Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D65/38—Packaging materials of special type or form
  • B65D65/40—Applications of laminates for particular packaging purposes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D33/00—Details of, or accessories for, sacks or bags
  • B65D33/16—End- or aperture-closing arrangements or devices
  • B65D33/18—End- or aperture-closing arrangements or devices using adhesive applied to integral parts, e.g. to flaps
  • B65D33/22—End- or aperture-closing arrangements or devices using adhesive applied to integral parts, e.g. to flaps using heat-activatable adhesive
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D33/00—Details of, or accessories for, sacks or bags
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • 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
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/267—Marking of plastic artifacts, e.g. with laser
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D65/38—Packaging materials of special type or form
  • B65D65/42—Applications of coated or impregnated materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes or webs of flexible sheet material, e.g. in folded wrappers
  • B65D75/28—Articles or materials wholly enclosed in composite wrappers, i.e. wrappers formed by associating or interconnecting two or more sheets or blanks
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/58—Cuttability
  • B32B2307/581—Resistant to cut
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
  • B32B2307/737—Dimensions, e.g. volume or area
  • B32B2307/7375—Linear, e.g. length, distance or width
  • B32B2307/7376—Thickness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/75—Printability
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles
  • B32B2439/70—Food packaging
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles
  • B32B2439/80—Medical packaging
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D2203/00—Decoration means, markings, information elements, contents indicators
  • B65D2203/02—Labels
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D2565/38—Packaging materials of special type or form
  • B65D2565/381—Details of packaging materials of special type or form

Definitions

• the present invention relates to a package having a laser-printed layer and formed by fusion sealing.
• packaging made of plastic film has been widely used for distribution goods such as food, pharmaceuticals, and industrial products.
• Packages have various forms depending on the bag-making method and application, and one of them is a package formed by fusion-cut sealing (hereinafter sometimes referred to as a fusion-cut bag) (for example, Patent Document 1).
• Fusion-cut sealing is a technique in which plastic films are layered and bonded with a hot blade.
• Many packages, including fusion bags not only protect the contents, but also display information (hereinafter sometimes referred to as "printing”) such as the product name, manufacturing date, raw materials, etc. there is
• An object of the present invention is to solve the problems of the prior art as described above. That is, an object of the present invention is to provide a packaging body which has laser markings without peeling and which is formed by fusion sealing under high productivity and economic efficiency.
• the present invention consists of the following configurations.
• (1) The thickness of the laser-printed layer is 5 ⁇ m or more and 200 ⁇ m or less
• the difference in color L* value between the laser-printed portion and the non-printed portion is 1.0 or more and 10 or less
• the fusion-cut seal strength is 5 N/15 mm or more and 40 N /15 mm or less 2.
• Either the height or the width of the print size in the laser-printed portion is 0.2 mm or more and 100 mm or less.
• the package described in . 3. 1.
• the package is characterized by having a laser-printed layer over the entire planar area of the package. or 2.
• the laser-printed layer contains at least one element or compound selected from the group consisting of bismuth, gadolinium, neodymium, titanium, antimony, tin, aluminum, calcium, and barium as the laser-printed pigment.
• the resin constituting the laser-printed layer is mainly polyester, polypropylene, or polyethylene. to 4.
• the package of the present invention will be described below. 1. Configuration of package 1.1. Layer Configuration, Thickness
• the package of the present invention must have at least one film layer (laser printable layer) that can be printed by laser irradiation.
• the laser-printed layer has a laser-printed portion at least partially printed with a laser, and has a non-printed portion.
• the package has a laser-printed layer over the entire area (in the planar direction).
• the package of the present invention may be provided with a printed layer on which characters or patterns other than the printed characters formed by laser are described. Necessary or preferred requirements for these layers will be described later.
• the laser-printed layer may be provided with a fusion-sealing performance, or a layer having a fusion-sealing performance may be provided separately from the laser-printed layer in order to satisfy the regulation of fusion-seal strength.
• the requirements for expressing the fusion cut seal strength will be described later.
• the package of the present invention can be further provided with an anchor coat layer laminated on the substrate layer or the adhesive layer and an overcoat layer laminated on the gas barrier layer, if necessary. By providing these layers, the gas barrier properties and abrasion resistance of the package can be improved.
• the thickness of the film layer constituting the package (hereinafter sometimes referred to as the thickness of the package) is not particularly limited, but is preferably 5 ⁇ m or more and 300 ⁇ m or less. If the thickness of the package is less than 5 ⁇ m, not only is the visibility of the laser marking lowered, but also the mechanical strength and fusion-cut seal strength are likely to be lowered, which is not preferable. On the other hand, if the thickness of the package exceeds 300 ⁇ m, heat transfer in the thickness direction of the film is insufficient at the time of fusion-cut sealing, which is not preferable because defective fusion-cutting tends to occur.
• the thickness of the package is more preferably 10 ⁇ m or more and 295 ⁇ m or less, and even more preferably 15 ⁇ m or more and 290 ⁇ m or less.
• the thickness of the laser-printed layer that constitutes the package of the present invention must be 5 ⁇ m or more and 200 ⁇ m or less. If the thickness is less than 5 ⁇ m, the visibility of laser printing may be lowered even if the concentration of the laser-printing pigment described later is increased. On the other hand, if the thickness of the printed layer exceeds 200 ⁇ m, the above-described defective fusion tends to occur, which is not preferable.
• the thickness of the laser-printed layer is more preferably 10 ⁇ m or more and 195 ⁇ m or less, and further preferably 15 ⁇ m or more and 190 ⁇ m or less.
• all the layers constituting the package of the present invention can be provided with layers subjected to corona treatment, coating treatment, flame treatment, etc., in order to improve properties such as surface printability and slipperiness. and can be provided arbitrarily within the scope of the requirements of the present invention.
• Laser-printed layer 1.2.1. Type, Addition Amount, and Addition Method of Laser Print Pigment
• a laser print pigment having a discoloration function by laser irradiation. Since the plastics that make up the package generally do not react very well to laser light, they cannot be printed by laser irradiation.
• the laser-printing pigment is excited by the energy of the laser light, and the surrounding plastic is carbonized to enable printing. In addition to the carbonization of plastics, some types of laser-printed pigments themselves turn black.
• the carbonization effect and the discoloration effect of the laser-printing pigment can be printed on the printing layer by a single effect or a combined effect. From the viewpoint of printing density, it is preferable to select a laser-printing pigment that has both the carbonization action of the plastic and the discoloration action of itself.
