm, most preferably 10 to 30 ppm. If it is less than the above, the catalytic activity may be poor, and if it exceeds the above, aluminum-based foreign matter may be generated. Even when the aluminum compound is placed in a reduced pressure environment during polyester polymerization, almost 100% of the used amount remains, so it can be considered that the used amount becomes the residual amount.
• the phosphorus compound used in the polymerization catalyst is not particularly limited, but a phosphonic acid-based compound, a phosphinic acid-based compound is preferably used because the effect of improving the catalytic activity is large, and among these, a phosphonic acid-based compound is used to improve the catalytic activity. Is particularly large and preferred.
• phosphorus compounds having a phenol part in the same molecule are preferable.
• a phosphorus compound having a phenol structure but it is a catalyst when one or more compounds selected from the group consisting of a phosphonic acid compound and a phosphinic acid compound having a phenol moiety in the same molecule are used.
• This is preferable because the effect of improving activity is large.
• it is preferable to use one or two or more kinds of phosphonic acid compounds having a phenol moiety in the same molecule because the effect of improving the catalytic activity is particularly large.
• examples of the phosphorus compound having a phenol moiety in the same molecule include compounds represented by the following general formulas (Formula 1) and (Formula 2).
• R 1 is a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, a substituent such as a hydroxyl group, a halogen group, an alkoxyl group or an amino group, and a carbon including a phenol moiety.
• R 4 represents hydrogen, a hydrocarbon group of 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or a carbon group of 1 to 50 carbon atoms containing a substituent such as an amino group.
• R 2 and R 3 each independently represent 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.
• the hydrocarbon group may contain a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl.
• the ends of R 2 and R 4 may be bonded to each other.
• Examples of the phosphorus compound having a phenol moiety in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, diphenyl p-hydroxyphenylphosphonate, and bis( p-hydroxyphenyl)phosphinic acid, methyl bis(p-hydroxyphenyl)phosphinate, phenyl bis(p-hydroxyphenyl)phosphinate, p-hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, p-hydroxy Examples thereof include phenyl phenylphenylphosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, and phenyl p-hydroxyphenylphosphinate.
• Other examples include phosphorus compounds represented by the following general formula (Formula 3).
• X 1 and X 2 each represent hydrogen, an alkyl group having 1 to 4 carbon atoms, or a monovalent or higher valent metal. Further, X 1 may be a metal having a valence of 2 or more and X 2 may be absent. Furthermore, an anion corresponding to the excess valence of the metal with respect to the phosphorus compound may be arranged. Li, Na, K, Ca, Mg, and Al are preferable as the metal.
• the phosphorus compound preferably used as the polycondensation catalyst is at least one phosphorus compound selected from the compounds represented by the chemical formulas (chemical formula 4) and chemical formula (chemical formula 5).
• Irganox 1222 (manufactured by BSF) is commercially available.
• Irganox 1425 (manufactured by BSF) is commercially available and can be used.
• the amount of the phosphorus compound used in the polymerization catalyst according to the present invention is preferably 10 to 100 ppm, more preferably 15 to 90 ppm, as a phosphorus atom based on the total mass of the obtained raw material polyester resin. %, more preferably 20 to 80 ppm, particularly preferably 25 to 70 ppm, and most preferably 30 to 60 ppm. If the phosphorus atom is present in an amount exceeding the above upper and lower limits, the polymerization activity may be reduced. When the phosphorus compound is placed in a reduced pressure environment during polyester polymerization, about 10 to 30% of the used amount is removed out of the system depending on the conditions. Therefore, in practice, it is necessary to carry out several trial experiments to determine the residual ratio of the phosphorus compound in the polyester and then determine the amount to be used.
• the heat resistance of the resin can be improved by using the above phosphorus compound. Although the cause is not clear, it is considered that the heat resistance of the polyester resin is improved by the hindered phenol portion in the phosphorus compound.
• the residual amount of the phosphorus compound is less than 10 ppm, the effect of improving the heat resistance is diminished, and as a result, the effect of improving the heat resistance and coloring of the polyester resin of the present invention may not be observed.
• a metal-containing polycondensation catalyst such as an antimony compound, a titanium compound, a tin compound, or a germanium compound may be used together in order to further improve the catalytic activity.
