WO2021079868A1 - レーザー印字可能なフィルムおよびそれを用いた包装体 - Google Patents

レーザー印字可能なフィルムおよびそれを用いた包装体 Download PDF

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Publication number
WO2021079868A1
WO2021079868A1 PCT/JP2020/039354 JP2020039354W WO2021079868A1 WO 2021079868 A1 WO2021079868 A1 WO 2021079868A1 JP 2020039354 W JP2020039354 W JP 2020039354W WO 2021079868 A1 WO2021079868 A1 WO 2021079868A1
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WO
WIPO (PCT)
Prior art keywords
film
layer
polyester
laser
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/039354
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
慎太郎 石丸
雅幸 春田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
Original Assignee
Toyobo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Priority to JP2021553449A priority Critical patent/JP7243851B2/ja
Priority to KR1020227015619A priority patent/KR20220086602A/ko
Priority to US17/768,346 priority patent/US11919280B2/en
Priority to CN202080069541.3A priority patent/CN114502480B/zh
Priority to EP20880190.2A priority patent/EP4049839A4/en
Publication of WO2021079868A1 publication Critical patent/WO2021079868A1/ja
Anticipated expiration legal-status Critical
Priority to JP2023031783A priority patent/JP7448052B2/ja
Ceased legal-status Critical Current

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    • 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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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
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    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
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    • B32B2310/0843—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using laser
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
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    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Definitions

  • the present invention relates to a film that can be suitably used for a package including a display such as printing.
  • the present invention relates to a polyester-based film that can be printed by a laser, and also relates to a packaging material including a lid material and a label corresponding thereto.
  • packaging has been used for distribution articles represented by foods, pharmaceuticals and industrial products. Many of these packages not only protect the contents, but also display information on the product name, date of manufacture, raw materials, and the like.
  • a label in which an adhesive is applied to the back surface of a base material that can be printed by ink, thermal transfer, or the like is used. It has been widely used.
  • the tack label is attached to a release paper (mounting paper) in a state where information is printed on the front surface which is a display surface in advance, and when used, it is peeled off from the backing paper and attached to the packaging body.
  • Patent Document 2 discloses a heat-sensitive film having a heat-sensitive recording layer. Since the film of Patent Document 2 is discolored by heat, it becomes a packaging body having display performance by itself. Therefore, it is not necessary to use the above tack label. Further, by incorporating a printing machine such as a thermal printer into the process of bag-making a package using a film as in Patent Document 2, bag-making and display are completed in one process, which saves labor and costs. Also contributes to. Because of these merits, the method of printing directly on the packaging itself has recently become widespread. However, if the heat-sensitive layer is provided on the film as the base material, there is a concern that the heat-sensitive layer may be peeled off due to rubbing against the outside or the like.
  • a protective layer is usually provided on the heat-sensitive layer (surface layer side).
  • Coatings are widely used as a means of providing these functional layers. Since the coating goes through at least the steps of coating, drying, and winding, the number of steps increases by the amount of each functional layer, and the productivity decreases. Further, since these functional layers have particles, there is a problem that the transparency is lowered according to the layer thickness.
  • Patent Document 3 discloses a multi-layer laminated film for laser printing, which includes a layer in which the printing layer is made of an ink composition that can be printed by laser light. By using this film, the laser-irradiated portion is discolored and can be printed.
  • the multilayer laminated film such as the film of Patent Document 3 needs to provide a printing layer on the film base material, so that the problems of layer peeling and productivity decrease cannot be solved.
  • Patent Document 4 discloses an additive for laser marking composed of bismuth oxide.
  • Patent Document 5 discloses a polyester film that is colored by laser light.
  • This film has a surface roughness of 0.10 to 1.00 ⁇ m, and at least one of the outermost surfaces has a matte finish. Therefore, there is a problem that it cannot be applied in applications where transparency and printability are required. Further, Patent Document 5 does not mention the thickness unevenness of the film.
  • An object of the present invention is to solve the above-mentioned problems of the prior art. That is, an object of the present invention is to provide a film having high transparency, excellent thickness unevenness, and capable of clear printing by a laser. At the same time, an object of the present invention is to provide a package directly printed using this film.
  • the present invention has the following configuration. 1. 1. It has at least one layer capable of printing by laser irradiation, the entire film layer contains a metal capable of laser printing at 100 ppm or more and 3000 ppm or less, and the haze is 1% or more and 40% or less. A polyester-based film characterized by. 2. 1. As a metal capable of printing by laser irradiation, at least one kind of bismuth, gadolinium, neodymium, titanium, antimony, tin, aluminum, or any one of oxides is contained. The polyester film described in. 3. 3. 1. The thickness of the layer capable of printing by laser irradiation is 5 ⁇ m or more and 100 ⁇ m or less. Or 2. The polyester film according to any one. 4. 1.
  • the color L * value is 90 or more and 95 or less and the color b * value is 0.1 or more and 2 or less.
  • ⁇ 3. The polyester film according to any one. 5. 1. The thickness unevenness in either the longitudinal direction or the width direction is 0.1% or more and 20% or less. ⁇ 4. The polyester film according to any one. 6. 1. A layer that is not printed by laser irradiation is provided on at least one layer adjacent to a layer that can be printed by laser irradiation. ⁇ 5. The polyester film according to any one. 7. 1. The higher value of the refractive index (Nx or Ny) in either the longitudinal direction or the width direction is 1.63 or more. ⁇ 6. The polyester film according to any one. 8. 1. The heat shrinkage rate after exposure to hot air at 140 ° C.
  • the film of the present invention can provide a film having high transparency, excellent thickness unevenness, and capable of clear printing by a laser.
  • the subject of the present invention is to be able to provide a package directly printed using this film.
  • the polyester-based film of the present invention has at least one layer capable of printing by laser irradiation, and has the following preferable characteristics and a preferable configuration.
  • Pigment for Laser Printing In order to make the film of the present invention laser printable, it is necessary to add a pigment having a function of discoloring the film by laser irradiation (hereinafter, may be simply referred to as a pigment). is there. Normally, the polyester resin itself that constitutes the film hardly reacts to laser light, and therefore cannot be printed by laser irradiation. The pigment is excited by the energy of the laser beam and carbonizes the surrounding polyester resin (preferable conditions for laser irradiation will be described later). In addition to the carbonization of polyester resin, some pigments themselves turn black depending on the type of pigment. These single or composite color changes make it possible to print on film. Considering the printing accuracy on the film, it is preferable to use a pigment that discolors itself.
  • the type of pigment examples include elemental substances of bismuth, gadolinium, neodymium, titanium, antimony, tin, and aluminum, or oxides.