• laser-printed pigments include bismuth, gadolinium, neodymium, titanium, antimony, tin, aluminum, calcium, and barium either singly or as an oxide.
• titanium oxide, calcium carbonate, bismuth trioxide, antimony trioxide, and barium sulfate are preferable, and titanium oxide, calcium carbonate, and bismuth trioxide are more preferable.
• the particle size of the laser-printed pigment is preferably 0.1 ⁇ m or more and 10 ⁇ m or less. If the particle size of the laser-printed pigment is less than 0.1 ⁇ m, there is a possibility that the color change during laser irradiation will be insufficient.
• the particle size of the laser-printed pigment is more preferably 1 ⁇ m or more and 9 ⁇ m or less, and more preferably 2 ⁇ m or more and 8 ⁇ m or less.
• the amount of laser-printed pigment added to the laser-printed layer is preferably 0.05% by mass or more and 50% by mass or less. If the amount of pigment added is less than 0.05% by mass, the printing density by laser becomes insufficient, which is not preferable. On the other hand, if the amount of pigment added exceeds 50% by mass, the amount (volume) of the carbonized plastic is relatively reduced, so there is a risk that the print density will be insufficient.
• the amount of laser-printed pigment added is more preferably 0.1% by mass or more and 49% by mass or less, more preferably 0.15% by mass or more and 48% by mass or less, and 0.2% by mass or more and 47% by mass or less. It is especially preferable to have When the laser-printed layer has a plurality of layers, the amount of laser-printed pigment added to the entire laser-printed layer can be obtained by proportionally dividing the thickness ratio of each layer and the amount of laser-printed pigment added.
• the method of blending the laser-printed pigment it can be added at any stage during the production of the resin that is the raw material for the laser-printed layer or the film that will be the laser-printed layer.
• the stage of producing the resin there is a method of blending a slurry of particles dispersed in a solvent and a plastic raw material using a vented kneading extruder, or a method of blending dried particles and a plastic resin using a kneading extruder. and a method of blending (masterbatching).
• the method of using a masterbatch containing a laser-printed pigment as a raw material for the film is preferred.
• Type of plastic The type of plastic that constitutes the laser-printed layer of the present invention is not particularly limited, and any plastic can be used without departing from the gist of the present invention.
• Types of plastics include, for example, polyesters, polyolefins, and polyamides.
• polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), polybutylene naphthalate (PBN), polylactic acid (PLA), polyethylene furano ate (PEF), polybutylene succinate (PBS), and the like.
• modified polyesters obtained by changing the monomers of these acid or diol sites may be used.
• acid moiety monomers 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 decanedicarboxylic 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 decanedicarboxylic acid.
• Aliphatic dicarboxylic acids and alicyclic dicarboxylic acids are included.
• diol moiety monomers examples include neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, 2,2-diethyl-1,3-propanediol, and 2-nbutyl-2-ethyl-1,3-propane.
• Long-chain diols such as diols, 2,2-isopropyl-1,3-propanediol, 2,2-di-n-butyl-1,3-propanediol, hexanediol, 1,4-butanediol, hexanediol, etc. and aromatic diols such as bisphenol A.
• polyester elastomers containing ⁇ -caprolactone, tetramethylene glycol, etc. may be included as components constituting the polyester.
• a homopolyester in which a carboxylic acid monomer and a diol monomer are polymerized in a one-to-one ratio may be used by mixing (dry blending) a plurality of types, or two or more types of carboxylic acid may be used. Acid monomers or two or more diol monomers may be copolymerized and used. A mixture of homopolyester and copolyester may also be used.
• the intrinsic viscosity (IV) of the polyester as a raw material is not particularly limited and any one can be used, but it is preferably 0.5 to 1.2 dL/g. If the IV is less than 0.5 dL/g, the molecular weight of the raw material is too low, and problems such as breakage during film formation and the tensile strength at break of the display body being less than 40 MPa are likely to occur. On the other hand, if the IV exceeds 1.2 dL/g, the resin pressure in the extrusion process during film formation becomes too high, which is not preferable because filter deformation and the like tend to occur. IV is more preferably 0.55 dL/g or more and 1.15 dL/g or less, and even more preferably 0.6 dL/g or more and 1.1 dL/g or less.
• polyolefins examples include polypropylene (PP) and polyethylene (PE).
• PP polypropylene
• PE polyethylene
• the stereoregularity is not particularly limited, and it may be isotactic, syndiotactic, or atactic, and may be contained in any proportion.
• polyethylene its density (degree of branching) is not particularly limited, and may be high density (HDPE), linear low density (LLDPE), or low density (LDPE).
• HDPE high density
• LLDPE linear low density
• monomers used for copolymerization examples include ethylene and ⁇ -olefins.
• melt flow rate (MFR) of polyolefin as a raw material is not particularly limited and any one can be used, but it is preferably 1 to 10 g/10 minutes.
• MFR is less than 1 g/10 minutes, the melt viscosity of the raw material becomes too high, and the resin pressure in the extrusion process during film formation becomes too high, which is not preferable because filter deformation and the like tend to occur.
• MFR exceeds 10 g/10 minutes, the molecular weight will be extremely low, so there is a risk that breakage will easily occur during film formation or that blocking resistance will be reduced.
• MFR is more preferably 2 g/10 minutes or more and 8 g/10 minutes, and more preferably 3 g/10 minutes or more and 7 g/10 minutes.
• polyamides examples include polycapramide (nylon 6), polyhexamethylene adipamide (nylon 66), caprolactam/lauryllactam copolymer (nylon 6/12), caprolactam/hexamethylenediammonium adipate copolymer (nylon 6 /66), ethylene ammonium adipate/hexamethylenediammonium adipate/hexamethylenediammonium sebacate copolymer (nylon 6/66/610), polymer of metaxylylenediamine and adipic acid (MXD-6), hexamethylene
• examples include one resin selected from isophthalamide/terephthalamide copolymers (amorphous nylon), or a mixed material obtained by mixing two or more of these resins.
• an adhesion-improving layer can be provided on the surface of the film made of the above plastics.
• Materials for the adhesion-improving layer include, for example, acrylic, water-soluble or water-dispersible polyester, and hydrophobic polyester graft-copolymerized with acrylic.
