WO2023243607A1 - Corps multicouche, son procédé de production et sac d'emballage - Google Patents

Corps multicouche, son procédé de production et sac d'emballage Download PDF

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Publication number
WO2023243607A1
WO2023243607A1 PCT/JP2023/021759 JP2023021759W WO2023243607A1 WO 2023243607 A1 WO2023243607 A1 WO 2023243607A1 JP 2023021759 W JP2023021759 W JP 2023021759W WO 2023243607 A1 WO2023243607 A1 WO 2023243607A1
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Prior art keywords
layer
adhesive
laminate
solvent
laminate according
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PCT/JP2023/021759
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English (en)
Japanese (ja)
Inventor
亮太 田中
吏里 北原
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Ｔｏｐｐａｎホールディングス株式会社
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Priority claimed from JP2022097246A external-priority patent/JP2023183634A/ja
Priority claimed from JP2022097244A external-priority patent/JP2023183632A/ja
Priority claimed from JP2022097245A external-priority patent/JP2023183633A/ja
Application filed by Ｔｏｐｐａｎホールディングス株式会社 filed Critical Ｔｏｐｐａｎホールディングス株式会社
Publication of WO2023243607A1 publication Critical patent/WO2023243607A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • B65D29/00—Sacks or like containers made of fabrics; Flexible containers of open-work, e.g. net-like construction
    • 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

Definitions

  • the present disclosure relates to a laminate, a method for manufacturing the same, and a packaging bag. More specifically, the present disclosure relates to a laminate with excellent material recyclability and low environmental impact, a method for manufacturing the same, and a packaging bag.
  • Packaging bags are made of various materials, depending on the nature of the contents to be packaged, the amount of contents, post-treatment to prevent deterioration of the contents, the form in which the packaging bags are transported, the method of opening the packaging bags, the method of disposal, etc. are used in combination.
  • biaxially stretched films such as polypropylene and polyester are used to obtain the mechanical strength of the packaging bags, and polyethylene and polyester are used to seal the contents as packaging bags. It is used in combination with polypropylene, ethylene vinyl acetate copolymer, etc. as the heat seal material. Additionally, in order to suppress the deterioration of the contents, aluminum foil or ethylene vinyl alcohol copolymer is laminated.
  • packaging materials are considered to be highly recyclable if their main resin content is 90% by mass or more, but many conventional packaging materials contain multiple resin materials and, in some cases, paper and metal materials. Currently, it is not recycled because it does not meet this standard.
  • Patent Document 1 describes that in a laminate including a base material, an adhesive layer, and a heat seal layer, the base material and the heat seal layer are made of polyethylene. By configuring the base material and the heat-sealing layer from the same material, it becomes easier to meet the above-mentioned recyclability criteria. Moreover, Patent Document 1 proposes using a stretched polyethylene film as a base material, and describes that printability can be improved thereby.
  • the base layer tends to be thermally deformed during the laminate manufacturing process that involves heat drying due to the material's soft and easily heat-sealable properties.
  • the base material layer is thermally deformed, the dimensions of the pattern printed on the base material layer expand and contract, resulting in problems such as poor appearance and misalignment of the eye marks, making it impossible to make bags.
  • problems may also occur when a polypropylene film or the like is used as the base layer.
  • the present disclosure has been made in view of the problems of the prior art described above, and provides a laminate with good dimensional stability of printed patterns and lamination strength, a method for manufacturing the same, and a packaging bag using the laminate.
  • the primary purpose is to provide.
  • the packaging bag formed using the laminate is filled with various contents such as an acidic component, a fragrance component, an oil component, and an alcohol component. Even when these contents are filled, it is required that delamination (separation between layers) does not occur in the laminate forming the packaging bag.
  • the present disclosure has been made in view of the problems of the prior art described above, and provides a laminate having good dimensional stability of printed patterns and good resistance to contents, a method for manufacturing the same, and a packaging bag using the laminate.
  • the second purpose is to provide
  • the present disclosure provides the following laminate, method for manufacturing the same, and packaging bag.
  • the laminate, the method for producing the same, and the packaging bag using the laminate described in [1] to [16] below are the first aspect of the present disclosure for achieving the first object.
  • the laminate, the method for manufacturing the same, and the packaging bag using the laminate described in [17] to [23] below are the second aspect of the present disclosure for achieving the second object.
  • [1] It has a structure in which a base material layer, a printing layer, a first adhesive layer, and a sealant layer are laminated in this order, and the base material layer is composed of an unstretched polyethylene film.
  • the base layer contains high-density polyethylene or medium-density polyethylene.
  • the sealant layer contains low-density polyethylene.
  • the base material layer described in any one of [1] to [3] above stretches by 3% or more in the tensile direction when pulled under a tension of 100 N/m in a temperature environment of 70°C. laminate.
  • the solvent-free adhesive is a two-part curable urethane adhesive.
  • the solvent-free adhesive is a urethane adhesive containing adipic acid and isophthalic acid.
  • the second adhesive layer is a gas barrier adhesive layer formed using a gas barrier adhesive.
  • It has a structure in which a base material layer, a printing layer, a first adhesive layer, a barrier layer, and a sealant layer are laminated in this order, and the base material layer and the sealant layer are laminated in this order.
  • the barrier layer includes an inorganic oxide layer, and the inorganic oxide layer contains a metal oxide.
  • the barrier layer includes a gas barrier coating layer.
  • the above [17] to [19] comprising an intermediate layer between the first adhesive layer and the sealant layer, and a second adhesive layer between the intermediate layer and the sealant layer.
  • the laminate according to any one of the above. [21] The laminate according to [20] above, wherein the second adhesive layer is a layer formed using a solvent-based adhesive.
  • the second adhesive layer is a gas barrier adhesive layer formed using a gas barrier adhesive.
  • the solvent-free adhesive is a two-part curable urethane adhesive.
  • a method for producing a laminate according to any one of [1] to [23] above which comprises forming the printed layer on the base layer by a printing method using ink to form a printed base material.
  • a method for producing a laminate the method comprising: a printing step to obtain a laminate; and a bonding step of bonding the printing base material and a laminate film including the sealant layer or the sealant layer using the solvent-free adhesive.
  • a method for manufacturing a laminate comprising: [27] A method for producing a laminate according to any one of [17] to [23] above, which comprises forming the printing layer on the substrate layer by a printing method using ink to form a printing substrate.
  • a method for manufacturing a laminate the method comprising: a printing step to obtain a laminate; and a bonding step of bonding the printing substrate and a laminate film including the barrier layer and the sealant layer using the solvent-free adhesive.
  • the first aspect of the present disclosure it is possible to provide a laminate with good dimensional stability of a printed pattern and good lamination strength, a method for manufacturing the same, and a packaging bag using the laminate.
  • the second aspect of the present disclosure it is possible to provide a laminate with good dimensional stability of printed patterns and good content resistance, a method for manufacturing the same, and a packaging bag using the laminate.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a laminate of the present disclosure.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a laminate of the present disclosure.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a laminate of the present disclosure.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a laminate of the present disclosure.
  • the laminate according to the present embodiment has a structure in which a base material layer, a printing layer, a first adhesive layer, and a sealant layer are laminated in this order, and the base material layer is an unstretched polyethylene film.
  • the first adhesive layer is a layer formed using a solvent-free adhesive, and the proportion of polyethylene in the laminate is 90% by mass or more.
  • the first adhesive layer is formed using a solvent-free adhesive, it is possible to form the first adhesive layer using a solvent-based adhesive.
  • Heat drying for removing the solvent is not performed, and there is no residual solvent in the first adhesive layer. Therefore, even when an unstretched polyethylene film is used as the base layer, expansion and contraction of the base layer can be suppressed, and good dimensional stability of the printed pattern can be obtained.
  • there is no residual solvent in the first adhesive layer after being made into a packaging bag, the contents are prevented from deteriorating due to solvent, odor is not transferred to the contents, and in the case of food, the flavor is not impaired.
  • the laminate having the above structure has excellent flexibility and can obtain good compressive strength.
  • the laminate according to this embodiment has a structure in which a base layer, a printing layer, a first adhesive layer, an intermediate layer, a second adhesive layer, and a sealant layer are laminated in this order.
  • the base layer, the intermediate layer, and the sealant layer are all made of unstretched polyethylene film
  • the first adhesive layer is a layer formed using a solvent-free adhesive
  • the laminate It may be a laminate in which the proportion of polyethylene is 90% by mass or more. According to the above laminate, by using an unstretched polyethylene film as the base layer, the adhesion between the base layer and the intermediate layer is improved compared to when a stretched polyethylene film is used, and good laminate strength is achieved. is obtained.
  • the laminate having the above structure has excellent flexibility and can obtain good compressive strength.
  • FIGS. 1, 2, 3, and 4 are schematic cross-sectional views each showing an embodiment of a laminate according to the first aspect of the present disclosure.
  • the laminate 1 shown in FIG. 1 includes a base layer 10, a print layer 12, a first adhesive layer 40, and a sealant layer 30.
  • the laminate 2 shown in FIG. 2 includes a base layer 10, a printed layer 12, a first adhesive layer 40, an intermediate layer 20, a second adhesive layer 50, and a sealant layer 30.
  • the laminate 3 shown in FIG. 3 includes a base material layer 10, a printed layer 12, a first adhesive layer 40, an intermediate layer 20, an anchor coat layer 13, an inorganic oxide layer 14, and a second adhesive layer 12. It includes an adhesive layer 50 and a sealant layer 30.
  • the base layer 10 includes a base layer 10, a printed layer 12, a first adhesive layer 40, an intermediate layer 20, an anchor coat layer 13, an inorganic oxide layer 14, and a gas barrier coating. layer 15, a second adhesive layer 50, and a sealant layer 30.
  • the base material layer 10 is composed of an unstretched polyethylene film.
  • the first adhesive layer 40 is a layer formed using a solvent-free adhesive. Further, the proportion of polyethylene in the laminate is 90% by mass or more.
  • both the intermediate layer 20 and the sealant layer 30 may be made of unstretched polyethylene film. Each layer will be explained below.
  • the base layer 10 is a layer made of an unstretched polyethylene film.
  • the base material layer 10 is a portion that becomes the outer surface when a packaging bag is formed using the laminates 1, 2, 3, and 4.
  • the base layer 10 is a film made of high density polyethylene (density 0.94 g/cm 3 or more) or medium density polyethylene (density 0.925 to 0.945 g/cm 3 ). can be used. These materials may be derived from petroleum or plants, or may be a mixture thereof. Further, the surface of the base material layer 10 can be subjected to adhesion-facilitating treatment by dry surface treatment such as corona treatment or atmospheric pressure plasma treatment. Furthermore, it is also possible to use as the base layer 10 a multilayered unstretched polyethylene film obtained by extruding polyethylenes having different densities by a coextrusion method.