  • the particle size of the pigment is preferably 0.1 ⁇ m or more and 10 ⁇ m or less. If the particle size of the pigment is less than 0.1 ⁇ m, the color change during laser irradiation may not be sufficient. Further, when the particle size exceeds 10 ⁇ m, the haze of the film tends to exceed 40% and the color b value tends to exceed 2.
  • the particle size is more preferably 0.5 ⁇ m or more and 9 ⁇ m or less.
  • TOMATEC COLOR manufactured by Tokan Material Technology
  • Iriotec registered trademark
  • Merck Performance Materials manufactured by Merck Performance Materials
  • the amount of pigment added into the laser printing layer needs to be 100 ppm or more and 3000 ppm or less. If the amount of the pigment added is less than 100 ppm, the printing density by the laser becomes insufficient, which is not preferable. On the other hand, if the amount of the pigment added exceeds 3000 ppm, the haze, color value, and thickness unevenness of the film tend to exceed a predetermined range, which is not preferable.
  • the effect of pigment addition on haze and color value occurs because the pigment particles scatter light in addition to the fact that the pigment itself is colored. In addition, when the film is stretched, the inclusion of pigment particles causes a phenomenon in which the thickness unevenness of the film is deteriorated.
  • FIG. 3 (b) of Non-Patent Document 1 shows a stretch-strain curve of a polyethylene terephthalate film to which titanium dioxide as fine particles has been added, and the stress at the end of stretching increases as the concentration of titanium dioxide added increases. It has been shown to decrease. It is considered that this is because the presence of the fine particles suppresses the orientation crystallization of the polymer chains that occurs during stretching, as shown in FIGS. 10 and 11 of Non-Patent Document 1. Since the thickness unevenness of the film becomes better as the stretching stress increases, it can be said that the thickness unevenness worsens as the addition concentration of the fine particles increases.
  • the amount of the pigment added is more preferably 150 ppm or more and 2950 ppm or less, and further preferably 200 ppm or more and 2900 ppm or less. Further, in the present invention, the amount of the pigment added per whole layer of the film may be 100 ppm or more and 3000 ppm or less.
  • the amount of pigment converted per all layers of the film is calculated to be smaller than the amount of the laser printing layer.
  • most of the thickness of all layers (50% or more) is composed of the laser printing layer, and when the thickness of the other layers is increased, the laser printing layer becomes relatively thin and the printing accuracy is improved. Considering the sacrifice point, the amount of pigment converted per all layers of the film may be approximated to the amount of pigment contained in the laser printing layer.
  • a method of blending the laser pigment into the polyester resin constituting the film of the present invention for example, it can be added at any stage in the production of the polyester resin.
  • a method of blending is preferable.
  • polyester raw material constituting the film of the present invention is not particularly limited as long as it is a polymer type having an ester bond, and can be freely used as long as it does not deviate from the gist of the present invention.
  • polyester raw materials include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), polybutylene naphthalate (PBN), polylactic acid (PLA), and the like.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PTT polytrimethylene terephthalate
  • PBN polybutylene naphthalate
  • PLA polylactic acid
  • PBS polyethylene furanoate
  • PBS polybutylene succinate
  • modified polyesters in which the monomers of these acid or diol moieties are modified may be used.
  • the acid moiety monomer include aromatic dicarboxylic acids such as isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and orthophthalic acid, adipic acid, azelaic acid, sebacic acid and decandicarboxylic acid.
  • aromatic dicarboxylic acids such as isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and orthophthalic acid, adipic acid, azelaic acid, sebacic acid and decandicarboxylic acid.
  • aliphatic dicarboxylic acids and alicyclic dicarboxylic acids include aliphatic dicarboxylic acids and alicyclic dicarboxylic acids.
  • Examples of the monomer of the diol moiety include neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, 2,2-diethyl 1,3-propanediol, and 2-n-butyl-2-ethyl-1,3-.
  • Long-chain diols such as propanediol, 2,2-isopropyl-1,3-propanediol, 2,2-di-n-butyl-1,3-propanediol, hexanediol, 1,4-butanediol, and hexanediol.
  • polyester raw material listed above a plurality of types of homopolyester in which a carboxylic acid monomer and a diol monomer are polymerized in a one-to-one ratio may be mixed (dry blended), or two or more types of carboxylics may be used.
  • An acid monomer or two or more kinds of diol monomers may be copolymerized and used. Further, the homopolyester and the copolymerized polyester may be mixed and used.
  • additives other than laser pigments in the polyester resin constituting the film of the present invention, various additives such as waxes, antioxidants, antistatic agents, crystal nucleating agents, thickeners, etc.
  • a heat stabilizer, a coloring pigment, a coloring inhibitor, an ultraviolet absorber, and the like can be added.
  • fine particles as a lubricant for improving the slipperiness of the film to at least the outermost layer of the film. Any fine particles can be selected.
  • examples of the inorganic fine particles include silica, alumina, titanium dioxide, calcium carbonate, kaolin, and barium sulfate
  • examples of the organic fine particles include acrylic resin particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene. Particles and the like can be mentioned.
  • the average particle size of the fine particles can be appropriately selected within the range of 0.05 to 3.0 ⁇ m when measured with a Coulter counter, if necessary.
  • the lower limit of the fine particle content in the film is preferably 0.01% by weight, more preferably 0.015% by weight, and even more 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, and even more preferably 0.1% by weight. If it exceeds 1% by weight, the transparency may decrease, which is not preferable.
  • a method of blending particles into the polyester resin constituting the film of the present invention for example, it can be added at any stage of producing a polyester resin, but it is heavy at the stage of esterification or after the completion of the transesterification reaction. It is preferable to add it as a slurry dispersed in ethylene glycol or the like at a stage before the start of the condensation reaction to proceed with the polycondensation reaction.
  • a method of blending a slurry of particles dispersed in ethylene glycol, water, or other solvent with a polyester resin raw material using a kneading extruder with a vent, or using a kneading extruder of dried particles and polyester is also a method of blending.
  • Layer structure of film 2.1 Layer structure
  • the film of the present invention is described in 1.1. It is necessary to have at least one layer capable of printing by laser irradiation (hereinafter referred to as a laser printing layer) containing the pigment described in "Pigment for laser printing".
  • a laser printing layer As the layer structure of the film, it may be a single layer having only a laser printing layer, or a layer other than the laser printing layer may be laminated.
  • laser printing is achieved by carbonizing the polyester resin that constitutes the laser printing layer. Therefore, in the case of a single-layer structure consisting of only a laser printing layer, when the printed portion is touched with a finger or the like, the touch feeling tends to be rough.
  • the most preferable layer structure is a layer that does not react to laser irradiation, and has a two-kind three-layer structure in which a laser printing layer is sandwiched (used as a central layer).