• the relative viscosity (RV) of polyamide as a raw material is preferably 2.2 or more and 4 or less. When the RV is less than 2.2, the crystallization speed becomes too fast, and breakage or the like may easily occur during stretching during the film-forming process. On the other hand, if the RV exceeds 4, the load on the extruder becomes too high, and deformation of the filter tends to occur, which is undesirable.
• RV is more preferably 2.3 or more and 3.9 or less, and even more preferably 2.4 or more and 3.8 or less.
• the relative viscosity in the present invention is a value measured at 25° C. using a solution of 0.5 g of polymer dissolved in 50 ml of 97.5% sulfuric acid.
• polyester, polypropylene, and polyethylene are preferable from the viewpoint of mechanical strength, film-forming stability, and laser-printing performance.
• the content of the plastic constituting the laser-printed layer is preferably 50% by mass or more and 99.95% by mass or less.
• the plastic content is less than 50% by mass, the tensile strength at break, which will be described later, tends to be less than 40 MPa, which is not preferable. Also, if the plastic content exceeds 99.95% by mass, the content of the laser printing pigment will relatively fall below 0.05% by mass, and the color L* value between the printed area and the non-printed area will change. This is not preferable because the difference tends to fall below 1.0.
• the plastic content is more preferably 51% by mass or more and 99.9% by mass or less, more preferably 52% by mass or more and 99.85% by mass or less, and particularly 53% by mass or more and 99.8% by mass or less. preferable.
• the plastic content of the entire laser-printed layer can be obtained by proportionally dividing the thickness ratio of each layer and the plastic content.
• additives other than laser-printed pigments in the laser-printed layer constituting the package of the present invention, various additives such as waxes, antioxidants, antistatic agents, crystal nucleating agents, reducing agents may be added as necessary. Viscous agents, heat stabilizers, coloring pigments, anti-coloring agents, UV absorbers, etc. can be added.
• fine particles when the laser-printed layer is the outermost layer, it is preferable to add fine particles as a lubricant to improve slipperiness. Any fine particles can be selected.
• inorganic fine particles include silica, alumina, kaolin, lead white, titanium white, zeolite, zinc white, lithopone, etc.
• organic fine particles include acrylic particles, melamine particles, silicone particles, crosslinked particles, and the like.
• Polystyrene particles, carbon black, iron oxide 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 as measured by a Coulter counter.
• the lower limit of the fine particle content is preferably 0.01% by mass, more preferably 0.015% by mass, and still more preferably 0.02% by mass. If it is less than 0.01% by mass, the lubricity may deteriorate.
• the upper limit is preferably 1% by mass, more preferably 0.2% by mass, still more preferably 0.1% by mass. If the amount exceeds 1% by mass, the smoothness of the surface may be lowered and problems such as faint printability may occur, which is not preferable.
• the method of blending the particles into the laser-printed layer the particles can be added at any stage in the production of the plastic raw material. The same method can be adopted.
• the laser-printed layer may also serve as the fusion-cut seal layer, or the laser-printed layer may include a separate fusion seal layer. Layers may be provided. Here, the layer that develops the fusion-cut seal strength described later (including the laser-printed layer) is described as the fusion-cut seal layer.
• the fusion sealing layer is not particularly limited as long as it has fusion sealing properties, and conventionally known materials can be arbitrarily used without departing from the scope of the present invention. Types of plastics constituting the fusion seal layer include, for example, polyesters and polyolefins.
• polyesters examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), polybutylene naphthalate (PBN), polylactic acid (PLA), polyethylene furano ate (PEF), polybutylene succinate (PBS), and the like. Furthermore, in addition to the polyesters exemplified above, modified polyesters obtained by changing the monomers of these acid or diol sites may be used.
• acid moiety monomers examples 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 decanedicarboxylic acid. Aliphatic dicarboxylic acids and alicyclic dicarboxylic acids are included.
• diol moiety monomer examples include neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, 2,2-diethyl 1,3-propanediol, 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, hexanediol and aromatic diols such as bisphenol A.
• polyester elastomers containing ⁇ -caprolactone, tetramethylene glycol, etc. may be included as components constituting the polyester.
• a homopolyester in which a carboxylic acid monomer and a diol monomer are polymerized in a one-to-one ratio may be used by mixing (dry blending) a plurality of types, or two or more types of carboxylic acid may be used. Acid monomers or two or more diol monomers may be copolymerized and used.
• a mixture of homopolyester and copolyester may also be used. Copolyester has a low melting point and a low degree of crystallinity, and can be suitably used in order to develop fusion-cut seal strength.
• polyolefins examples include polypropylene (PP) and polyethylene (PE).
• PP polypropylene
• PE polyethylene
• the stereoregularity is not particularly limited, and it may be isotactic, syndiotactic, or atactic, and may be contained in any proportion.
• polyethylene its density (degree of branching) is not particularly limited, and may be high density (HDPE), linear low density (LLDPE), or low density (LDPE).
• HDPE high density
• LLDPE linear low density
• monomers used for copolymerization examples include ethylene and ⁇ -olefins.
• olefins propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 4-methyl-1-hexene; etc.
• the form of copolymerization may be either random copolymerization or block copolymerization.
• polyolefin elastomers and ionomers may be used.
• Low stereoregularity or copolymerized polyolefins have a low melting point and low crystallinity, and can be suitably used to develop fusion-cut seal strength.
• the melt flow rate (MFR) of polyolefin as a raw material is not particularly limited and any one can be used, but it is preferably 1 to 10 g/10 minutes. If the MFR is less than 1 g/10 minutes, the melt viscosity of the raw material becomes too high, and the resin pressure in the extrusion process during film formation becomes too high, which is not preferable because filter deformation and the like tend to occur. On the other hand, if the MFR exceeds 10 g/10 minutes, the molecular weight will be extremely low, so there is a risk that breakage will easily occur during film formation or that blocking resistance will be reduced. MFR is more preferably 2 g/10 minutes or more and 8 g/10 minutes, and more preferably 3 g/10 minutes or more and 7 g/10 minutes.
• the fusion seal layer may contain a lubricant in order to improve lubricity, and the content concentration is preferably 100 ppm or more and 2000 ppm or less. If the concentration of the lubricant is less than 100 ppm, the lubricity deteriorates, which is not preferable. On the other hand, the lubricant concentration may exceed 2000 ppm, but no further improvement in lubricity can be expected.