  • unstretched polyethylene film is a film that is not stretched during film formation, and has spherical crystals (spherulites) of about 10 to 100 ⁇ m composed of randomly folded polyethylene molecular chains, which are non-crystalline molecules.
  • An unstretched polyethylene film has the property that when it receives a strong impact, the spherulites are destroyed and the molecular chains are oriented and stretched, thereby preventing the film itself from tearing. Therefore, packaging made of a laminate in which unstretched polyethylene films are laminated as the base layer 10 and sealant layer 30, or a laminate in which unstretched polyethylene films are laminated as the base layer 10, intermediate layer 20, and sealant layer 30.
  • the body (a packaging bag made, filled with contents and sealed) is characterized by excellent drop bag strength.
  • the thickness of the base material layer 10 is preferably 10 ⁇ m or more and 50 ⁇ m or less, more preferably 12 ⁇ m or more and 35 ⁇ m or less. By setting the thickness of the base material layer 10 to 10 ⁇ m or more, the strength of the laminates 1, 2, 3, and 4 can be improved. By setting the thickness of the base material layer 10 to 50 ⁇ m or less, the processability of the laminates 1, 2, 3, and 4 can be improved.
  • the base material layer 10 can be produced by forming polyethylene into a film by a T-die method, an inflation method, or the like.
  • the melt flow rate (MFR) of polyethylene is preferably 3 g/10 minutes or more and 20 g/10 minutes or less.
  • MFR melt flow rate
  • the MFR of polyethylene is preferably 0.5 g/10 minutes or more and 5 g/10 minutes or less.
  • the processability of the laminate can be improved.
  • the MFR is set to 5 g/10 minutes or less, film formability can be improved.
  • the melting points of high-density polyethylene and medium-density polyethylene used as the base material layer 10 are approximately 120°C to 140°C.
  • the melting point of low density polyethylene used as the sealant layer 30 described below is approximately 90°C to 120°C.
  • a heat seal bar which is a jig of a heat sealing machine, is heated to about 130°C to 140°C, and the base material layer 10 and the intermediate layer to be described later are Heat is conducted to the sealant layer 30 through the sealant layer 20, and the sealant layer 30 is thermally welded.
  • the base material layer 10 elongates by 3% or more in the tensile direction when it is pulled under a tension of 100 N/m in a temperature environment of 70°C. Since the base layer 10 is composed of an unstretched polyethylene film, it can have an elongation rate of 3% or more when stretched under the above conditions.
  • the base material layer having the above elongation rate has excellent adhesion to the sealant layer 30 or the intermediate layer 20, compared to a base material layer composed of a stretched polyethylene film having an elongation rate of less than 3%.
  • the elongation rate of the base material layer 10 is preferably 3% or more, but may be 4% or more, or 4.5% or more. Moreover, the elongation rate of the base material layer 10 may be 10% or less, or 8% or less.
  • the elongation rate of the base material layer 10 can be measured using, for example, a thermal analyzer.
  • the printed layer 12 is formed on the surface of the base layer 10 on the first adhesive layer 40 side.
  • the pattern can be formed by any printing method such as ordinary gravure printing or flexographic printing, using ink suitable for each printing method, without any particular limitation. Inks include solvent-based inks and water-based inks, and from an environmental standpoint, it is preferable to use water-based inks. Further, the surface of the base layer 10 may be subjected to surface treatment such as corona treatment or plasma treatment in order to improve the adhesion of the printed layer 12.
  • the first adhesive layer 40 is a layer formed using a solvent-free adhesive, and is provided between the base layer 10 and the sealant layer 30 or the intermediate layer 20 to bond them together.
  • a solvent-free adhesive either a one-component curing type or a two-component curing type adhesive can be used.
  • solvent-free adhesives include urethane adhesives, epoxy adhesives, silicone adhesives, etc. From the viewpoint of impact resistance, urethane adhesives are preferred, and two-component curing urethane adhesives are preferred. Particularly preferred are agents.
  • the two-component curable urethane-based solvent-free adhesive includes a polyol component as a main ingredient and a polyisocyanate component as a curing agent.
  • the polyol component may be one type or a mixture of two or more types selected from the group consisting of polyester polyol, polyether polyol, polyether ester polyol, and polyurethane polyol.
  • the polyester polyol may be, for example, an ester reaction product of a polycarboxylic acid, a dialkyl ester of a polycarboxylic acid, or a mixture thereof, and a glycol solvent.
  • the polycarboxylic acid may be, for example, succinic acid, glutaric acid, isophthalic acid, terephthalic acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid.
  • the glycol solvent may be, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol.
  • the polyether polyol may be, for example, a polymer of an oxirane compound and a low-molecular polyol.
  • the oxirane compound may be, for example, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran.
  • the low molecular weight polyol may be water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin.
  • the polyether ester polyol may be obtained, for example, by reacting a polycarboxylic acid, a dialkyl ester of a polycarboxylic acid, or a mixture thereof with a polyether polyol.
  • the polyurethane polyol may be, for example, a reaction product of a polyester polyol, a polyether polyol, a polyether ester polyol, and a polyisocyanate monomer.
  • the polyisocyanate component may be an aliphatic polyisocyanate, an aromatic polyisocyanate, or a mixture thereof.
  • the aliphatic polyisocyanate may be, for example, a polyisocyanate monomer, a polyisocyanate derivative, or a polyisocyanate-terminated prepolymer.
  • the polyisocyanate monomer may be, for example, tetramethylene diisocyanate, isopropylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate.
  • the polyisocyanate derivative may be 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, lysine diisocyanate, isophorone diisocyanate.
  • the aromatic polyisocyanate may be, for example, a polyisocyanate monomer, a polyisocyanate derivative, or a polyisocyanate-terminated prepolymer.
  • the polyisocyanate monomer may be, for example, tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate.
  • the polyisocyanate derivative may be, for example, an isocyanurate derived from a polyisocyanate monomer.
  • the polyisocyanate-terminated prepolymer may be a difunctional polyisocyanate containing terminal isocyanate groups obtained by reacting a polyisocyanate monomer with a difunctional polyol compound such as polypropylene glycol. Further, the polyisocyanate-terminated prepolymer may be a polyfunctional polyisocyanate containing terminal isocyanate groups obtained by reacting a polyisocyanate monomer with a trifunctional or higher functional polyol compound such as trimethylolpropane.
  • the solvent-free adhesive is preferably a urethane adhesive containing adipic acid and isophthalic acid from the viewpoint of further improving lamination strength. Furthermore, when a urethane adhesive containing adipic acid and isophthalic acid is used, it is possible to improve resistance to heat sterilization treatments such as boiling treatment and retort treatment, and to suppress a decrease in laminate strength due to heat sterilization treatment. Can be done.
  • the solvent-free adhesive does not need to contain glycidoxyalkylalkoxysilane.
  • glycidoxyalkylalkoxysilane examples include 3-glycidyloxypropyltrimethoxysilane (GPTMS), 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxy Examples include cyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and the like.
  • the solvent-free adhesive does not contain glycidoxyalkylalkoxysilane. Even if it is not, sufficient lamination strength can be obtained.
  • the solvent-free adhesive is a urethane-based adhesive containing adipic acid and isophthalic acid, even if the solvent-free adhesive does not contain glycidoxyalkylalkoxysilane, more sufficient lamination strength can be achieved. Obtainable.
  • the coating amount of the first adhesive layer 40 is preferably 0.5 g/m 2 or more and 3.0 g/m 2 or less, more preferably 1.0 g/m 2 or more and 2.0 g/m 2 or less.
  • the coating amount of the first adhesive layer 40 is 0.5 g/m 2 or more, the effect of suppressing delamination between the base layer 10 and the sealant layer 30 or the intermediate layer 20 can be enhanced.
  • the coating amount of the first adhesive layer 40 is 3.0 g/m 2 or less, it is possible to suppress the occurrence of winding misalignment during processing of the laminate, and to improve the appearance quality of the laminate. In addition, appropriate lamination strength can be obtained.
  • the intermediate layer 20 may be a layer containing polyethylene, for example, a layer composed of an unstretched polyethylene film.
  • the polyethylene contained in the intermediate layer 20 is preferably high-density polyethylene or medium-density polyethylene from the viewpoint of strength and heat resistance. These materials may be derived from petroleum or plants, or may be a mixture thereof.
  • the thickness of the intermediate layer 20 is preferably 9 ⁇ m or more and 50 ⁇ m or less, more preferably 12 ⁇ m or more and 35 ⁇ m or less. By setting the thickness of the intermediate layer 20 to 9 ⁇ m or more, the strength and heat resistance of the laminate can be improved. By setting the thickness of the intermediate layer 20 to 50 ⁇ m or less, the processability of the laminate can be improved.
  • the intermediate layer 20 can be produced by forming a polyethylene film by a T-die method, an inflation method, or the like.
  • the melt flow rate (MFR) of polyethylene is preferably 3 g/10 minutes or more and 20 g/10 minutes or less.
  • MFR melt flow rate
  • the MFR of polyethylene is preferably 0.5 g/10 minutes or more and 5 g/10 minutes or less.
  • the processability of the laminate can be improved.
  • the MFR is set to 5 g/10 minutes or less, film formability can be improved.
  • an anchor coat layer 13 and an inorganic oxide layer 14 are formed on at least one surface of the intermediate layer 20. Furthermore, in the laminate 4, an anchor coat layer 13, an inorganic oxide layer 14, and a gas barrier coating layer 15 are formed on at least one surface of the intermediate layer 20.
  • the anchor coat layer 13 can be formed using a known anchor coat agent.
  • anchor coating agent examples include polyester polyurethane resins and polyether polyurethane resins. From the viewpoint of heat resistance and interlayer adhesive strength, polyester-based polyurethane resins are preferred.
  • a polyvinyl alcohol resin may be used as the anchor coating agent.
  • the polyvinyl alcohol resin may be any resin having a vinyl alcohol unit formed by saponifying a vinyl ester unit, and examples thereof include polyvinyl alcohol (PVA) and ethylene-vinyl alcohol copolymer (EVOH).
  • methods for forming the anchor coating layer include coating using a polyvinyl alcohol resin solution, multilayer extrusion, and the like.
  • the layers may be laminated via an adhesive resin such as maleic anhydride graft-modified polyethylene.
  • the inorganic oxide layer 14 provides the laminates 3 and 4 with oxygen barrier properties and water vapor barrier properties.
  • the anchor coat layer 13 and the inorganic oxide layer 14 are formed on the surface of the intermediate layer 20 facing the second adhesive layer 50, but they may be formed on the opposite surface.
  • the anchor coat layer 13, the inorganic oxide layer 14, and the gas barrier coating layer 15 are formed on the surface of the intermediate layer 20 facing the second adhesive layer 50; may be formed.
  • Examples of the structure of the inorganic oxide layer 14 include a vapor deposited layer made of metal oxide such as aluminum oxide, silicon oxide, magnesium oxide, and tin oxide.
