WO2023032595A1 - 二軸配向ポリエチレンテレフタレートフィルムロール - Google Patents
二軸配向ポリエチレンテレフタレートフィルムロール Download PDFInfo
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- WO2023032595A1 WO2023032595A1 PCT/JP2022/030148 JP2022030148W WO2023032595A1 WO 2023032595 A1 WO2023032595 A1 WO 2023032595A1 JP 2022030148 W JP2022030148 W JP 2022030148W WO 2023032595 A1 WO2023032595 A1 WO 2023032595A1
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- film
- biaxially oriented
- stretching
- polyethylene terephthalate
- film roll
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- C—CHEMISTRY; METALLURGY
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- Aromatic polyesters typified by polyethylene terephthalate (PET) have excellent mechanical properties and chemical resistance, and are widely used as molded products such as fibers and films.
- PET resin is inexpensive and excellent in terms of sanitation, so it is widely used as food containers and beverage containers.
- used PET containers have been recycled for some time, and attention is being focused on how to utilize them.
- Recycled raw materials derived from PET containers are produced by recovering A-PET used in PET bottles for beverages and containers for salads, vegetables, and the like.
- waste materials on the market are collected and used as recycled raw materials, the amount of foreign matter contained in the raw materials is greater than that of PET raw materials derived from fossil fuels. Therefore, the resulting biaxially oriented polyester film is often broken due to foreign matter, and the problem is that the productivity deteriorates.
- the term "foreign matter" as used herein refers to substances other than PET resin, such as band labels of PET bottles, gravel, and chemicals such as pesticides and insecticides that consumers have filled in PET bottles.
- Patent Document 1 discloses a biaxially oriented polyester film using recycled PET bottle raw materials.
- the coefficient of increase in filter back pressure of the recycled raw material is suppressed to the same level as that of the fossil fuel-derived PET raw material, and the resulting biaxially oriented polyester film also contains less foreign matter.
- the effect of environmental measures is insufficient.
- even if a sufficient filtration process is carried out during the production of the recycled raw material it is expected that the filter replacement cycle will be shortened and the productivity will be reduced.
- Thermal shrinkage in the longitudinal direction of the film when measured at 150° C. for 30 minutes is 0.5% or more and 2.0% or less.
- the plane orientation coefficient ( ⁇ P) of the film calculated from the refractive index measured according to JIS K 7142-1996 A method is 0.16 or more and 0.17 or less.
- the number of foreign matter with a maximum length of 1.3 mm or more per 1000 m 2 of film roll is 1 or more.
- the biaxially oriented polyethylene terephthalate film roll of [1], wherein the recycled raw material derived from the PET container of [1] is a mechanically recycled polyester resin and/or a chemically recycled polyester resin.
- the biaxially oriented polyester film roll of the present invention uses a recycled raw material derived from a PET container as a raw material, and the thermal shrinkage in the longitudinal direction of the film, the plane orientation coefficient ( ⁇ P), and the number of foreign substances are within a predetermined range.
- a biaxially oriented polyester film roll which is friendly to the global environment, can be obtained with good film productivity even when the amount of foreign matter in the recycled raw material is large, and which can be made long.
- FIG. 1 is a schematic diagram showing a logarithmic pattern TD stretching method in the present invention
- FIG. It is a schematic diagram showing a TD stretching method of a multi-stage stretching pattern in the present invention.
- the recycled raw material derived from the PET container preferably used in the present invention is mainly composed of polyethylene terephthalate, and the form of the container to be recycled is not limited, and may contain some coloring components.
- a polyester resin made from recycled PET bottles will be described below as an example, but the present invention is not limited to this.
- polyester resin made from recycled PET bottles As the polyester resin made from recycled PET bottles in the present invention, used PET bottles collected from the market and society are sorted, pulverized, and washed to sufficiently remove surface stains and foreign matter, and then exposed to high temperature. Polyester resin obtained by a physical recycling method (hereinafter sometimes referred to as mechanically recycled polyester resin) that is pelletized again after thoroughly washing contaminants remaining inside the resin, and used packaging containers Any polyester resin obtained by decomposing the contained polyester resin to the monomer level, removing contaminants, etc. and polymerizing again (hereinafter sometimes referred to as chemically recycled polyester resin) can be suitably used. can.
- mechanically recycled polyester resin any polyester resin obtained by decomposing the contained polyester resin to the monomer level, removing contaminants, etc. and polymerizing again
- polyester resin recycled from the market or society including the following PET bottles.
- polyester resin recycled from the market and society, including PET bottles the ratio of recycled raw materials in the film can be increased, making it possible to obtain an environmentally friendly film.
- Polyester resin recycled from the market and society, including PET bottles used in the biaxially oriented polyester film of the present invention is mainly composed of recycled containers mainly made of polyethylene terephthalate.
- Recycled containers for beverages such as soft drinks can be preferably used, and may be appropriately oriented, and preferably colorless, but may contain a small amount of coloring component.
- the PET container-derived recycled raw material preferably used in the present invention is a polyester produced and molded by a conventional polymerization method and a solid phase polymerization method, preferably mainly composed of polyethylene terephthalate, and other polyester components, It may contain a copolymer component.
- a metal compound such as antimony, germanium or titanium as a catalyst and a phosphorus compound as a stabilizer may be included.
- Germanium is often used as a catalyst in polyester for PET bottles, and if a film is made using recycled PET bottle raw materials, the film will contain 1 ppm or more of germanium. However, since this is just the content of the catalyst, it is usually at most 100 ppm or less, and usually 50 ppm or less.
- Alkali cleaning and rinsing may be repeated several times.
- the aqueous solution component of the alkali metal hydroxide used for washing remains in the flakes, so that the flakes go through the melt extrusion process in the subsequent pellet granulation process and the melt extrusion process during film formation. may affect the physical properties of the resulting film.
- the concentration of sodium and potassium in the film obtained using the polyester resin recycled from the market or society, including these PET bottles is greater than 0 ppm and 150 ppm or less, more preferably 3 to 3. 120 ppm, more preferably 5 to 80 ppm. If the concentration of sodium or potassium contained in the film is higher than 150 ppm, the heat resistance and thermal stability of the film will be lowered, and the film will be colored, which is not preferable. In addition, if it is completely absent, the effect of suppressing the production of diethylene glycol is diminished, which is not preferable. Polyester resins recycled from the market and society, including PET bottles, may contain a small amount of these components, and it is difficult to completely eliminate them.
- the washed flakes or the flakes melt-extruded and pelletized are continuously solid-phase polymerized in an inert gas such as nitrogen gas or rare gas at 180 to 245 ° C., preferably 200 to 240 ° C. It can be done by
- the melting process in the extruder can be carried out by melt-kneading usually at 260-300°C, preferably at 265-295°C.
- the flakes obtained by pulverizing the PET bottle to be charged must be sufficiently dried, and the drying is preferably performed under conditions of 5 to 200 ppm, preferably 10 to 100 ppm, more preferably 15 to 50 ppm.
- the hydrolysis reaction proceeds in the melting process, and the intrinsic viscosity of the obtained polyester resin decreases.
- the extruder preferably has a filter capable of filtering and removing solid foreign matters having a particle size of 25 ⁇ m or more, preferably 15 ⁇ m or more, more preferably 10 ⁇ m or more, of the molten resin as filtering means.
- polyester resins may be copolymerized with other components as long as the object of the present invention is not impaired.
- copolymerization components include dicarboxylic acid components such as isophthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, adipic acid, sebacic acid and ester-forming derivatives thereof.
- Diol components include diethylene glycol, hexamethylene glycol, neopentyl glycol, and cyclohexanedimethanol.
- polyoxyalkylene glycols such as polyethylene glycol and polypropylene glycol.
- the amount of copolymerization is preferably 10 mol % or less, more preferably 5 mol % or less, most preferably 3 mol % or less per constituent repeating unit.