  • the film of the present invention may be provided with a layer that has been subjected to corona treatment, coating treatment, flame treatment, etc. in order to improve the printability and slipperiness of the film surface, and is within the range that does not deviate from the requirements of the present invention. Can be provided arbitrarily with.
  • the layer structure of the film is 2 types and 3 layers
  • the central layer is a laser printing layer, and for example, the outermost layer may contain a lubricant or be subjected to corona treatment, so that each layer can have a different function.
  • the film of the present invention may be provided with a gas barrier layer.
  • the presence of the gas barrier layer improves the gas barrier property as a film and can improve the shelf life of the contents when used as a package.
  • the gas barrier layer is preferably composed of an inorganic thin film containing a metal or a metal oxide as a main component, and may be located on either the outermost layer or the intermediate layer. Further, the gas barrier layer is preferably transparent. Further, in addition to the gas barrier made of the inorganic thin film, the present invention has an anchor coat layer provided under the inorganic thin film layer (between the film made of resin and the inorganic thin film) and an overcoat layer provided on the inorganic thin film layer. May be. By providing these layers, it is expected that the adhesion between the gas barrier layer and the film layer will be improved, the gas barrier property will be improved, and the like. The configuration requirements for each layer will be described later.
  • the film of the present invention may be provided with characters or patterns in addition to printing by laser irradiation.
  • known materials such as ink for gravure printing and ink for flexographic printing can be used.
  • the number of printing layers may be one layer or a plurality of layers.
  • the thickness of the laser printing layer is preferably 5 ⁇ m or more and 100 ⁇ m or less. If the thickness of the laser printing layer is less than 5 ⁇ m, the printing density when irradiated with laser light is lowered, and it becomes difficult to visually recognize the characters, which is not preferable. On the other hand, if the thickness of the laser printing layer exceeds 100 ⁇ m, haze and color values tend to exceed a predetermined range, which is not preferable.
  • the thickness of the laser printing layer is more preferably 10 ⁇ m or more and 95 ⁇ m or less, and further preferably 15 ⁇ m or more and 90 ⁇ m or less.
  • the film of the present invention preferably has a haze of 1% or more and 40% or less. If the haze exceeds 40%, the transparency of the film is lost, the visibility of the contents is deteriorated when it is used as a package, and the characters obtained by laser irradiation are difficult to see, which is not preferable. In contrast to the technique of discoloration by simple laser marking conventionally disclosed, the film of the present invention needs to be able to read characters produced by laser irradiation, and therefore requires a high degree of sharpness.
  • the haze is more preferably 35% or less, and even more preferably 30% or less. On the other hand, the lower the haze value, the better the transparency, which is preferable. However, at the technical level of the present invention, 1% is the lower limit, and even if the lower limit is 2%, it is practically sufficient.
  • the film of the present invention preferably has a color L * value of 90 or more and 95 or less.
  • the color L * value represents the lightness of the film, and the higher the value, the higher the lightness. If the color L * value is less than 90, the film will have a dull hue, and not only will it look inferior when it is packaged, but also the characters obtained by laser irradiation will be difficult to see. Not preferable. Similar to the content described in the haze above, the film of the present invention requires a high degree of sharpness because it is necessary to be able to read the characters produced by laser irradiation.
  • the color L * value is more preferably 90.5 or more, and further preferably 91 or more.
  • the upper limit of the color L * value is 95 at the technical level of the present invention, and even if the upper limit is 94.5, it is practically sufficient.
  • Color b * value The film of the present invention preferably has a color b * value of 0.1 or more and 2 or less.
  • the color b * value represents the yellowness of the film, and the higher the value, the greater the yellowness.
  • the color b * value is 2 or more, the color tone of the film becomes strongly yellowish. It is not preferable to use such a film because, for example, after the printing process, the yellowish color becomes stronger than the initially assumed printing hue, and problems such as deterioration of the design property are likely to occur.
  • the color b * value is more preferably 1.8 or less, and further preferably 1.6 or less.
  • the lower limit of the color b * value is 0.1 at the technical level of the present invention, and even if the lower limit is 0.2, it is practically sufficient.
  • Thickness spots The film of the present invention preferably has thickness spots of 0.1% or more and 20% or less in either the longitudinal direction or the width direction.
  • the thickness unevenness here refers to a value obtained by dividing the difference between the maximum value and the minimum value by an average value when the thickness of the film is measured over an arbitrary length using a continuous contact type thickness gauge. The smaller the value of the thickness spot, the better the thickness accuracy. If the thickness unevenness exceeds 20%, winding defects such as wrinkles, sagging, and unevenness are likely to occur when the roll is wound, which is not preferable.
  • the thickness unevenness is more preferably 18% or less, and further preferably 16% or less.
  • the lower limit of the thickness unevenness 0.1% is the limit at the technical level of the present invention. It is sufficient that the lower limit of the thickness spot is 1%. It is more preferable that the thickness is within the above-mentioned thickness spots in both the longitudinal direction and the width direction.
  • the thickness of all layers of the film of the present invention is preferably 8 ⁇ m or more and 200 ⁇ m or less. If the thickness of the film is thinner than 8 ⁇ m, the handleability is deteriorated and it becomes difficult to handle during secondary processing such as printing, which is not preferable. On the other hand, the film thickness may exceed 200 ⁇ m, but this is not preferable because the weight of the film used increases and the chemical cost increases.
  • the thickness of the film is more preferably 13 ⁇ m or more and 195 ⁇ m or less, and further preferably 18 ⁇ m or more and 190 ⁇ m or less.
  • the film of the present invention preferably has a higher refractive index (Nx or Ny) in either the longitudinal direction or the width direction, which is 1.63 or more.
  • the refractive index refers to the molecular orientation of the film, and the higher the refractive index, the higher the molecular orientation. Especially in a stretched film, the higher the stretching stress, the higher the refractive index tends to be. 1.1 above. Considering the relationship between the stretching stress and the thickness unevenness described in "Pigment for laser printing", it is preferable to set the refractive index to 1.63 or more because the thickness unevenness can be easily reduced to 20% or less.
  • the refractive index is 1.63 or more because the tensile breaking strength of the film can be easily set to 80 MPa or more.
  • the refractive index is more preferably 1.635 or more, and even more preferably 1.64 or more.
  • the film of the present invention preferably has a heat shrinkage rate of 0.5% or more and 8% or less after being exposed to hot air at 140 ° C. for 30 minutes in either the longitudinal direction or the width direction. If the heat shrinkage rate exceeds 8%, the film is easily deformed during processing including heating such as heat sealing, which is not preferable.
  • the upper limit of the heat shrinkage rate is more preferably 7.8% or less, and more preferably 7.6% or less.