• the lubricant concentration is more preferably 200 ppm or more and 1900 ppm or less, and even more preferably 300 ppm or more and 1800 ppm or less.
• the fusion seal layer may be provided with a layer that has been subjected to corona treatment, coating treatment, flame treatment, or the like in order to improve the wettability and slipperiness of the surface, as long as it does not deviate from the requirements of the present invention.
• a film formed by any one of non-stretching, uniaxial stretching, and biaxial stretching can be arbitrarily used using the plastics of the above-mentioned types as raw materials.
• the package of the present invention may have layers other than the laser-printed layer and the fusion seal layer described above.
• the gas barrier layer (transparent, opaque) and print layer described in the above "1.1. Layer structure and thickness” will be described.
• the gas barrier layer that can be optionally laminated on the package of the present invention is preferably composed of an inorganic thin film containing a metal or metal oxide as a main component. Furthermore, in addition to the gas barrier composed of the inorganic thin film, an anchor coat layer provided under the inorganic thin film layer (between the plastic film and the inorganic thin film) and an overcoat layer provided above the inorganic thin film layer may be provided. By providing these layers, improvement in adhesion to the gas barrier layer, improvement in gas barrier properties, etc. can be expected.
• the kind of raw material for the gas barrier layer is not particularly limited, and conventionally known materials can be used, and can be appropriately selected according to the purpose so as to satisfy the desired gas barrier property 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. , carbides, fluorides, and the like. These inorganic substances or inorganic compounds may be used singly or in combination.
• silicon oxide (SiOx) and aluminum oxide (AlOx) can be used alone (mono-element) or in combination (binary element).
• the content of aluminum oxide is preferably 20% by mass or more and 80% by mass or less, more preferably 25% by mass or more and 70% by mass or less. . If the content of aluminum oxide is 20% by mass or less, the density of the gas barrier layer may decrease and the gas barrier properties may deteriorate, which is not preferable. On the other hand, if the content of aluminum oxide is 80% by mass or more, the flexibility of the gas barrier layer is lowered, cracks are likely to occur, and as a result, the gas barrier properties may be lowered, which is not preferable.
• the oxygen/metal element ratio of the metal oxide used for the gas barrier layer is 1.3 or more and less than 1.8, the gas barrier properties are less varied, and excellent gas barrier properties are always obtained, which is preferable.
• the oxygen/metal element ratio can be obtained by measuring the amount of each element of oxygen and metal by X-ray photoelectron spectroscopy (XPS) and calculating the oxygen/metal element ratio.
• the thickness of the gas barrier layer that can be preferably used in the package of the present invention is preferably 2 nm or more and 100 nm or less when a metal or metal oxide is vapor-deposited and used as the gas barrier layer. If the thickness of this layer is less than 2 nm, the gas barrier properties tend to deteriorate, which is not preferable.
• the thickness of the inorganic thin film layer is more preferably 5 nm or more and 97 nm or less, and even more preferably 8 nm or more and 94 nm or less.
• the thickness of the metal foil is preferably 3 ⁇ m or more and 100 ⁇ m or less. If the thickness of this layer is less than 3 ⁇ m, the gas barrier properties tend to deteriorate, which is not preferable. On the other hand, even if the thickness of this layer exceeds 100 nm, there is no corresponding effect of improving the gas barrier property, and the production cost increases, which is not preferable.
• the thickness of the inorganic thin film layer (metal foil) is more preferably 5 ⁇ m or more and 97 ⁇ m or less, and further preferably 8 ⁇ m or more and 94 ⁇ m or less.
• the gas barrier layer can be formed by adhering aluminum foil or vapor-depositing aluminum.
• the thickness of the aluminum foil is preferably 1 ⁇ m or more and 100 ⁇ m or less.
• the gas barrier laminate thus provided has a water vapor transmission rate of 0.05 [g/(m 2 ⁇ d)] or more and 4 [g/(m 2 ⁇ d)] is preferably below. If the water vapor transmission rate 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. On the other hand, when the water vapor permeability is less than 0.05 [g/(m 2 ⁇ d)], the gas barrier property is enhanced and the shelf life of the contents is increased, which is preferable, but the current technical level is 0.05 [g /(m 2 ⁇ d)] is the lower limit.
• the gas barrier laminate has an oxygen permeability of 0.05 [cc/(m 2 ⁇ d ⁇ atm)] or more and 4 [cc/(m 2 ⁇ d ⁇ atm)] 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 less than 0.05 [cc/(m 2 ⁇ d ⁇ atm)]
• the gas barrier property is enhanced and the shelf life of the contents is increased, which is preferable, but the current technical level is oxygen permeability is 0.05 [cc/(m 2 ⁇ d ⁇ atm)].
• the upper limit of the oxygen permeability is preferably 3.8 [cc/(m 2 ⁇ d ⁇ atm)], more preferably 3.6 [cc/(m 2 ⁇ d ⁇ atm)].
• an overcoat layer may be provided on the gas barrier layered product described above for the purpose of improving scratch resistance and gas barrier properties.
• the type of overcoat layer is not particularly limited, it may be a composition comprising a urethane resin and a silane coupling agent, a compound comprising an organosilicon and its hydrolyzate, a water-soluble polymer having a hydroxyl group or a carboxyl group, and the like.
• 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 additives are added to the overcoat layer for the purpose of imparting antistatic properties, ultraviolet absorbency, coloration, thermal stability, slipperiness, etc., within the range that does not impair the object of the present invention.
• the type and amount of each additive can be appropriately selected according to the desired purpose.
• the package of the present invention may be provided with letters or patterns for the purpose of improving the design.
• known materials such as ink for gravure printing and ink for flexographic printing can be used.
• the number of printed layers may be one or multiple layers. In order to print in a plurality of colors and improve designability, it is preferable to have a printing layer consisting of a plurality of layers. The printed layer may be positioned either on the outermost layer or on the intermediate layer.
• the absolute value of the difference in color L* value between the printed portion and the non-printed portion (hereinafter sometimes simply referred to as “the difference in L* value”) is 1.0 or more and 10.0 or less. need to be If this difference is less than 1.0, the color tone of the printed portion and the non-printed portion will be close to each other, making it difficult to visually recognize the print. On the other hand, if the difference in L* value exceeds 10.0, the print becomes easy to see, but the power of laser irradiation must be increased accordingly, which increases the damage to the package and causes problems such as holes. It is not preferable because it is likely to occur.