- the lower limit of the filter back pressure increase coefficient is preferably 10 MPa/kg ⁇ cm 2 , It is more preferably 20 MPa/kg ⁇ cm 2 , and particularly preferably 30 MPa/kg ⁇ cm 2 .
- the coefficient of increase in filter back pressure referred to here represents the resistance to clogging of the filtration filter when the resin is melt-extruded, and is obtained by the following formula.
- the coefficient of increase in filter back pressure By setting the coefficient of increase in filter back pressure to 10 MPa/kg ⁇ cm 2 or more when melt-extruded under the conditions described above, it indicates that the recycled raw material is in a state where the PET container is not substantially sorted. , a sufficient environmental response effect can be obtained.
- the upper limit of the filter back pressure increase coefficient is preferably 100 MPa/kg ⁇ cm 2 , It is more preferably 90 MPa/kg ⁇ cm 2 , and particularly preferably 80 MPa/kg ⁇ cm 2 .
- the method for producing the chemically recycled polyester resin used in the present invention is not particularly limited, but specifically, for example, as described in JP-A-2000-169623, collected used PET bottles are sorted, crushed, and washed. After removing the foreign matter, depolymerization is carried out to decompose and refine the raw material or intermediate raw material of the PET resin, and the material is polymerized to produce a new PET resin.
- depolymerization ethylene glycol (EG) is added in the presence of a catalyst to return to bis-2-hydroxyethyl terephthalate (BHET), which is an intermediate raw material used in resin production. After purification, this is repolymerized into PET.
- EG ethylene glycol
- BHET bis-2-hydroxyethyl terephthalate
- polyester resin obtained by oxidizing polyethylene terephthalate as an essential component as described in JP-A-2000-302707 to produce terephthalic acid and ethylene glycol. , and a method of polymerizing again.
- the feature of chemically recycled polyester resin is that foreign matter and different materials are removed during depolymerization/repolymerization, and it can be recycled into polyester resin with the same high quality as virgin resin, so it is more hygienic than the mechanically recycled polyester resin mentioned above. Since it is excellent, it can be used particularly preferably for food packaging.
- PET bottle bales obtained by volume-reducing and compressing PET bottle waste are put into a pulverizer, and hot water, room temperature water, or hot water or room temperature water containing a detergent is poured into the pulverizer, and pulverized in water.
- the mixture of PET bottle flakes and washing water discharged from the crusher is immediately subjected to specific gravity separation treatment to separate metal, stone, glass, sand and flakes.
- the flakes are separated from the washing water, and the flakes are rinsed with ion-exchanged water and dehydrated by centrifugation.
- the crude polyethylene terephthalate flakes obtained in the above pretreatment step are depolymerized and melted and at the same time hydrolyzed to obtain a polyethylene terephthalate melt with a low degree of polymerization, which is then depolymerized with excess ethylene glycol to produce two types of crude BHET and crude ethylene glycol. A mixed solution is obtained.
- the mixed solution of crude BHET and crude ethylene glycol is cooled and filtered to remove unreacted linear and cyclic oligomers as high-melting precipitates, coagulates of residual different plastics other than polyethylene terephthalate, Solid contaminants such as metals are removed, followed by adsorption/ion exchange treatment to remove colored substances and dissolved ions, thereby removing contaminants contained in the crude BHET.
- the mixed solution of crude BHET and crude ethylene glycol obtained through the pre-purification step is subjected to distillation/evaporation operation to separate and distill ethylene glycol to obtain concentrated BHET, or the mixed solution of the two types is heated at 10°C.
- ethylene glycol and BHET are solid-liquid separated to obtain concentrated BHET, and this concentrated BHET is concentrated at a temperature exceeding 190 ° C. and not exceeding 250 ° C. in an evaporator.
- Purified bis- ⁇ -hydroxyethyl terephthalate is obtained by vacuum evaporation so that the BHET has a retention time of 10 minutes or less.
- polyester resins constituting the biaxially oriented polyester film of the present invention as a method for producing a fossil fuel-derived polyester resin other than the mechanically recycled polyester resin and the chemically recycled polyester resin, first, the above-mentioned dicarboxylic acid or its ester-forming property Using a derivative and a diol or an ester-forming derivative thereof as main starting materials, a method of producing by carrying out an esterification or transesterification reaction according to a conventional method, and then further carrying out a polycondensation reaction at high temperature and under reduced pressure. be done.
- the biaxially oriented polyester film of the present invention may contain conventionally known additives such as lubricants, stabilizers, colorants, antioxidants, antistatic agents, ultraviolet absorbers, etc., in addition to the polyester resin composition. .
- the content of the polyester resin composition is preferably 99.5% by mass or more, more preferably 99.6% by mass, and most preferably It is 99.7% by mass.
- the lower limit of the lubricant content in the biaxially oriented polyester film of the present invention is preferably 100 mass ppm, more preferably 300 mass ppm, and most preferably 500 mass ppm. By making it 100 ppm by mass or more, the slipperiness of the film can be improved.
- the upper limit of the lubricant content in the biaxially oriented polyester film of the present invention is preferably 10000 mass ppm, more preferably 6000 mass ppm, and most preferably 2000 mass ppm. By making it 10000 ppm by mass or less, the transparency of the film can be improved.
- the thickness of the unstretched sheet is preferably in the range of 15-2500 ⁇ m. It is more preferably 600 ⁇ m or less, and most preferably 400 ⁇ m or less.
- the lower limit of the stretching temperature in the longitudinal direction is preferably 90°C, more preferably 100°C, and particularly preferably 110°C.
- the upper limit of the stretching temperature in the MD direction is preferably 140°C, more preferably 130°C, and particularly preferably 120°C. If the temperature is 140° C. or less, the stretching stress increases due to crystallization, and as a result, not only is it possible to suppress breakage due to foreign matter, but also the mechanical strength of the film is improved.
- the lower limit of the draw ratio in the MD direction is preferably 2.5 times, more preferably 2.8 times, and particularly preferably 3.1 times. If it is 2.5 times or more, not only will the mechanical strength of the film be good, but also the thickness unevenness will be good, leading to an improvement in the winding quality of the roll.
- the upper limit of the draw ratio in the MD direction is preferably 4.0 times, more preferably 3.8 times, and particularly preferably 3.6 times. When it is 4.0 times or less, the stretching stress can be lowered, so breakage due to foreign matter can be suppressed.
- the lower limit of the MD relaxation rate is preferably 1%, more preferably 3%, particularly preferably 5%.
- the upper limit of the MD relaxation rate is preferably 10%, more preferably 8%, particularly preferably 6%.
- the lower limit of the stretching temperature in the TD direction is preferably 90°C, more preferably 100°C, and particularly preferably 110°C.
- the upper limit of the stretching temperature in the TD direction is preferably 140°C, more preferably 130°C, and particularly preferably 120°C. If the temperature is 140° C. or less, the stretching stress increases due to crystallization, and as a result, not only is it possible to suppress breakage due to foreign matter, but also the mechanical strength of the film is improved.
- the lower limit of the draw ratio in the TD direction is preferably 2.5 times, more preferably 3.0 times, and particularly preferably 3.5 times. If it is 2.5 times or more, not only will the mechanical strength of the film be good, but also the thickness unevenness will be good, leading to an improvement in the winding quality of the roll.
- the upper limit of the draw ratio in the TD direction is preferably 5.0 times, more preferably 4.5 times, and particularly preferably 4.0 times. When it is 5.0 times or less, the stretching stress can be reduced, so breakage due to foreign matter can be suppressed.
- the drawing pattern in the TD direction is preferably logarithmic or multistage drawing.
- the logarithmic TD stretching pattern is a TD stretching pattern that stretches greatly in the first half of the stretching and gently stretches in the second half of the stretching, as opposed to the normal linear TD stretching pattern. ing.
- TD stretching pattern By using such a TD stretching pattern, most of the stretching can be completed in the first half when the film stretching stress is low, and the stretching stress applied during stretching can be reduced. As a result, breakage due to foreign matter can be suppressed.