  • the metal oxide may be selected from the group consisting of aluminum oxide, silicon oxide, and magnesium oxide.
  • aluminum oxide and silicon oxide are selected.
  • the vapor-deposited layer made of metal oxide is transparent, compared to the vapor-deposited layer made of metal, the user holding the packaging material made of the laminate may misunderstand that metal foil is used. It has the advantage of being difficult to do.
  • the thickness of the inorganic oxide layer made of aluminum oxide is preferably 5 nm or more and 30 nm or less.
  • the film thickness is 5 nm or more, sufficient gas barrier properties can be obtained.
  • the film thickness is 30 nm or less, it is possible to suppress generation of cracks due to deformation due to internal stress of the thin film, and to suppress deterioration of gas barrier properties. It should be noted that if the film thickness exceeds 30 nm, the cost tends to increase due to an increase in the amount of materials used, a longer film formation time, etc., which is not preferable from an economic point of view. From the same viewpoint as above, the thickness of the inorganic oxide layer made of aluminum oxide is more preferably 7 nm or more and 15 nm or less.
  • the thickness of the inorganic oxide layer made of silicon oxide is preferably 10 nm or more and 50 nm or less.
  • the film thickness is 10 nm or more, sufficient gas barrier properties can be obtained.
  • the film thickness is 50 nm or less, it is possible to suppress the occurrence of cracks due to deformation of the thin film due to internal stress, and to suppress deterioration of gas barrier properties. It should be noted that if the film thickness exceeds 50 nm, the cost tends to increase due to an increase in the amount of materials used, a longer film formation time, etc., which is not preferable from an economic point of view. From the same viewpoint as above, the thickness of the inorganic oxide layer made of silicon oxide is more preferably 20 nm or more and 40 nm or less.
  • the inorganic oxide layer 14 can be formed, for example, by vacuum film formation.
  • a physical vapor deposition method or a chemical vapor deposition method can be used.
  • the physical vapor deposition method include, but are not limited to, a vacuum evaporation method, a sputtering method, an ion plating method, and the like.
  • the chemical vapor deposition method include, but are not limited to, a thermal CVD method, a plasma CVD method, a photo CVD method, and the like.
  • the above vacuum film formation methods include resistance heating vacuum evaporation method, EB (Electron Beam) heating vacuum evaporation method, induction heating vacuum evaporation method, sputtering method, reactive sputtering method, dual magnetron sputtering method, and plasma chemical vapor deposition method. (PECVD method) etc. are particularly preferably used. However, in terms of productivity, vacuum evaporation is currently the best method.
  • a heating means for the vacuum evaporation method it is preferable to use one of an electron beam heating method, a resistance heating method, and an induction heating method.
  • a gas barrier coating layer 15 is provided on the inorganic oxide layer 14 for the purpose of improving gas barrier properties and protecting the inorganic oxide layer 14.
  • the gas barrier coating layer 15 may contain a hydroxyl group-containing polymer compound, specifically, at least one of a hydroxyl group-containing polymer compound and its hydrolyzate, metal alkoxide, silane, etc. It may be a heat-dried product of a composition containing at least one selected from the group consisting of a coupling agent and a hydrolyzate thereof.
  • the gas barrier coating layer 15 is made of, for example, a composition obtained by adding a hydroxyl group-containing polymer compound, a metal alkoxide, and/or a silane coupling agent to water or a water/alcohol mixture (hereinafter referred to as an overcoat agent).
  • the overcoat agent can be made by directly combining a solution of a hydroxyl group-containing polymer compound, which is a water-soluble polymer, in an aqueous (water or water/alcohol mixed) solvent with a metal alkoxide and/or a silane coupling agent; It can be prepared by mixing these with those that have been subjected to a treatment such as hydrolysis in advance.
  • hydroxyl group-containing polymer compound examples include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylpyrrolidone, starch, methylcellulose, carboxymethylcellulose, sodium alginate, and the like.
  • PVA polyvinyl alcohol
  • Examples of the metal alkoxide include compounds represented by the following general formula (I). M(OR 1 ) m (R 2 ) nm ...(I)
  • R 1 and R 2 are each independently a monovalent organic group having 1 to 8 carbon atoms, and are preferably an alkyl group such as a methyl group or an ethyl group.
  • M represents an n-valent metal atom such as Si, Ti, Al, and Zr.
  • m is an integer from 1 to n.
  • R 1 or R 2 may be the same or different.
  • metal alkoxide examples include tetraethoxysilane [Si(OC 2 H 5 ) 4 ], triisopropoxyaluminum [Al(O-2′-C 3 H 7 ) 3 ], and the like. Tetraethoxysilane and triisopropoxyaluminum are preferred because they are relatively stable in aqueous solvents after hydrolysis.
  • Examples of the silane coupling agent include compounds represented by the following general formula (II). Si(OR 11 ) p (R 12 ) 3-p R 13 ...(II)
  • R 11 represents an alkyl group such as a methyl group or an ethyl group
  • R 12 represents an alkyl group, an aralkyl group, an aryl group, an alkenyl group, an alkyl group substituted with an acryloxy group, or a methacryloxy group.
  • R 13 represents a monovalent organic functional group
  • p represents an integer of 1 to 3.
  • R 11 or R 12 may be the same or different.
  • the monovalent organic functional group represented by R13 is a monovalent organic functional group containing a glycidyloxy group, an epoxy group, a mercapto group, a hydroxyl group, an amino group, an alkyl group substituted with a halogen atom, or an isocyanate group. Examples include groups.
  • the silane coupling agent includes vinyltrimethoxysilane, ⁇ -chloropropylmethyldimethoxysilane, ⁇ -chloropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, Examples include silane coupling agents such as ⁇ -methacryloxypropylmethyldimethoxysilane.
  • the silane coupling agent may be a polymer obtained by polymerizing the compound represented by the above general formula (II).
  • the multimer is preferably a trimer, more preferably 1,3,5-tris(3-trialkoxysilylalkyl)isocyanurate.
  • This is a condensation polymer of 3-isocyanatealkylalkoxysilane. It is known that in this 1,3,5-tris(3-trialkoxysilylalkyl) isocyanurate, the isocyan moiety has no chemical reactivity, but the reactivity is ensured by the polarity of the nurate moiety.
  • 3-isocyanate alkyl alkoxylane like 3-isocyanate alkyl alkoxylane, it is added to adhesives, etc., and is known as an adhesion improver. Therefore, by adding 1,3,5-tris(3-trialkoxysilylalkyl)isocyanurate to the hydroxyl group-containing polymer compound, the water resistance of the gas barrier coating layer 15 can be improved due to hydrogen bonding.
  • 3-Isocyanate alkyl alkoxyrane has high reactivity and low liquid stability, whereas 1,3,5-tris(3-trialkoxysilylalkyl) isocyanurate is not water-soluble due to the polarity of the nurate moiety. However, it is easily dispersed in aqueous solutions and can maintain stable liquid viscosity. Furthermore, the water resistance properties of 3-isocyanatealkylalkoxyrane and 1,3,5-tris(3-trialkoxysilylalkyl)isocyanurate are equivalent.
  • 1,3,5-Tris(3-trialkoxysilylalkyl)isocyanurate is sometimes produced by thermal condensation of 3-isocyanatepropylalkoxysilane, and may also contain the raw material 3-isocyanatepropylalkoxysilane. However, there is no particular problem. More preferred is 1,3,5-tris(3-trialkoxysilylpropyl)isocyanurate, and even more preferred is 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate. 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate is practically advantageous because the methoxy group has a high hydrolysis rate and those containing a propyl group are available at relatively low cost.
  • the amount of metal alkoxide in the overcoat agent can be 1 to 4 parts by mass per 1 part by mass of the hydroxyl group-containing polymer compound from the viewpoint of adhesion with the inorganic oxide layer 14 and maintaining gas barrier properties, and 2 It may be up to 3 parts by weight.
  • the amount of the silane coupling agent can be 0.01 to 1 part by weight, and may be 0.1 to 0.5 part by weight, per 1 part by weight of the hydroxyl group-containing polymer compound.
  • the amount of the silane compound (metal alkoxide and silane coupling agent) in the overcoat agent is 1 to 4 parts by mass per 1 part by mass of the hydroxyl group-containing polymer compound.
  • the amount may be 2 to 3 parts by mass.
  • additives such as isocyanate compounds, dispersants, stabilizers, viscosity modifiers, and colorants may be added to the overcoat agent within a range that does not impair gas barrier properties.
  • the overcoat agent may be applied by, for example, a dipping method, a roll coating method, a gravure coating method, a reverse gravure coating method, an air knife coating method, a comma coating method, a die coating method, a screen printing method, a spray coating method, a gravure offset method, etc. Can be done.
  • the coating film formed by applying the overcoat agent can be dried by, for example, a hot air drying method, a hot roll drying method, a high frequency irradiation method, an infrared irradiation method, a UV irradiation method, or a combination thereof.
  • the temperature at which the coating film is dried can be, for example, 50 to 150°C, preferably 70 to 100°C. By setting the temperature during drying within the above range, it is possible to further suppress the occurrence of cracks in the inorganic oxide layer 14 and the gas barrier coating layer 15, and it is possible to exhibit excellent barrier properties.
  • the gas barrier coating layer 15 may be formed using an overcoat agent containing a hydroxyl group-containing polymer compound (for example, polyvinyl alcohol resin) and a silane compound.
  • An acid catalyst, an alkali catalyst, a photoheavy initiator, etc. may be added to the overcoat agent as necessary.
  • silane compound examples include silane coupling agents, polysilazane, siloxane, etc. Specifically, tetramethoxysilane, tetraethoxysilane, glycidoxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, hexamethyldisilazane, etc. etc.
  • the thickness of the gas barrier coating layer 15 is preferably 50 to 1000 nm, more preferably 100 to 500 nm. When the thickness of the gas barrier coating layer 15 is 50 nm or more, it tends to be able to obtain more sufficient gas barrier properties, and when it is 1000 nm or less, it tends to be able to maintain sufficient flexibility.
  • the second adhesive layer 50 is a layer containing at least one type of adhesive, and is provided between the intermediate layer 20 and the sealant layer 30 to bond them together. Either a one-component curing type or a two-component curing type adhesive can be used for the second adhesive layer 50. Examples of the adhesive include urethane adhesive, epoxy adhesive, silicone adhesive, and the like. These adhesives may contain a layered inorganic compound for the purpose of further enhancing barrier properties.
  • the second adhesive layer 50 (gas barrier adhesive layer) having gas barrier properties can also be formed using an adhesive that can exhibit gas barrier properties after curing. Thereby, the gas barrier performance of the laminates 2, 3, and 4 can be further improved. Further, when the second adhesive layer 50 is a gas barrier adhesive layer, the laminate 4 does not need to include the gas barrier coating layer 15. By forming an adhesive layer in contact with the inorganic oxide layer 14 with an adhesive that exhibits gas barrier properties, deterioration of gas barrier properties due to cracking in the inorganic oxide layer 14 can be suppressed even without the gas barrier coating layer 15. is possible.