• the difference in L* value is more preferably 1.5 or more and 9.5 or less, and more preferably 2.0 or more and 9.0 or less.
• the package body of the present invention needs to have a weld-cut seal strength of 5 N/15 mm or more and 40 N/15 mm or less.
• a seal strength of less than 5 N/15 mm is not preferable because the seal portion is easily peeled off.
• the seal strength is more preferably 6 N/15 mm or more, and even more preferably 7 N/15 mm or more.
• the higher the seal strength the better the sealability of the package, but the upper limit that can be obtained at present is about 40 N/15 mm. Even if the upper limit of the seal strength is 30 N/15 mm, it is practically sufficient.
• the size of the print formed on the package of the present invention by laser is preferably 0.2 mm or more and 100 mm or less in either height or width.
• the resolution of the human eye is said to be about 0.2 mm, and if the character size is less than 0.2 mm, the difference in color L* value tends to be less than 1.0, making it difficult to recognize the print. .
• the print size exceeds 100 mm, it is easy to recognize the print, which is preferable.
• the print size is more preferably 0.5 mm or more and 90 mm or less, and more preferably 1 mm or more and 80 mm or less.
• the package of the present invention When the package of the present invention is treated with hot air at 120° C. for 30 minutes by cutting an arbitrary portion where the innermost layers are not sealed, the package can be heated in at least one arbitrary direction on the plane of the package. It is preferable that the shrinkage rate is -10% or more and 10% or less. If the heat shrinkage rate exceeds 10%, deformation becomes large when placed in a high temperature environment, and the original shape cannot be maintained, which is not preferable. On the other hand, if the heat shrinkage ratio is less than -10%, it means that the package is stretched, and like the case where the heat shrinkage ratio is high, it becomes difficult for the package to maintain its original shape, which is not preferable.
• the heat shrinkage rate of the package is more preferably ⁇ 9% or more and 9% or less, and more preferably ⁇ 8% or more and 8% or less.
• the package of the present invention preferably has a tensile breaking strength of 40 MPa or more and 400 MPa when an arbitrary portion that is not welded and sealed is cut and the tensile breaking strength is measured in at least one arbitrary direction on the plane of the package. If the tensile breaking strength is less than 40 MPa, the package is easily broken by external tension, which is not preferable.
• the lower limit of the tensile strength at break is more preferably 50 MPa, and even more preferably 60 MPa.
• the tensile strength at break exceeds 400 MPa, it is preferable as a mechanical strength, but 400 MPa is the upper limit according to the technical level of the present invention. Even a tensile breaking strength of 300 MPa is practically sufficient.
• the laser-printed layer constituting the package of the present invention can be produced by the method and conditions exemplified below. 3.1.1. Raw Material Mixing and Supply In producing the laser-printed layer contained in the package of the present invention, it is necessary to add the laser-printed pigment described in the above "1.2.1. Type, amount and method of addition of laser-printed pigment". There is Since the laser-printed pigment is a metal, it usually has a higher specific gravity than the resin forming the film. When two or more kinds of raw materials having different specific gravities are mixed and put into an extruder, the raw materials are likely to be supplied unevenly (segregation).
• a stirrer is installed in the pipe directly above the extruder or in the hopper, or a pipe (inner pipe) is inserted inside the hopper directly above the extruder filled with base resin to supply the laser-printed pigment. It is preferable to carry out the melt extrusion by taking measures such as installing a pincushion for cutting the grain pressure of the raw material in each raw material hopper.
• the laser-printed layer is formed by melt-extrusion of the raw material supplied in the above “3.1.1. can be obtained through When laminating the laser-printed layer and the fusion-cut seal layer, it is preferable to laminate them by an extrusion process. It is preferable to adopt a co-extrusion method as the lamination method, in which the raw material resins for each layer are melt-extruded by separate extruders, and joined using a feed block or the like in the middle of the resin flow path. . Further, extrusion lamination may be employed in which a resin to be the seal layer is melt-extruded from a slot die and laminated in any process from extrusion of the laser-printed layer to winding.
• a known method can be used as a method for melt-extrusion of the raw material resin, and a method using an extruder equipped with a barrel and a screw is preferable.
• the moisture content is 100 ppm or less, more preferably 90 ppm or less, more preferably 90 ppm or less, and more preferably using a dryer such as a hopper dryer, paddle dryer, or vacuum dryer in advance. Drying to 80 ppm or less is preferred. After such drying of the raw material, an unstretched film can be obtained by quenching the resin melted by the extruder. Any existing method such as a T-die method, a tubular method, or the like can be employed for the extrusion.
• an unstretched film can be obtained.
• a method for rapidly cooling the molten resin a method of obtaining a substantially non-oriented resin sheet by casting the molten resin from a die onto a rotating drum and rapidly cooling and solidifying the resin can be suitably employed.
• the film to be the printing layer may be formed by any method of non-stretching, uniaxial stretching (stretching in at least one of the vertical (longitudinal) direction and horizontal (width) direction), and biaxial stretching. However, in consideration of mechanical strength, uniaxial stretching is preferred, and biaxial stretching is more preferred.
• the film is preferably introduced into a longitudinal stretching machine in which a plurality of roll groups are continuously arranged.
• a longitudinal stretching machine in which a plurality of roll groups are continuously arranged.
• the temperature for preheating is set between Tg and melting point Tm+50° C. based on the glass transition temperature (Tg) or melting point (Tm) of the plastic constituting the film. If the preheating temperature is lower than the Tg, it becomes difficult to stretch in the longitudinal direction, and breakage tends to occur, which is not preferable.
• the film tends to stick to the roll and the film tends to wind, which is not preferable.
• the longitudinal draw ratio is preferably 1-fold or more and 5-fold or less. Since 1 time means no longitudinal stretching, the longitudinal stretching ratio is 1 time to obtain a transversely uniaxially stretched film, and the longitudinal stretching ratio is 1.1 times or more to obtain a biaxially stretched film. A longitudinal draw ratio of 1.1 times or more is preferable because voids appear in the printed layer.
• the upper limit of the draw ratio in the longitudinal direction may be any number of times, but if the draw ratio in the longitudinal direction is too high, the film is likely to break in the next transverse draw, so it is preferably 10 times or less.
• the longitudinal draw ratio is more preferably 1.2 times or more and 9.8 times or less, and further preferably 1.4 times or more and 9.6 times or less.