- Multi-stage stretching is to perform two or more stages of stretching in contrast to ordinary one-stage stretching, and the stretching stress applied during TD stretching can be reduced. As a result, breakage due to foreign matter can be suppressed.
- the TD multi-stage drawing is preferably two-stage stretching or more and five-stage stretching or less.
- Multi-stage stretching is preferable because it is possible to change the stretching stress by changing the stretching temperature, and the stretching stress during the TD stretching can be reduced.
- FIG. 2 it is preferable to adopt a temperature pattern in which a temperature difference of 2° C. or more is provided in each stage of stretching in the multi-stage stretching, and the temperature is lowered from the first stage of stretching to the final stage of stretching.
- the lower limit of the number of drawing steps is preferably two or more steps. Stretching stress can be lowered
- the lower limit of the heat setting temperature is preferably 170°C, more preferably 180°C, and particularly preferably 190°C.
- a heat shrinkage rate can be made small as it is 170 degreeC or more.
- the upper limit of the heat setting temperature is preferably 230°C, more preferably 220°C, and particularly preferably 210°C. When the temperature is 230° C. or less, it is possible to suppress a decrease in mechanical strength due to brittleness of the biaxially oriented polyester film.
- the lower limit of the thickness of the biaxially oriented polyester film of the present invention is preferably 5 ⁇ m, more preferably 10 ⁇ m, particularly preferably 15 ⁇ m. By setting the thickness to 5 ⁇ m or more, it is possible to suppress breakage caused by foreign matter.
- the upper limit of the thickness of the biaxially oriented polyester film of the present invention is preferably 100 ⁇ m, more preferably 70 ⁇ m, and particularly preferably 40 ⁇ m.
- the lower limit of the plane orientation coefficient ( ⁇ P) of the biaxially oriented polyester film of the invention is preferably 0.160, more preferably 0.161, and particularly preferably 0.162. By making it 0.160 or more, the mechanical strength can be kept sufficiently high.
- the upper limit of ⁇ P of the biaxially oriented polyester film of the present invention is preferably 0.170, more preferably 0.169, particularly preferably 0.168. By making it 0.170 or less, it is possible to suppress the stretching stress in the stretching process, and as a result, it is possible to suppress breakage caused by foreign matter in the stretching process.
- the lower limit of the breaking strength in the MD direction of the biaxially oriented polyester film of the present invention is preferably 180 MPa, more preferably 185 MPa, and particularly preferably 190 MPa. When it is 180 MPa or more, the mechanical strength of the bag product is sufficient.
- the upper limit of the breaking strength in the MD direction of the biaxially oriented polyester film of the present invention is 260 MPa, more preferably 255 MPa, particularly preferably 250 MPa. When it is 260 MPa or less, it is possible to substantially suppress breakage caused by foreign matter in the stretching step, resulting in good film formability.
- the lower limit of the breaking elongation in the MD direction of the biaxially oriented polyester film of the present invention is preferably 80%, more preferably 90%, and particularly preferably 100%. When it is 80% or more, it is possible to substantially suppress breakage caused by foreign matter in the stretching step, resulting in good film formability.
- the upper limit of the breaking elongation in the MD direction of the biaxially oriented polyester film of the present invention is 170%, preferably 160%, and particularly preferably 150%. When it is 170% or less, the mechanical strength is sufficient when made into a bag product.
- the upper limit of thickness unevenness per 800 mm in the width direction of the biaxially oriented polyester film roll of the present invention is preferably 18%, more preferably 16%, and particularly preferably 14%. When it is 18% or less, the winding quality of the roll becomes good.
- the number of foreign matter having a maximum length of 1.3 mm or more per 1000 m 2 of the biaxially oriented polyester film roll of the present invention is 1 or more. If there is at least one foreign matter with a maximum length of 1.3 mm or more per 1000 m2, the foreign matter tends to cause breakage during stretching under conventional film forming conditions, making stable film formation difficult. On the other hand, by stretching the film so that the heat shrinkage rate and the degree of plane orientation of the film are within a predetermined range using the film forming conditions described in the present invention, even if foreign matter is present as described above, stable Stretching becomes possible.
- the lower limit of the number of foreign substances having a maximum length of 1.3 mm or more per 1000 m 2 of the biaxially oriented polyester film roll of the present invention is preferably 10 or less. If there are more than 10 foreign substances of 1.3 mm or more, the number of defects after printing increases, and there is a risk of lowering the yield of the secondary processing step.
- the number of foreign matters having a maximum length of 1.0 mm or more per 8000 m 2 of the biaxially oriented polyester film roll of the present invention is 16 or more.
- there are 16 or more foreign substances with a maximum length of 1.0 mm or more per 8000 m2 there are many triggers for breakage in conventional films, and it is difficult to continuously form a long film.
- by stretching the film so that the heat shrinkage rate and the degree of plane orientation of the film are within a predetermined range using the film-forming conditions described in the present invention even if foreign substances are present as described above, stable stretchability can be ensured, and a long film roll can be obtained.
- the printing method for providing the printed layer is not particularly limited, and known printing methods such as offset printing, gravure printing, and screen printing can be used.
- a known drying method such as hot air drying, hot roll drying, or infrared drying can be used.
- the biaxially oriented polyester film of the present invention can be provided with a gas barrier layer such as an inorganic thin film layer or metal foil as long as it does not impair the purpose of the present invention.
- the mixing ratio of silicon oxide and aluminum oxide is preferably in the range of 20 to 70% by mass of Al in terms of the metal content.
- the inorganic thin film layer can be softened, and it is possible to suppress deterioration of the gas barrier properties due to destruction of the thin film during secondary processing such as printing and lamination.
- silicon oxide means various silicon oxides such as SiO and SiO 2 or mixtures thereof
- aluminum oxide means various aluminum oxides such as AlO and AL 2 O 3 or mixtures thereof.
- the film thickness of the inorganic thin film layer is usually 1 to 100 nm, preferably 5 to 50 nm.
- the film thickness of the inorganic thin film layer is 1 nm or less, it becomes easier to obtain more satisfactory gas barrier properties.
- it is 100 nm or less, it is advantageous in terms of bending resistance and manufacturing cost.
- a gas barrier layer made of a metal oxide is not a completely dense film, and is dotted with minute defects.
- the resin in the protective compatible resin composition penetrates into the defective portions of the metal oxide layer, As a result, the effect of stabilizing the gas barrier property is obtained.
- the gas barrier properties of the laminated film are greatly improved.
- Examples of the protective layer include resins such as urethane, polyester, acrylic, titanium, isocyanate, imine, and polybutadiene with addition of curing agents such as epoxy, isocyanate, and melamine.
- Examples of the solvent (solvent) used for forming the protective layer include aromatic solvents such as benzene and toluene; alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate and butyl acetate.
- ester-based solvents such as ethylene glycol monomethyl ether
- polyhydric alcohol derivatives such as ethylene glycol monomethyl ether.
- a layer of other materials may be laminated on the biaxially oriented polyester film of the present invention.
- a method of laminating the biaxially oriented polyester film after production and a method of laminating the film during film formation can be employed.
- the biaxially oriented polyester film of the present invention can be used as a packaging material, for example, by forming a heat-sealable resin layer (also referred to as a sealant layer) called a sealant on the biaxially oriented polyester film. Formation of the sealant layer is usually carried out by an extrusion lamination method or a dry lamination method.
- a heat-sealable resin layer also referred to as a sealant layer
- a sealant layer a sealant layer
- the sealant layer is usually carried out by an extrusion lamination method or a dry lamination method.
- the thermoplastic copolymer for forming the heat-sealable resin layer any one can be used as long as it can sufficiently exhibit sealant adhesiveness, and HDPE, LDPE.
- Polyethylene resins such as LLDPE, polypropylene resins, ethylene-vinyl acetate copolymers, ethylene- ⁇ -olefin random copolymers, ionomer resins and the like
- the sealant layer may be a single layer film or a multilayer film, and may be selected according to the required functions.
