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
  • 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
  • B32—LAYERED PRODUCTS
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  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • 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
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  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
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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
  • B32—LAYERED PRODUCTS
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  • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • 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
• • 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
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/20—Inorganic coating
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/20—Inorganic coating
  • B32B2255/205—Metallic coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2255/00—Coating on the layer surface
  • B32B2255/26—Polymeric coating
• • 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
  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/10—Inorganic particles
  • B32B2264/102—Oxide or hydroxide
• • 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
  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/10—Inorganic particles
  • B32B2264/102—Oxide or hydroxide
  • B32B2264/1022—Titania
• • 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
  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/10—Inorganic particles
  • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
• • 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
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/308—Heat stability
• • 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
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/31—Heat sealable
• • 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
  • B32B2307/402—Coloured
  • B32B2307/4023—Coloured on the layer surface, e.g. ink
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/402—Coloured
  • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/514—Oriented
  • B32B2307/518—Oriented bi-axially
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2307/00—Properties of the layers or laminate
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  • B32B2307/54—Yield strength; Tensile strength
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7244—Oxygen barrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2307/00—Properties of the layers or laminate
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  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7246—Water vapor barrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2307/00—Properties of the layers or laminate
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  • B32B2307/748—Releasability
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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  • 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
  • B32B2439/02—Open containers
  • B32B2439/06—Bags, sacks, sachets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2439/00—Containers; Receptacles
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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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  • B32B2439/00—Containers; Receptacles
  • B32B2439/80—Medical packaging

Definitions

• the present invention relates to a package printed by a laser.
• packaging made of plastic film has been widely 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, manufacturing date, raw materials, etc. (hereinafter, may be referred to as "printing").
• a package printed by a laser as described in Patent Document 1 has been disclosed. This expresses the laser printing function by applying (coating) an ink layer containing a color former (pigment) that reacts with a laser to a film as a base material.
• the laminating strength of the coated surface may be lowered by coating with a laser-printable pigment.
• the package is required to have a plurality of functions such as sealing strength and mechanical strength in addition to the above-mentioned display function, and therefore, a plurality of films are adopted accordingly.
• Lamination is widely used when laminating a plurality of films, and the use of a laser pigment may cause peeling (delamination) of the laminated portion.
• Patent Document 1 does not mention a method of ensuring the laminate strength when a laser pigment is used.
• Patent Document 2 is a technique relating to a package having a laser printing function by applying a laser pigment as in Patent Document 1, and here, the lamination strength of a printing layer (a layer containing a laser pigment) and a base material layer is provided. It is disclosed that laser printing performance and delamination suppression can be achieved at the same time by designing the laminate strength of the print layer and the sealant layer to be higher (for example, 3.8 N / 15 mm or more) than (1.8 to 3.5 N / 15 mm). Has been done. However, in general, lowering the laminate strength (intentionally) lowers the performance as a package, and there is a problem that it cannot be used in applications requiring high laminate strength.
• Patent Document 2 it is complicated to control the laminating strength between each layer as in Patent Document 2, and considering that a wide variety of quality items are required at a high level in recent packaging, the degree of freedom of the packaging is high. Was sometimes restricted. Further, in Patent Document 2, the content of the resin component in the white ink constituting the laser printing layer is low, 50% by weight or less, and if the amount of the resin component is larger than that, it is difficult to form a discolored region by laser light irradiation. Is disclosed. A small amount of resin component means a large amount of laser pigment and the like, which leads to an increase in cost.
• the region where the ink layer containing the laser pigment is formed is often limited to only a part of the package, not the entire package. This is because coating the entire package with the laser pigment leads not only to the above-mentioned delamination but also to a decrease in productivity and an increase in cost.
• coating only a part of the package with the laser pigment causes a new problem of impairing the design of the package. This is because titanium oxide and carbon black, which are widely used for laser pigments, are white or black, and therefore the color tone changes only in the portion coated with the laser pigment. That is, the current situation is that packaging using laser printing technology is not satisfied with quality, productivity / economy, and design.
• 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 laser-printed package made of a laminate having excellent lamination strength and visibility of a printed portion without using an ink containing a laser pigment.
• the present invention has the following configuration. 1. 1. It has at least one laser printing layer that can be printed by laser irradiation, and the laser printing layer is composed of a laminate having a laser-printed portion and a non-printing portion, and further having a seal layer. The package has the seal layer at least in the innermost layer, and at least a part of the seal layers of the innermost layer is adhered to each other. A package that meets the following requirements (1) to (3).
• the difference in color L * value between the laser-printed part and the non-printed part is 1.0 or more and 10 or less
• the adhesive strength between the seal layers is 2N / 15mm or more and 80N / 15mm or less
• the lamination strength with the layer adjacent to at least one side of the laser printing layer is 2N / 15mm or more and 10N / 15mm or less.
• the height or width of the print size in the laser-printed portion is 0.2 mm or more and 100 mm or less.
• the laser printing layer contains one or more simple substances or compounds selected from the group consisting of bismuth, gadolinium, neodymium, titanium, antimony, tin, aluminum, calcium, and barium as the laser printing pigment.
• the main resin constituting the laser printing layer is either polyester, polypropylene, or polyethylene.
• the content of the resin constituting the laser printing layer is more than 50% by mass and 99.95% by mass or less.
• the packaging described in either. 7 is further laminated with a base material layer. From 6.
• a gas barrier layer is further laminated on the laminated body. From 7.
• the thickness of the laser printing layer is 5 ⁇ m or more and 200 ⁇ m or less. From 8.
• the present invention it is possible to satisfy the laminate strength without complicating the design of the package, and further, it is possible to provide a package having high productivity, economy and design.
• the package of the present invention is composed of a laminated body, has at least one film layer (laser printing layer) that can be printed by laser irradiation, and the laser printing layer has a laser-printed portion printed by a laser.
• the non-printed portion must be present, and the seal layer must be at least in the innermost layer, and at least a part of the seal layers in the innermost layer must be adhered to each other. From the viewpoint that the present invention holds even if the design of the packaging material is simplified, it is a preferable form to have the laser printing layer in the entire region (in the plane direction) of the laminate constituting the packaging body.
• the package of the present invention may be provided with a printing layer on which characters and patterns other than the printing formed by the laser are described. The necessary or preferable requirements for these layers will be described later.
• the laminate may be abbreviated as "Lami”.
• “Lami” and “seal” are essentially the same “adhesive”, but in the present invention, when laminating each layer, “Lami” is used, and the package is sealed (the innermost layers of the laminated body are partially sealed). When (adhesive), it is described as “seal” to distinguish it.
