Transfer films and barrier laminates

Abstract

To provide a transfer film that can be suitably used in the manufacture of barrier laminates with excellent interlayer adhesion and suppressed delamination. [Solution] A transfer film comprising a support substrate, a heat seal layer, and an inorganic vapor-deposited film in this order in the thickness direction, wherein the inorganic vapor-deposited film and the heat seal layer are in contact, or the transfer film further comprises an anchor coat layer between the inorganic vapor-deposited film and the heat seal layer, wherein the inorganic vapor-deposited film and the anchor coat layer are in contact.

Description

[Technical Field]

[0001] This disclosure relates to transfer films and barrier laminates. [Background technology]

[0002] In recent years, the environmental problem caused by microplastics has been widely discussed. Even in paper-based products, there is a growing demand to improve recyclability by constructing products using as much paper as possible to reduce the environmental impact.

[0003] Conventionally, packaging materials with high gas barrier properties have been used to suppress the deterioration of the quality of contents (e.g., food, pharmaceuticals, chemical products, and cosmetics) due to moisture or oxygen. In this context, packaging materials with a paper base, considering the recycling or incineration of used packaging materials, are attracting attention. However, paper bases generally have insufficient gas barrier properties. Therefore, to improve the gas barrier properties of packaging materials with a paper base, methods such as coating the paper base with resin or laminating a resin film with an inorganic vapor-deposited film onto the paper base are being considered.

[0004] Patent Document 1 discloses a laminate in which a gas barrier thin film layer is laminated by plasma polymerization onto a substrate made of paper or pulp mold having a sealing layer on its surface made of a polycondensate of polysaccharides and silicon compounds. In Patent Document 1, since the substrate made of paper or pulp mold is placed inside the plasma polymerization apparatus when forming the gas barrier thin film layer, paper dust or pulp dust generated from the paper or pulp mold tends to hinder the reduction of pressure inside the plasma polymerization apparatus to a pressure suitable for plasma polymerization. Therefore, it is difficult to form a thin film layer with stable gas barrier properties, the adhesion between the sealing layer and the thin film layer tends to be insufficient, and the gas barrier properties tend to be unstable. Patent Document 1 relates to chemical vapor deposition for the formation of a gas barrier thin film layer, but similar problems exist in physical vapor deposition as well. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 4622201 [Overview of the project] [Problems that the invention aims to solve]

[0006] There is a need for barrier laminates that are not limited to paper substrates, but also have substrates that are difficult to directly vapor-deposit, and that exhibit excellent interlayer adhesion. Furthermore, packaging materials typically include a heat-seal layer to seal the packaging material. Therefore, barrier laminates such as barrier paper, which are suitable for use as packaging materials, preferably include a heat-seal layer.

[0007] One objective of this disclosure is to provide a barrier laminate comprising a substrate, an inorganic vapor-deposited film, and a heat-seal layer, wherein the barrier laminate exhibits excellent interlayer adhesion and suppresses delamination. Another objective of this disclosure is to provide a transfer film that can be suitably used in the manufacture of such a barrier laminate. [Means for solving the problem]

[0008] The transfer film of this disclosure comprises a support substrate, a heat seal layer, and an inorganic vapor-deposited film in this order in the thickness direction, wherein the inorganic vapor-deposited film and the heat seal layer are in contact, or the transfer film further comprises an anchor coat layer between the inorganic vapor-deposited film and the heat seal layer, wherein the inorganic vapor-deposited film and the anchor coat layer are in contact.

[0009] In one embodiment, the barrier laminate of the present disclosure comprises a substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-seal layer in this order in the thickness direction, wherein the inorganic vapor-deposited film and the heat-seal layer are in contact, or the barrier laminate further comprises an anchor coat layer between the inorganic vapor-deposited film and the heat-seal layer, wherein the inorganic vapor-deposited film and the anchor coat layer are in contact.

[0010] In one embodiment, the barrier laminate of the present disclosure comprises a substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-seal layer in this order in the thickness direction, and does not have a release layer between the inorganic vapor-deposited film and the heat-seal layer. [Effects of the Invention]

[0011] According to this disclosure, a barrier laminate comprising a substrate, an inorganic vapor-deposited film, and a heat-seal layer can be provided, which exhibits excellent interlayer adhesion and suppressed delamination. According to this disclosure, a transfer film that can be suitably used in the manufacture of such a barrier laminate can be provided. [Brief explanation of the drawing]

[0012]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

[0013] The embodiments of this disclosure will be described below with reference to the drawings and other illustrations. This disclosure can be implemented in many different forms and should not be construed as being limited to the embodiments described below.