• the antimony compound is preferably 10 ppm or less as an antimony atom with respect to the mass of the obtained copolyester resin
• the germanium compound is preferably 10 ppm or less as a germanium atom with respect to the mass of the obtained polyester resin.
• the compound preferably has a titanium atom content of 3 ppm or less with respect to the mass of the obtained polyester resin, and the tin compound preferably has a tin atom content of 3 ppm or less with respect to the mass of the obtained polyester resin.
• these metal-containing polycondensation catalysts such as antimony compounds, titanium compounds, tin compounds and germanium compounds as much as possible.
• a small amount of at least one selected from alkali metals, alkaline earth metals and compounds thereof may coexist as the second metal-containing component.
• the coexistence of such a second metal-containing component in the catalyst system is effective for improving the productivity, since in addition to the effect of suppressing the production of diethylene glycol, the catalytic activity is enhanced, and thus the catalyst component having a higher reaction rate is obtained. ..
• the amount used (mol %) is preferably 1 ⁇ 10 ⁇ 5 with respect to the number of moles of the dicarboxylic acid component constituting the polyester resin. ⁇ 0.01 mol %.
• Alkali metal, alkaline earth metal, or a compound thereof remains almost 100% of the amount used even when placed in a reduced pressure environment during polyester polymerization, and therefore it may be considered that the amount used remains.
• the polymerization catalyst according to the present invention has catalytic activity not only for polycondensation reaction but also for esterification reaction and transesterification reaction.
• the transesterification reaction between an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate and a glycol such as ethylene glycol is usually carried out in the presence of a transesterification catalyst such as zinc, but the catalyst of the present invention is used in place of these catalysts.
• the polymerization catalyst according to the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization or solution polymerization.
• the polyester polymerization catalyst used in the present invention can be added to the reaction system at any stage of the polymerization reaction.
• it can be added to the reaction system at any stage before and during the esterification reaction or transesterification reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction.
• the addition of the aluminum compound and the phosphorus compound according to the present invention is preferably performed immediately before the start of the polycondensation reaction.
• the biaxially stretched polyester film of the present invention may have a laminated structure of one layer, two layers, three layers, or four or more layers.
• each layer contains polyethylene terephthalate-based resin, inorganic particles, and a resin other than polyethylene terephthalate-based resin as a constituent component as described above, but any constituent component of each layer adjacent to each other. It is preferable that the types or the contents of are different.
• the A layer in the present invention is the entire biaxially stretched polyester film.
• the A layer in the present invention is either one or both layers.
• the A layer in the present invention is any one layer or two layers of both side surface layers.
• the surface roughness of the film can be controlled by controlling the amount of added particles only in the surface layer portion, and the inorganic particles are contained in the film.
• the amount can be made smaller, which is preferable. This is because the odor component escapes through the voids (voids) formed at the boundary between the inorganic particles and the polyester resin, which also leads to the improvement of the deterioration in aroma retention.
• the inorganic particles for example, silica, alumina, titanium dioxide, calcium carbonate, kaolin, barium sulfate and the like can be used.
• the average particle size of the inorganic particles is preferably in the range of 0.05 to 3.0 ⁇ m when measured with a Coulter counter.
• the lower limit of the content of inorganic particles in the film is preferably 0.01% by weight, more preferably 0.015% by weight, and further preferably 0.02% by weight. If it is less than 0.01% by weight, the slipperiness may decrease.
• the upper limit is preferably 1% by weight, more preferably 0.2% by weight, still more preferably 0.1% by weight. If it exceeds 1% by weight, the transparency may decrease, which is not preferable.
• inorganic particles are dispersed in a predetermined ratio in ethylene glycol which is a diol component, and the ethylene glycol slurry is added at an arbitrary stage before completion of polyester polymerization.
• the particles when the particles are added, for example, it is preferable to add the water sol or alcohol sol obtained during the synthesis of the particles without once drying, because the dispersibility of the particles is good and the generation of coarse projections can be suppressed.
• a method in which an aqueous slurry of particles is directly mixed with a predetermined polyester pellet, supplied to a vent type twin-screw kneading extruder, and kneaded into polyester.