• the package of the present invention may be further provided with an anchor coat layer laminated on the base material layer or the adhesive layer or an overcoat layer laminated on the gas barrier layer, if necessary.
• the thickness of the package is not particularly limited, but is preferably 5 ⁇ m or more and 500 ⁇ m or less. If the thickness of the package is thinner than 5 ⁇ m, the mechanical strength and heat seal strength may be insufficient, which is not preferable.
• the thickness of the package may be thicker than 500 ⁇ m, but this is not preferable because the cost of the material (film or lamination material) used increases accordingly.
• the thickness of the package is more preferably 10 ⁇ m or more and 495 ⁇ m or less, and further preferably 15 ⁇ m or more and 490 ⁇ m or less.
• the thickness of the print layer constituting the laminate of the present invention is preferably 3 ⁇ m or more and 190 ⁇ m or less. If this thickness is less than 3 ⁇ m, the visibility of laser printing may decrease even if the concentration of the laser printing pigment described later is increased. On the other hand, if the thickness of the printing layer exceeds 190 ⁇ m, the volume of the film that absorbs the laser becomes extremely large and the damage becomes large, which may cause deformation or perforation of the laminated body.
• the thickness of the printing layer is more preferably 10 ⁇ m or more and 180 ⁇ m or less, and further preferably 15 ⁇ m or more and 170 ⁇ m or less.
• Laser printing layer 1.2.1. Types of Laser Printing Pigments, Addition Amount, Addition Method
• a laser printing pigment having a discoloration function by laser irradiation. Since the plastics constituting the laminate usually hardly react 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 carbonizing action of plastics, some types of laser printing pigments themselves turn black. Printing on the printing layer becomes possible by the single or combined effect of this carbonization action and the discoloration action of the laser printing pigment. From the viewpoint of print density, it is preferable to select a laser printing pigment having both a carbonizing action of plastic and a discoloring action of itself.
• laser printing pigments include elemental substances or oxides of bismuth, gadolinium, neodymium, titanium, antimony, tin, aluminum, calcium, and barium.
• 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 printing pigment is preferably 0.1 ⁇ m or more and 10 ⁇ m or less. If the particle size of the laser printing pigment is less than 0.1 ⁇ m, the color change during laser irradiation may not be sufficient.
• the particle size of the laser printing pigment exceeds 10 ⁇ m, there is a concern that the filter may be clogged in the extrusion process when the film is formed.
• the particle size of the laser printing pigment is more preferably 1 ⁇ m or more and 9 ⁇ m or less, and further preferably 2 ⁇ m or more and 8 ⁇ m or less.
• the amount of the laser printing pigment added to the laser printing layer is preferably 0.05% by mass or more and 50% by mass or less. If the amount of the pigment added is less than 0.05% by mass, the printing density by the laser becomes insufficient, which is not preferable. On the other hand, if the amount of the pigment added exceeds 50% by mass, the amount (volume) of the carbonized plastic is relatively reduced, so that the print density may not be sufficient.
• the amount of the laser printing pigment added is more preferably 0.1% by mass or more and 49% by mass or less, further 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 particularly preferable to have it.
• the amount of the laser printing pigment added to the entire laser printing layer can be obtained by proportionally dividing the thickness ratio of each layer and the amount of the laser printing pigment added.
• a method of blending the laser printing pigment it can be added at any stage of manufacturing a resin as a raw material of the laser printing layer or a film to be the laser printing layer.
• a method of blending a slurry of particles dispersed in a solvent with a plastic raw material using a kneading extruder with a vent, or a kneading extruder of dried particles and a plastic resin is used in the stage of producing a resin.
• a method of blending master batching.
• a method of using a masterbatch containing a laser printing pigment as a raw material for a film is preferable.
• Types of Plastics The types of plastics that make up the laser-printed layer of the present invention are not particularly limited and can be freely used without departing from the spirit of the present invention.
• Examples of the type of plastic (resin) include polyester, polyolefin, polyamide and the like.
• polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBN), polylacticene (PLA), and polyethylene furano. Examples thereof include ate (PEF) and polybutylene succinate (PBS).
• 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, and 1,4-butanediol, hexanediol
• aliphatic diols, aromatic diols such as bisphenol A, and the like can be mentioned.
• a polyester elastomer containing ⁇ -caprolactone, tetramethylene glycol or the like may be contained.
• a 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 carboxylic acids 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.
• the ultimate viscosity (IV) of 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, so that problems such as breakage easily occur during film formation and the tensile breaking strength of the display body is less than 40 MPa are likely to occur. On the other hand, if IV exceeds 1.2 dL / g, the resin pressure in the extrusion process during film formation becomes too high, and filter deformation and the like are likely to occur, which is not preferable.
• polyolefin IV is more preferably 0.55 dL / g or more and 1.15 dL / g or less, and further preferably 0.6 dL / g or more and 1.1 dL / g or less.
• polyolefins 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 each of them may be contained in an arbitrary ratio.
• polyethylene its density (branching degree) is not particularly limited, and may be high density (HDPE), linear low density (LLDPE), or low density (LDPE).
• a raw material obtained by copolymerizing two or more kinds of dissimilar monomers may be used, and examples of the monomer used for the copolymerization include ethylene and ⁇ -olefin, and ⁇ -As olefins, propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 4-methyl-1-hexene. And so on.
• the form of copolymerization may be either random copolymerization or block copolymerization.
• polyolefin elastomers and ionomers may be used.
• 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, so that the resin pressure in the extrusion process during film formation becomes too high, and the filter is easily deformed, which is not preferable. On the other hand, if the MFR exceeds 10 g / 10 minutes, the molecular weight is extremely lowered, so that there is a possibility that fracture is likely to occur during film formation and the blocking resistance is lowered.
• the MFR is more preferably 2 g / 10 minutes or more and 8 g / 10 minutes, and further 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 / hexamethylene diammonide adipate copolymer (nylon 6).
• an adhesive modification layer can be provided on the surface of the above-mentioned plastic film.
• the material of the adhesive modification layer include acrylic, water-soluble or water-dispersible polyester, and hydrophobic polyester in which acrylic is graft-copolymerized.
• the relative viscosity (RV) of polyamide as a raw material is preferably 2.2 or more and 4 or less. If the RV is less than 2.2, the crystallization rate becomes too high, 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 the filter is easily deformed, which is not preferable.