- a multi-layer film in which a resin such as an ethylene-cyclic olefin copolymer or polymethylpentene is interposed can be used in order to impart moisture resistance.
- the sealant layer may contain various additives such as flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers and tackifiers.
- the thickness of the sealant layer is preferably 10-100 ⁇ m, more preferably 20-60 ⁇ m.
- the lower limit of the roll width of the polyester film roll of the present invention is preferably 400 mm or more, more preferably 1000 mm or more from the viewpoint of improving productivity in the secondary processing step, and further preferably 1500 mm or more. preferable.
- the upper limit of the width of the polyester film roll of the present invention is preferably 3000 mm or less, more preferably 2500 mm or less. When the width of the polyester film roll exceeds 3000 mm, handling becomes difficult, and the film tends to wrinkle due to roll deflection.
- the lower limit of the winding length of the polyester film roll of the present invention is preferably 1000 m or more, more preferably 2000 m or more, and even more preferably 4000 m or more from the viewpoint of productivity in the secondary processing step.
- a paper tube, a plastic core, a metal core, or the like is preferably used as the core for winding the film, and can be appropriately selected depending on the application. It is preferable that the gap difference in the width direction of the core after removing the film from the polyester film roll of the present invention is 0.5 mm or less.
- the gap difference in the width direction of the core after removing the film from the polyester film roll of the present invention is 0.5 mm or less.
- the gap between the paper tubes after removing the film from the film roll is preferably 0.4 mm or less, more preferably 0.3 mm or less.
- the flat pressure resistance of the core paper tube after removing the film from the film roll is preferably 1700 N/100 mm or more. If the compressive strength is lower than 1700 N/100 mm, the paper tube will be distorted by the internal stress applied after winding the film, and wrinkles will occur in the roll core, which is not preferable. It is preferably 1800 N/100 mm or more, more preferably 1900 N/100 mm or more. The higher the pressure resistance, the better. Examples of means for obtaining a high flat pressure resistance strength of a paper tube include methods such as increasing the thickness of the paper tube, and using a hard paper tube or an ultra-hard paper tube designed to have high strength.
- the average value of the roll hardness in the width direction of the surface layer of the polyester film roll of the present invention is preferably 500 or more and 850 or less. If it is less than 500, the wound state will be soft and the core wrinkles will be in a good direction, but the end face of the film roll will be displaced, which is not preferable. If the winding hardness is higher than 850, the wound state becomes hard and wrinkles are likely to occur due to uneven thickness, which is not preferable.
- the average value of the roll hardness in the width direction of the surface layer of the film roll is preferably 550 or more and 800 or less, more preferably 600 or more and 750 or less. Particularly preferably, it is more than 650 and 750 or less.
- Thermal Shrinkage of Biaxially Oriented Film was measured by the dimensional change test method according to JIS-C-2318 except that the test temperature was 150° C. and the heating time was 15 minutes.
- Polyester B PET container-derived mechanically recycled polyester resin
- Polyester B was obtained in the same manner as Polyester A.
- the back pressure increase coefficient of polyester B was 64 MPa/kg ⁇ cm 2 .
- Polyester C PET container-derived mechanically recycled polyester resin
- Polyester C was obtained in the same manner as Polyester A.
- the back pressure increase coefficient of Polyester C was 32 MPa/kg ⁇ cm 2 .
- Polyester D PET container-derived mechanically recycled polyester resin
- Polyester D was obtained in the same manner as Polyester A.
- the back pressure increase coefficient of polyester D was 10 MPa/kg ⁇ cm 2 .
- Polyester E PET container-derived mechanically recycled polyester resin
- Polyester E was obtained in the same manner as polyester A, except that the PET container used was selected only for clean ones.
- the back pressure increase coefficient of Polyester E was 8 MPa/kg ⁇ cm 2 .
- Polyester F PET container-derived mechanically recycled polyester resin
- Polyester F was obtained in the same manner as Polyester A.
- the back pressure increase coefficient of Polyester F was 105 MPa/kg ⁇ cm 2 .
- the temperature of the contents of the reactor was lowered to 97-98°C, and the contents were filtered while hot with a filter to remove floating matter and sediment.
- the above-mentioned prepurification treatment liquid was charged again into the stirring autoclave and heated to distill excess ethylene glycol at 198°C under normal pressure to obtain a concentrated BHET melt.
- melt polymerization was performed to obtain a chemically recycled polyester resin G having an intrinsic viscosity of 0.696 dl/g.
- the back pressure increase coefficient of polyester G was 7 MPa/kg ⁇ cm 2 .
- Polyester A was charged into the extruder. After melting the resin at 280° C. in an extruder, the molten resin was passed through a filter mesh of 50 ⁇ m and then through a filter mesh of 100 ⁇ m. Thereafter, it was cast from a T-die at 280° C. and brought into close contact with a cooling roll at 10° C. by an electrostatic adhesion method to obtain an unstretched sheet. Then, the obtained unstretched sheet was stretched 3.6 times in the MD direction at a temperature of 115°C. The film immediately after longitudinal stretching was passed through a heating furnace set at 95° C.
- Example 3 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1, except that the relaxation rate immediately after longitudinal stretching was changed to 0% and the stretching pattern in the tenter was changed to logarithmic. The stretching angle of the tenter was adjusted so that the first stage refraction angle ⁇ 1: 12.6°, the second stage refraction angle ⁇ 2: 8.2°, and the angle change rate was 34.9%. The draw ratio was set so as to be the same as in Example 1. Table 1 shows physical properties and evaluation results.
- Example 4 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1, except that the relaxation rate immediately after longitudinal stretching was changed to 1%. Table 1 shows physical properties and evaluation results.
- Example 5 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1, except that the relaxation rate immediately after longitudinal stretching was changed to 10%. Table 1 shows physical properties and evaluation results.
- Example 6 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1 except that the longitudinal draw ratio was changed to 3.9 times. Table 1 shows physical properties and evaluation results.
- Example 7 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1 except that the longitudinal draw ratio was changed to 2.6 times. Table 1 shows physical properties and evaluation results.
- Example 8 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1, except that the transverse draw ratio was changed to 4.9 times. Table 1 shows physical properties and evaluation results.
- Example 9 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1 except that the transverse draw ratio was changed to 2.6 times. Table 1 shows physical properties and evaluation results.
- Example 10 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1, except that polyester B was used as the resin. Table 1 shows physical properties and evaluation results.
- Example 12 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1, except that polyester D was used as the resin. Table 1 shows physical properties and evaluation results.
- Example 13 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1, except that polyester G was used as the resin. Table 1 shows physical properties and evaluation results.
- Example 1 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1, except that the filter mesh through which the molten resin was passed was changed to 20 ⁇ m and 50 ⁇ m, and the relaxation rate immediately after longitudinal stretching was changed to 0%. . Clogging of the filter mesh occurred and it was defective.
- Example 2 A film having a thickness of 12 ⁇ m was formed in the same manner as in Example 1 except that the filter mesh through which the molten resin was passed was changed to 20 ⁇ m and 50 ⁇ m, the resin was changed to polyester D, and the relaxation rate immediately after longitudinal stretching was changed to 0%. A biaxially oriented polyester film was obtained. Clogging of the filter mesh occurred and it was defective.
- Example 3 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1 except that the resin was changed to polyester E and the relaxation rate immediately after longitudinal stretching was changed to 0%.
- the obtained biaxially oriented polyester film contained few foreign matter and did not clog the filter mesh, but the environmental friendliness effect was insufficient because clean PET containers were sorted out and used as recycled raw materials.
- Example 5 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1 except that the relaxation rate immediately after longitudinal stretching was changed to 12%. The obtained biaxially oriented polyester film had a low plane orientation coefficient and poor mechanical strength.