[0014] Drawings may schematically represent the width, thickness, angles, and shape of each part compared to the actual form, in order to clarify the explanation. However, drawings are merely examples and do not limit the interpretation of this disclosure. In this specification and each drawing, elements similar to those described in previously shown drawings are denoted by the same reference numerals, and detailed explanations may be omitted as appropriate. For the sake of explanation, terms such as "up" or "down" may be used, but the vertical direction may be reversed. The same applies to the horizontal direction.

[0015] In the following description, each component (for example, additives, resin components such as various resins, colorants, and hardeners) can be used individually or in combination of two or more types.

[0016] [Transfer film] The transfer film of this disclosure comprises a support substrate, a heat seal layer, and an inorganic vapor-deposited film in this order in the thickness direction. The transfer film may further include an anchor coat layer between the heat seal layer and the inorganic vapor-deposited film. The heat seal layer, the anchor coat layer if necessary, and the inorganic vapor-deposited film constitute the transfer layer. In one embodiment, the transfer film and the transfer layer may further include a functional layer such as a protective layer.

[0017] In other words, the transfer film of the present disclosure comprises a support substrate and a transfer layer provided on the support substrate, wherein the transfer layer comprises a heat seal layer and an inorganic vapor-deposited film in this order in the thickness direction. In one embodiment, the transfer layer may further comprise an anchor coat layer between the heat seal layer and the inorganic vapor-deposited film. The heat seal layer is in contact with the support substrate and is provided so as to be removable from the support substrate.

[0018] In this case, the transfer layer is either in contact with the inorganic vapor-deposited film and the heat seal layer (or the anchor coat layer if an anchor coat layer is provided), or the transfer layer does not have a release layer between the inorganic vapor-deposited film and the heat seal layer.

[0019] In one embodiment, the transfer film comprises a protective layer on an inorganic vapor-deposited film. In one embodiment, when the inorganic vapor-deposited film is composed of metal oxides such as aluminum oxide and silicon oxide, the transfer film includes a barrier coat layer on the inorganic vapor-deposited film.

[0020] The support substrate used as the transfer substrate, and therefore the transfer film, may be a single-sheet film or a continuous film wound into a roll.

[0021] Figure 1 shows one embodiment of the transfer film of the present disclosure. The transfer film 2 in Figure 1 comprises a support substrate 50, a heat seal layer 40, and an inorganic vapor-deposited film 30 in this order in the thickness direction.

[0022] Figure 2 shows another embodiment of the transfer film of the present disclosure. The transfer film 2 in Figure 2 comprises a support substrate 50, a heat seal layer 40, an anchor coat layer 32, and an inorganic vapor-deposited film 30 in this order in the thickness direction.

[0023] <Supporting base material> The transfer film of this disclosure comprises a support substrate as a transfer substrate. As the supporting substrate, a film made of resin (hereinafter also referred to as "resin film") is preferred. Examples of the above resins include polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyamides such as various nylons, especially aromatic polyamides such as nylon MXD6; vinyl resins such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and polyvinyl alcohol; polyolefins such as polyethylene, polypropylene, polybutene, and cyclic polyolefins; styrene-based resins such as styrene homopolymer, acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin); (meth)acrylic resin, polycarbonate, polyimide, diaryl phthalate resin, silicone-based resin, polysulfone-based resin, polyphenylene sulfide-based resin, polyethersulfone-based resin, polyurethane, cellulose-based resin, and fluororesin-based resin.

[0024] The resin film may consist of a single layer, or it may consist of two or more layers of the same or different compositions. The resin film may be an unstretched film, or a stretched film such as a uniaxially oriented film or a biaxially oriented film.

[0025] The thickness of the support substrate is preferably 5 μm or more, more preferably 8 μm or more, even more preferably 10 μm or more, preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 80 μm or less.

[0026] The support substrate is preferably capable of forming a heat-seal layer on it and has the property of being easily peelable from the heat-seal layer during the peeling process. From this viewpoint, among resin films, polyester films and polyamide films are preferred, polyester films are more preferred, and polyethylene terephthalate films are even more preferred.