• the RV is more preferably 2.3 or more and 3.9 or less, and further preferably 2.4 or more and 3.8 or less.
• the relative viscosity in the present invention means a value measured at 25 ° C. using a solution of 0.5 g of a polymer in 50 ml of 97.5% sulfuric acid.
• polyester, polypropylene, and polyethylene are preferable from the viewpoints of mechanical strength, film forming stability, and laser printing performance.
• the content of the plastic constituting the laser printing layer is preferably more than 50% by mass and 99.95% by mass or less. If the content of the plastic is less than 50% by mass, the tensile breaking strength described later may easily fall below 40 MPa, which is not preferable. Further, when the content of the plastic exceeds 99.95% by mass, the content of the laser printing pigment is relatively less than 0.05% by mass, and the color L * value of the printed portion and the non-printed portion This is not preferable because the difference tends to be less than 1.0.
• the content of the plastic is more preferably 51% by mass or more and 99.9% by mass or less, further preferably 52% by mass or more and 99.85% by mass, and particularly preferably 53% by mass or more and 99.8% by mass or less. preferable.
• the plastic content of the entire laser printing 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, and reductions are included as required.
• a viscous agent, 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. Any fine particles can be selected.
• examples of the inorganic fine particles include silica, alumina, kaolin, lead white, titanium white, zeolite, zinc flower, and lithopone
• examples of the organic fine particles include acrylic particles, melamine particles, silicone particles, and crosslinked particles. Examples thereof include polystyrene particles, carbon black, and iron oxide.
• 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 is preferably 0.01% by mass, more preferably 0.015% by mass, and further preferably 0.02% by mass. If it is less than 0.01% by mass, the slipperiness may decrease.
• the upper limit is preferably 1% by mass, more preferably 0.2% by mass, and even more preferably 0.1% by mass. If it exceeds 1% by mass, the smoothness of the surface is lowered and problems such as faint printability may occur, which is not preferable.
• the particles can be added at any stage in the production of the plastic raw material, and the above-mentioned "1.2.1. Types of laser printing pigments, addition amount, addition method". The same method can be adopted.
• the seal layer constituting the package of the present invention is not particularly limited as long as it has adhesiveness, and conventionally known ones can be arbitrarily used as long as the gist of the present invention is not deviated.
• a heat-sealing layer that develops adhesiveness by heat and an adhesive (tack) layer that has adhesiveness at room temperature can be mentioned.
• the type of plastic constituting the heat seal layer include polyester, polyolefin, polyamide and the like.
• polyesters examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBN), polylacticene (PLA), and polyethylene furano. Examples thereof include ate (PEF) and polybutylene succinate (PBS). Further, in addition to the polyesters mentioned in the above examples, modified polyesters in which the monomers of these acid or diol moieties are modified may be used.
• Examples of 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. Examples thereof 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.
• aliphatic diols aromatic diols such as bisphenol A, and the like can be mentioned.
• a polyester elastomer containing ⁇ -caprolactone, tetramethylene glycol or the like may be contained.
• 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 carboxylic acids 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.
• 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 each of them may be contained in an arbitrary ratio.
• polyethylene its density (branching degree) is not particularly limited, and may be high density (HDPE), linear low density (LLDPE), or low density (LDPE).
• a raw material obtained by copolymerizing two or more kinds of dissimilar monomers may be used, and examples of the monomer used for the copolymerization include ethylene and ⁇ -olefin, and ⁇ -As olefins, propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 4-methyl-1-hexene. And so on.
• the form of copolymerization may be either random copolymerization or block copolymerization.
• melt flow rate (MFR) of the 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, so that the resin pressure in the extrusion process during film formation becomes too high, and the filter is easily deformed, which is not preferable.
• the MFR is more preferably 2 g / 10 minutes or more and 8 g / 10 minutes, and further 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 / hexamethylene diammonide adipate copolymer (nylon 6).
• ethyleneammonium adipate / hexamethylene diammonium adipate / hexamethylene diammonium sevacate copolymer nylon 6/66/610
• polymer of metaxylylene diamine and adipic acid MXD-6
• hexamethylene examples thereof include one type of resin selected from an isophthalamide / terephthalamide copolymer (amorphous nylon), or a mixed raw material obtained by mixing two or more of these types.
• an adhesive modification layer can be provided on the surface of the above-mentioned plastic film.
• the material of the adhesive modification layer examples include acrylic, water-soluble or water-dispersible polyester, and hydrophobic polyester in which acrylic is graft-copolymerized.
• the lower limit of the relative viscosity (RV) of the polyamide as a raw material is preferably 2.2, more preferably 2.3. If it is less than the above, the crystallization rate may be too fast and biaxial stretching may be difficult.
• the upper limit of the RV of the polyamide is preferably 4, more preferably 3.9. If it exceeds the above, the load on the extruder becomes too high, and the productivity may decrease.
• the relative viscosity in the present invention means a value measured at 25 ° C. using a solution of 0.5 g of a polymer in 50 ml of 97.5% sulfuric acid.
• the type of plastic constituting the adhesive layer examples include polyester, polyolefin, polystyrene, acrylic resin and the like, and it is particularly preferable that the glass transition temperature Tg is lower than room temperature (around 25 ° C.).
• polyester it is preferable to use a saturated carboxylic acid component or a saturated diol component as a monomer capable of lowering Tg.
• saturated carboxylic acid include adipic acid, azelaic acid, sebacic acid, decandicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like. Among these, adipic acid and azelaic acid are preferable.
• Saturated diol components include long-chain diols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 2,2-diethyl-1,3-propanediol and 1,4-butanediol, and aliphatic diols such as hexanediol. Can be mentioned. Of these, diethylene glycol, 1,3-propanediol, and 1,4-butanediol are preferably used. Further, a polyester elastomer containing ⁇ -caprolactone, tetramethylene glycol, or the like may be used as a component constituting the polyester resin. The polyester elastomer can be preferably used because it has an effect of lowering Tg.
• polyolefin-based products include polyolefin-based elastomers.
• polyolefin-based elastomers include ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, and ethylene-4-methyl-1-.
• Penten copolymer ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer, ethylene-1-butene-1-hexene copolymer, propylene-1-butene copolymer, propylene -1-Hexene copolymer, propylene-1-octene copolymer, propylene-4-methyl-1-pentene copolymer, propylene-1-butene-1-hexene copolymer, propylene-1-butene-4 -Methyl-1-pentene copolymer and the like can be mentioned. Further, a small amount of styrene-based elastomer such as SBS and SEBS may be added thereto.