• Second (horizontal) stretching After the first (longitudinal) stretching, 2 to 13 times at Tg ⁇ Tm + 50 ° C with both ends of the film in the width direction (direction perpendicular to the longitudinal direction) held by clips in the tenter. It is preferable to carry out the lateral stretching at a stretching ratio of approximately. Preheating is preferably performed before stretching in the transverse direction, and the preheating is preferably performed until the surface temperature of the display material or package reaches Tg to Tm+50°C.
• the transverse draw ratio is more preferably 2.2 times or more and 12.8 times or less, and more preferably 2.4 times or more and 12.6 times or less.
• the preferred draw ratio range differs.
• the area ratio obtained by multiplying the ratios of longitudinal stretching and transverse stretching is preferably 2.2 times or more and 64 times.
• the film is preferably passed through an intermediate zone in which no active heating operation is performed. Since the temperature in the final heat treatment zone is higher than that in the transverse stretching zone of the tenter, the heat (hot air itself or radiant heat) in the final heat treatment zone flows into the transverse stretching process unless an intermediate zone is provided. In this case, the temperature of the lateral stretching zone is not stable, resulting in variations in physical properties.
• the transversely stretched film is passed through an intermediate zone for a predetermined period of time, and then subjected to final heat treatment.
• this intermediate zone when a strip of paper is suspended without the film passing through it, the accompanying flow accompanying the running of the film, the transverse stretching zone, and the final It is important to block hot air from the heat treatment zone. About 1 to 5 seconds is sufficient for passing through the intermediate zone. If it is shorter than 1 second, the length of the intermediate zone will be insufficient and the heat shielding effect will be insufficient. On the other hand, it is preferable that the intermediate zone is long.
• heat treatment is preferably performed at 100 to 280° C. in the heat treatment zone. Since the heat treatment promotes crystallization of the film, not only can the heat shrinkage rate generated in the stretching process be reduced, but also the tensile strength at break tends to increase. If the heat treatment temperature is lower than 100°C, the heat shrinkage rate of the film tends to increase, which is not preferable. On the other hand, if the heat treatment temperature exceeds 280° C., the film tends to melt and the tensile strength at break tends to decrease, which is not preferable.
• the heat treatment temperature is more preferably 110°C to 270°C, more preferably 120°C to 260°C.
• the passing time through the heat treatment zone is preferably 2 seconds or more and 20 seconds or less. If the passing time is less than 2 seconds, the film passes through the heat treatment zone before the surface temperature of the film reaches the set temperature, so the heat treatment is meaningless. The longer the passing time, the more effective the heat treatment, so it is more preferable that the passing time is 5 seconds or longer. However, if the transit time is increased, the equipment will become huge, so 20 seconds or less is practically sufficient.
• the widthwise thermal shrinkage rate can be reduced by reducing the distance between the clips of the tenter by an arbitrary ratio (relaxation in the widthwise direction).
• the upper limit of the relaxation rate in the width direction is 10%. It is also possible to shorten the distance between the clips in the longitudinal direction by an arbitrary magnification (relaxation in the longitudinal direction) during the heat treatment.
• the film After passing through the heat treatment zone, the film is preferably cooled in the cooling zone using cooling air at 10°C or higher and 50°C or lower for a passing time of 2 seconds or longer and 20 seconds or shorter. After that, the film roll is obtained by winding the film while cutting and removing both ends of the film.
• Gas Barrier Layer A method for producing a gas barrier layer that can optionally be provided on the package of the present invention will be described below.
• the method for forming the gas barrier layer is not particularly limited, and known production methods can be employed as long as the object of the present invention is not impaired.
• known manufacturing methods it is preferable to employ a vapor deposition method.
• vapor deposition methods include PVD (physical vapor deposition) such as vacuum deposition, sputtering, and ion blasting, and CVD (chemical vapor deposition).
• PVD physical vapor deposition
• CVD chemical vapor deposition
• 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.
• a heating method in the vacuum deposition method resistance heating, high-frequency induction heating, electron beam heating, or the like can be used.
• a 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, such as applying a bias to the substrate, raising the substrate temperature, cooling the substrate, etc., as long as the object of the present invention is not compromised.
• the film (laser-printed layer, etc.) forming the package of the present invention is conveyed to a gas barrier layer manufacturing apparatus via a metal roll.
• a gas barrier layer manufacturing apparatus includes an unwinding roll, a coating drum, a winding roll, an electron beam gun, a crucible, and a vacuum pump.
• the film is set on an unwinding roll, passes through a coating drum, and is wound up by a winding roll.
• the film pass line (inside the gas barrier layer manufacturing equipment) is evacuated by a vacuum pump, and the inorganic material set in the crucible is evaporated by the beam emitted from the electron gun and deposited onto the film passing through the coating drum. .
• the film is subjected to heat and tension between the unwind and take-up rolls. If the temperature applied to the film is too high, not only will the heat shrinkage of the film increase, but the softening will proceed, so that elongation deformation due to tension will easily occur.
• 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 even more preferably 120° C. or higher and 160° C. or lower.
• Overcoat Layer a method for producing an overcoat layer that can optionally be provided on the package of the present invention will be described.
• the film (laser-printed layer, etc.) forming the package of the present invention is conveyed to coating equipment via metal rolls.
• equipment configuration include an unwinding roll, a coating process, a drying process, and a winding process.
• the film set on the unwinding roll is passed through a metal roll, a coating process and a drying process, and finally led to a take-up roll.
• the coating method is not particularly limited, and gravure coating, reverse coating, dipping, low coating, air knife coating, comma coating, screen printing, spray coating, gravure offset, die coating, bar coating, etc.
• a conventionally known method can be employed, and can be appropriately selected according to the 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 drying process heats the film and also applies tension between metal rolls.
• the temperature at which the film is heated in the drying process is too high, not only will the heat shrinkage of the film increase, but the softening will also proceed, making it easier for stretching deformation due to tension to occur, and cracks will easily occur in the gas barrier layer of the film. Furthermore, the temperature drop (cooling) of the film after leaving the drying process increases, and the amount of shrinkage after expansion (different from heat shrinkage) increases accordingly, and cracks occur in the gas barrier layer and overcoat layer, resulting in the desired deterioration. It is not preferable because it becomes difficult to satisfy the gas barrier property of On the other hand, the lower the temperature at which the film is heated, the more preferable it is because deformation of the film is suppressed.