• the resin it is preferable to extrude the resin at an extruder at a resin melting point +2°C or higher and a resin melting point +6°C or lower. If the extrusion temperature is lower than the melting point +2° C., the resin is not melted and an unmelted material is discharged, which becomes a foreign matter, which is not preferable. Further, extruding at a temperature higher than the melting point +6° C. is not preferable because the resin is thermally deteriorated and foreign matter is generated.
• an unstretched film can be obtained by extruding the extruded sheet-shaped molten resin with a T-die and then rapidly cooling it.
• a method of quenching the molten resin a method of obtaining a substantially unoriented resin sheet by casting the molten resin on a rotary drum from a T die and quenching and solidifying can be suitably adopted.
• Sublimates (oligomers, etc.) of the molten resin are likely to adhere to the T-die, and if the deposits fall off, the unstretched sheet becomes foreign matter in the film, which is not preferable. Therefore, attach a sticky sheet to the T-die in advance to prevent sublimates from falling, and also clean it with a cleaner so that it will not transfer to the unstretched sheet even if foreign matter adheres to the cooling roll.
• a sticky sheet to the T-die in advance to prevent sublimates from falling, and also clean it with a cleaner so that it will not transfer to the unstretched sheet even if foreign matter
• the obtained unstretched film is biaxially stretched, and then heat set and relaxed.
• film-forming conditions such as the following stretching conditions in the longitudinal direction and the width direction, heat setting conditions, and heat relaxation conditions, the preferable film properties described below can be achieved. The details will be described below.
• the stretching method may be simultaneous biaxial stretching or sequential biaxial stretching, but sequential biaxial stretching is preferred from the viewpoint of high film forming speed and high productivity.
• sequential biaxial stretching method in which longitudinal stretching is performed first and then transverse stretching is performed-longitudinal stretching-horizontal stretching is described.
• the stretching temperature in the longitudinal (longitudinal) direction (hereinafter sometimes abbreviated as MD) is (Tg+15) to (Tg+55)° C. and the stretching ratio is 3.3 to 4.7 times from the viewpoint of reducing bowing. It is preferable to stretch.
• the stretching temperature is higher than (Tg+55)° C. or lower than 3.3 times, bowing is reduced, but the molecular orientation in the width direction becomes larger than that in the longitudinal direction, which is not preferable because the orientation balance is lost. Further, the flatness of the obtained biaxially stretched polyester film is also deteriorated, which is not preferable.
• shrinkage stress increases and bowing increases, which is not preferable.
• the unstretched film is guided to a tenter device that can heat by holding both ends of the film with clips, and the film is heated to a predetermined temperature by hot air. After being heated to, the film is stretched in the width direction by increasing the distance between the clips while being conveyed in the longitudinal direction.
• the stretching temperature in the width direction is less than Tg+5°C, breakage easily occurs during stretching, which is not preferable.
• Tg+40° C. uniform stretching in the width direction cannot be performed and thickness unevenness in the width direction becomes large, so that the hardness of the film roll becomes large, which is not preferable.
• the stretching ratio in the width direction is not particularly limited, but is preferably 2 times or more and 6 times or less. If the draw ratio is less than 2 times, it is difficult to obtain a high yield in terms of mass balance, the mechanical strength is reduced, and the thickness unevenness in the width direction causes variations in the hardness of the film roll, which is not preferable. On the other hand, if the stretching ratio exceeds 6 times, the film is likely to be broken during the stretch film formation, which is not preferable.
• the heat setting temperature (heat treatment temperature) after TD stretching is preferably 220 to 245°C. If the heat setting temperature is higher than 245°C, bowing increases, which is not preferable. On the other hand, when the temperature is lower than 220° C., the thermal shrinkage ratio becomes high in both the longitudinal direction and the width direction, and the thermal dimensional stability during vapor deposition processing deteriorates, which is not preferable. If the heat setting temperature after TD stretching exceeds 245°C, bowing increases, which is not preferable.
• the orientation angle of the obtained biaxially stretched polyester film and the amount of change in the difference in the oblique heat shrinkage ratio vary greatly depending on the transport state of the film.