  • the lower the heat shrinkage rate the more preferable, but at the technical level of the present invention, 0.5% is the lower limit. Even if the lower limit of the heat shrinkage rate is 0.7%, it is sufficient for practical use. It is more preferable that the heat shrinkage rate is within the above range in both the longitudinal direction and the width direction.
  • the film of the present invention preferably has a tensile breaking strength of 80 MPa or more and 300 MPa in either the longitudinal direction or the width direction. If the tensile breaking strength is less than 80 MPa, it is not preferable because it is easily broken by the tension received from the pass line when unwinding on the production line during secondary processing such as printing, vapor deposition, and laminating. On the other hand, the higher the tensile breaking strength, the higher the mechanical strength of the film, which is preferable, but at the technical level of the present invention, 300 MPa is the upper limit. For practical purposes, an upper limit of 290 MPa is sufficient. It is more preferable that the tensile breaking strength is within the above range in both the longitudinal direction and the width direction.
  • Intrinsic viscosity (IV) The film of the present invention preferably has an intrinsic viscosity (IV) of 0.5 dL / g or more and 0.9 dL / g. If the IV is less than 0.5 dL / g, it is not only difficult to make the tensile fracture strength of the film 80 MPa or more, but also the possibility of breakage in the stretching step during film formation increases, which is not preferable. On the other hand, if IV exceeds 0.9 dL / g, the resin pressure in the melt line becomes too high when the raw material resin is mixed and melt-extruded, and the filter is deformed to remove foreign substances in the molten resin. Is not preferable because it is likely to occur.
  • the IV of the heat seal layer is more preferably 0.52 dL / g or more and 0.88 dL / g or less, and further preferably 0.54 dL / g or more and 0.86 dL / g or less.
  • the film needs to contain a pigment that can be printed by laser irradiation. Since the pigment is preferably used in a masterbatch, two or more kinds of raw materials are usually mixed. Conventionally, when two or more kinds of raw materials are mixed and put into an extruder, there has been a problem that the supply of raw materials varies (segregates), which worsens the thickness unevenness.
  • the film of the present invention has the above 1.
  • the raw materials described in "Raw materials constituting the film” are used in the above 4.1. Obtained by supplying the raw material to the extruder by the method described in "Raw Material Mixing and Supply”, melt-extruding the raw material from the extruder to form an unstretched film, and stretching the raw material by a predetermined method shown below. be able to.
  • the timing of laminating each layer may be before or after stretching.
  • laminating before stretching it is preferable to adopt a method in which the resins used as raw materials for each layer are melt-extruded by separate extrusion machines and joined using a feed block or the like in the middle of the resin flow path.
  • laminating after stretching it is preferable to employ laminating in which films formed separately are bonded together with an adhesive, or extrusion laminating in which a molten polyester resin is poured and laminated on the surface layer of a single or laminated film. From the viewpoint of productivity, a method of laminating each layer before stretching is preferable.
  • the polyester raw material is preferably dried in advance using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer until the moisture content is 100 ppm or less, more preferably 90 ppm or less, and further preferably 80 ppm or less. After the polyester raw material is dried in this way, it is extruded as a film by an extruder.
  • a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer until the moisture content is 100 ppm or less, more preferably 90 ppm or less, and further preferably 80 ppm or less.
  • the extrusion temperature is preferably 200 ° C. or higher and 300 ° C. or lower.
  • the extrusion temperature is less than 200 ° C., the melt viscosity of the polyester resin becomes too high, the extrusion pressure increases, and the filter in the melt line is deformed, which is not preferable.
  • the heating temperature exceeds 300 ° C., thermal decomposition of the resin proceeds, and it becomes difficult to set IV to 0.5 dL / g or more.
  • the shear rate when the resin is discharged from the die mouth portion is high because the thickness unevenness (particularly the maximum recess) in the width direction of the film can be reduced. This is because the higher the shear rate, the more stable the pressure at the time of resin discharge at the T-die outlet.
  • Preferred shear rate was 100 sec -1 or more, more preferably 150 sec -1 or more, and particularly preferably 170Sec -1 or more.
  • a higher draft ratio is preferable because the thickness unevenness in the longitudinal direction is better, but a high draft ratio is not preferable because resin residue or the like adheres to the resin discharge portion of the die and productivity is deteriorated.
  • the shear rate at the die outlet can be obtained from the following equation 1.
  • the unstretched film can be obtained by quenching the film melted by extrusion.
  • a method for rapidly cooling the molten resin a method of casting the molten resin from a base onto a rotating drum and quenching and solidifying the molten resin to obtain a substantially unoriented resin sheet can be preferably adopted.
  • the film may be formed by any method of non-stretching, uniaxial stretching (stretching in at least one of the longitudinal (longitudinal) direction and the horizontal (width) direction), and biaxial stretching. From the viewpoint of mechanical strength and productivity, uniaxial stretching is preferable, and biaxial stretching is more preferable.
  • the description will be focused on the sequential biaxial stretching method by longitudinal stretching-transverse stretching in which longitudinal stretching is first performed and then transverse stretching is performed. However, even in the case of transverse stretching-longitudinal stretching in which the order is reversed. It doesn't matter because it only changes the main orientation direction. Further, a simultaneous biaxial stretching method in which the vertical direction and the horizontal direction are stretched at the same time may be used.
  • First (longitudinal) stretching For stretching in the first direction (longitudinal or longitudinal direction), it is preferable to introduce the unstretched film into a longitudinal stretching machine in which a plurality of roll groups are continuously arranged. In the longitudinal stretching, it is preferable to preheat the film with a preheating roll until the film temperature reaches 65 ° C. to 100 ° C. If the film temperature is lower than 65 ° C., it becomes difficult to stretch the film when it is stretched in the vertical direction, and breakage is likely to occur, which is not preferable. Further, if the temperature is higher than 100 ° C., the film tends to adhere to the roll, and the film is easily wrapped around the roll or the roll is easily soiled due to continuous production, which is not preferable.
  • the longitudinal stretching ratio is preferably 1 to 5 times or less. Since 1x is not longitudinally stretched, the longitudinal stretching ratio is 1x to obtain a horizontally uniaxially stretched film, and 1.1 times or more is required to obtain a biaxially stretched film.
  • the longitudinal stretching ratio is preferably 2.5 times or more. As described in "1.1. Pigments for laser printing", the thickness unevenness improves as the stretching stress increases.
  • the orientation crystallization of the film can be promoted and the draw stress can be increased.
  • the upper limit of the longitudinal stretching ratio may be any number, but if the longitudinal stretching ratio is too high, it becomes difficult to laterally stretch and fracture is likely to occur, so it is preferably 5 times or less.