  • gas barrier adhesives include epoxy adhesives and polyester/polyurethane adhesives. Specific examples include "Maxive" manufactured by Mitsubishi Gas Chemical Co., Ltd. and "Paslim” manufactured by DIC Corporation.
  • the second adhesive layer 50 may be formed using a solvent-free adhesive.
  • a solvent-free adhesive the same adhesive as used for forming the first adhesive layer 40 can be used.
  • the thickness of the second adhesive layer 50 is preferably 0.5 ⁇ m or more and 6 ⁇ m or less, more preferably 0.8 ⁇ m or more and 5 ⁇ m or less, and even more preferably 1.0 ⁇ m or more and 4.5 ⁇ m or less. preferable.
  • the thickness of the second adhesive layer 50 is preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more and 5 ⁇ m or less, and even more preferably 1.0 ⁇ m or more and 4.5 ⁇ m or less. preferable.
  • the thickness of the second adhesive layer 50 By setting the thickness of the second adhesive layer 50 to 0.5 ⁇ m or more, the adhesiveness of the second adhesive layer 50 can be improved.
  • the thickness of the second adhesive layer 50 By setting the thickness of the second adhesive layer 50 to 6 ⁇ m or less, the processability of the laminates 2, 3, and 4 can be improved.
  • the sealant layer 30 is made of polyethylene, and is joined by heat sealing when forming a packaging material such as a packaging bag using the laminates 1, 2, 3, and 4.
  • the sealant layer 30 may be a layer made of an unstretched polyethylene film.
  • the polyethylene constituting the sealant layer 30 is preferably low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), or very low-density polyethylene (VLDPE).
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • VLDPE very low-density polyethylene
  • biomass-derived polyethylene or recycled polyethylene may be used for the sealant layer 30.
  • the sealant layer 30 may be composed of an unstretched polyethylene film.
  • polyethylene having a density of 0.900 g/cm 3 or more and less than 0.925 g/cm 3 can be used.
  • linear low density polyethylene polyethylene having a density of 0.900 g/cm 3 or more and less than 0.925 g/cm 3 can be used.
  • ultra-low density polyethylene polyethylene having a density of less than 0.900 g/cm 3 can be used.
  • sealant layer 30 a copolymer of ethylene and other monomers can be used as long as the properties of the laminates 1, 2, 3, and 4 are not impaired.
  • the thickness of the sealant layer 30 can be changed as appropriate depending on the weight of the contents to be filled into the packaging bag to be produced.
  • the thickness of the sealant layer 30 is preferably 20 ⁇ m or more and 60 ⁇ m or less.
  • the thickness is preferably 20 ⁇ m or more and 60 ⁇ m or less.
  • the thickness of the sealant layer 30 is preferably 50 ⁇ m or more and 200 ⁇ m or less.
  • the thickness is set to 50 ⁇ m or more, it is possible to prevent the filled contents from leaking due to damage to the sealant layer 30.
  • the thickness is set to 200 ⁇ m or less, the processability of the laminates 1, 2, 3, and 4 can be improved, and it is further preferable to set the thickness to 180 ⁇ m or less or 150 ⁇ m or less.
  • Additives such as an antioxidant, an antistatic agent, a nucleating agent, and an ultraviolet absorber may be added to the polyethylene used for the base layer 10, the intermediate layer 20, and the sealant layer 30.
  • the proportion of polyethylene in the laminate 1 is 90% by mass or more.
  • the laminates 2, 3, 4 of this embodiment configured as described above are such that the base layer 10, the intermediate layer 20, and the sealant layer 30 are made of polyethylene. , 4, the proportion of polyethylene is 90% by mass or more.
  • the laminates 1, 2, 3, and 4 have high recyclability.
  • the proportion (mass%) of polyethylene in the laminates 1, 2, 3, and 4 can be calculated by the following formula (1).
  • the laminates 1, 2, 3, and 4 of this embodiment configured as described above have a solvent content of 5 mg/m 2 or less. Thereby, the dimensional stability of the printed pattern can be improved.
  • the first adhesive layer 40 is formed of a solvent-free adhesive
  • the solvent content can be reduced to 5 mg/m 2 or less. It is.
  • the second adhesive layer 50 is formed of a solvent-based adhesive
  • the laminates 1, 2, 3, and 4 of this embodiment can satisfy the above solvent content conditions. It is.
  • the solvent content of the laminates 1, 2, 3, and 4 may be 4.5 mg/m 2 or less, or 4 mg/m 2 or less.
  • the solvent content of the laminates 1, 2, 3, and 4 can be measured using, for example, a gas chromatograph under the following conditions.
  • the laminate according to this embodiment has a structure in which a base material layer, a printing layer, a first adhesive layer, a barrier layer, and a sealant layer are laminated in this order, and the base material layer and A laminate in which all of the sealant layers contain polyolefin, the first adhesive layer is a layer formed using a solvent-free adhesive, and the proportion of polyolefin in the laminate is 90% by mass or more. .
  • the first adhesive layer is formed using a solvent-free adhesive, a solvent is not used when forming the first adhesive layer, unlike when a solvent-based adhesive is used.
  • Heat drying (oven drying, etc.) for removal is not performed, and there is no residual solvent in the first adhesive layer. Therefore, expansion and contraction of the base material layer can be suppressed, and good dimensional stability of the printed pattern can be obtained. Further, since no residual solvent is present in the first adhesive layer, it is possible to suppress the occurrence of rubbing or bleeding in the printed pattern. Further, since there is no residual solvent, it is possible to suppress the odor of the solvent when it is packaged. On the other hand, the first adhesive layer formed using a solvent-free adhesive tends to have poor adhesion depending on the components of the contents when the laminate is used as a packaging bag.
  • the laminate according to this embodiment must include a barrier layer between the first adhesive layer and the sealant layer.
  • the presence of this barrier layer can prevent the components of the contents from reaching the first adhesive layer, and the laminate can prevent the first adhesive layer formed using a solvent-free adhesive from reaching the first adhesive layer. Even with this, it is possible to obtain good content resistance that can suppress the occurrence of delamination due to the influence of the contents.
  • the above-mentioned laminate can obtain good contents resistance even after heat sterilization treatment such as boiling treatment and retort treatment.
  • FIGS. 3 and 4 are schematic cross-sectional views each showing an embodiment of a laminate according to the second aspect of the present disclosure.
  • the laminate 3 shown in FIG. 3 includes a barrier layer 60 consisting of a base material layer 10, a printed layer 12, a first adhesive layer 40, an intermediate layer 20, an anchor coat layer 13, and an inorganic oxide layer 14. , a second adhesive layer 50 , and a sealant layer 30 .
  • the laminate 4 shown in FIG. 4 includes a base layer 10, a printed layer 12, a first adhesive layer 40, an intermediate layer 20, an anchor coat layer 13, an inorganic oxide layer 14, and a gas barrier coating layer. 15, a second adhesive layer 50, and a sealant layer 30.
  • the base layer 10, the intermediate layer 20, and the sealant layer 30 all contain polyolefin.
  • the first adhesive layer 40 is a layer formed using a solvent-free adhesive. Further, the proportion of polyolefin in the laminate is 90% by mass or more. Each layer will be explained below.
  • the base material layer 10 is a layer containing polyolefin.
  • the base material layer 10 is made of, for example, a polyolefin film. Examples of the polyolefin include polyethylene and polypropylene.
  • the base material layer 10 is a portion that becomes the outer surface when a packaging bag is formed using the laminates 3 and 4.
  • the polyolefin film constituting the base layer 10 may be a stretched film or a non-stretched film. From the viewpoints of impact resistance, heat resistance, water resistance, dimensional stability, etc., the polyolefin film may be a stretched film.
  • the stretching method is not particularly limited, and any method may be used as long as it can provide a dimensionally stable film, such as inflation stretching, uniaxial stretching, biaxial stretching, etc.
  • the polyolefin film may be an unstretched film.
  • the base material layer 10 is composed of a polyethylene film
  • the base material layer 10 is made of high density polyethylene (density 0.94 g/cm 3 or more) or medium density polyethylene (density 0 .925 to 0.945 g/cm 3 ) can be used.
  • the base layer 10 When the base layer 10 is made of a polypropylene film, the base layer 10 may be made of a stretched polypropylene film.
  • polypropylene is broadly classified into homopolymers, random copolymers, block copolymers, and terpolymers, and the polymer type is selected according to the application and required performance.
  • the polymer polypropylene is preferred.
  • a multilayer film in which a copolymer or terpolymer is formed as a skin layer on a homopolymer core layer by a coextrusion method may be used as the base layer 10. good.
  • the materials constituting these base material layers 10 may be petroleum-derived, plant-derived, or a mixture thereof. Further, the surface of the base material layer 10 can be subjected to adhesion-facilitating treatment by dry surface treatment such as corona treatment or atmospheric pressure plasma treatment. Further, it is also possible to use as the base layer 10 a polyolefin film having a multilayer structure in which polyolefins having different densities are extruded by a coextrusion method.
  • the base layer 10 may be made of an unstretched polyethylene film.
  • unstretched polyethylene film is a film that is not stretched during film formation, and has spherical crystals (spherulites) of about 10 to 100 ⁇ m composed of randomly folded polyethylene molecular chains, which are non-crystalline molecules.
  • An unstretched polyethylene film has the property that when it receives a strong impact, the spherulites are destroyed and the molecular chains are oriented and stretched, thereby preventing the film itself from tearing. Therefore, a package made of a laminate in which unstretched polyethylene films are laminated as the base layer 10, intermediate layer 20, and sealant layer 30 (a packaging bag is made, filled with contents, and sealed) cannot be dropped. It is characterized by excellent bag strength.
  • the thickness of the base material layer 10 is preferably 10 ⁇ m or more and 50 ⁇ m or less, more preferably 12 ⁇ m or more and 35 ⁇ m or less. By setting the thickness of the base material layer 10 to 10 ⁇ m or more, the strength of the laminates 3 and 4 can be improved. By setting the thickness of the base material layer 10 to 50 ⁇ m or less, the processability of the laminates 3 and 4 can be improved.
  • the printed layer 12 can have the same configuration as the printed layer 12 of the laminate according to the first aspect described above.
  • the first adhesive layer 40 can have the same configuration as the first adhesive layer 40 of the laminate according to the first side described above.
  • the intermediate layer 20 may be a layer containing polyolefin.
  • the intermediate layer 20 is made of, for example, a polyolefin film. Examples of the polyolefin include polyethylene and polypropylene.
  • the intermediate layer 20 may be made of the same polyolefin as the base layer 10. Further, the surface of the intermediate layer 20 can be subjected to adhesion-facilitating treatment by dry surface treatment such as corona treatment or atmospheric pressure plasma treatment.