• the heat relaxation rate in the width direction is preferably 4 to 8%.
• the thermal relaxation rate is less than 4%, the resulting biaxially stretched polyester film has a high thermal shrinkage in the width direction, and the dimensional stability during vapor deposition processing deteriorates, which is not preferable.
• the thermal relaxation rate is higher than 8%, bowing increases or sagging occurs, and the thickness unevenness in the width direction becomes large, so that the hardness of the film roll varies greatly, which is not preferable.
• the film stretched and formed by the above method is wound by a winder device to produce a master roll.
• the master roll is slit into an arbitrary width while applying tension in the longitudinal direction of the film and further applying pressure (hereinafter, surface pressure) by the contact roll from above the roll. Is wound up as.
• the content of antimony in the film is preferably 10 ppm or less. Since antimony is a substance that may cause carcinogenicity, the smaller the amount, the more preferable. It is preferably 5 ppm, and more preferably 0 ppm.
• the antimony of the raw material resin used in the present invention is preferably 0 ppm, but may be mixed in during production, and was set to 10 ppm or less.
• the biaxially stretched polyester film of the present invention preferably has one or less defects having a size of 1 mm or more per 1000 square meters (for example, a film width of 500 mm and a film winding length of 2000 m). In this way, by reducing the number of defects having a size of 1 mm or more per large area of 1000 square meters (m 2 ) to 1 or less, the printability becomes very good. If the number of defects due to foreign matter is large, ink will be removed during printing, which is not preferable.
• the smaller the number of defects having a size of 1 mm or more the smaller the number of defects, more preferably 0.5 or less, further preferably 0.3 or less, particularly preferably 0.1 or less, and most preferably 0. In the present invention, there is a possibility that foreign matter may be mixed in when an unexpected trouble occurs, and the number is set to 1 or less.
• the difference between the intrinsic viscosity of the polyester resin and the intrinsic viscosity of the polyester film is preferably 0.06 dl/g or less.
• the difference in the intrinsic viscosity is an index of the degree of deterioration when the polyester resin is melt-extruded. When it is higher than 0.06 dl/g, the resin deteriorates in the extruder and causes foreign matter, which is not preferable.
• the difference in intrinsic viscosity is preferably 0 dl/g, but it is difficult to set it to 0 dl/g because it substantially melts. It is preferably 0.05 dl/g or less, and more preferably 0.04 dl/g or less.
• the resin in order to control the difference in the intrinsic viscosity as described above, in the present invention, it is preferable to extrude the resin at a resin temperature of the melting point of the resin+2° C. or higher and the melting point of the resin+6° C. or lower. If the extrusion temperature is lower than the melting point +2° C., the resin is not melted and an unmelted material is discharged, which becomes a foreign matter, which is not preferable. Also, extruding at a temperature higher than the melting point +6° C. is not preferable because the resin is thermally deteriorated and becomes a foreign substance.
• the haze of the biaxially stretched polyester film of the present invention is preferably 1% or more and 8% or less. When it is higher than 8%, the transparency of the film is impaired, which is not preferable. It is preferable that the haze is low, but in the present invention, the lower limit of the haze was 1% in order to impart the slip property, and therefore the haze was set as such.
• the haze is preferably 7% or less, more preferably 6% or less.
• the biaxially stretched polyester film of the present invention preferably has a heat shrinkage percentage measured in the vertical direction of 150° C. for 15 minutes of 0.8% or more and 3% or less. If the heat shrinkage ratio is higher than 3%, the film shrinks when the film is dried in the post-printing process, resulting in misalignment of the printed pattern, which is not preferable. There is no problem with less than 0.8%, but in the production method of the present invention, 0.8% was the lower limit, so it was set to 0.8% or less.
• the upper limit of the heat shrinkage in the vertical direction is preferably 2.5% or less, more preferably 2% or less.
• the value of the heat shrinkage is a value calculated by the equation (3) described later.
• the thickness unevenness in the lengthwise and widthwise directions of the biaxially stretched polyester film of the present invention measured over a length of 1 m is preferably 1% or more and 10% or less in both the thicknesswise and widthwise directions of the film. If the thickness unevenness is larger than 10%, it is not preferable because print omission or meandering due to wrinkles occurs during processing such as printing. It is preferable that the thickness unevenness in the film width direction and the width direction is low, but in the present invention, about 1% is the lower limit of the thickness unevenness.