  • the longitudinal stretching ratio is more preferably 2.2 times or more and 4.8 times or less, and further preferably 2.4 times or more and 4.6 times or less.
  • Second (horizontal) stretching After the first (longitudinal) stretching, the film is gripped by clips at both ends in the width direction (direction orthogonal to the longitudinal direction) in the tenter, and 3 to 5 at 65 ° C to 130 ° C. It is preferable to perform transverse stretching at a stretching ratio of about twice. Preheating is preferably performed before stretching in the lateral direction, and preheating is preferably performed until the film surface temperature reaches 70 ° C. to 135 ° C. The higher the lateral stretching ratio, the better the thickness unevenness. Therefore, the stretching ratio is preferably 2.5 times or more. As described in "4.2. Longitudinal stretching", the higher the stretching ratio, the higher the stretching stress, so that the thickness unevenness is improved.
  • the transverse stretching ratio is more preferably 2.7 times or more and 5.3 times or less, and more preferably 2.9 times or more and 5.1 times or less. Since the stretching speed is different between the longitudinal stretching and the transverse stretching (the stretching speed is faster in the longitudinal stretching), the range of the preferable stretching ratio is different. After transverse stretching, it is preferable to pass the film through an intermediate zone where no aggressive heating operation is performed. Since the temperature is higher in the next final heat treatment zone than in the transverse stretching zone of the tenter, the heat of the final heat treatment zone (hot air itself or radiant heat) will flow into the transverse stretching process unless the intermediate zone is provided.
  • the film after the transverse stretching is passed through the intermediate zone to allow a predetermined time to elapse, and then the final heat treatment is performed.
  • the accompanying flow accompanying the running of the film, the lateral stretching zone, and the final so that when the strip-shaped piece of paper hangs down without passing through the film, the piece of paper hangs down almost completely in the vertical direction. It is important to block hot air from the heat treatment zone. It is sufficient that the transit time of the intermediate zone is about 1 second to 5 seconds. If it is shorter than 1 second, the length of the intermediate zone becomes insufficient and the heat blocking effect is insufficient. On the other hand, it is preferable that the intermediate zone is long, but if it is too long, the equipment will become large, so about 5 seconds is sufficient.
  • the heat treatment intermediate zone After passing through the heat treatment intermediate zone, it is preferable to heat-treat at 170 ° C. or higher and 250 ° C. or lower in the heat treatment zone. Since the heat treatment promotes the crystallization of the film, not only the heat shrinkage rate generated in the stretching step can be reduced, but also the tensile breaking strength tends to increase. If the heat treatment temperature is less than 150 ° C., it is difficult to set the heat shrinkage rate to 3% or less and the tensile breaking strength to 80 MPa, which is not preferable. On the other hand, if the heat treatment temperature exceeds 250 ° C., the haze tends to exceed 40%, which is not preferable.
  • the heat treatment temperature is more preferably 175 ° C. or higher and 245 ° C. or lower, and further preferably 180 ° C. or higher and 240 ° C. or lower.
  • the passage time of the heat treatment zone is preferably 2 seconds or more and 20 seconds or less. If the passing time is 2 seconds or less, the surface temperature of the film passes through the heat treatment zone without reaching the set temperature, which makes the heat treatment meaningless. The longer the transit time, the higher the effect of the heat treatment, so 5 seconds or more is more preferable. However, if the transit time is to be lengthened, the equipment will become huge, so 20 seconds or less is sufficient for practical use.
  • the heat shrinkage rate in the width direction can be reduced by reducing the distance between the clips of the tenter at an arbitrary magnification (relaxation in the width direction). Therefore, in the final heat treatment, it is preferable to relax in the width direction in the range of 0% or more and 10% or less (a relaxation rate of 0% means that relaxation is not performed).
  • a relaxation rate of 0% means that relaxation is not performed.
  • the higher the relaxation rate in the width direction, the lower the shrinkage rate in the width direction, but the upper limit of the relaxation rate (shrinkage rate in the width direction of the film immediately after lateral stretching) is the raw material used, the stretching conditions in the width direction, and the heat treatment temperature. It is not possible to carry out relaxation beyond this, as it is determined by.
  • the relaxation rate in the width direction is limited to 10%.
  • the distance between the clips in the longitudinal direction can be shortened by an arbitrary magnification (relaxation in the longitudinal direction).
  • a film roll After passing through the cooling heat treatment zone, it is preferable to cool the film in the cooling zone with a cooling air of 10 ° C. or higher and 30 ° C. or lower with a passing time of 2 seconds or more and 20 seconds or less. After that, a film roll can be obtained by winding while cutting and removing both ends of the film.
  • Gas barrier layer The film of the present invention may be provided with a gas barrier layer mainly composed of an inorganic thin film.
  • a film provided with a gas barrier layer of the present invention is referred to as a "gas barrier layer laminate”.
  • gas barrier layer laminate 5.1.1. Water vapor permeability
  • the gas barrier laminate using the film of the present invention has a water vapor permeability of 0.05 [g / (m 2 ⁇ d)] or more and 4 [g / g /) in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH. (M 2 ⁇ d)] or less is preferable. If the water vapor permeability exceeds 4 [g / (m 2 ⁇ d)], the shelf life of the contents will be shortened when used as a package containing the contents, which is not preferable.
  • the water vapor permeability is smaller than 0.05 [g / (m 2 ⁇ d)], the gas barrier property is enhanced and the shelf life of the contents is extended, which is preferable.
  • / (M 2 ⁇ d)] is the lower limit. Even if the lower limit of water vapor permeability is 0.05 [g / (m 2 ⁇ d)], it can be said that it is practically sufficient.
  • the upper limit of the water vapor permeability is preferably 3.8 [g / (m 2 ⁇ d)], more preferably 3.6 [g / (m 2 ⁇ d)].
  • the gas barrier laminate using the film of the present invention has an oxygen permeability of 0.05 [cc / (m 2 ⁇ d ⁇ atm)] or more in an environment of a temperature of 23 ° C. and a relative humidity of 65% RH 4 [ cc / (m 2 ⁇ d ⁇ atm)] or less is preferable. If the oxygen permeability exceeds 4 [cc / (m 2 ⁇ d ⁇ atm)], the shelf life of the contents will be shortened, which is not preferable.
  • the oxygen permeability is smaller than 0.05 [cc / (m 2 ⁇ d ⁇ atm)]
  • the gas barrier property is enhanced and the shelf life of the contents is extended, which is preferable.
  • Is 0.05 [cc / (m 2 ⁇ d ⁇ atm)] is the lower limit. Even if the lower limit of oxygen permeability is 0.05 [cc / (m 2 ⁇ d ⁇ atm)], it can be said that it is practically sufficient.