- Example 6 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1, except that the relaxation rate immediately after longitudinal stretching was 0%. The resulting biaxially oriented polyester film was often broken due to foreign matter, and was poor in film formability.
- Example 7 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1 except that the longitudinal draw ratio was changed to 4.1 times. The resulting biaxially oriented polyester film was often broken due to foreign matter, and was poor in film formability.
- Example 8 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1 except that the longitudinal draw ratio was changed to 2.3 times. The obtained biaxially oriented polyester film had a low plane orientation coefficient and poor mechanical strength.
- Example 9 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1, except that the transverse draw ratio was changed to 5.1 times. The resulting biaxially oriented polyester film was often broken due to foreign matter, and was poor in film formability.
- Example 10 A biaxially oriented polyester film having a thickness of 12 ⁇ m was obtained in the same manner as in Example 1, except that the transverse draw ratio was changed to 2.3 times. The obtained biaxially oriented polyester film had a low plane orientation coefficient and poor mechanical strength.
- the biaxially oriented polyester film roll of the present invention has good productivity of the film obtained even if the amount of foreign matter in the recycled raw material is large and can be made long, and is widely used in the field of packaging films such as food packaging. It can be applied, and it is expected that it will greatly contribute to the industrial world because there is a strong desire to reduce the environmental burden these days.
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Abstract
Description
一方で、回収したPET容器で汚れ等が無くきれいな状態の物だけを選別して再生原料にすると異物の問題は解決できる。しかし汚れたPET容器をリサイクルできないと環境に悪い。
すなわち本発明は、以下の構成からなる。
[1]PET容器由来の再生原料を使用し、下記(1)~(3)を満たす二軸配向ポリエチレンテレフタレートフィルムをロール状に巻き取ってなる二軸配向ポリエチレンテレフタレートフィルムロール。
(1)150℃30分で測定した時のフィルム長手方向の熱収縮率が0.5%以上2.0%以下。
(2)JIS K 7142-1996 A法に基づいて測定した屈折率から算出したフィルムの面配向係数(ΔP)が0.16以上0.17以下。
(3)フィルムロール1000m2あたりに最大長さが1.3mm以上の異物数が1個以上。
[2]前記[1]に記載のPET容器由来の再生原料が、メカニカルリサイクルポリエステル樹脂及び/またはケミカルリサイクルポリエステル樹脂であることを特徴とする[1]に記載の二軸配向ポリエチレンテレフタレートフィルムロール。
[3]フィルム幅方向で800mm辺りの厚みムラが18%以下であることを特徴とする前記[1]又は[2]に記載の二軸配向ポリエチレンテレフタレートフィルムロール。
[4]フィルム長手方向の破断強度が180MPa以上260MPa以下、破断伸度が80%以上170%以下であることを特徴とする前記[1]~[3]のいずれかに記載の二軸配向ポリエチレンテレフタレートフィルムロール。
[5]フィルムロール8000m2あたりに最大長さが1.0mm以上の異物数が16個以上あることを特徴とする前記[1]~[4]のいずれかに記載の二軸配向ポリエチレンテレフタレートのフィルムロール。
[6]巻長が10000m以上である前記[1]~[5]のいずれかに記載の二軸配向ポリエチレンテレフタレートフィルムロール。
本発明で好ましく使用されるPET容器由来の再生原料は、ポリエチレンテレフタレートを主体とし、リサイクル元の容器形態は限定されず、若干の着色成分を含んでいても良い。以下、ペットボトルをリサイクル使用したポリエステル樹脂を例に挙げて説明するが、これに限定されるものではない。
本発明おけるペットボトルをリサイクル使用したポリエステル樹脂としては、市場や社会から回収された使用済みペットボトルを選別、粉砕、洗浄して表面の汚れ、異物を十分に取り除いた後に高温下に曝して、樹脂内部に留まっている汚染物質等を高度に洗浄した後に再度ペレット化する物理的再生法により得られたポリエステル樹脂(以下、メカニカルリサイクルポリエステル樹脂と称する場合がある)及び、使用済みの包装容器に含まれるポリエステル樹脂をモノマーレベルまで分解した後に汚染物質等の除去を行い、再度重合を行うことにより得られるポリエステル樹脂(以下、ケミカルリサイクルポリエステル樹脂と称する場合がある)のいずれも好適に用いることができる。
本発明の二軸配向ポリエステルフィルムに使用されるペットボトルを含む、市場や社会からリサイクルされたポリエステル樹脂は、ポリエチレンテレフタレートを主体とする容器のリサイクル品を主体とするものであり、例えば、茶飲料、清涼飲料などの飲料用容器のリサイクル品が好ましく使用でき、適宜配向されていても良く、無色のものが好ましいが、若干の着色成分を含んでいても良い。
集められた使用済のリサイクルペットボトルは、他の材料やごみが混ざらないように選別され、ラベルなどを除去した後、粉砕されフレークとなる。これらのフレークには、異物が付着、混入している場合が多くある。また、薬品や溶剤などの化学物質を消費者が使用済みのPETボトルに充填して使用している場合も考えられる。例えば、食器などの洗剤、殺虫剤、除草剤、農薬や各種オイル類などが考えられる。通常の洗浄ではPETボトル表面に吸着した化学物質を十分に取り除くことができないため、アルカリ洗浄を行うことが好ましい。この洗浄工程で用いるアルカリ金属水酸化物の溶液としては水酸化ナトリウム溶液、または水酸化カリウム溶液を用いる。このような洗浄工程では、アルカリ洗浄の前に予備洗浄を行っても良い。
アルカリ洗浄を行わないと、原料の樹脂中に異物として残存してしまうため、これらが混入して製膜時の破断のきっかけとなり生産性を低下させてしまうばかりか、フィルム中に異物として残り、フィルムの外観や、後に行われる印刷工程での印刷抜けの原因となりうる。
[ポリエステル樹脂組成物]
本発明における二軸配向ポリエステルフィルムは下記のポリエステル樹脂を主成分として含むポリエステル樹脂組成物からなる。
本発明の二軸配向ポリエステルフィルムを構成するポリエステル樹脂は、ジカルボン酸またはそのエステル形成性誘導体と、ジオールまたはそのエステル形成性誘導体から合成されるポリマーである。例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレン-2,6-ナフタレートが挙げられ、機械的特性および耐熱性、コストなどの観点からポリエチレンテレフタレートが好ましい。
ここでの主成分とはポリエステル樹脂組成物中の含有率が80重量%以上であることを意味し、90重量%以上であることが好ましく、95重量%以上がより好ましく、98重量%以上が最も好ましい。