• the thickness unevenness in the vertical direction and the horizontal direction is more preferably 8% or less, further preferably 6% or less.
• the thickness of the biaxially stretched polyester film of the present invention is not particularly limited, but is preferably 2 ⁇ m or more and 300 ⁇ m or less. When the thickness is less than 2 ⁇ m, the film lacks a feeling of stiffness, and wrinkles easily occur in the processing such as printing, and the lack of a sense of stiffness tends to cause problems in the process of forming a bag or a label, which is not preferable. Although the thickness is thick, there is no problem, but it is not preferable that the thickness is more than 300 ⁇ m because it is contrary to the volume reduction due to the thinning as a measure for environment and cost. The thickness is more preferably 4 ⁇ m or more and 250 ⁇ m or less, and further preferably 6 ⁇ m or more and 200 ⁇ m or less.
• the width of the product roll of the biaxially stretched polyester film of the present invention is not particularly limited, but is preferably 300 mm or more and 5000 mm or less. If the width is less than 300 mm, the efficiency in printing and processing is reduced, which is not preferable. Although the width is wide, there is no problem, but if the width is too wide in the printing or processing step, handling becomes large. Therefore, it is not preferable that the width is longer than 5000 mm.
• the width of the film roll is more preferably 400 mm or more and 4500 mm or less, and further preferably 500 mm or more and 4000 mm or less.
• the evaluation method of the film is as follows. [Tg (glass transition point), Tm (melting point)] Using a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd., DSC220), 5 mg of an unstretched film was put in a sample pan, the pan was covered, and the temperature was changed from -40°C to 300°C at 10°C/under a nitrogen gas atmosphere. The temperature was raised at a heating rate of a minute to measure. Tg (°C) and Tm (°C) were determined based on JIS-K7121-1987.
• the ink used at this time was a gravure printing ink (manufactured by Toyo Ink: trade name: Finestar R92 ink), which was mixed with a diluent solvent (manufactured by Toyo Ink: trade name SL302) at a ratio of 77:23. ..
• the obtained printed sample was rewound using a rewinding machine.
• Thickness variation The film was sampled in a strip shape of 1 m in the measuring direction and 40 mm in the width direction, and the thickness of the film sample was continuously measured at a speed of 5 (m/min) using a continuous contact thickness meter manufactured by Micron Measuring Instruments Co., Ltd. Was measured.
• the solution was filtered through a glass filter (3G) to obtain an aqueous solution of an aluminum compound.
• 3G glass filter
• 2.0 liters of the aqueous solution of the aluminum compound and 2.0 liters of ethylene glycol were charged into a flask equipped with a distillation apparatus at room temperature and normal pressure, and the mixture was stirred at 200 rpm for 30 minutes, and then a uniform water/ethylene glycol mixed solution was added. Obtained.
• the jacket temperature setting was changed to 110° C. and the temperature was raised to distill water from the solution. When the amount of distilled water reached 2.0 liters, heating was stopped and the mixture was allowed to cool to room temperature to obtain an ethylene glycol solution of aluminum compound.
• part means “part by mass”. 2130 parts of terephthalic acid, 1955 parts of ethylene glycol and 0.7 part of triethylamine were added to a reaction can equipped with a stirrer, a thermometer and a distilling cooler, and gradually increased from 220°C to 250°C under a pressure of 0.35 MPa. The temperature was raised and the esterification reaction was carried out while removing the distilled water out of the system.
• the above polymerization catalyst solution was mixed with an ethylene glycol solution of a phosphorus compound and an ethylene glycol mixed solution of an aluminum compound in an amount of 0.047 mol% as a phosphorus atom and 0 as an aluminum atom with respect to the dicarboxylic acid component in the polyester resin.
• initial pressure-reducing polymerization was carried out to 1.3 kPa over 1 hour, the temperature was raised to 270° C., and further polymerization was carried out at 0.13 kPa or less to obtain polyester 1.