• the temperature at which the 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 even more preferably 100° C. or higher and 160° C. or lower.
• fusion-cut sealing As a method for making the packaging of the present invention, it is necessary to employ fusion-cut sealing.
• the fusion seal is established, for example, by heat-sealing (side seal or side weld) the left and right edges of the package with a heated blade (fusion blade).
• fusion blade a heated blade
• the shape of the package is not particularly limited, and any shape such as a rectangle, square, or triangle can be adopted.
• the equipment and conditions used for fusion sealing can be arbitrarily used conventionally known ones, and are not particularly limited as long as they do not deviate from the gist of the present invention.
• Examples of the fusion-cut sealing conditions include the temperature of the fusion-cutting blade, the angle of the cutting edge, and the bag-making speed (stroke frequency of the fusion-cutting blade).
• the temperature of the fusing blade is preferably 300° C. or higher and 450° C. or lower.
• the temperature of the fusing blade varies depending on the melting point of the film to be used, but the melting point of the polyester or polyolefin is 110° C. or higher and 300° C. or lower, so it is necessary to set the temperature higher than this. If the temperature of the cutting blade is less than 300° C., defective cutting tends to occur, which is not preferable. On the other hand, when the temperature of the cutting blade exceeds 450° C., although defective cutting is less likely to occur, the film at the cutting portion is likely to be deformed due to heat shrinkage, which is not preferable.
• the temperature of the fusing blade is more preferably 310° C.
• the cutting edge angle of the fusing blade should be 50° or more and 130° with respect to the horizontal direction (direction in which the film flows). It is preferable that it is below. If the angle of the cutting edge is less than 50° or more than 130°, the efficiency of heat transfer to the fused portion of the film will deteriorate, and the fused seal strength will decrease, which is not preferable.
• the angle of the cutting edge is more preferably 52° or more and 128° or less, and more preferably 54° or more and 126° or less.
• the bag-making speed is preferably 60 pieces/minute or more and 240 pieces/minute or less.
• the bag-making speed is less than 60 bags/minute, the productivity of the package is extremely lowered, which is not preferable. On the other hand, if the bag-making speed is 240 bags/minute, it is not preferable because defective fusion tends to occur.
• the bag-making speed is more preferably 65 bags/minute or more and 235 bags/minute or less, and more preferably 70 bags/minute or more and 230 bags/minute or less.
• laser marking conditions Examples of laser types (wavelengths) that can be used for laser marking on the package of the present invention include CO2 laser (10600 nm), YAG laser (1064 nm), YVO4 laser (1064 nm), fiber laser (1064 nm), 1090 nm), green laser (532 nm), and UV laser (355 nm).
• the type of laser used for marking in the present invention is not particularly limited, but the CO2 laser is often used for burning off plastics, and is used for a purpose different from the marking that is the gist of the present invention. Therefore, it is not preferable as a laser source.
• YAG lasers, YVO4 lasers, fiber lasers, green lasers, UV lasers are preferred as laser sources, and YAG lasers, fiber lasers, UV lasers are more preferred.
• Commercially available devices can be used for laser printing, and typical examples are LM-2550 (YAG laser) manufactured by Brother Industrial Printing, MX-Z2000H-V1 (fiber laser) manufactured by Omron, and 8028 Trotec Speedy 100 flexx manufactured by Trotec. (fiber laser), Keyence MD-X1000 (YVO4 laser), MD-U1000C (UV laser) and the like.
• the specifications and conditions that can be set differ depending on the device manufacturer and model, and also vary depending on the film to be printed. As an example, it is as follows.
• the laser power is preferably 20% or more and 80% or less of the maximum 13W of the device specifications. If the output is less than 20%, the print density is lowered and the visibility is lowered, which is not preferable. If the output is 80% or more, it is not preferable because the display body is perforated. The output is more preferably 25% or more and 75% or less, and even more preferably 30% or more and 70% or less.
• the pulse frequency is preferably 10 kHz or more and 100 kHz or less. If the frequency is less than 10 kHz, the laser energy per irradiation becomes high and the thickness reduction rate of the printed portion tends to exceed 80 vol %, which is not preferable.
• the thickness reduction rate of the printed portion is likely to be 80 vol % or less, but it may be difficult to make the difference in the color L* values of the printed portion 1 or more. It is more preferably 15 kHz or more and 95 kHz or less, and even more preferably 20 kHz or more and 90 kHz or less.
• the scan speed is preferably 10 mm/sec or more and 3000 mm/sec or less. If the scanning speed is less than 10 mm/sec, the printing speed will be extremely low, which is not preferable because the production speed of the display will be low.
• the scan speed is more preferably 100 mm/sec to 2900 mm/sec, more preferably 200 mm/sec to 2800 mm/sec.
• Polyolefin C was obtained by kneading 30% by mass of CaCO 3 and 5% by mass of TiO 2 as laser printing pigments into polyolefin A.
• Polyolefin D was obtained by kneading 5% by mass of TOMATEC COLOR 42-920A (main component Bi 2 O 3 , manufactured by Tokan Material Technology Co., Ltd.) as a laser pigment into polyolefin A.
• Polyester raw material As polyester A, RE553 (manufactured by Toyobo Co., Ltd.), which is homopolyethylene terephthalate, was used.
• polyester B As polyester B, SR173 (manufactured by Toyobo Co., Ltd.), which is a neopentyl glycol copolymer (copolymerization ratio: 30 mol %), was used.
• Polyester C Polyester C was obtained by kneading 50% by mass of TiO 2 into polyester A.
• Polyester D was prepared by kneading 5% by mass of TOMATEC COLOR 42-920A (main component Bi 2 O 3 , manufactured by Tokan Material Technology Co., Ltd.) as a laser pigment into polyester A.
• TOMATEC COLOR 42-920A main component Bi 2 O 3 , manufactured by Tokan Material Technology Co., Ltd.
• RE555 manufactured by Toyobo Co., Ltd.
• Table 1 shows the composition of each polyolefin raw material and polyester raw material.
• Example 1 Polyolefin A, polyolefin D, and polyolefin E were mixed at a mass ratio of 92:3:5 as the raw material for the A layer, and polyolefin B and polyolefin E were mixed at a mass ratio of 95:5 as the raw material for the B layer.