• SBS styrene-based elastomer
• polystyrene examples include polystyrene-based elastomers.
• examples of the polystyrene-based elastomer include a polymer obtained by block-copolymerizing an aromatic alkenyl compound and a conjugated diene, and examples of the aromatic alkenyl compound include styrene, tert-butyl styrene, ⁇ -methyl styrene, p-methyl styrene, and the like.
• Examples include p-ethylstyrene, divinylbenzene, 1,1-diphenylethylene, vinylnaphthalene, vinylanthracene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and vinylpyridine.
• conjugated diene monomer for example, 1,3-butadiene, 1,2-butadiene, isoprene, 2,3-dimethyl-butadiene, 1,3-pentadiene, 2-methyl-1,3-butadiene can be used.
• the acrylic resin may be a copolymer of an acrylic monomer, or a copolymer of an acrylic monomer and another copolymerizable monomer.
• the acrylic monomer include (meth) acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, isopropyl acrylate, n-butyl (meth) acrylic acid, and acrylic acid.
• Examples thereof include copolymers derived from the monomer of.
• Examples of copolymerizable monomers other than acrylic include maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like as monomers having at least one carboxyl group in a radically polymerizable unsaturated group. ..
• Examples of a monomer having at least one hydroxyl group in addition to the radically polymerizable unsaturated group 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydrokibutyl (meth) acrylate, and diethylene glycol mono Examples include (meth) acrylate.
• vinyl monomers copolymerizable with acrylic monomers for example, aromatic vinyl monomers such as styrene and ⁇ -styrene; trialkyloxysilyl group-containing vinyl monomers such as vinyl trimethoxysilane; acrylonitrile, methacrylylonitrile.
• aromatic vinyl monomers such as styrene and ⁇ -styrene
• trialkyloxysilyl group-containing vinyl monomers such as vinyl trimethoxysilane
• acrylonitrile methacrylylonitrile
• examples thereof include nitrile group-containing vinyl-based monomers such as bnitrile, acrylamide, methacrylicamide group-containing vinyl-based monomers, vinyl esters such as vinyl acetate and vinyl versaticate, and the like.
• plastics as raw materials, they can be arbitrarily used as a film formed by any of non-stretching, uniaxial stretching, and biaxial stretching, or as a coating agent dispersed in a solvent or the like.
• the film is formed as a film, it is preferably unstretched or uniaxially stretched, and more preferably non-stretched, in order to exhibit the sealing property.
• the print layer and the seal layer may be laminated via the adhesive layer described later, or the seal layer may be laminated in the extrusion process when the print layer is formed.
• the thickness of the seal layer constituting the laminate of the present invention is preferably 2 ⁇ m or more and 190 ⁇ m or less.
• the thickness of the seal layer is less than 2 ⁇ m, the heat seal strength of the laminated body is lowered, which is not preferable.
• the thickness of the seal layer exceeds 190 ⁇ m, the heat sealability of the laminated body is improved, but the thickness of the print layer is relatively reduced, which is not preferable because the visibility of printing is lowered.
• the thickness of the seal layer is more preferably 3 ⁇ m or more and 180 ⁇ m or less, and further preferably 4 ⁇ m or more and 170 ⁇ m or less.
• Laminating agent As a laminating agent that can be used when laminating each layer of the package of the present invention, an adhesive for dry laminating or a resin layer made by extrusion laminating can be used. Any known material can be adopted.
• the adhesive may be either a one-component type (drying type) or a two-component type (curing reaction type).
• dry laminating a commercially available polyurethane-based or polyester-based adhesive for dry lamination can be used. Typical examples are DIC Dick Dry (registered trademark) LX-703VL, DIC KR-90, Mitsui Chemicals Takenate (registered trademark) A-4, and Mitsui Chemicals Takerack (registered trademark) A-905.
• the laminating agent is applied to one of the films, and then the laminating agent dries or reacts and cures to complete the laminating.
• the thickness of the laminated layer after drying is preferably 1 ⁇ m or more and 6 ⁇ m or less, and more preferably 2 ⁇ m or more and 5 ⁇ m or less.
• the laminated strength tends to be less than 2N / 15 mm, which is not preferable.
• the thickness of the laminated layer after drying exceeds 6 ⁇ m, the drying time required for curing the laminating agent becomes long, and the productivity of the package is lowered, which is not preferable.
• Base material layer examples of the type of plastic constituting the base material layer that can be preferably contained in the package of the present invention include polyester, polyolefin, polyamide and the like.
• polyesters examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBN), polylacticene (PLA), and polyethylene furano. Examples thereof include ate (PEF) and polybutylene succinate (PBS). Further, in addition to the polyesters mentioned in the above examples, modified polyesters in which the monomers of these acid or diol moieties are modified may be used.
• Examples of 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. Examples thereof 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.
• aliphatic diols aromatic diols such as bisphenol A, and the like can be mentioned.
• a polyester elastomer containing ⁇ -caprolactone, tetramethylene glycol or the like may be contained.
• 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 carboxylic acids 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.
• 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 each of them may be contained in an arbitrary ratio.
• polyethylene its density (branching degree) is not particularly limited, and may be high density (HDPE), linear low density (LLDPE), or low density (LDPE).
• a raw material obtained by copolymerizing two or more kinds of dissimilar monomers may be used, and examples of the monomer used for the copolymerization include ethylene and ⁇ -olefin, and ⁇ -As olefins, propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 4-methyl-1-hexene. And so on.
• the form of copolymerization may be either random copolymerization or block copolymerization.
• melt flow rate (MFR) of the 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, so that the resin pressure in the extrusion process during film formation becomes too high, and the filter is easily deformed, which is not preferable.
• the MFR is more preferably 2 g / 10 minutes or more and 8 g / 10 minutes, and further 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 / hexamethylene diammonide adipate copolymer (nylon 6).
• ethyleneammonium adipate / hexamethylene diammonium adipate / hexamethylene diammonium sevacate copolymer nylon 6/66/610
• polymer of metaxylylene diamine and adipic acid MXD-6
• hexamethylene examples thereof include one type of resin selected from an isophthalamide / terephthalamide copolymer (amorphous nylon), or a mixed raw material obtained by mixing two or more of these types.
• an adhesive modification layer can be provided on the surface of the above-mentioned plastic film.
• the material of the adhesive modification layer examples include acrylic, water-soluble or water-dispersible polyester, and hydrophobic polyester in which acrylic is graft-copolymerized.