  • the upper limit of oxygen permeability is preferably 3.8 [cc / (m 2 ⁇ d ⁇ atm)], more preferably 3.6 [cc / (m 2 ⁇ d ⁇ atm)].
  • raw material species of the gas barrier layer are not particularly limited, conventionally known materials can be used, and can be appropriately selected according to the purpose in order to satisfy desired gas barrier properties and the like.
  • raw material species for the gas barrier layer include metals such as silicon, aluminum, tin, zinc, iron, and manganese, and inorganic compounds containing one or more of these metals.
  • Applicable inorganic compounds include oxides and nitrides. , Carbide, fluoride and the like. These inorganic substances or inorganic compounds may be used alone or in combination of two or more.
  • silicon oxide (SiOx) and aluminum oxide (AlOx) are a single element (unit) or in combination (binary) because the transparency of the film provided with the gas barrier layer can be improved.
  • the component of the inorganic compound is a binary substance of silicon oxide and aluminum oxide
  • the content of aluminum oxide is preferably 20% by mass or more and 80% by mass or less, and more preferably 25% by mass or more and 70% by mass or less. ..
  • the content of aluminum oxide is 20% by mass or less, the density of the gas barrier layer is lowered and the gas barrier property may be lowered, which is not preferable.
  • the content of aluminum oxide is 80% by mass or more, the flexibility of the gas barrier layer is lowered and cracks are likely to occur, and as a result, the gas barrier property may be lowered, which is not preferable.
  • the element ratio of oxygen / metal of the metal oxide used for the gas barrier layer is 1.3 or more and less than 1.8, there is little variation in the gas barrier property, and it is preferable that excellent gas barrier property can always be obtained.
  • the elemental ratio of oxygen / metal can be obtained by measuring the amounts of each element of oxygen and metal by X-ray photoelectron spectroscopy (XPS) and calculating the elemental ratio of oxygen / metal.
  • Method for forming a gas barrier layer is not particularly limited, and a known production method can be adopted as long as the object of the present invention is not impaired.
  • the known production methods it is preferable to adopt the vapor deposition method.
  • the vapor deposition method include a vacuum vapor deposition method, a sputtering method, a PVD method (physical vapor deposition method) such as ion plating, a CVD method (chemical vapor deposition method), and the like.
  • the vacuum vapor deposition method and the physical vapor deposition method are preferable, and the vacuum vapor deposition method is particularly preferable from the viewpoint of production speed and stability.
  • the heating method in the vacuum vapor deposition method resistance heating, high frequency induction heating, electron beam heating and the like can be used.
  • the reactive gas oxygen, nitrogen, water vapor or the like may be introduced, or reactive vapor deposition using means such as ozone addition or ion assist may be used.
  • the film forming conditions may be changed as long as the object of the present invention is not impaired, such as applying a bias to the substrate or raising or cooling the substrate temperature.
  • the film of the present invention is conveyed to the gas barrier layer manufacturing apparatus via a metal roll.
  • An example of the configuration of the gas barrier layer manufacturing apparatus includes a take-up roll, a coating drum, a take-up roll, an electron beam gun, a crucible, and a vacuum pump.
  • the film is set on a take-up roll and is taken up on a take-up roll via a coating drum.
  • the film pass line (inside the gas barrier layer manufacturing equipment) is depressurized by a vacuum pump, and the inorganic material set in the crucible is evaporated by the beam emitted from the electron gun and deposited on the film passing through the coating drum.
  • the film is heated and tension is also applied between the unwinding rolls. If the temperature applied to the film is too high, not only the thermal shrinkage of the film becomes large, but also the softening progresses, so that elongation deformation due to tension is likely to occur. Further, after leaving the vapor deposition process, the temperature drop (cooling) of the film becomes large, the amount of shrinkage after expansion (different from heat shrinkage) becomes large, cracks occur in the gas barrier layer, and it is difficult to exhibit the desired gas barrier property. Therefore, it is not preferable. On the other hand, the lower the temperature applied to the film, the more the deformation of the film is suppressed, which is preferable.
  • the temperature applied to the film is preferably 100 ° C. or higher and 180 ° C. or lower, more preferably 110 ° C. or higher and 170 ° C. or lower, and further preferably 120 ° C. or higher and 160 ° C. or lower.
  • Overcoat layer 6.1 Types of Overcoat Layer
  • the film of the present invention or the gas barrier laminate using the film of the present invention (in this section 6., these are collectively referred to as a base film) is described in the above "5. Gas barrier layer”.
  • an overcoat layer may be provided for the purpose of improving scratch resistance and further gas barrier property.
  • the type of the overcoat layer is not particularly limited, but conventionally, a composition composed of a urethane resin and a silane coupling agent, a compound composed of an organosilicon and a hydrolyzate thereof, a water-soluble polymer having a hydroxyl group or a carboxyl group, and the like have been conventionally used.
  • a known material can be used, and it can be appropriately selected according to the purpose in order to satisfy the desired gas barrier property and the like.
  • one or more kinds of additives are added to the overcoat layer for the purpose of imparting antistatic property, ultraviolet absorption, coloring, thermal stability, slipperiness, etc., as long as the object of the present invention is not impaired.
  • the type and amount of the various additives may be appropriately selected according to the desired purpose.
  • Method of forming an overcoat layer When forming an overcoat layer, the base film is conveyed to a coating facility via a metal roll.
  • equipment configurations include unwinding rolls, coating steps, drying steps, and take-up steps.
  • the laminate set on the unwinding roll is passed through the metal roll through the coating step and the drying step, and finally led to the take-up roll.
  • the coating method is not particularly limited, and the gravure coating method, reverse coating method, dipping method, low coating method, air knife coating method, comma coating method, screen printing method, spray coating method, gravure offset method, die coating method, bar coating method, etc.
  • a conventionally known method can be adopted, and can be appropriately selected according to a desired purpose.
  • the gravure coating method, the reverse coating method, and the bar coating method are preferable from the viewpoint of productivity.
  • the drying method one or a combination of two or more heating methods such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation can be used.
  • the base film is heated and tension is also applied between the metal rolls. If the temperature at which the base film is heated in the drying step is too high, not only the heat shrinkage of the base film becomes large, but also the softening progresses, so that elongation deformation due to tension is likely to occur, and the gas barrier layer of the base film becomes Cracks are likely to occur. Furthermore, after leaving the drying process, the temperature drop (cooling) of the laminate increases, and the amount of shrinkage after expansion (different from heat shrinkage) increases accordingly, causing cracks in the gas barrier layer and overcoat layer. It is not preferable because it becomes difficult to satisfy the desired gas barrier property.
  • the temperature at which the base film is heated is preferably 60 ° C. or higher and 200 ° C. or lower, more preferably 80 ° C. or higher and 180 ° C. or lower, and further preferably 100 ° C. or higher and 160 ° C. or lower.