[0027] The support substrate should have excellent mechanical, physical, and chemical properties to withstand the inorganic vapor deposition film formation process, and preferably possesses particularly high strength and heat resistance. Polyethylene terephthalate film is preferred from this viewpoint as well.

[0028] Preferably, the resin film does not have a known easy-adhesion treatment applied to the surface in contact with the heat-seal layer, and it is also preferable that no known easy-adhesion layer is provided on the surface in contact with the heat-seal layer. With such a configuration, for example, the peelability between the support substrate and the heat-seal layer in the peeling process can be improved.

[0029] <Heat seal layer> The transfer film of this disclosure comprises a heat-sealable layer. The heat-sealable layer functions as a heat-sealable sealant layer when a barrier laminate, such as barrier paper, is used as a packaging material. The heat-sealable layer also functions as a release layer from the support substrate when a barrier laminate, such as barrier paper, is manufactured by a transfer method described later.

[0030] A heat-sealable layer is a layer that has heat-sealing properties, specifically a layer that can be bonded to an object by heating and pressing, or a layer that can be bonded by fusing itself to another layer by heating and pressing. It should be noted that there is no prejudice to using the transfer film of this disclosure for applications that do not involve heat sealing.

[0031] In the transfer film of this disclosure, it is preferable that the heat seal layer is in contact with the support substrate. With this configuration, the support substrate can be easily peeled off from the heat seal layer. For example, since the heat seal layer is less likely to remain on the support substrate after peeling, the support substrate can be easily recycled or reused.

[0032] A heat-seal layer that can be peeled from the support substrate can be formed, for example, using a thermoplastic resin. Examples of thermoplastic resins include olefin polymers and (meth)acrylic resins. Among these, olefin polymers are preferred.

[0033] In one embodiment, the heat seal layer contains an olefin polymer. This configuration provides, for example, a heat seal layer with excellent heat sealability and peelability, as well as a barrier laminate for packaging materials that has sufficient rigidity, strength, and heat resistance, and is highly recyclable.

[0034] Examples of olefin polymers include ethylene polymers and propylene polymers. Among these, ethylene polymers are preferred from the viewpoint of balancing heat sealability and peelability.

[0035] Examples of ethylene polymers include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. From the viewpoint of heat sealability, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene are preferred. From the viewpoint of reducing environmental impact, biomass-derived polyethylene and / or recycled polyethylene may be used.

[0036] The density of high-density polyethylene is preferably greater than 0.945 g / cm 3 . The upper limit of the density of high-density polyethylene is, for example, 0.965 g / cm 3 . The density of medium-density polyethylene is preferably greater than 0.925 g / cm 3 and less than or equal to 0.945 g / cm 3 . The density of low-density polyethylene is preferably greater than 0.900 g / cm 3 and less than or equal to 0.925 g / cm 3 . The density of linear low-density polyethylene is preferably greater than 0.900 g / cm 3 and less than or equal to 0.925 g / cm 3 . The density of ultra-low-density polyethylene is preferably less than or equal to 0.900 g / cm 3 . The lower limit of the density of ultra-low-density polyethylene is, for example, 0.860 g / cm 3 . The density of polyethylene is measured in accordance with JIS K7112 (1999).

[0037] Examples of the ethylene-based polymer include ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, modified ethylene-vinyl acetate copolymers, ethylene-maleic anhydride copolymers, ethylene-(meth)acrylic acid copolymers, and ethylene-(meth)acrylic acid alkyl ester copolymers (such as ethylene-ethyl acrylate copolymers), etc., i.e., ethylene-(meth)acrylic acid ester copolymers.

[0038] Examples of propylene polymers include propylene homopolymers, propylene random copolymers, and propylene block copolymers. A propylene homopolymer is a polymer composed solely of propylene. A propylene random copolymer is a random copolymer of propylene and ethylenically unsaturated monomers other than propylene (e.g., ethylene, 1-butene, 4-methyl-1-pentene, and other α-olefins). A propylene block copolymer is a copolymer having polymer blocks made of propylene and polymer blocks made of ethylenically unsaturated monomers other than propylene (e.g., ethylene, 1-butene, 4-methyl-1-pentene, and other α-olefins). From the viewpoint of reducing environmental impact, biomass-derived polypropylene and / or recycled polypropylene may be used. A propylene-maleic anhydride copolymer is also an example of a propylene polymer.