• the lower limit of the relative viscosity (RV) of the polyamide as a raw material is preferably 2.2, more preferably 2.3. If it is less than the above, the crystallization rate may be too fast and biaxial stretching may be difficult.
• the upper limit of the RV of the polyamide is preferably 4, more preferably 3.9. If it exceeds the above, the load on the extruder becomes too high, and the productivity may decrease.
• the relative viscosity in the present invention means a value measured at 25 ° C. using a solution of 0.5 g of a polymer in 50 ml of 97.5% sulfuric acid.
• plastics as raw materials, they can be arbitrarily used as a film formed by any of non-stretching, uniaxial stretching, and biaxial stretching, or as a coating agent dispersed in a solvent or the like.
• uniaxial stretching or biaxial stretching is preferable, and biaxial stretching is more preferable in order to develop mechanical strength.
• the print layer and the base material layer may be laminated via the adhesive layer described later, or the base material layer may be laminated in the extrusion step when the print layer is formed.
• the base material layer contains a lubricant in order to improve the slipperiness
• 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 slipperiness deteriorates, which is not preferable because not only the position shift or the like occurs when the laminated body is produced (bonded), but also the handleability is deteriorated when the laminated body is formed. On the other hand, if the lubricant concentration exceeds 2000 ppm, the transparency of the base material layer is lowered, which is not preferable.
• the lubricant concentration is more preferably 200 ppm or more and 1900 ppm or less, and further preferably 300 ppm or more and 1800 ppm or less.
• the base material layer 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 surface, and is within the range that does not deviate from the requirements of the present invention. Can be provided arbitrarily with.
• the package of the present invention may have a layer other than the above-mentioned laser printing layer and sealing layer. Taking the configuration described in "1.1. Layer structure and thickness" as an example, the base material layer, the gas barrier layer (transparent, opaque), and the printing layer will be described below.
• the gas barrier layer that can be arbitrarily laminated on the laminate of the present invention is preferably composed of an inorganic thin film containing a metal or a metal oxide as a main constituent. Further, in addition to the gas barrier made 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 on the inorganic thin film layer may be provided. By providing these layers, it is expected that the adhesion to the gas barrier layer will be improved, the gas barrier property will be improved, and the like.
• the raw material type of the gas barrier layer is not particularly limited, and conventionally known materials can be used, and can be appropriately selected according to the purpose in order 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.
• the 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) can be used alone (unit) or in combination (binary).
• the component of the inorganic compound is a binary product 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 excellent gas barrier property can always be obtained, which is preferable.
• 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.
• the thickness of the gas barrier layer that can be preferably used for the laminate of the present invention is preferably 2 nm or more and 100 nm or less when a metal or a metal oxide is vapor-deposited and used as the gas barrier layer.
• the thickness of the inorganic thin film layer is more preferably 5 nm or more and 97 nm or less, and further 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 property tends to decrease, 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 manufacturing cost increases, which is not preferable.
• the thickness of the inorganic thin film layer (metal leaf) 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 bonding aluminum foil or vapor deposition of aluminum.
• the thickness of the aluminum foil is preferably 1 ⁇ m or more and 100 ⁇ m or less.
• the gas barrier laminate provided in this way has a water vapor transmission rate of 0.05 [g / (m 2 ⁇ d)] or more and 4 [g / (m 2 ⁇ d)] in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH. d)]
• the following is preferable. 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 transmission rate 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.
• the gas barrier laminate has an oxygen permeability of 0.05 [cc / (m 2 ⁇ d ⁇ atm)] or more and 4 [cc / (m 2 ⁇ d ⁇ ) in an environment of a temperature of 23 ° C. and a relative humidity of 65% RH. atm)] or less is preferable.
• 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)].
• the gas barrier laminated body using the laminated body of the present invention (in this section, these are collectively referred to as "laminated body") has the above-mentioned gas barrier layer laminated, and has scratch resistance and further gas barrier property.
• An overcoat layer may be provided for the purpose of improvement or the like.
• 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 organic silicon and its hydrolyzate, 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.
• 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.
• Printing layer In addition to printing by laser irradiation, characters and patterns may be provided for the purpose of improving design. As the material constituting these characters and patterns, 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. In order to improve the design by using a plurality of colors for printing, it is preferable to have a printing layer composed of a plurality of layers. The print layer may be located on either the outermost layer or the intermediate layer.
• L * value difference the absolute value of the difference between the color L * values of the printed portion and the non-printed portion. Need to be. If this difference is less than 1.0, the color tones of the printed portion and the non-printed portion become close to each other, and it becomes difficult to visually recognize the print. On the other hand, if the difference in L * values exceeds 10.0, the print will be easier to see, but it will be necessary to increase the power of laser irradiation by that amount, and the damage to the package will increase, causing problems such as holes. It is not preferable because it is likely to occur.
• the difference between the L * values is more preferably 1.5 or more and 9.5 or less, and further preferably 2.0 or more and 9.0 or less.
• the package of the present invention needs to have a peel strength (hereinafter, sometimes referred to as seal strength) of the portion where the seal layers are adhered to be 2N / 15 mm or more and 80N / 15 mm or less. .. If the seal strength is less than 2N / 15 mm, the seal portion is easily peeled off, which is not preferable.
• the seal strength is more preferably 3N / 15 mm or more, and further preferably 4N / 15 mm or more. The greater the seal strength, the higher the sealing performance of the package, which is preferable. However, the upper limit that can be obtained at present is about 80 N / 15 mm. Even if the seal strength is 40 N / 15 mm, it can be said that it is sufficiently preferable in practical use.
• Laminate strength The package of the present invention needs to have a laminate strength of 2N / 15 mm or more and 10N / 15 mm or less between the laser-printed layer and the layer adjacent to one of the layers. If the laminate strength is less than 2N / 15 mm, not only delamination is likely to occur, but also the seal strength is likely to be less than 2N / 15 mm, which is not preferable. On the other hand, even if the laminate strength exceeds 10 N / 15 mm, the performance of the package is preferable, but the upper limit that can be obtained at present is about 10 N / 15 mm. Even if the laminate strength is about 4N / 15 mm, it can be said that it is sufficiently preferable in practical use.
• the difference in lamination strength between the lami layers when two or more lami layers are present, the difference in laminate strength).