• the mixed raw materials for the A layer and the B layer were put into separate screw extruders, melted, and extruded through a T-die. Each molten resin was joined by a feed block in the middle of the flow path, discharged from a T-die, and taken off while being cooled on a chill roll whose surface temperature was set to 30° C. to obtain an unstretched laminated film.
• the discharge amount of the laminated film was adjusted so that the thickness ratio of the A layer and the B layer was 95/5.
• 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 preheated rolls until the film temperature reaches 125° C., and then stretched 3.8 times. did.
• the longitudinally stretched film was introduced into a lateral stretching machine (tenter), preheated for 8 seconds until the surface temperature reached 155° C., and then stretched 8.6 times in the width direction (horizontal direction). After the transverse stretching, the film was guided as it was to the intermediate zone and passed through for 1.0 second.
• the film was unwound from the resulting film roll and continuously folded in half using a folding machine so that the B layers overlapped with each other and the creases were along the machine direction.
• This half-folded film is guided to a fusion-cut sealing machine (manufactured by Kyoei Printing Machinery Materials Co., Ltd.: PP500 type), continuously fusion-cut and sealed along the width direction of the film, A4 size (flow direction 210 mm ⁇ width direction 300 mm)
• a package was created.
• the fusion cutting sealing conditions were a fusion cutting blade temperature of 400° C., a cutting edge angle of 60°, and a bag making speed of 120 bags/minute.
• a fiber laser with a wavelength of 1064 nm (Trotec Speedy 100 flexx laser marker 8028 by Trotec) was used for the resulting package at a pulse frequency of 30 kHz, a scan speed of 1500 mm / min, and an output of 80% to mark "12345ABCDE" in the center of the film. ” was printed to produce a display.
• the size of each character was about 8 mm high ⁇ about 5 mm wide. Table 2 shows the production conditions and the evaluation results of the produced laser-printed packages.
• Examples 2 to 4 In Examples 2 to 4, packages were produced in the same manner as in Example 1 with various conditions changed. Table 2 shows the manufacturing conditions with laser marking and the evaluation results in each example.
• a white ink layer was continuously coated with a gravure roll to form a laser-printed layer on one side of a polypropylene film Pylen Film (registered trademark) P5562-30 ⁇ m manufactured by Toyobo Co., Ltd. to obtain a laminate.
• the white ink layer was prepared by mixing methyl ethyl ketone, isopropyl alcohol, polyurethane and TiO 2 in a ratio of 11:3:38:48 mass %.
• the thickness of the laser-printed layer was 3 ⁇ m.
• a film having a thickness of 33 ⁇ m was continuously produced over a predetermined length by cutting off both edges of the laminate and winding it into a roll having a width of 600 mm.
• the film was unwound from the resulting film roll and continuously folded in half using a folding machine so that the TiO 2 -coated surfaces overlapped and the creases were along the flow direction.
• This half-folded film is guided to a fusion-cut sealing machine (manufactured by Kyoei Printing Machinery Materials Co., Ltd.: PP500 type), continuously fusion-cut and sealed along the width direction of the film, A4 size (flow direction 210 mm ⁇ width direction 297 mm)
• a package was produced.
• the fusion cutting sealing conditions were a fusion cutting blade temperature of 400° C., a cutting edge angle of 60°, and a bag making speed of 120 bags/minute.
• the resulting package was irradiated with a UV laser having a wavelength of 355 nm (laser marker MD-U1000C manufactured by Keyence Corporation) at a pulse frequency of 40 kHz, a scan speed of 2000 mm/min, and an output of 30%. printed.
• the size of each character was about 3 mm high ⁇ about 3 mm wide.
• Table 2 shows the production conditions and the evaluation results of the produced laser-printed packages.
• Comparative Example 2 A laminate coated with TiO 2 obtained in the same manner as in Comparative Example 1 was continuously folded in half using a folding machine so that the side opposite to the TiO 2 coated surface overlapped and the crease was along the flow direction. Then, in the same manner as in Comparative Example 1, fusion-cut sealing and laser marking were performed. Table 2 shows the production conditions and the evaluation results of the produced laser-printed packages.
• the evaluation method of the package is as follows. As a sample of the non-printed portion, a portion separated by 1 mm or more from the printed portion and the fusion-cut seal portion was cut out and used as a sample.
• a 6 ⁇ sample stand (the opening with which the measuring light hits is about 1 cm in diameter) and a 6 ⁇ viewing aperture were used as the measurement light source of the color difference meter, and the letter "B" was placed in the opening of the sample stand.
• the sample stage may be changed as necessary (for example, 10 ⁇ , 30 ⁇ , etc.). Even if the print protrudes, part of the print should enter the opening of the sample table and be exposed to the measurement light.
• the non-printed portion a 3 cm square sample was cut out from the non-printed portion, and the color L* value was measured using a color difference meter with a viewing aperture and a sample stage of 6 ⁇ .
• the aperture of the color difference meter and the sample stand may be changed to 10 ⁇ , 30 ⁇ , etc., if necessary, and in that case, the sample size should cover the opening of the sample stand (measurement light will not leak). It can be of any size.
• a tensile test was performed with a distance between chucks of 50 mm and a tensile speed of 200 mm/min, and the peel strength was measured when the fusion seal portion was broken.
• the maximum value of the peel strength was taken as the weld-cut seal strength, which was recorded as the strength per 15 mm sample width (N/15 mm), and the average value of ten samples was taken as the average weld-cut seal strength. If the length of the sample cannot be cut out with a length of 100 mm or more due to the limitation of the size of the package, the length of the sample may be less than 100 mm (for example, 50 mm).
• the chuck-to-chuck distance may be set to 50 mm or less (for example, when the sample length is 50 mm, the chuck-to-chuck distance is 40 mm).
• Print size Among the characters printed as "12345ABCDE", the height and width of "345ABC” are visually measured in increments of 0.5mm using a stainless steel straightedge (TZ-RS15 manufactured by Kokuyo Co., Ltd.) and the average value was used as the print size. When the print size was less than 0.5 mm, the print size was separately measured using a digital microscope RH-2000 manufactured by HIROX. Software attached to a digital microscope RH-2000 manufactured by HIROX was used to measure the print size.
• the laser-printed package of the present invention has a laser-printed portion that does not peel off, and a package formed by fusion sealing can be provided with high productivity and economic efficiency.

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• 2022
  • 2022-03-04 US US18/282,911 patent/US20240166414A1/en not_active Abandoned
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