  • the film of the present invention Structure of package, manufacturing method A film having the above characteristics, a laminate provided with the gas barrier layer described in “5. Gas barrier layer”, and a laminate provided with the overcoat layer described in “6. Overcoat layer” ( In Section 7., these are collectively referred to as "the film of the present invention"), which can be suitably used as a packaging body.
  • the package include a bag made by a heat seal such as a vertical pillow, a horizontal pillow, and a gusset bag, and a fusing bag made by a fusing seal.
  • the lid material of the plastic container and the label for the bottle formed in a tubular shape by the center seal are also included in the package.
  • the film of the present invention can be made into a bag by itself, but other materials may be laminated.
  • the other layer include a non-stretched film containing polyethylene terephthalate as a component, a non-stretched film containing another amorphous polyester as a component, a uniaxially stretched or biaxially stretched film, and a non-stretched film containing nylon as a component.
  • the other layer include uniaxially stretched or biaxially stretched films, non-stretched films containing polypropylene as constituents, uniaxially stretched or biaxially stretched films, non-stretched films containing polyethylene as constituent components, uniaxially stretched or biaxially stretched films, and the like. It's not something.
  • the package may be at least partially composed of the film of the present invention. Further, the film of the present invention may be provided on any layer of the package, but considering the visibility of printing, it is not preferable to arrange the opaque film on the outside of the film of the present invention.
  • the method for producing the package having the film of the present invention is not particularly limited, and conventionally known production methods such as heat sealing using a heat bar (heat jaw), adhesion using a hot melt, and center sealing using a solvent are adopted. be able to.
  • Types of lasers Examples of the types (wavelengths) of lasers to irradiate the film of the present invention include CO2 laser (10600 nm), YAG laser (1064 nm), YVO 4 laser (1064 nm), fiber laser (1090 nm), and green laser (532 nm). , UV laser (355 nm). These laser types are not particularly limited, and can be arbitrarily used without departing from the spirit of the present invention. Among these, YAG laser, YVO 4 laser, a fiber laser, a green laser, the use of UV lasers are preferred, Nd: YAG lasers, fiber lasers, green laser, the use of UV lasers are particularly preferred.
  • the packaging body having the film of the present invention can be suitably used as a packaging material for various articles such as foods, pharmaceuticals, and industrial products.
  • a stainless steel autoclave equipped with a stirrer, thermometer and partial recirculation cooler contains 100 mol% of dimethyl terephthalate (DMT) as a dicarboxylic acid component and 100 mol% of ethylene glycol (EG) as a polyhydric alcohol component.
  • DMT dimethyl terephthalate
  • EG ethylene glycol
  • Ethylene glycol was charged so as to be 2.2 times the molar ratio of dimethyl terephthalate, and 0.05 mol% (relative to the acid component) of zinc acetate was used as a transesterification catalyst to distill off the produced methanol. While doing so, the transesterification reaction was carried out.
  • polyester A was obtained.
  • the polyester A is ethylene terephthalate.
  • the composition of polyester A is shown in Table 1.
  • Polyester A and laser pigment "IRIOTEC (registered trademark) 8825 (main components Sn, Sb)" (manufactured by Merck Performance Materials Co., Ltd.) are mixed (dry blended) at a weight ratio of 95: 5, and the same method as in Mixing Example 1 is used.
  • Polyester C (master batch) was obtained.
  • the intrinsic viscosity IV of polyester C was 0.72 dL / g.
  • the composition of polyester C is shown in Table 1.
  • Polyester A and polyester B were mixed at a mass ratio of 97: 3 as raw materials for the laser printing layer (A), and polyester A and polyester D were mixed at a mass ratio of 90:10 as raw materials for the other layers (layer B).
  • the mixed raw materials of the A layer and the B layer were put into separate screw extruders, and both the A layer and the B layer were melted at 285 ° C. and extruded from the T die at a shear rate of 280 sec-1.
  • a stirrer was installed directly above the extruder, and the mixed raw materials were put into the extruder while being agitated by the stirrer.
  • Each molten resin was joined by a feed block in the middle of the flow path, discharged from a T-die, and cooled on a chill roll set to a surface temperature of 30 ° C. to obtain an unstretched laminated film.
  • the flow path of the molten resin is set so that the central layer is the A layer and both outermost layers are the B layer (B / A / B 2 types and 3 layers), and the thickness ratio of the A layer and the B layer is set.
  • the unstretched laminated film obtained by cooling and solidifying is guided to a longitudinal stretching machine in which a plurality of roll groups are continuously arranged, preheated on preheating rolls until the film temperature reaches 90 ° C., and then stretched 3.5 times. did.
  • the film after longitudinal stretching was guided to a transverse stretching machine (tenter), preheated for 5 seconds until the surface temperature reached 110 ° C., and then stretched 4.1 times in the width direction (horizontal direction).
  • the film after the transverse stretching was directly led to the intermediate zone and passed in 1.0 second.
  • the intermediate zone of the tenter hot air from the heat treatment zone and the transverse stretching zone so that when the strip-shaped piece of paper hangs down without passing through the film, the piece of paper hangs down almost completely in the vertical direction. The hot air was cut off. Then, the film that passed through the intermediate zone was led to the heat treatment zone and heat-treated at 220 ° C. for 7 seconds.
  • Example 2 to 8 polyester films in which the mixing conditions, discharge conditions, longitudinal stretching temperature, longitudinal stretching ratio, transverse stretching temperature, transverse stretching ratio, and heat treatment temperature of the raw materials are variously changed are continuously applied.
  • a film was formed.
  • the film of Example 6 is a single-layer film having only the A layer.
  • the film of Example 7 is a uniaxially stretched film which is not vertically stretched (stretching ratio is 1) and is formed only by lateral stretching. Table 2 shows the production conditions and evaluation results of each film.
  • Example 9 a gas barrier layer was laminated on one side of the film roll of Example 2 to continuously prepare a gas barrier laminate to obtain a roll. Specifically, aluminum was used as a vapor deposition source, and aluminum oxide (AlOx) was laminated on one side of the film by a vacuum vapor deposition method while introducing oxygen gas with a vacuum vapor deposition machine. The thickness of the gas barrier layer was 10 nm. Table 2 shows the production conditions and evaluation results of the obtained laminate.
  • Example 10 a gas barrier layer was laminated on one side of the film roll of Example 2 to continuously prepare a gas barrier laminate, and then an overcoat layer was continuously formed on the gas barrier layer to obtain a roll. It was. Specifically, aluminum oxide (AlOx) and silicon oxide (SiOx) were used as vapor deposition sources, and a gas barrier layer was laminated on one side of the film by a vacuum vapor deposition method. The thickness of the gas barrier layer was 30 nm. A drying furnace set at a temperature of 120 ° C.