• Polyesters 2 and 3 were produced by partially modifying the production method of polyester 1 as follows. Table 1 shows the composition and physical properties of each polyester.
• the polyesters used in Examples and Comparative Examples are as follows.
• ⁇ Polyester 1 Polyethylene terephthalate (IV 0.73 dl/g)
• Polyester 2 Polyethylene terephthalate (IV 0.73 dl/g) in which SiO 2 (Silysia 266 manufactured by Fuji Silysia Chemical Ltd.) was added as a lubricant at a ratio of 8,000 ppm to the polyester when the above Polyester 1 was manufactured.
• -Polyester 3 An antimony catalyst was added in place of aluminum so as to be 0.084 mol% in the production of Polyester 1 (IV 0.73 dl/g).
• Example 1 The above polyester 1 and polyester 2 were mixed at a weight ratio of 97:3 and charged into an extruder. Then, the mixed resin is melted at 270° C., cooled to 260° C., extruded from a T-die, wound around a rotating metal roll cooled to a surface temperature of 30° C., and rapidly cooled to obtain a layer having a thickness of 220 ⁇ m. An unstretched film was obtained. The take-up speed (rotational speed of the metal roll) of the unstretched film at this time was about 80 m/min. The unstretched film had Tg of 75°C and Tm of 256°C.
• An adhesive sheet made of high melting point polyimide was attached to the T-die to prevent volatile matter of the molten resin from falling.
• a UV irradiation type cleaner was used to remove foreign matter that had fallen onto the cooling roll.
• the resulting unstretched sheet was heated to 115° C., and the total draw ratio was 4 by a three-stage drawing in which the first stage was 1.24 times, the second stage was 1.4 times, and the third stage was 2.6 times. It was stretched in the longitudinal direction at a stretch ratio of 0.5. Subsequently, the film was stretched in the width direction at a temperature of 140° C. and a stretching ratio of 4.3 times, heat-set at 243° C., and heat-relaxed by 5% in the width direction.
• both ends of the stretched film were cut and removed, and then the roll was wound into a roll with a winder through a corona discharge treatment to prepare a master roll of a biaxially stretched polyester film having a thickness of 12 ⁇ m and a width of 8 m.
• the characteristics of the obtained film were evaluated by the above methods.
• the number of defects was evaluated by the above method using a roll obtained by slitting a width of 800 mm and a winding length of 10,000 m.
• the film manufacturing method is shown in Table 2, and the evaluation results are shown in Table 3.
• the amount of antimony was low enough to ensure hygiene, and it was a good film with few defects and excellent print appearance.
• Example 2 A biaxially stretched polyester film roll was obtained in the same manner as in Example 1 except that polyester 1 and polyester 2 were mixed at a weight ratio of 99.5:0.5 and charged into an extruder.
• the film manufacturing method is shown in Table 2, and the evaluation results are shown in Table 3.
• the film was excellent in transparency and good in quality as compared with Example 1. In addition, there were few printing omissions and it was good.
• Example 3 A biaxially stretched polyester film roll was obtained in the same manner as in Example 1 except that polyester 1, polyester 2 and polyester 3 were mixed in a weight ratio of 96.5:3:0.5 and charged into an extruder.
• the film manufacturing method is shown in Table 2, and the evaluation results are shown in Table 3. Although the amount of antimony was slightly increased and the number of defects was slightly increased from Example 1, the number of defects was sufficiently small, and the film was of good quality.
• Polyester 3 and polyester 2 were mixed at a weight ratio of 97:3 and charged into an extruder. Otherwise in the same manner as in Example 1, a biaxially stretched polyester film roll was obtained.
• the film manufacturing method is shown in Table 2, and the evaluation results are shown in Table 3.
• the amount of antimony was larger than that in Example 1, the number of defects was increased, and the film was inferior in quality.
• the number of print omissions was larger than that of Example 1 and was inferior.
• the biaxially stretched polyester film of the present invention has an extremely low amount of antimony and has good printability, processability, and productivity, it is a film suitable for food packaging bags and labels with excellent hygiene. is there.

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• Chemical & Material Sciences (AREA)
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• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Mechanical Engineering (AREA)
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• Materials Engineering (AREA)
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• Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
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• 2020
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