• the one having the largest difference in laminate strength is preferably 1.5 N / 15 mm or less. If the difference in the laminating strength between the laminating layers exceeds 1.5 N / 15 mm, delamination is likely to occur in the laminating layer having the lowest laminating strength, which is not preferable. It is considered that when partial peeling (notch) occurs in the laminated layer having the lowest laminate strength, stress is concentrated there and delamination is likely to occur.
• the difference in laminate strength is more preferably 1 N / 15 mm or less, further preferably 0.5 N / 15 mm or less, and particularly preferably 0 N / 15 mm.
• the difference in the laminating strength between the laminated layers is 0N / 15 mm, the laminating strengths between the laminating layers are all the same, so that delamination is less likely to occur, which is preferable.
• the size of printing formed on the package of the present invention by a 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 * values tends to be less than 1.0, making it difficult to recognize printing. ..
• the print size exceeds 100 mm, it is preferable that the print is easily recognized, but if the print size is too large, the amount of information written on the package is reduced, which is not preferable.
• the print size is more preferably 0.5 mm or more and 90 mm or less, and further preferably 1 mm or more and 80 mm or less.
• Heat shrinkage rate In the package of the present invention, when any part where the innermost layers are not sealed is cut out and treated in hot air at 150 ° C. for 30 minutes, the heat in any at least one direction of the surface of the package is obtained.
• the shrinkage rate is preferably ⁇ 5% or more and 5% or less. If the heat shrinkage rate exceeds 5%, the package will not retain its original shape due to large deformation when placed in a high temperature environment such as hot water treatment such as boiling or retort or heating with a microwave oven. It is not preferable because it significantly impairs the design.
• the heat shrinkage rate of hot water is less than -5%, it means that the package is stretched, which is not preferable because it becomes difficult for the package to maintain its original shape as in the case of a high heat shrinkage rate.
• the heat shrinkage rate of the package is more preferably -4% or more and 4% or less, and further preferably -3% or more and 3% or less.
• Tensile breaking strength In the package of the present invention, when the tensile breaking strength is measured in any at least one direction of the flat surface of the package by cutting out arbitrary portions where the innermost layers are not sealed, this is preferably 40 MPa or more and 400 MPa. .. 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 breaking strength is more preferably 50 MPa, and even more preferably 60 MPa.
• 400 MPa is the upper limit. Even if the tensile breaking strength is 300 MPa, it is practically sufficient.
• the laser printing pigment is a metal, it usually has a higher specific density than the resin constituting the film.
• the supply of the raw materials tends to vary (segregation).
• a stirrer is installed in the pipe or hopper directly above the extruder, or a pipe (inner pipe) is inserted inside the hopper directly above the extruder filled with base resin to supply laser printing pigment. It is preferable to perform melt extrusion by taking measures such as installing a Jinkasa that cuts the grain pressure of the raw material in each raw material hopper.
• the laser printing layer is obtained by melting and extruding the raw materials supplied in the above "3.1.1. Mixing and supplying raw materials" from an extruder to form an unstretched film, which is obtained through a predetermined step shown below. be able to.
• the seal layer and the base material layer may be laminated together with the laser printing layer in the extrusion step, and each layer can be laminated at an arbitrary timing. It is preferable to adopt the co-extrusion method for laminating at the time of melt extrusion.
• a method for melt extrusion of the raw material resin a known method can be used, 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, and further using a dryer such as a hopper dryer or paddle dryer, or a vacuum dryer. It is preferable to dry until it becomes 80 ppm or less.
• the unstretched film can be obtained by quenching the resin melted by the extruder.
• any existing method such as a T-die method or a tubular method can be adopted.
• 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 mouthpiece onto a rotary drum and quenching and solidifying the molten resin to obtain a substantially unoriented resin sheet can be preferably adopted.
• the film to be the laser printing layer 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.
• uniaxial stretching is preferable, and biaxial stretching is more preferable.
• the base material layer is preferably uniaxially stretched, and more preferably biaxially stretched.
• the seal layer is preferably unstretched in order to develop the seal strength.
• the film may be 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 preheating temperature is set between the glass transition temperature Tg and the melting point Tm + 50 ° C., based on the Tg of the plastic constituting the film. If the preheating temperature is lower than Tg, it becomes difficult to stretch when stretching in the vertical direction, and breakage is likely to occur, which is not preferable.
• the film tends to adhere to the roll and the film easily wraps around, which is not preferable.
• Tg to Tm + 50 ° C. longitudinal stretching is performed.
• 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. It is preferable to set the longitudinal stretching ratio to 1.1 times or more because cavities appear in the printing layer.
• the upper limit of the longitudinal stretching ratio may be any number, but if the longitudinal stretching ratio is too high, fracture is likely to occur in the next transverse stretching, so it is preferably 10 times or less.
• the longitudinal stretching 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, the film is held by clips at both ends in the width direction (direction orthogonal to the longitudinal direction) in the tenter, and is 2 to 13 times at Tg to Tm + 50 ° C. It is preferable to perform transverse stretching at a stretching ratio of about. Preheating is preferably performed before stretching in the lateral direction, and the preheating is preferably performed until the surface temperature of the display material or the package becomes Tg to Tm + 50 ° C.
• the transverse stretching 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 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.
• the area magnification obtained by multiplying the magnifications of the longitudinal stretching and the transverse stretching is preferably 2.2 times or more and 64 times.
• 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. In this case, the temperature of the transverse stretching zone is not stable, so that the physical properties vary.
• 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.
• this intermediate zone 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.
• Heat treatment After passing through the intermediate zone, it is preferable to heat-treat at 100 to 280 ° C. 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 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 breaking strength tends to decrease, which is not preferable.
• the heat treatment temperature is more preferably 110 ° C. to 270 ° C., and even more preferably 120 ° C.
• 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%. Further, during the heat treatment, it is possible to reduce the distance between the clips in the longitudinal direction 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 50 ° 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.
• Laminate When manufacturing a laminate used for the packaging of the present invention, a laser printing layer, a seal layer, and other layers (if necessary, a gas barrier layer, an anchor coat layer, and an overcoat layer laminated on any of the layers are used. When laminating after separately forming a film by the method described in "3.1. Film manufacturing conditions" above, the laminating method is not particularly limited, as described in "1.4. Laminating agent”. Adjacent layers can be laminated with a conventionally known dry laminate or extrusion laminate using a laminating agent.
• a laminating agent is applied to one of the layers, the other layer is attached to the coated surface, and the solvent is volatilized by drying. There is a way to make it.
• the drying conditions differ depending on the laminating agent, but the laminating agent is cured by, for example, leaving it in an environment of 40 ° C. for 1 day or more.