  • Comparative Examples 1 to 4 In Comparative Examples 1 to 3, similarly to Example 1, polyester films in which the mixing conditions, discharge conditions, longitudinal stretching temperature, longitudinal stretching ratio, transverse stretching temperature, transverse stretching ratio, and heat treatment temperature of the raw materials were variously changed were continuously produced. A film was formed. Table 2 shows the production conditions and evaluation results of each film.
  • the film evaluation method is as follows. As the measurement sample, the one in the central portion in the film width direction was used. If the longitudinal direction and the width direction cannot be specified immediately because the area of the film is small, the longitudinal direction and the width direction may be determined and the measurement may be performed, and the temporarily determined longitudinal direction and the width direction become the true direction. On the other hand, the difference of 90 degrees does not cause any particular problem.
  • the mixture was cooled to room temperature, the treatment liquid was placed in a 50 mL Digitube, and the treated Teflon (registered trademark) container was placed in the same tube while being washed with ultrapure water to make a constant volume of 50 mL, and a measurement sample was prepared. Then, the treatment liquid was measured with a high-frequency inductively coupled plasma emission spectrometer (SpectroBLUE, manufactured by Hitachi High-Tech Science Co., Ltd.), and the amount of metal element in the sample was quantified by a calibration curve prepared with a standard solution of the target element.
  • SpectroBLUE high-frequency inductively coupled plasma emission spectrometer
  • the element content in the sample is A (ppm)
  • the element concentration in the pretreatment solution is B (mg / L)
  • the element concentration in the blank test solution (measurement blank) is C (mg / L)
  • the amount of metal element in 1 g was calculated by the following formula (2).
  • A (BC) ⁇ 50 / 0.1 Equation (2)
  • -Quantitative samples of other metal elements 0.1 g were weighed in a platinum crucible and precarbonized on a hot plate to 400 ° C. Then, the ashing treatment was carried out at 550 ° C. for 8 hours using an electric furnace FO610 manufactured by Yamato Scientific Co., Ltd.
  • the element content in the sample is A (ppm)
  • the element concentration in the pretreatment solution is B (mg / L)
  • the element concentration in the blank test solution (measurement blank) is C (mg / L)
  • the amount of metal element in 1 g was calculated by the following formula (3).
  • A (BC) ⁇ 20 / 0.1 formula (3)
  • the film was sampled in a roll shape of 11 m in the longitudinal direction and 40 mm in the width direction, and the measurement speed was 5 m / min using a continuous contact thickness gauge manufactured by Micron Measuring Instruments Co., Ltd.
  • the thickness was continuously measured along the longitudinal direction of the film (measurement length was 10 m).
  • the maximum thickness at the time of measurement was Tmax.
  • the minimum thickness was Tmin.
  • the average thickness was Tave.
  • the thickness unevenness in the longitudinal direction of the film was calculated from the following formula 4.
  • Thickness spot ⁇ (Tmax.-Tmin.)/Tave. ⁇ ⁇ 100 (%) ⁇ ⁇ Equation (4)
  • Thiickness spot in the width direction The film was sampled in a wide strip of 40 mm in the longitudinal direction and 500 mm in the width direction, and the measurement speed was 5 m / min using a continuous contact type thickness gauge manufactured by Micron Measuring Instruments Co., Ltd. The thickness was continuously measured along the width direction of the film sample (measurement length was 400 mm). The maximum thickness at the time of measurement was Tmax., The minimum thickness was Tmin., And the average thickness was Tave., And the thickness unevenness in the width direction of the film was calculated from the above equation 4.
  • Refractive index It was measured with an Abbe refractive index meter (NAR-4T, manufactured by Atago Co., Ltd., measurement wavelength 589 nm). Diiodomethane was used as the mounting solution, and the refractive index (Nx) in the longitudinal direction, the refractive index (Ny) in the width direction, and the refractive index (Nz) in the thickness direction were measured. The measurement was performed twice, and the average value was calculated.
  • NAR-4T Abbe refractive index meter
  • As the measurement solvent a mixture of phenol and 1,1,2,2-tetrachloroethane at 60/40 (wt%) was used.
  • the water vapor permeability was measured according to the JIS K7126 B method. Using a water vapor permeability measuring device (PERMATRAN-W3 / 33MG MOCON), measure the water vapor permeability in the direction in which the humidity control gas permeates from the heat seal layer side in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH. did. Before the measurement, the sample was left for 4 hours in a humidity of 65% RH environment to control the humidity.
  • PERMATRAN-W3 / 33MG MOCON PERMATRAN-W3 / 33MG MOCON
  • Oxygen permeability was measured according to the JIS K7126-2 method. Using an oxygen permeation measuring device (OX-TRAN 2/20 MOCON), the oxygen permeation was measured in the direction in which oxygen permeates from the heat seal layer side in an atmosphere of a temperature of 23 degrees and a humidity of 65% RH. .. Before the measurement, the sample was left for 4 hours in a humidity of 65% RH environment to control the humidity.
  • OX-TRAN 2/20 MOCON oxygen permeation measuring device
  • the polyester film of the present invention can provide a film having high transparency, excellent thickness unevenness, and capable of clear printing by a laser, it can be suitably used for applications such as labels. At the same time, it is possible to provide a directly printed package using this film.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laser Beam Processing (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
PCT/JP2020/039354 2019-10-25 2020-10-20 レーザー印字可能なフィルムおよびそれを用いた包装体 Ceased WO2021079868A1 (ja)

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JP2021553449A JP7243851B2 (ja) 2019-10-25 2020-10-20 レーザー印字可能なフィルムおよびそれを用いた包装体
KR1020227015619A KR20220086602A (ko) 2019-10-25 2020-10-20 레이저 인자 가능한 필름 및 그것을 사용한 포장체
US17/768,346 US11919280B2 (en) 2019-10-25 2020-10-20 Laser-printable film and packaging in which same is used
CN202080069541.3A CN114502480B (zh) 2019-10-25 2020-10-20 能够激光印字的膜及使用了该膜的包装体
EP20880190.2A EP4049839A4 (en) 2019-10-25 2020-10-20 Laser-printable film and packaging in which same is used
JP2023031783A JP7448052B2 (ja) 2019-10-25 2023-03-02 レーザー印字可能なフィルムおよびそれを用いた包装体

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WO2022153965A1 (ja) * 2021-01-18 2022-07-21 東洋紡株式会社 レーザー印字された包装体
WO2023243486A1 (ja) * 2022-06-13 2023-12-21 東洋紡株式会社 レーザー印字用熱収縮性ポリエステル系フィルム

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