尚、ここでいうフィルター背圧上昇係数とは、樹脂を溶融押し出しした際の濾過フィルターの目詰まりのしにくさを表しており、下記式で求められる。
K=ΔP/(Q/S)
ここで、K:フィルター背圧上昇係数、ΔP=P1-P0
P1:押し出し4時間後の圧力(MPa)、P0:押し出し開始時の圧力(MPa)、Q:押し出し吐出量(kg/hr)、S:フィルター濾過面積(cm2)
本発明のPET容器由来の再生原料を、温度285℃、フィルター濾過径20μm、濾過速度6g/分で溶融押し出しした際のフィルター背圧上昇係数の上限は好ましくは100MPa/kg・cm2であり、より好ましくは90MPa/kg・cm2であり、特に好ましくは80MPa/kg・cm2である。100MPa/kg・cm2以下とすることで、二軸配向ポリエステルフィルムの生産条件の調整のみで、生産性を良好なものにできる。
本発明で用いられるケミカルリサイクルポリエステル樹脂の製造方法としては特に限定されないが、具体的には例えば、特開2000-169623号公報に記載の如く、回収された使用済みペットボトルを選別、粉砕、洗浄して異物を取り除いた後に、解重合を行うことによりPET樹脂の原料または中間原料まで分解、精製したものを重合して新たなPET樹脂とするものある。解重合にはエチレングリコール(EG)を加えて触媒の存在下で、樹脂製造時の中間原料であるビス-2-ヒドロキシエチルテレフタレート(BHET)にまで戻し、これを精製した後、PETに再重合する方法や、特開2000-302707号公報に記載の如くポリエチレンテレフタレートを酸化した鉄を必須成分とする触媒の存在下に非水系有機溶媒中で加熱処理してテレフタル酸とエチレングリコールを生成した後、再度重合する方法が挙げられる。
ケミカルリサイクルポリエステル樹脂の特徴は解重合/再重合の間に異物、異種材質が取り除かれ、バージン樹脂と同等に品質の高いポリエステル樹脂に再生できるため、前述したメカニカルリサイクルポリエステル樹脂と比べ、衛生性に優れているため、食品包装用途として特に好ましく用いることができる。
は、製膜性や再回収性などの点から0.50~0.90dl/gの範囲が好ましく、より
好ましくは0.55~0.80dl/gの範囲である。
本発明の二軸配向ポリエステルフィルムにおける滑剤含有量の上限は、好ましくは10000質量ppmであり、より好ましくは6000質量ppmであり、最も好ましくは2000質量ppmである。10000質量ppm以下とすることで、フィルムの透明性を良好なものとすることができる。
本発明の二軸配向ポリエステルフィルムを得るための方法として、特に限定はなくTダイ方式やインフレーション方式など適宜選択することができる。
冷却ロールの温度の下限は好ましくは0℃である。0℃以上であると、溶融したポリエステル樹脂組成物が冷却固化する際の結晶化抑制効果を十分に発揮できる。また、冷却ロール温度を上記の範囲とする場合、結露防止のため冷却ロール付近の環境の湿度を下げておくことが好ましい。
MD方向の延伸温度の上限は好ましくは140℃であり、より好ましくは130℃であり、特に好ましくは120℃である。140℃以下であると、結晶化により延伸応力が増大し、結果的に異物起因による破断を抑制することができるばかりだけでなく、フィルムの力学強度も良好なものとなる。
MD方向延伸倍率の上限は好ましくは4.0倍である、より好ましくは3.8倍であり、特に好ましくは3.6倍である。4.0倍以下であると、延伸応力を下げることができるので、異物起因による破断を抑制することができる。
MDリラックス率の下限は好ましくは1%であり、より好ましくは3%であり、特に好ましくは5%である。1%以上であると、フィルム中の非晶成分が緩和され、その後に続くTD延伸工程での延伸応力を下げることができ、結果的に異物起因による破断を抑制することができる。
MDリラックス率の上限は好ましくは10%であり、より好ましくは8%であり、特に好ましくは6%である。10%以下であると、収縮によるシワを抑制することができ、フィルムの品位を向上させることができるばかりか、配向緩和による力学強度の低下を抑制することができる。
MDリラックスの方法は特に限定されないが、例えば熱風ヒーターで加熱した後にロール間の速度差を利用してリラックス処理を施す方法が挙げられる。
TD方向の延伸温度の上限は好ましくは140℃であり、より好ましくは130℃であり、特に好ましくは120℃である。140℃以下であると、結晶化により延伸応力が増大し、結果的に異物起因による破断を抑制することができるばかりだけでなく、フィルムの力学強度も良好なものとなる。
TD方向延伸倍率の上限は好ましくは5.0倍である、より好ましくは4.5倍であり、特に好ましくは4.0倍である。5.0倍以下であると、延伸応力を下げることができるので、異物起因による破断を抑制することができる。
延伸角度θnから延伸角度θn+1へ延伸角度が変化する際の変化量も目的とする性能を得るために適宜選択できる。ただし、{(θn-θn+1)/θn}×100(単位;%)で表す角度変化率が50%を超えて大きい場合には、所定の最大倍率まで延伸するために必然的にTD延伸初期の延伸倍率極端に大きくする必要が生じるため、延伸初期の延伸応力が大きくなりすぎ、逆に製膜性を悪化させる恐れがある。角度変化率が0%の場合には、θ1=θ2なので従来のテンターでの延伸条件と同じであるので、対数型のTD延伸パターンを採用する場合は、角度変化率は0.5%以上50%以下の範囲内が好ましく、1%以上30%以下の範囲がより好ましく、1.5%以上20%以下の範囲内が特に好ましい。対数型のTD延伸パターンにおける延伸角度を上記範囲内とすることで、フィルム延伸応力が低い前半で延伸の大部分を完了することができ、延伸時にかかる延伸応力を低くすることができる。結果的に、異物による破断を抑制することができる。
延伸段数の下限は好ましくは2段延伸以上である。2段延伸以上であると、延伸応力を下げることができ、異物起因の破断を抑制することができる。
延伸段数の上限は好ましくは5段以下である。5段延伸以下であると、設備が大きくなりすぎることを防ぐことができる。
また、多段延伸を行う場合、各延伸段階の後に定長とするゾーンを適宜設けることができる。各延伸段階の後に定長とするゾーンを設けることで、延伸時に発生した内部応力を定長ゾーンで緩和することにより、次の延伸を行う際の延伸応力をより低減でき、フィルムの破断を抑制することができる。
熱固定温度の上限は好ましくは230℃であり、より好ましくは220℃であり、特に好ましくは210℃である。230℃以下であると、二軸配向ポリエステルフィルムが脆くなることによる力学強度の低下を抑制することができる。
TDリラックス率の上限は好ましくは10%であり、より好ましくは8%であり、特に好ましくは6%である。10%以下であると弛みなどが生じることを防止でき、平面性を向上させることができる。
本発明の二軸配向ポリエステルフィルムの厚みの下限は好ましくは5μmであり、より好ましくは10μmであり、特に好ましくは15μmである。5μ以上とすることで、異物起因の破断を抑制することができる。
本発明の二軸配向ポリエステルフィルムの厚みの上限は好ましくは100μmであり、より好ましくは70μmであり、特に好ましくは40μmである。
本発明の二軸配向ポリエステルフィルムのΔPの上限は好ましくは0.170であり、より好ましくは0.169であり、特に好ましくは0.168である。0.170以下とすることで、延伸工程での延伸応力を抑制することができ、結果的に延伸工程での異物起因の破断を抑制することができる。
本発明の二軸配向ポリエステルフィルムのMD方向の破断強度の上限は260MPaであり、より好ましくは255MPaであり、特に好ましくは250MPaである。260MPa以下であると、実質的に延伸工程での異物起因の破断を抑制することができ、製膜性が良好なものとなる。
本発明の二軸配向ポリエステルフィルムのMD方向の破断伸度の上限は170%であり、より好ましくは160%であり、特に好ましくは150%である。170%以下であると、製袋品としたときの力学強度が十分なものとなる。
本発明の二軸配向ポリエステルフィルムのMD方向の熱収縮率の上限は好ましくは2.0%であり、より好ましくは1.7%であり、特に好ましくは1.4%である。2.0%以下であると、実質的に延伸工程での異物起因の破断を抑制することができ、製膜性が良好なものとなる。
一方、本発明の二軸配向ポリエステルフィルムロールの1000m2あたりの最大長さが1.3mm以上の異物数の下限は10個以下であることが好ましい。1.3mm以上の異物が10個を超えて多くなると、印刷後の欠点が増えてしまい、二次加工工程の歩留まりを低下させてしまう恐れがある。
一方、本発明の二軸配向ポリエステルフィルムロールの8000m2あたりの最大長さが1.0mm以上の異物数の上限は80個以下であることが好ましい。1.0mm以上の異物が80個を超えて多くなると、印刷後の欠点が増えてしまい、二次加工工程の歩留まりを低下させてしまう恐れがある。
シーラント層の厚さは、10~100μmが好ましく、20~60μmがより好ましい。