• the method for forming the 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 and 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 laminate 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 laminate is set on a take-up roll and is taken up by a take-up roll via a coating drum.
• the pass line of the laminate (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 laminate passing through the coating drum. Will be done.
• the inorganic material is vapor-deposited, heat is applied to the laminate, and tension is also applied between the unwinding rolls and the winding rolls. If the temperature applied to the laminated body is too high, not only the thermal shrinkage of the laminated body becomes large, but also the softening progresses, so that elongation deformation due to tension is likely to occur.
• the temperature drop (cooling) of the laminate becomes large, the amount of shrinkage after expansion (different from heat shrinkage) becomes large, cracks occur in the gas barrier layer, and the desired gas barrier property is exhibited. It is not preferable because it becomes difficult.
• the lower the temperature applied to the laminated body the more the deformation of the laminated body is suppressed, which is preferable. Occurs.
• the temperature applied to the laminate 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 When the overcoat layer is formed, the laminate is conveyed to the coating equipment 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 laminate In the drying process, the laminate is heated and tension is also applied between the metal rolls. If the temperature at which the laminated body is heated in the drying step is too high, not only the thermal shrinkage of the laminated body becomes large, but also the softening progresses, so that elongation deformation due to tension is likely to occur, and cracks occur in the gas barrier layer of the laminated body. It will be easier. 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 laminate 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 shape and bag-making method of the packaged body of the present invention conventionally known techniques can be arbitrarily adopted.
• the shape of the package include a vertical pillow, a horizontal pillow, a three-way seal bag, a four-way seal bag, a gusset bag, a stick package, and a standing pouch.
• the innermost layers of the laminate can be sealed to form a bag.
• a sealing method a heat seal such as heat seal or impulse seal, or an adhesive such as hot melt may be used, and as long as the sealing strength between the innermost layers is within the specified range, the seal layers are adhered. It can be arbitrarily selected according to the performance.
• the types (wavelengths) of lasers that can be used for laser printing on the packaging of the present invention include, for example, CO2 laser (10600 nm), YAG laser (1064 nm), YVO4 laser (1064 nm), fiber laser (1064, 1090 nm), green laser (532 nm), UV laser (355 nm).
• the type of laser used for printing of the present invention is not particularly limited, but the CO2 laser is often used for burning off plastic, and is used for a purpose different from the printing which is the purpose of the present invention. It is not preferable as a laser source because it is often used.
• a YAG laser, a YVO4 laser, a fiber laser, a green laser, and a UV laser are preferable as a laser source, and a YAG laser, a fiber laser, and a UV laser are more preferable.
• Commercially available equipment can be used for laser printing, as typical examples: Brother Industrial Printing LM-2550 (YAG laser), OMRON MX-Z2000H-V1 (fiber laser), Trotec 8028 Trotec Speedy 100 flexx. (Fiber laser), MD-X1000 (YVO4 laser) manufactured by Keyence, MD-U1000C (UV laser) and the like.
• KEYENCE MD-U1000C UV laser, wavelength 355 nm
• the laser power is preferably 20% or more and 80% or less with respect to the maximum device specification of 13 W. 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, holes are generated in the display body, which is not preferable. The output is more preferably 25% or more and 75% or less, and further 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 lower 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 tends to be 80 vol% or less, but it may be difficult to make the difference between 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 further 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 is extremely lowered, which is not preferable because the production speed of the display body is slowed down.
• the scan speed is more preferably 100 mm / sec or more and 2900 mm / or less, and further preferably 200 mm / sec or more and 2800 mm / or less.
• polyester raw material As polyester A, RE553 manufactured by Toyobo Co., Ltd. was used.
• polyester B As the polyester B, 50% by mass of TiO2 was kneaded into the polyester A to obtain a polyester B.
• polyester C As polyester C, laser pigment "TOMATEC COLOR42-920A (main component Bi 2 O 3 )" (manufactured by Tokan Material Technology Co., Ltd.) is mixed (dry blended) with polyester A at a mass ratio of 95: 5 and used in a screw extruder. It was charged and heated at 275 ° C. to melt and mix.
• polyester D As the polyester D, RE555 manufactured by Toyobo Co., Ltd. (a master batch in which 7000 ppm of SiO2 was kneaded) was used. Table 1 shows the compositions of each polyolefin raw material and polyester raw material.
• Polyolefin A, polyolefin C, and polyolefin D were mixed as raw materials for the layer A at a mass ratio of 40:50:10, and polyolefin A, polyolefin B, and polyolefin C were mixed as raw materials for the layer B at a mass ratio of 10:70:20.
• the mixed raw materials of the A layer and the B layer were put into separate screw extruders, melted, and extruded from the T die at a shear rate of 1000 sec-1.
• Each molten resin is joined by a feed block in the middle of the flow path, discharged from a T-die, and taken up at a draft ratio of 1.2 while being cooled on a chill roll set at a surface temperature of 30 ° C. to form an unstretched laminated film. Obtained.
• 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 was led to a longitudinal stretching machine in which a plurality of roll groups were continuously arranged, preheated on preheating rolls until the film temperature reached 125 ° C., and then stretched four times.
• the film after the longitudinal stretching was guided to a transverse stretching machine (tenter), preheated for 8 seconds until the surface temperature reached 160 ° C., and then stretched 9.8 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 film that passed through the intermediate zone was led to the heat treatment zone and heat-treated at 165 ° C. for 9 seconds.
• the heat treatment was performed and at the same time, the clip interval in the film width direction was narrowed to perform a 3% relaxation treatment in the width direction.
• the film was cooled with cooling air at 30 ° C. for 5 seconds.
• the films 5 and 6 are non-stretched polypropylene film Pyrene film CT (registered trademark) P1128-30 ⁇ m manufactured by Toyo Boseki Co., Ltd.
• the film 6 is a non-stretched linear low-density polyethylene film manufactured by Toyo Boseki Co., Ltd.
• Example 1 A urethane-based two-component curable adhesive (Mitsui Chemicals'"Takelac (registered trademark) A525S” and “Takenate (registered trademark) A50" are mixed at a weight ratio of 13.5: 1) on the film 1.
• a laminate was obtained by laminating the film 5 with the film 5 and aging at 40 ° C. for 4 days by the dry laminating method. At this time, the thickness of the adhesive layer was 3 ⁇ m.
• This laminated body is cut into a size of 15 cm square, two sheets are laminated so that the film 5 to be a sealant is on the inside, and the three sides of the laminated body are adhered by heat sealing to prepare a bag having an inner size of 13 cm. did.