  • the thickness of the intermediate layer 20 is preferably 9 ⁇ m or more and 50 ⁇ m or less, more preferably 12 ⁇ m or more and 35 ⁇ m or less. By setting the thickness of the intermediate layer 20 to 9 ⁇ m or more, the strength and heat resistance of the laminate can be improved. By setting the thickness of the intermediate layer 20 to 50 ⁇ m or less, the processability of the laminate can be improved.
  • the anchor coat layer 13 can have the same structure as the anchor coat layer 13 of the laminate according to the first aspect described above.
  • the laminates 3 and 4 include an inorganic oxide layer 14 as a layer constituting a barrier layer 60.
  • the inorganic oxide layer 14 provides the laminates 3 and 4 with oxygen barrier properties and water vapor barrier properties. Further, the inorganic oxide layer 14 provides the laminates 3 and 4 with resistance to contents.
  • the anchor coat layer 13, the inorganic oxide layer 14, and the gas barrier coating layer 15 are formed on the surface of the intermediate layer 20 facing the second adhesive layer 50; may be formed.
  • the inorganic oxide layer 14 can have the same configuration as the inorganic oxide layer 14 of the laminate according to the first aspect described above.
  • a gas barrier coating layer 15 is provided as a layer constituting the barrier layer 60 on the inorganic oxide layer 14 for the purpose of improving gas barrier properties and protecting the inorganic oxide layer 14.
  • the gas barrier coating layer 15 can have the same configuration as the gas barrier coating layer 15 of the laminate according to the first aspect described above.
  • the second adhesive layer 50 is a layer containing at least one type of adhesive, and is provided between the intermediate layer 20 and the sealant layer 30 in the laminates 3 and 4 to bond them together.
  • Either a one-component curing type or a two-component curing type adhesive can be used for the second adhesive layer 50.
  • the adhesive include urethane adhesive, epoxy adhesive, silicone adhesive, and the like. These adhesives may contain a layered inorganic compound for the purpose of further enhancing barrier properties.
  • the second adhesive layer 50 is preferably a layer formed using a solvent-based adhesive. Thereby, the content resistance of the laminates 3 and 4 can be improved.
  • the second adhesive layer 50 (gas barrier adhesive layer) having gas barrier properties can also be formed using an adhesive that can exhibit gas barrier properties after curing. Thereby, the gas barrier performance and content resistance of the laminates 3 and 4 can be further improved. Further, when the second adhesive layer 50 is a gas barrier adhesive layer, the laminate does not need to include the gas barrier coating layer 15 like the laminate 3 shown in FIG. If an adhesive layer that contacts the inorganic oxide layer 14 is formed using an adhesive that exhibits gas barrier properties, the gas barrier properties and content resistance will decrease due to the occurrence of cracks in the inorganic oxide layer 14 even without the gas barrier coating layer 15. It is possible to suppress the Examples of such gas barrier adhesives include epoxy adhesives and polyester/polyurethane adhesives. Specific examples include "Maxive" manufactured by Mitsubishi Gas Chemical Co., Ltd. and "Paslim” manufactured by DIC Corporation.
  • the thickness of the second adhesive layer 50 is preferably 0.5 ⁇ m or more and 6 ⁇ m or less, more preferably 0.8 ⁇ m or more and 5 ⁇ m or less, and even more preferably 1.0 ⁇ m or more and 4.5 ⁇ m or less. preferable.
  • the thickness of the second adhesive layer 50 is preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more and 5 ⁇ m or less, and even more preferably 1.0 ⁇ m or more and 4.5 ⁇ m or less. preferable.
  • the thickness of the second adhesive layer 50 is preferably 0.5 ⁇ m or more and 6 ⁇ m or less, more preferably 0.8 ⁇ m or more and 5 ⁇ m or less, and even more preferably 1.0 ⁇ m or more and 4.5 ⁇ m or less.
  • the thickness of the second adhesive layer 50 is preferably 0.5 ⁇ m or more and 6 ⁇ m or less, more preferably 0.8 ⁇ m or more and 5 ⁇ m or less, and even more preferably 1.0 ⁇ m
  • the sealant layer 30 is a layer containing polyolefin.
  • the sealant layer 30 is a layer made of, for example, an unstretched polyolefin film, and is joined by heat sealing when the laminates 3 and 4 are used to form a packaging material such as a packaging bag.
  • the polyethylene may be low density polyethylene (LDPE), linear low density polyethylene (LLDPE), or very low density polyethylene (VLDPE) from the viewpoint of heat sealability. is preferred. Furthermore, from the viewpoint of environmental impact, biomass-derived polyethylene or recycled polyethylene may be used for the sealant layer 30.
  • the sealant layer 30 may be composed of an unstretched polyethylene film.
  • polyethylene having a density of 0.900 g/cm 3 or more and less than 0.925 g/cm 3 can be used.
  • linear low density polyethylene polyethylene having a density of 0.900 g/cm 3 or more and less than 0.925 g/cm 3 can be used.
  • ultra-low density polyethylene polyethylene having a density of less than 0.900 g/cm 3 can be used.
  • sealant layer 30 a copolymer of ethylene and other monomers can be used as long as the properties of the laminates 3 and 4 are not impaired.
  • the sealant layer 30 is a layer composed of a polypropylene film
  • examples of the polypropylene include homopolypropylene resin (PP), propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene- ⁇ -olefin copolymer, etc.
  • PP homopolypropylene resin
  • a polypropylene resin or the like can be used.
  • biomass-derived polypropylene or recycled polypropylene may be used for the sealant layer 30.
  • the sealant layer 30 may be composed of an unstretched polypropylene film.
  • the thickness of the sealant layer 30 can be changed as appropriate depending on the weight of the contents to be filled into the packaging bag to be produced.
  • the thickness of the sealant layer 30 is preferably 20 ⁇ m or more and 60 ⁇ m or less.
  • the thickness is preferably 20 ⁇ m or more and 60 ⁇ m or less.
  • the thickness of the sealant layer 30 is preferably 50 ⁇ m or more and 200 ⁇ m or less.
  • the thickness is set to 50 ⁇ m or more, it is possible to prevent the filled contents from leaking due to damage to the sealant layer 30.
  • the thickness is set to 200 ⁇ m or less, the processability of the laminates 3 and 4 can be improved, and it is further preferable to set the thickness to 150 ⁇ m or less.
  • Additives such as an antioxidant, an antistatic agent, a nucleating agent, and an ultraviolet absorber may be added to the polyolefin used for the base layer 10, the intermediate layer 20, and the sealant layer 30.
  • the laminates 3 and 4 of this embodiment configured as described above have the base layer 10, the intermediate layer 20, and the sealant layer 30 made of polyolefin, so that the polyolefin content in the laminates 3 and 4 is The proportion is 90% by mass or more. Thereby, the laminates 3 and 4 have high recyclability.
  • the base layer 10, the intermediate layer 20, and the sealant layer 30 may be made of different materials, they are preferably made of the same material from the viewpoint of ease of reformation through melting of the resin material.
  • being made of the same material means, for example, that each layer is made of polyethylene or that each layer is made of polypropylene.
  • the preferred solvent content of the laminates 3 and 4 of this embodiment configured as described above is the same as that of the laminate according to the first aspect described above.
  • the method for manufacturing a laminate according to the present embodiment includes a printing process of forming a printed layer on a base material layer by a printing method using ink to obtain a printed base material, and a laminated film including the printed base material and a sealant layer. or a bonding step of bonding the sealant layer using a solvent-free adhesive to form a first adhesive layer.
  • the method for manufacturing the laminate according to the present embodiment includes forming a printed layer on the base layer by a printing method using ink.
  • the printing base material consisting of the base layer 10 and the printing layer 12 and the sealant layer 30 are bonded together using a solvent-free adhesive.
  • the printing base material and the sealant layer 30 are bonded together, for example, using a laminator for solvent-free adhesives equipped with a device for applying a heat-melted solvent-free adhesive to the substrate to be coated by roll coating. be able to.
  • the solvent-free adhesive is, for example, a two-component curing urethane adhesive
  • the main agent containing a polyol component and the curing agent containing a polyisocyanate component are normally supplied separately, and then supplied to the coating section of the laminating machine. mixed before serving.
  • the mixed adhesive is supplied, for example, between a doctor roll and a metering roll that rotate in opposite directions of the laminating apparatus.
  • the supplied adhesive is transferred from the metering roll to the coating roll, and is applied to the surface of the printing layer 12 side of the printing base material supplied between the coating roll and the impression roll.
  • the printing base material coated with the adhesive is bonded to the sealant layer 30 and wound up by a winding machine to obtain a laminate.
  • the obtained laminate is preferably aged at 20 to 50°C for 24 to 96 hours.
  • the doctor roll, metaling roll, and coating roll mentioned above are examples of the structure of a lamination apparatus, and may differ depending on the lamination apparatus used.
  • the solvent-free adhesive so low in viscosity that it can be applied without a solvent
  • metal rolls such as doctor rolls and coating rolls are heated, and the solvent-free adhesive is melted by the temperature. It is preferable to lower the viscosity and perform coating and bonding.
  • the heating temperature of the solvent-free adhesive in the bonding step within the range of 50 to 90°C.
  • the heating temperature is preferably set within the range of 50 to 90° C. so that the viscosity of the solvent-free adhesive at the heating temperature is 200 to 2000 mPa ⁇ s.
  • the heating temperature is more preferably a temperature at which the viscosity of the solvent-free adhesive is 300 to 1,500 mPa ⁇ s, and more preferably 500 to 1,000 mPa ⁇ s, from the viewpoint of obtaining a laminate with a more uniform coated appearance. More preferably, it is temperature.
  • the heating temperature is more preferably 50 to 80°C, more preferably 50 to 70°C, from the viewpoint of further improving the lamination strength of the laminate and further suppressing expansion and contraction of the printing base material. More preferred.
  • the viscosity of the urethane adhesive immediately after mixing the two components is preferably 200 to 2,500 mPa ⁇ s at 40°C, and preferably 500 to 2,500 mPa ⁇ s. It is more preferably 2000 mPa ⁇ s, and even more preferably 800 to 1500 mPa ⁇ s.
  • the viscosity of a solvent-free adhesive can be measured, for example, by using a Visco Tester (for high viscosity) VT-04FS (manufactured by Rion Co., Ltd.) by inserting a measuring rotor into the adhesive at a predetermined temperature.
  • Visco Tester for high viscosity
  • VT-04FS manufactured by Rion Co., Ltd.
  • the laminate 1 according to this embodiment can be manufactured.
  • a laminate film production process of producing a laminate film including the intermediate layer 20, the second adhesive layer 50, and the sealant layer 30 is performed before the bonding process.
  • an intermediate film is obtained by forming an anchor coat layer 13 and a barrier layer 60 (inorganic oxide layer 14) on the intermediate layer 20 before the laminate film production process. Perform the manufacturing process.