一方本発明のポリエステルフィルムロール幅の上限は3000mm幅以下であることが好ましく2500mm以下が更に好ましい。ポリエステルフィルムロールの幅が3000mm幅を超えると、ハンドリングが困難となるほか、ロールのたわみによりフィルムにシワが入りやすくなる。
また本発明のポリエステルフィルムロールの巻き長の下限は1000m以上であることが好ましく、二次加工工程における生産性の観点から、2000m以上であることがより好ましく、4000m以上であることが更に好ましい。
一方本発明のポリエステルフィルムロールの巻き長の下限は100000mであり、好ましくは80000mであり、さらに好ましくは70000mである。
ポリエステルフィルムロールの巻き長が100000mを超えるとロールの重量が大きくなり、ハンドリングが困難となる。
本発明のポリエステルフィルムロールからフィルムを除去した後のコアの幅方向の隙間差が0.5mm以下である事が好ましい。コアとして特に紙管を用いる場合、フィルムを巻取った後に保管していると、フィルムの歪みや自然収縮等により紙管は変形(歪み)が生じる。その際、幅方向における紙管の歪み差(幅方向の隙間差)が大きいと、フィルムロールの巻芯側に皴が生じてくるので好ましくない。従って、フィルムロールからフィルムを除去した後の紙管に隙間差は、好ましくは0.4mm以下であり、更に好ましくは0.3mm以下である。
再生原料ペレットを135℃で12時間乾燥後、温度285℃、フィルター濾過径20μm、吐出量6g/分、吐出時間4時間の条件で押し出し、下記式にてフィルター背圧上昇係数を求めた。
K=ΔP/(Q/S)
ここで、K:フィルター背圧上昇係数、ΔP=P1-P0
P1:押し出し4時間後の圧力(MPa)、P0:押し出し開始時の圧力(MPa)、Q:押し出し吐出量(kg/hr)、S:フィルター濾過面積(cm2)
JIS K7130-1999 A法に準拠し、ダイアルゲージを用いて測定した。
熱収縮率は試験温度150℃、加熱時間15分間とした以外は、JIS-C-2318に準拠した寸法変化試験法で実施した。
フィルム幅方向の中央位置から縦5mm×横5mmのサンプルを切り出した。
サンプルについてJIS K 7142-1996 A法により、ナトリウムD線を光源として接触液としてジヨードメタンを用いてアッべ屈折率計(株式会社アタゴ社製 NAR-1T)によりフィルム長手方向の屈折率(Nx)、幅方向の屈折率(Ny)、厚み方向の屈折率(Nz)を測定した。面配向係数(ΔP)は下式により算出した。
面配向係数(ΔP)=[(Nx+Ny)/2]-Nz
JIS K 7127に準拠し、フィルムの長手方向に15mm幅、100mm長の試験サンプルを切り出した。引張試験機(株式会社島津製作所社製 オートグラフAG-I)にて、標点間距離50mm、引張速度200mm/minの条件で、試験サンプルを引張試験した。得られた応力―歪み曲線から試験サンプルの破断強度および破断伸度を算出した。
各実施例、比較例のフィルム製膜時に破断無く10000mを連続成膜可能であった場合を〇、破断が生じ10000mを連続製膜不可であった場合を×と評価した。
幅800mm、巻長1250m(1000平方メートル)で巻き取ったフィルムロールを、巻き返し機を用いて巻き返した。巻き返し時に、欠点検知機(FUTEC社製 F MAX MR)を用いて欠点数を調査した。欠点の最も長い部分が1.3mm以上のサイズの欠点数を求めた。
1.3mm以上の欠点数1個未満:C
1.3mm以上の欠点数1個以上、10個以下:A
幅800mm、巻長10000m(8000平方メートル)で巻き取ったフィルムロールを、巻き返し機を用いて巻き返した。巻き返し時に、欠点検知機(FUTEC社製 F MAX MR)を用いて欠点数を調査した。欠点の最も長い部分が1.0mm以上のサイズの欠点数を求めた。
1.0mm以上の欠点数15個以下:C
1.0mm以上の欠点数16個以上、80個以下:A
フィルムロールから幅方向に800mm、長手方向に40mmサンプリングし、フィルムテスター連続厚み測定器(フジワーク社製)を用いて、5m/秒で連続的に幅方向の厚みを測定した。測定時の最大厚みをTmax.、最小厚みをTmin.、平均厚みをTave.とし、下式からフィルム幅方向の厚みムラを算出した。
厚みムラ={(Tmax.-Tmin.)/Tave.}×100(%)
各実施例、比較例のフィルム製膜時にフィルター交換せずに1週間連続で製膜できた場合を〇、1週間未満でフィルターの目詰まりが生じ、連続で製膜が困難となった場合を×と評価した。
PET容器から内容残留物などの異物を洗い流した後、粉砕してフレークを得た。得られたフレークをフレーク濃度10重量%、85℃、30分の条件で3.5重量%の水酸化ナトリウム溶液で攪拌下、洗浄を行った。アルカリ洗浄後、フレークを取り出し、フレーク濃度10重量%。25℃、20分の条件で蒸留水を用いて攪拌下、洗浄を行った。この水洗を蒸留水で交換してさらに2回繰り返して実施した。水洗後、フレークを乾燥した後、平均粒子径2.5μmのシリカ粒子をフレークに対して0.10質量部添加した。その後、押出機で溶融し、順次目開きサイズの細かなものにフィルターを変えて2回さらに細かな異物を濾別し、3回目に50μmの最も小さな目開きサイズのフィルターで濾別してポリエステルAを得た。なお、ポリエステルAの背圧上昇係数は96MPa/kg・cm2であった。
ポリエステルAと同様の方法でポリエステルBを得た。なお、ポリエステルBの背圧上昇係数は64MPa/kg・cm2であった。
ポリエステルAと同様の方法でポリエステルCを得た。なお、ポリエステルCの背圧上昇係数は32MPa/kg・cm2であった。
ポリエステルAと同様の方法でポリエステルDを得た。なお、ポリエステルDの背圧上昇係数は10MPa/kg・cm2であった。
使用するPET容器をきれいなもののみに選別した以外は、ポリエステルAと同様の方法でポリエステルEを得た。なお、ポリエステルEの背圧上昇係数は8MPa/kg・cm2であった。
ポリエステルAと同様の方法でポリエステルFを得た。なお、ポリエステルFの背圧上昇係数は105MPa/kg・cm2であった。
後述する二軸配向ポリエステルフィルムの作製において使用するペットボトルより再生されたケミカルリサイクルポリエステル樹脂として、以下の方法を用いて合成したものを用いた。
分別収集・回収されたペットボトルベールを湿式粉砕機に投入し、水1,000リッターに液体台所洗剤500gを加えたものを、上記湿式粉砕機内に循環させながら粉砕を行い、粉砕機に接続している比重分離機によって金属、砂、ガラス等の比重の大きいものを沈殿させ、上層部からフレークを取り出した。このフレークを純水で濯ぎ、遠心脱水して回収フレークとした。
押出機に、ポリエステルAを投入した。押出機にて樹脂を280℃で融解させた後、溶融樹脂をフィルターメッシュ50μmに通し、続いてフィルターメッシュ100μmに通した。その後280℃のT-ダイスからキャストし、10℃の冷却ロールに静電密着法により密着させて未延伸シートを得た。
次いで、得られた未延伸シートを115℃の温度でMD方向に3.6倍で延伸した。縦延伸直後のフィルムを熱風ヒーターで95℃に設定された加熱炉へ通し、加熱炉の入り口と出口のロール間の速度差を利用して、長手方向に3%リラックス処理を行った。次いでテンターに通して120℃でTD方向に4.6倍延伸し、210℃で3秒間の熱固定処理と1秒間5%の緩和処理を実施して、厚さ12μmの二軸配向ポリエステルフィルムを得た。二軸配向ポリエステルフィルムの樹脂組成、および製膜条件を表1に示した。また、得られたフィルムの物性および評価結果を表1に示した。
縦延伸直後のリラックス率を0%に変更し、さらにテンターでの延伸方式を3段延伸に変更し、1段目と2段目及び2段目と3段目との間で1mの定長領域を設けた以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。物性および評価結果を表1に示した。
縦延伸直後のリラックス率を0%に変更し、さらにテンターでの延伸パターンを対数形に変更した以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。尚、テンターの延伸角度としては1段目の屈折角θ1:12.6°、2段目の屈折角θ2:8.2°、角度変化率34.9%となるよう調整し、トータルの延伸倍率は実施例1と同等になるよう延伸倍率を設定した。物性および評価結果を表1に示した。
縦延伸直後のリラックス率を1%に変更した以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。物性および評価結果を表1に示した。
縦延伸直後のリラックス率を10%に変更した以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。物性および評価結果を表1に示した。
縦延伸倍率を3.9倍に変更した以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。物性および評価結果を表1に示した。
縦延伸倍率を2.6倍に変更した以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。物性および評価結果を表1に示した。
横延伸倍率を4.9倍に変更した以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。物性および評価結果を表1に示した。