• the heat sealing conditions at this time were a temperature of 140 ° C., a pressure of 0.2 MPa, a time of 1 second, and a sealing width of 1.0 cm.
• the obtained bag was printed with "12345 ABCDE" in the center of the film at a pulse frequency of 40 kHz, a scan speed of 2000 mm / min, and an output of 30% using a UV laser with a wavelength of 355 nm (laser marker MD-U1000C manufactured by KEYENCE). did.
• the size of each character was about 5 mm in height ⁇ about 3 mm in width.
• Table 3 shows the layer structure of the obtained package and the evaluation results of physical properties.
• Example 2 Aluminum was used as a vapor deposition source on one side of the film 7, and an aluminum oxide (Al 2 O 3 ) thin film was formed as a gas barrier layer 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. The gas barrier layer side of the film 7 and the film 1 were bonded together in the same manner as in Example 1. A film 6 was further bonded to the film 1 side of the bonded film in the same manner as described above to prepare a laminated body.
• Al 2 O 3 aluminum oxide
• This laminate was heat-sealed on three sides in the same manner as in Example 1 to prepare a bag, and a fiber laser having a wavelength of 1064 nm (Laser marker 8028 Trotec Speedy 100 flexx manufactured by Trotec) was used to generate a pulse frequency of 30 kHz.
• a display body was produced by printing "12345 ABCDE" in the center of the film at a scan speed of 1500 mm / min and an output of 80%. The size of each character was about 8 mm in height ⁇ about 5 mm in width.
• Table 3 shows the layer structure of the obtained package and the evaluation results of physical properties.
• Example 3 to 6 and Comparative Examples 1 and 2 the display body was prepared by changing the type of film used, the laser source, and the irradiation conditions in the same manner as in Examples 1 and 2. Keyence's laser marker MD-U1000C was used for all UV lasers, and Trotec's laser marker 8028 Trotec Speedy 100 flexx was used for all fiber lasers. In Comparative Example 2, only the laser printing layer (film 1) was used as a single substance, and heat sealing was not performed. Therefore, one film was used for laser printing. Table 3 shows the layer structure of the obtained package and the evaluation results of physical properties.
• a laser printing layer was formed by coating a white ink layer with a gravure roll on one surface of the film 8.
• the white ink layer was prepared by mixing methyl ethyl ketone, isopropyl alcohol, polyurethane, and titanium oxide in a ratio of 11: 3: 38: 48% by mass.
• the thickness of the laser printing layer was 3 ⁇ m.
• the laser printing layer (white ink layer) formed on the film 8 and the film 5 were bonded together in the same manner as in Example 1 and heat-sealed on three sides to obtain a package.
• a print was formed by irradiating this package with a laser in the same manner as in Example 1.
• Table 3 shows the layer structure of the obtained package and the evaluation results of physical properties.
• the evaluation method of the laminated body is as follows. As the sample of the non-printed portion, a portion separated by 1 mm or more from the printed portion and the sealed portion was cut out and used as a sample. [Thickness] Five points were measured using a micrometer (Millitron 1254D manufactured by Fine Eck), and the average value was calculated.
• a 6 ⁇ sample table (the opening exposed to the measurement light has a diameter of about 1 cm) and a 6 ⁇ opening were used as the measurement light source of the color difference meter, and the letter “B” was inserted in the opening of the sample table.
• the sample table may be changed as necessary (for example, 10 ⁇ , 30 ⁇ , etc.). Even if the print protrudes, it is sufficient that a part of the print enters the opening of the sample table and is exposed to the measurement light.
• the non-printed portion a sample of 3 cm square was cut out from the non-printed portion, and the color L * value was measured using a 6 ⁇ sample as the opening of the color difference meter and the sample stand.
• the opening of the color difference meter and the sample table may be changed to 10 ⁇ , 30 ⁇ , etc. as necessary, and the sample size in that case should cover the opening of the sample table (measurement light does not leak). It can be of any size.
• the adhesive sample has the width direction of the sealed portion (the direction of 1 cm in the heat seal of the package) as the tensile direction, the length of the two bonded laminated bodies is 60 mm or more, and the direction perpendicular to the tensile direction (sample at the time of the tensile test). It was cut out so that the width) was 15 mm.
• the seal strength of this sample was measured by a universal tensile tester "Autograph AG-Xplus" (manufactured by Shimadzu Corporation) at a distance between chucks of 50 mm and a tensile speed of 200 mm / min.
• the peel strength is indicated by the strength per 15 mm (N / 15 mm). If the sample length cannot be cut out at 60 mm or more due to the limitation of the package size, the length may be shorter than that (for example, 20 mm). In this case, if the chuck on one side is provided with at least a length of 5 mm or more for gripping the sample, the inter-chuck distance may be 50 mm or less (for example, when the sample length is 20 mm, the inter-chuck distance is 10 mm).
• Laminate strength A sample is cut out from the laser-printed and unsealed part of the package to a width of 15 mm and a length of 200 mm to make a test piece, which is a universal tensile tester under the conditions of a temperature of 23 ° C. and a relative humidity of 65%.
• the laminate strength was measured using "Autograph AG-Xplus” (manufactured by Shimadzu Corporation). When measuring the laminate strength, the tensile speed was 200 mm / min and the peeling angle was 90 degrees.
• Total light transmittance (non-printed part) In accordance with JIS-K-7136, the total light transmittance of the non-printed portion was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., 300A). The measurement was performed twice, and the average value was calculated.
• the water vapor transmission rate was measured according to the JIS K7126 B method. Using a water vapor transmission rate measuring device (PERMATRAN-W3 / 33MG MOCON), humidity control gas permeates from the heat seal layer side of the laminate to the inorganic thin film layer side in an atmosphere of temperature 40 ° C. and humidity 90% RH. The water vapor transmission rate was measured in the direction of 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 JIS K7126-2 method. Oxygen permeates from the heat seal layer side of the laminate to the inorganic thin film layer side in an atmosphere of a temperature of 23 degrees and a humidity of 65% RH using an oxygen permeation measuring device (OX-TRAN 2/20 MOCOM). Oxygen permeability was measured in the direction. Before the measurement, the sample was left for 4 hours in a humidity of 65% RH environment to control the humidity.
• the present invention is excellent in laminate strength and visibility of the laser printed portion without using ink containing a laser pigment. Therefore, it is possible to provide a highly productive, economical and well-designed package without complicating the design of the package.

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• 2022
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