  • the anchor coat layer 13 and the barrier layer 60 are formed on the intermediate layer 20 before the laminate film production process to form the intermediate film.
  • An intermediate film production process is performed to obtain.
  • the anchor coat layer 13 and the barrier layer 60 (the inorganic oxide layer 14 or the inorganic oxide layer 14 and the gas barrier coating layer 15) can be formed on the intermediate layer 20 by a known method. can.
  • the intermediate layer 20 or intermediate film and the sealant layer 30 are bonded together using a method that corresponds to the adhesive used.
  • the solvent-based adhesive is applied onto the intermediate layer 20 or the intermediate film and bonded to the sealant layer 30 using a general dry lamination method, and the solvent is removed by heat drying. By doing so, a laminated film can be obtained.
  • Thermal drying can be carried out using an oven or the like, for example, at a temperature of 50 to 80° C., an oven length of 5 to 20 m, and a processing speed of 50 to 200 m/min.
  • the printed base material and the laminated film are laminated together in the lamination process described above, thereby making it possible to manufacture the laminated bodies 2, 3, and 4 according to the present embodiment.
  • the packaging bag according to this embodiment is made by bag-making the laminate according to this embodiment.
  • the packaging bag is made by folding one laminate 1, 2, 3, 4 with the sealant layer 30 facing each other, or by stacking two laminates 1, 2, 3, 4 with the sealant layer 30 facing each other.
  • the sealant layer 30 can be formed by heat sealing the sealant layer 30 at the peripheral edge while leaving the filled part of the contents. Further, by performing the above-described joining while sandwiching the folded bottom film, a standing pouch can be formed as a packaging bag.
  • the laminates 1, 2, 3, and 4 can be used to form various packaging bags such as pillow packaging, four-sided seals, three-sided seals, and gusset bags. In this way, the laminates 1, 2, 3, and 4 can be applied to various packaging bags.
  • the anchor coat layer 13 and barrier layer 60 may be arranged on the first adhesive layer 40 side of the intermediate layer 20.
  • the laminate may have a structure in which one or more of the anchor coat layer 13 and the inorganic oxide layer 14 are removed from the laminate 3 shown in FIG. 3.
  • the laminate may have a structure in which one or more of the anchor coat layer 13, the inorganic oxide layer 14, and the gas barrier coating layer 15 are removed from the laminate 4 shown in FIG.
  • the laminate may have a structure in which the intermediate layer 20 is removed from the laminates 3 and 4 shown in FIGS. 3 and 4.
  • the anchor coat layer 13 and the barrier layer 60 may be formed in sequence.
  • solvent-free adhesive A As the solvent-free adhesive A, the product name "LA7735” (polyisocyanate component) manufactured by Henkel Japan Ltd. and the product name "LA6159” (polyol component) manufactured by Henkel Japan Ltd. were blended at a mass ratio of 100:45. A two-component curing urethane adhesive was used. Solvent-free adhesive A contained adipic acid and isophthalic acid. The viscosity of the solvent-free adhesive A was 1500 mPa ⁇ s at 40°C immediately after mixing the two liquids, and 800 mPa ⁇ s at 60°C during lamination. Viscosity was measured using a Viscotester.
  • solvent-free adhesive B As the solvent-free adhesive B, the product name "LA7772" (polyisocyanate component) manufactured by Henkel Japan Ltd. and the product name "LA6172” (polyol component) manufactured by Henkel Japan Ltd. were blended at a mass ratio of 100:60. A two-component curing urethane adhesive was used. Solvent-free adhesive B contained adipic acid and isophthalic acid. The viscosity of the solvent-free adhesive B was 1500 mPa ⁇ s at 40°C immediately after mixing the two liquids, and 800 mPa ⁇ s at 60°C during lamination.
  • solvent-free adhesive C As the solvent-free adhesive C, the product name "AD-N369AF” (polyisocyanate component) manufactured by Toyo Morton Co., Ltd. and the product name "AD-N369B” (polyol component) manufactured by Toyo Morton Co., Ltd. were used in a mass ratio of 3: A two-component curing type urethane adhesive formulated in 1 was used. Solvent-free adhesive C contained oil and fat acids and did not contain adipic acid and isophthalic acid. The viscosity of the solvent-free adhesive C was 4000 mPa ⁇ s at 40°C immediately after mixing the two liquids, and 2000 mPa ⁇ s at 60°C during lamination.
  • solvent-free adhesive D As the solvent-free adhesive D, the product name "LA7735” (polyisocyanate component) manufactured by Henkel Japan Ltd. and the product name “LA6088” (polyol component) manufactured by Henkel Japan Ltd. were blended at a mass ratio of 100:40. A two-component curing urethane adhesive was used. The viscosity of the solvent-free adhesive D was 4500 mPa ⁇ s at 40°C immediately after mixing the two liquids, and 2000 mPa ⁇ s at 60°C during lamination.
  • solvent adhesive As a solvent-based adhesive, a urethane adhesive was used in which 100 parts by mass of Takelac A525 manufactured by Mitsui Chemicals, 11 parts by mass of Takenate A52 manufactured by Mitsui Chemicals, and 84 parts by mass of ethyl acetate were mixed. .
  • the solvent-based adhesive contained adipic acid and isophthalic acid.
  • Gas barrier adhesive As a solvent-type gas barrier adhesive, an epoxy gas barrier adhesive was used, which was a mixture of 16 parts by mass of Maxive C93T manufactured by Mitsubishi Gas Chemical Co., Ltd. and 5 parts by mass of Maxive M-100 manufactured by Mitsubishi Gas Chemical Company. Using. The gas barrier adhesive was free of adipic acid and isophthalic acid.
  • Acrylic polyol and tolylene diisocyanate are mixed so that the number of NCO groups in tolylene diisocyanate is equal to the number of OH groups in acrylic polyol, and the total solid content (total amount of acrylic polyol and tolylene diisocyanate) is ) was diluted with ethyl acetate to 5% by mass. Further, ⁇ -(3,4 epoxycyclohexyl)trimethoxysilane was added to the diluted mixed solution in an amount of 5 parts by mass based on 100 parts by mass of the total amount of acrylic polyol and tolylene diisocyanate, and these were mixed. An anchor coating agent was prepared by doing this.
  • overcoat agent An overcoat agent was prepared by mixing the following liquids A, B, and C at a mass ratio of 70/20/10, respectively.
  • Solution A 72.1 g of 0.1N hydrochloric acid was added to 17.9 g of tetraethoxysilane (Si(OC 2 H 5 ) 4 ) and 10 g of methanol, and the mixture was stirred for 30 minutes to be hydrolyzed, resulting in a solid content of 5% by mass (SiO 2 (conversion) hydrolysis solution.
  • Solution B 5% by mass water/methanol solution of polyvinyl alcohol (mass ratio of water:methanol is 95:5).
  • Solution C 1,3,5-tris(3-trialkoxysilylpropyl)isocyanurate was diluted to a solid content of 5% by mass with a mixed solution of water/isopropyl alcohol (mass ratio of water:isopropyl alcohol was 1:1). Hydrolysis solution.
  • the above-mentioned anchor coating agent was applied by gravure coating to the corona-treated surface of an unstretched high-density polyethylene (HDPE) film (manufactured by Tamapoly Co., Ltd., product name: HS31, thickness: 30 ⁇ m, one side corona-treated) as an intermediate layer. It was coated and dried to provide an anchor coat layer with a thickness of 0.05 ⁇ m.
  • a transparent vapor deposition layer inorganic oxide layer made of silicon oxide and having a thickness of 30 nm was formed on the anchor coat layer using a vacuum vapor deposition apparatus using an electron beam heating method.
  • the O/Si ratio of the inorganic oxide layer was set to 1.8 by adjusting the type of vapor deposition material.
  • the above-mentioned overcoat agent was applied onto the inorganic oxide layer by gravure coating and dried to form a gas barrier coating layer (overcoat layer) having a gas barrier function and having a thickness of 0.3 ⁇ m.
  • an intermediate film A in which the intermediate layer/anchor coat layer/inorganic oxide layer (SiO x )/gas barrier coating layer was laminated was obtained.
  • Intermediate film B The intermediate layer was prepared in the same manner as the above intermediate film A except that a 10 nm thick transparent vapor deposited layer (inorganic oxide layer) made of aluminum oxide was formed on the anchor coat layer using a vacuum evaporation apparatus using an electron beam heating method.
  • An intermediate film B was obtained in which the following layers were laminated: /anchor coat layer/inorganic oxide layer (AlO x )/gas barrier coating layer.
  • An intermediate film C in which an intermediate layer/anchor coat layer/inorganic oxide layer (SiO x ) was laminated was obtained in the same manner as the above intermediate film A except that a gas barrier coating layer was not formed.
  • An intermediate film D in which an intermediate layer/anchor coat layer/inorganic oxide layer (AlO x ) was laminated was obtained in the same manner as the intermediate film B except that a gas barrier coating layer was not formed.
  • Intermediate film E Polypropylene and ethylene-vinyl alcohol copolymer (EVOH) are coextruded with adhesive resin sandwiched between them, and successively biaxially stretched to create a multilayer product having a 1 ⁇ m anchor coat layer of EVOH on 18 ⁇ m biaxially stretched polypropylene (OPP). Got the film.
  • a transparent vapor deposition layer (inorganic oxide layer) made of silicon oxide and having a thickness of 30 nm was formed on the surface of this multilayer film on the anchor coat layer side using a vacuum vapor deposition apparatus using an electron beam heating method. The O/Si ratio of the inorganic oxide layer was set to 1.8 by adjusting the type of vapor deposition material.
  • the above-mentioned overcoat agent was applied onto the inorganic oxide layer by gravure coating and dried to form a gas barrier coating layer (overcoat layer) having a gas barrier function and having a thickness of 0.3 ⁇ m.
  • a gas barrier coating layer (overcoat layer) having a gas barrier function and having a thickness of 0.3 ⁇ m.
  • Intermediate film F The above-mentioned anchor coating agent was applied by gravure coating to the corona-treated surface of a biaxially oriented polypropylene (OPP) film (manufactured by AJ Plast, product name: GL4, thickness: 20 ⁇ m, one side corona-treated) as an intermediate layer. , and dried to provide an anchor coat layer with a thickness of 0.05 ⁇ m.
  • OPP biaxially oriented polypropylene
  • a transparent vapor deposition layer inorganic oxide layer made of silicon oxide and having a thickness of 30 nm was formed on the anchor coat layer using a vacuum vapor deposition apparatus using an electron beam heating method.
  • the O/Si ratio of the inorganic oxide layer was set to 1.8 by adjusting the type of vapor deposition material.
  • the above-mentioned overcoat agent was applied onto the inorganic oxide layer by gravure coating and dried to form a gas barrier coating layer (overcoat layer) having a gas barrier function and having a thickness of 0.3 ⁇ m.
  • a gas barrier coating layer (overcoat layer) having a gas barrier function and having a thickness of 0.3 ⁇ m.