横延伸倍率を2.6倍に変更した以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。物性および評価結果を表1に示した。
樹脂をポリエステルBに変更した以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。物性および評価結果を表1に示した。
樹脂をポリエステルCに変更した以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。物性および評価結果を表1に示した。
樹脂をポリエステルDに変更した以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。物性および評価結果を表1に示した。
樹脂をポリエステルGに変更した以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。物性および評価結果を表1に示した。
溶融樹脂を通すフィルターメッシュを20μmと50μmに変更し、縦延伸直後のリラックス率を0%に変更した以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。フィルターメッシュの目詰まりが発生し、不良であった。
溶融樹脂を通すフィルターメッシュを20μmと50μmに変更し、樹脂をポリエステルDに変更し、縦延伸直後のリラックス率を0%に変更した以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。フィルターメッシュの目詰まりが発生し、不良であった。
樹脂をポリエステルEに変更し、縦延伸直後のリラックス率を0%にした以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。得られた二軸配向ポリエステルフィルムは異物も少なく、フィルターメッシュの目詰まりもなかったが、きれいなPET容器を選別して再生原料としているため、環境対応効果が不十分であった。
樹脂をポリエステルFに変更し、縦延伸直後のリラックス率を10%にした以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。得られた二軸配向ポリエステルフィルムは異物起因の破断が多く、製膜性が不良であった。
縦延伸直後のリラックス率を12%にした以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。得られた二軸配向ポリエステルフィルムは面配向係数が低く、力学強度が不良であった。
縦延伸直後のリラックス率を0%にした以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。得られた二軸配向ポリエステルフィルムは異物起因の破断が多く、製膜性が不良であった。
縦延伸倍率を4.1倍にした以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。得られた二軸配向ポリエステルフィルムは異物起因の破断が多く、製膜性が不良であった。
縦延伸倍率を2.3倍にした以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。得られた二軸配向ポリエステルフィルムは面配向係数が低く、力学強度が不良であった。
横延伸倍率を5.1倍にした以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。得られた二軸配向ポリエステルフィルムは異物起因の破断が多く、製膜性が不良であった。
横延伸倍率を2.3倍にした以外、実施例1と同様に製膜して厚さ12μmの二軸配向ポリエステルフィルムを得た。得られた二軸配向ポリエステルフィルムは面配向係数が低く、力学強度が不良であった。
Claims (6)
- PET容器由来の再生原料を使用し、下記(1)~(3)を満たす二軸配向ポリエチレンテレフタレートフィルムをロール状に巻き取ってなる二軸配向ポリエチレンテレフタレートフィルムロール。
(1)150℃30分で測定した時のフィルム長手方向の熱収縮率が0.5%以上2.0%以下。
(2)JIS K 7142-1996 A法に基づいて測定した屈折率から算出したフィルムの面配向係数(ΔP)が0.16以上0.17以下。
(3)フィルムロール1000m2あたりの最大長さが1.3mm以上の異物数が1個以上。 - 請求項1に記載のPET容器由来の再生原料が、メカニカルリサイクルポリエステル樹脂及び/またはケミカルリサイクルポリエステル樹脂であることを特徴とする請求項1に記載の二軸配向ポリエチレンテレフタレートフィルムロール。
- フィルム幅方向で800mm当りの厚みムラが18%以下であることを特徴とする請求項1又は2に記載の二軸配向ポリエチレンテレフタレートフィルムロール。
- フィルム長手方向の破断強度が180MPa以上260MPa以下、破断伸度が80%以上170%以下であることを特徴とする請求項1~3のいずれかに記載の二軸配向ポリエチレンテレフタレートフィルムロール。
- フィルムロール8000m2あたりの最大長さが1.0mm以上の異物数が16個以上であることを特徴とする請求項1~4のいずれかに記載の二軸配向ポリエチレンテレフタレートフィルムロール。
- 巻長が10000m以上である請求項1~5のいずれかに記載の二軸配向ポリエチレンテレフタレートフィルムロール。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000169623A (ja) | 1998-12-10 | 2000-06-20 | Is:Kk | ポリエチレンテレフタレ―ト廃棄物のケミカルリサイクル方法 |
JP2000302707A (ja) | 1999-04-20 | 2000-10-31 | Japan Synthetic Textile Inspection Inst Foundation | ポリエチレンテレフタレートの熱分解方法 |
JP2012220879A (ja) * | 2011-04-13 | 2012-11-12 | Toyobo Co Ltd | 偏光子保護用二軸配向ポリエチレンテレフタレートフィルム |
JP2014065282A (ja) | 2012-09-27 | 2014-04-17 | Toyobo Co Ltd | Petボトル再生原料を使用した二軸配向ポリエステルフィルム |
WO2018159648A1 (ja) * | 2017-03-01 | 2018-09-07 | 東洋紡株式会社 | フランジカルボン酸ユニットを有するポリエステルフィルムの製造方法 |
WO2018159649A1 (ja) * | 2017-03-01 | 2018-09-07 | 東洋紡株式会社 | フランジカルボン酸ユニットを有するポリエステルフィルムとヒートシール性樹脂層とを備える積層体および包装袋 |
JP2020012087A (ja) * | 2018-07-20 | 2020-01-23 | 東洋紡株式会社 | フレキシブルディスプレイの表面保護フィルム用ポリエステルフィルム |
WO2020170819A1 (ja) * | 2019-02-18 | 2020-08-27 | 東洋紡株式会社 | 二軸延伸ポリエステルフィルムロール |
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000169623A (ja) | 1998-12-10 | 2000-06-20 | Is:Kk | ポリエチレンテレフタレ―ト廃棄物のケミカルリサイクル方法 |
JP2000302707A (ja) | 1999-04-20 | 2000-10-31 | Japan Synthetic Textile Inspection Inst Foundation | ポリエチレンテレフタレートの熱分解方法 |
JP2012220879A (ja) * | 2011-04-13 | 2012-11-12 | Toyobo Co Ltd | 偏光子保護用二軸配向ポリエチレンテレフタレートフィルム |
JP2014065282A (ja) | 2012-09-27 | 2014-04-17 | Toyobo Co Ltd | Petボトル再生原料を使用した二軸配向ポリエステルフィルム |
WO2018159648A1 (ja) * | 2017-03-01 | 2018-09-07 | 東洋紡株式会社 | フランジカルボン酸ユニットを有するポリエステルフィルムの製造方法 |
WO2018159649A1 (ja) * | 2017-03-01 | 2018-09-07 | 東洋紡株式会社 | フランジカルボン酸ユニットを有するポリエステルフィルムとヒートシール性樹脂層とを備える積層体および包装袋 |
JP2020012087A (ja) * | 2018-07-20 | 2020-01-23 | 東洋紡株式会社 | フレキシブルディスプレイの表面保護フィルム用ポリエステルフィルム |
WO2020170819A1 (ja) * | 2019-02-18 | 2020-08-27 | 東洋紡株式会社 | 二軸延伸ポリエステルフィルムロール |
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