  • Example 1-1 As a base material layer, an unstretched high-density polyethylene (HDPE) film (manufactured by Tamapoly Co., Ltd., trade name: HS31, thickness: 30 ⁇ m, one side corona treated) was prepared. A pattern was printed on the corona-treated surface of the base material layer by a flexographic printing method to form a 1 ⁇ m thick printed layer to obtain a printed base material. On the other hand, as a sealant layer, a single-sided corona-treated unstretched polyethylene film (manufactured by Tamapori Co., Ltd., trade name: SE620, single-layer structure of LLDPE) having a thickness of 60 ⁇ m was prepared.
  • HDPE high-density polyethylene
  • solvent-free adhesive A (first adhesive layer) was applied onto the printing layer of the printing base material.
  • the printing base material and the sealant layer were bonded together by applying a coating amount of 2.1 g/m 2 (forming adhesive) to the printed base material and the sealant layer.
  • a laminate having a laminate structure of base material layer/print layer/first adhesive layer/sealant layer was obtained.
  • Example 1-2 A laminated structure of base layer/print layer/first adhesive layer/sealant layer was prepared in the same manner as in Example 1-1 except that solvent-free adhesive B was used instead of solvent-free adhesive A. A laminate having the following properties was obtained.
  • Example 1-3 A laminated structure of base layer/print layer/first adhesive layer/sealant layer was prepared in the same manner as in Example 1-1 except that solvent-free adhesive C was used instead of solvent-free adhesive A. A laminate having the following properties was obtained.
  • Example 1-4 A printing base material and a sealant layer were prepared in the same manner as in Example 1-1. Next, the polyisocyanate component and polyol component of the above-mentioned solvent-free adhesive A were mixed using a two-component mixing supply device, and the solution temperature was set to 40°C. Using a laminator for solvent-free adhesives, the solvent-free adhesive A (second An adhesive (forming an adhesive layer) was applied in an amount of 2.1 g/m 2 , and the intermediate film C and the sealant layer were bonded together. Thereafter, by aging at 40° C. for one day, a laminated film in which the intermediate film C and the sealant layer were laminated via the second adhesive layer was obtained.
  • solvent-free adhesive A first adhesive layer was applied onto the printing layer of the printing base material.
  • the printing base material and the laminated film were bonded together by applying a coating amount of 2.1 g/m 2 (forming adhesive) to the printed base material and the laminated film.
  • Example 1-5 A printing base material and a sealant layer were prepared in the same manner as in Example 1-1. Next, the surface of the inorganic oxide layer side of the intermediate film C described above and the sealant layer were adhered by a dry lamination method using the gas barrier adhesive described above (the adhesive forming the second adhesive layer). . Adhesion was performed using a dry laminator at a drying temperature of 50° C. and a processing speed of 100 m/min. Moreover, the thickness of the second adhesive layer was 2 ⁇ m. Thereby, a laminated film in which the intermediate film C and the sealant layer were laminated via the second adhesive layer was obtained.
  • solvent-free adhesive A first adhesive layer was applied onto the printing layer of the printing base material.
  • the printing base material and the laminated film were bonded together by applying a coating amount of 2.1 g/m 2 (forming adhesive) to the printed base material and the laminated film.
  • Example 1-1 A printing base material and a sealant layer were prepared in the same manner as in Example 1-1. Next, the printing layer side surface of the printing base material described above and the sealant layer were adhered by a dry lamination method using the solvent-based adhesive described above (the adhesive forming the first adhesive layer). Adhesion was performed using a dry laminator at a drying temperature of 50° C. and a processing speed of 100 m/min. Moreover, the thickness of the first adhesive layer was 2.1 ⁇ m. Thereby, a laminate having a laminate structure of base material layer/print layer/first adhesive layer/sealant layer was obtained.
  • a stretched high-density polyethylene (HDPE) film manufactured by Tokyo Ink Co., Ltd., trade name: SMUQ, thickness: 25 ⁇ m, one side corona treated
  • a pattern was printed on the corona-treated surface of the base material layer by a flexographic printing method to form a 1 ⁇ m thick printed layer to obtain a printed base material.
  • a sealant layer a single-sided corona-treated unstretched polyethylene film (manufactured by Tamapori Co., Ltd., trade name: SE620, single-layer structure of LLDPE) having a thickness of 60 ⁇ m was prepared.
  • solvent-free adhesive A (first adhesive layer) was applied onto the printing layer of the printing base material.
  • the printing base material and the sealant layer were bonded together by applying a coating amount of 2.1 g/m 2 (forming adhesive) to the printed base material and the sealant layer.
  • a laminate having a laminate structure of base material layer/print layer/first adhesive layer/sealant layer was obtained.
  • ⁇ Elongation rate of base material layer> The elongation rate of the base material layer (HDPE film) used in each Example and Comparative Example was measured using a thermal analyzer (manufactured by Hitachi High-Tech Science, trade name: TA7000PC Station).
  • the HDPE film was 4mm wide, applied a load of 0.4N to a tension of 100N/m, heated from 25°C continuously to 100°C at a heating rate of 5°C/min, and then held for 5 minutes. , the elongation rate of the film was measured. The elongation rate at a temperature of 70° C. in this measurement was recorded.
  • ⁇ Analysis of glycidoxyalkylalkoxysilane> The presence or absence of glycidoxyalkylalkoxysilane in the first adhesive layer of the laminates obtained in each example and comparative example was confirmed by the following method. First, the laminate was peeled between the first adhesive layer and the printing substrate to obtain a test piece with the first adhesive layer exposed. After this test piece was immersed in toluene at 60° C. for one week, the toluene was analyzed using GC/MS to measure the content of glycidoxyalkylalkoxysilane. The above content included the content of components derived from glycidoxyalkylalkoxysilane (dimer, trimer, hydrolyzate, etc.).
  • the measurement was carried out using JCI-55 (trade name, manufactured by Nippon Analytical Kogyo Co., Ltd.), and after holding at 40°C for 3 minutes, the temperature was raised to 320°C at a heating rate of 20°C/1 minute, and held for 3 minutes. . If the above content is 0.15 mass ppb or less based on the mass of the test piece, the first adhesive layer does not contain glycidoxyalkylalkoxysilane (indicated as "absent" in the table). If the content exceeds 0.15 ppb by mass based on the mass of the test piece, the first adhesive layer contains glycidoxyalkyl alkoxysilane (described as "presence” in the table). It was determined that
  • ⁇ Printed pattern dimensional stability> The patterns of the laminates obtained in each Example and Comparative Example were visually observed, and the dimensional stability was evaluated based on the following evaluation criteria.
  • ⁇ Lamination strength> In accordance with JIS K6854, a strip-shaped test piece with a width of 15 mm was cut out from the laminate obtained in each example and comparative example, and the test piece was tested using a Tensilon universal testing machine RTC-1250 manufactured by Orientec. The interlayer peel strength (laminate strength) was measured as an index of adhesion. The measurement was performed using T-type peeling under normal conditions (23° C., 50% RH) at a peeling rate of 300 mm/min.
  • the obtained pouch was subjected to a static load test of 80 kgf for 3 minutes in accordance with JIS Z0238, and the compressive strength was evaluated based on the presence or absence of bag breakage according to the following criteria.
  • OTR> The oxygen permeability of the laminates obtained in Examples and Comparative Examples was measured by the Mocon method under conditions of 30° C. and 70% RH (relative humidity). However, the oxygen permeability was not measured for the laminate that did not have an inorganic oxide layer.
  • Example 2-1 As a base material layer, an unstretched high-density polyethylene (HDPE) film (manufactured by Tamapoly Co., Ltd., trade name: HS31, thickness: 30 ⁇ m, one side corona treated) was prepared. A pattern was printed on the corona-treated surface of the base material layer by a flexographic printing method to form a 1 ⁇ m thick printed layer to obtain a printed base material. On the other hand, as a sealant layer, a single-sided corona-treated unstretched polyethylene film (manufactured by Tamapori Co., Ltd., trade name: SE620, single-layer structure of LLDPE) having a thickness of 60 ⁇ m was prepared.
  • HDPE high-density polyethylene
  • the polyisocyanate component and polyol component of the above-mentioned solvent-free adhesive A were mixed using a two-component mixing supply device, and the solution temperature was set to 40°C.
  • An unstretched high-density polyethylene (HDPE) film manufactured by Tamapoly Co., Ltd., product name: Solvent-free adhesive A (adhesive that forms the second adhesive layer) was applied to the corona-treated surface of HS31 (thickness: 30 ⁇ m, one side corona treated) at a coating amount of 2.1 g/ m2 .
  • the intermediate layer and sealant layer were bonded together. Thereafter, by aging at 40° C. for one day, a laminated film in which the intermediate layer and the sealant layer were laminated via the second adhesive layer was obtained.
  • solvent-free adhesive A (first adhesive layer) was applied onto the printing layer of the printing base material.
  • the printing base material and the laminated film were bonded together by applying a coating amount of 2.1 g/m 2 (forming adhesive) to the printed base material and the laminated film.
  • a laminate having a laminate structure of base layer/print layer/first adhesive layer/intermediate layer/second adhesive layer/sealant layer was obtained.
  • Example 2-2 A printing base material and a sealant layer were prepared in the same manner as in Example 2-1. Next, the polyisocyanate component and polyol component of the above-mentioned solvent-free adhesive A were mixed using a two-component mixing supply device, and the solution temperature was set to 40°C. Using a laminator for solvent-free adhesives, under the conditions of processing speed 100 m/min, doctor roll and coating roll temperature 60°C, solvent-free adhesive A (second An adhesive (forming an adhesive layer) was applied in an amount of 2.1 g/m 2 , and the intermediate film A and the sealant layer were bonded together. Thereafter, by aging at 40° C. for one day, a laminated film in which the intermediate film A and the sealant layer were laminated via the second adhesive layer was obtained.
  • solvent-free adhesive A first adhesive layer was applied onto the printing layer of the printing base material.
  • the printing base material and the laminated film were bonded together by applying a coating amount of 2.1 g/m 2 (forming adhesive) to the printed base material and the laminated film.
  • the substrate layer/printed layer/first adhesive layer/intermediate layer/anchor coat layer/inorganic oxide layer/gas barrier coating layer/second adhesive layer/ A laminate having a laminate structure of sealant layers was obtained.
  • Example 2-3 Substrate layer/print layer/first adhesive layer/intermediate layer/anchor coat layer/inorganic oxide layer was prepared in the same manner as in Example 2-2 except that intermediate film B was used instead of intermediate film A. A laminate having a laminate structure of /gas barrier coating layer/second adhesive layer/sealant layer was obtained.
  • Example 2-4 A printing base material and a sealant layer were prepared in the same manner as in Example 2-1. Next, the surface of the inorganic oxide layer side of the intermediate film C described above and the sealant layer were adhered by the dry nate method using the gas barrier adhesive described above (the adhesive forming the second adhesive layer). . Adhesion was performed using a dry laminator at a drying temperature of 50° C. and a processing speed of 100 m/min. Moreover, the thickness of the second adhesive layer was 2.1 ⁇ m. Thereby, a laminated film in which the intermediate film C and the sealant layer were laminated via the second adhesive layer was obtained.
  • solvent-free adhesive A first adhesive layer was applied onto the printing layer of the printing base material.
  • the printing base material and the laminated film were bonded together by applying a coating amount of 2.1 g/m 2 (forming adhesive) to the printed base material and the laminated film.
  • Example 2-5 In the same manner as in Example 2-4 except that intermediate film D was used instead of intermediate film C, base layer/print layer/first adhesive layer/intermediate layer/anchor coat layer/inorganic oxide layer A laminate having a laminate structure of /second adhesive layer/sealant layer was obtained.
  • Example 2-6 In the same manner as in Example 2-2, except that solvent-free adhesive D was used instead of solvent-free adhesive A when forming the first adhesive layer and the second adhesive layer, A laminate having a laminated structure of base material layer/printing layer/first adhesive layer/intermediate layer/anchor coat layer/inorganic oxide layer/gas barrier coating layer/second adhesive layer/sealant layer was obtained. .
  • Example 2-1 Example 2-1 except that a stretched high-density polyethylene (HDPE) film (manufactured by Tokyo Ink Co., Ltd., product name: SMUQ, thickness: 25 ⁇ m, one side corona treated) was used as the base layer and intermediate layer. Similarly, a laminate having a laminate structure of base layer/printed layer/first adhesive layer/intermediate layer/second adhesive layer/sealant layer was obtained.
  • HDPE high-density polyethylene
  • Example 2-2 A printing base material and a sealant layer were prepared in the same manner as in Example 2-1. Next, the surface of the gas barrier coating layer side of the intermediate film A described above and the sealant layer were adhered by the dry nate method using the above-mentioned solvent-based adhesive (the adhesive forming the second adhesive layer). . Adhesion was performed using a dry laminator at a drying temperature of 50° C. and a processing speed of 100 m/min. Moreover, the thickness of the second adhesive layer was 3.5 ⁇ m. Thereby, a laminated film in which the intermediate film A and the sealant layer were laminated via the second adhesive layer was obtained.
  • the adhesive forming the first adhesive layer the surface of the printing layer side of the above-mentioned printing base material and the intermediate layer side of the above-mentioned laminated film are bonded. I glued the sides together. Adhesion was performed using a dry laminator at a drying temperature of 50° C. and a processing speed of 100 m/min. Moreover, the thickness of the first adhesive layer was 3.5 ⁇ m. As a result, a laminate having a laminated structure of base material layer/printed layer/first adhesive layer/intermediate layer/anchor coat layer/inorganic oxide layer/gas barrier coating layer/second adhesive layer/sealant layer is obtained. I got it.
  • ⁇ Printed pattern dimensional stability> The patterns of the laminates obtained in each Example and Comparative Example were visually observed, and the dimensional stability was evaluated based on the following evaluation criteria.
  • Example 3-1 As a base material layer, a biaxially oriented polypropylene (OPP) film (manufactured by AJ Plast, trade name: GL4, thickness: 20 ⁇ m, one side corona treated) was prepared. A pattern was printed on the corona-treated surface of the base material layer by a flexographic printing method to form a 1 ⁇ m thick printed layer to obtain a printed base material. On the other hand, as a sealant layer, a single-sided corona-treated unstretched polyethylene film (manufactured by Tamapori Co., Ltd., trade name: SE620, single-layer structure of LLDPE) having a thickness of 60 ⁇ m was prepared.
  • OPP polypropylene
  • the surface of the gas barrier coating layer side of the intermediate film E described above and the sealant layer were adhered by the dry nate method using the above-mentioned solvent-based adhesive (the adhesive forming the second adhesive layer).
  • Adhesion was performed using a dry laminator at a drying temperature of 50° C. and a processing speed of 100 m/min.
  • the thickness of the second adhesive layer was 2.1 ⁇ m.
  • solvent-free adhesive A first adhesive layer was applied onto the printing layer of the printing base material.
  • the printing base material and the laminated film were bonded together by applying a coating amount of 2.1 g/m 2 (forming adhesive) to the printed base material and the laminated film.
  • the substrate layer/printed layer/first adhesive layer/intermediate layer/anchor coat layer/inorganic oxide layer/gas barrier coating layer/second adhesive layer/ A laminate having a laminate structure of sealant layers was obtained.
  • Example 3-2 In the same manner as in Example 3-1 except that intermediate film F was used instead of intermediate film E, base layer/print layer/first adhesive layer/intermediate layer/anchor coat layer/inorganic oxide layer A laminate having a laminate structure of /gas barrier coating layer/second adhesive layer/sealant layer was obtained.
  • Example 3-3 As the sealant layer, a single-sided corona-treated unstretched polypropylene (CPP) film (manufactured by Toray Industries, Inc., product name: ZK207, single layer structure of CPP) with a thickness of 60 ⁇ m was used, and as the adhesive forming the first adhesive layer. Substrate layer/print layer/first adhesive layer/intermediate layer/anchor coat layer/inorganic oxide layer/gas barrier property was prepared in the same manner as in Example 3-2 except that solvent-free adhesive B was used. A laminate having a laminate structure of coating layer/second adhesive layer/sealant layer was obtained.
  • CPP polypropylene
  • Example 3-4 An unstretched high-density polyethylene (HDPE) film (manufactured by Tamapori Co., Ltd., product name: HS31, thickness: 30 ⁇ m, one side corona treated) was used as the base layer, and intermediate film A was used in place of intermediate film E. Other than that, the same steps as in Example 3-1 were made, including base layer/printed layer/first adhesive layer/intermediate layer/anchor coat layer/inorganic oxide layer/gas barrier coating layer/second adhesive layer/ A laminate having a laminate structure of sealant layers was obtained.
  • HDPE high-density polyethylene
  • Example 3 except that intermediate film C was used instead of intermediate film A, gas barrier adhesive was used as the adhesive forming the second adhesive layer, and the thickness of the second adhesive layer was 2 ⁇ m. -4, a laminated structure of base layer/print layer/first adhesive layer/intermediate layer/anchor coat layer/inorganic oxide layer/gas barrier coating layer/second adhesive layer/sealant layer A laminate having the following properties was obtained.
  • Example 3-1 A printing base material and a sealant layer were prepared in the same manner as in Example 3-4. Next, the surface of the gas barrier coating layer side of the intermediate film A described above and the sealant layer were adhered by the dry nate method using the above-mentioned solvent-based adhesive (the adhesive forming the second adhesive layer). . Adhesion was performed using a dry laminator at a drying temperature of 50° C. and a processing speed of 100 m/min. Moreover, the thickness of the second adhesive layer was 2.1 ⁇ m. Thereby, a laminated film in which the intermediate film A and the sealant layer were laminated via the second adhesive layer was obtained.
  • the adhesive forming the first adhesive layer the surface of the printing layer side of the above-mentioned printing base material and the intermediate layer side of the above-mentioned laminated film are bonded. I glued the sides together. Adhesion was performed using a dry laminator at a drying temperature of 50° C. and a processing speed of 100 m/min. Moreover, the thickness of the first adhesive layer was 2.1 ⁇ m. As a result, a laminate having a laminated structure of base material layer/printed layer/first adhesive layer/intermediate layer/anchor coat layer/inorganic oxide layer/gas barrier coating layer/second adhesive layer/sealant layer is obtained. I got it.
  • Example 3-2 The same procedure as Example 3-4 was carried out, except that an unstretched high-density polyethylene (HDPE) film (manufactured by Tamapoly Co., Ltd., product name: HS31, thickness: 30 ⁇ m, one side corona treated) was used instead of intermediate film A. As a result, a laminate having a laminate structure of base material layer/printed layer/first adhesive layer/intermediate layer/second adhesive layer/sealant layer was obtained.
  • HDPE high-density polyethylene
  • Print pattern dimensional stability was evaluated in the same manner as in the evaluation for Example 1-1 and the like described above.
  • ⁇ Lamination strength> In accordance with JIS K6854, a strip-shaped test piece with a width of 15 mm was cut out from the laminate obtained in each example and comparative example, and the test piece was tested using a Tensilon universal testing machine RTC-1250 manufactured by Orientec.
  • the interlayer peel strength (laminate strength) was measured as an index of adhesion. The measurement was performed using T-type peeling under normal conditions (23° C., 50% RH) at a peeling rate of 300 mm/min. This measurement was performed on the laminate before and after the sterilization treatment. Note that "base material fracture” in the table means that the base material was fractured before delamination occurred, and it means that the base material had sufficient lamination strength (3 N/15 mm or more).
  • OTR> The oxygen permeability of the laminates obtained in Examples and Comparative Examples was measured by the Mocon method under conditions of 30° C. and 70% RH (relative humidity). This measurement was performed on the laminate before and after the sterilization treatment.
  • Acidic component Manufactured by KINCHO, product name "Sunpol", pH 2-4 Fragrance component: Limonene solution with a concentration of 1% by mass (a solution prepared by dissolving limonene in ethanol and diluting it with water so that the mass ratio of water/ethanol/limonene is 80/19/1)
  • Oil component Salad oil Alcohol component: 60% by mass ethanol aqueous solution
  • Acidic oil component Mixed liquid of edible vinegar/ketchup/salad oil in a mass ratio of 1/1/1

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Abstract

Un corps multicouche selon un aspect de la présente invention a une structure dans laquelle une couche de matériau de base, une couche d'impression, une première couche adhésive et une couche d'étanchéité sont empilées dans cet ordre ; la couche de matériau de base est conçue à partir d'un film de polyéthylène non étiré ; la première couche adhésive est formée à l'aide d'un adhésif sans solvant ; et le rapport de polyéthylène dans le corps multicouche est supérieur ou égal à 90 % en masse.
PCT/JP2023/021759 2022-06-16 2023-06-12 Corps multicouche, son procédé de production et sac d'emballage WO2023243607A1 (fr)

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JP2022097246A JP2023183634A (ja) 2022-06-16 2022-06-16 積層体及びその製造方法、並びに、包装袋
JP2022097244A JP2023183632A (ja) 2022-06-16 2022-06-16 積層体及びその製造方法、並びに、包装袋
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JP2022088456A (ja) * 2018-04-27 2022-06-14 大日本印刷株式会社 包装材料用ポリエチレン積層体及び該積層体からなる包装材料
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WO2022131264A1 (fr) * 2020-12-17 2022-06-23 凸版印刷株式会社 Stratifié, sac d'emballage et sachet à fond plat

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024135510A1 (fr) * 2022-12-22 2024-06-27 Dic株式会社 Corps multicouches pour matériaux d'emballage de liquides, et matériau d'emballage

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