[0039] The barrier laminate of this disclosure is preferably manufactured by a transfer method, as described later. In the transfer method, a heat seal layer is formed on a support substrate, and then an inorganic vapor-deposited film is formed on the heat seal layer, after which the heat seal layer and the inorganic vapor-deposited film are transferred onto a substrate such as a paper substrate. Therefore, it is preferable to form the heat seal layer using a coating liquid that can form a coating film on a support substrate and that can form a coating film that has excellent peelability from the support substrate as well as heat sealability.

[0040] Such heat-seal layers are preferably formed using a heat-seal coating solution containing an ionomer of an olefin polymer. Ionomers are a general term for synthetic resins in which polymers are aggregated using the cohesive force of metal ions.

[0041] Examples of the above-mentioned metal ions include alkali metal ions and alkaline earth metal ions, specifically sodium, potassium, calcium, magnesium, and zinc.

[0042] Examples of ionomers of olefin polymers include metal salts of olefin-unsaturated carboxylic acid copolymers, metal salts of olefin-(meth)acrylic copolymers, metal salts of olefin-urethane copolymers, and metal salts of olefin-fluorine polymer copolymers.

[0043] Examples of the olefins mentioned above include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene, and 6-methyl-1-heptene. Among these, ethylene and propylene are preferred, with ethylene being more preferred.

[0044] Examples of the above-mentioned unsaturated carboxylic acids include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and β-carboxyethyl (meth)acrylate; and unsaturated dicarboxylic acids such as maleic acid, itaconic acid, fumaric acid, and citraconic acid.

[0045] Among the above ionomers, ionomers of ethylene polymers are preferred, metal salts of ethylene-(meth)acrylic acid copolymers, metal salts of ethylene-(meth)acrylic copolymers, metal salts of ethylene-urethane copolymers, and metal salts of ethylene-fluorine polymer copolymers are more preferred, and metal salts of ethylene-(meth)acrylic acid copolymers are even more preferred.

[0046] The content of the olefin polymer in the heat seal layer is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. This further improves the heat sealability of the barrier laminate.

[0047] The heat seal layer may contain a rubber-based material along with the thermoplastic resin. Examples of rubber-based materials include thermoplastic rubber, natural rubber, butyl rubber, nitrile rubber, and chloroprene rubber. The rubber-based material can be used, for example, in mixture with the thermoplastic resin.

[0048] The heat seal layer is typically an unstretched layer. For example, a heat seal layer can be formed by applying and drying a heat seal layer coating solution containing an olefin polymer onto a support substrate, or by melt-extruding a resin composition containing an olefin polymer onto a support substrate. For the reasons mentioned above, the heat seal layer is preferably a cast coat layer formed using a coating solution containing an olefin polymer.

[0049] Examples of solvents for the heat seal layer coating liquid include water; alcohol solvents such as methanol, ethanol, 2-propanol, and 1-butanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; glycol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; hydrocarbon solvents such as n-hexane, cyclohexane, benzene, toluene, and xylene; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ether solvents such as dioxolane and tetrahydrofuran; nitrogen-containing solvents such as acetonitrile and N,N-dimethylformamide; and sulfur-containing solvents such as dimethyl sulfoxide.

[0050] For the preparation of the coating liquid for the heat seal layer, it is preferable to use an emulsion of an ionomer of an olefin polymer, more preferably a self-emulsifying emulsion, and even more preferably a self-emulsifying emulsion of a metal salt of an ethylene-(meth)acrylic acid copolymer. Such a coating liquid can, for example, form a coating film well on a support substrate, and moreover, can form a coating film that has excellent peelability from the support substrate, and the coating film also has excellent heat sealability.

[0051] It is preferable to use an aqueous ionomer emulsion as the emulsion described above. Such emulsions allow for relatively low control of the coating amount and, since they do not emit VOCs, they provide packaging materials with a low environmental impact.

[0052] The coating liquid for the heat seal layer may contain additives. Examples of additives include viscosity modifiers, defoamers, surfactants, leveling agents, lubricants, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and dyes.

[0053] The thickness of the heat seal layer is preferably 1 μm or more, more preferably 3 μm or more, preferably 25 μm or less, and more preferably 15 μm or less. In one embodiment, the thickness of the heat seal layer is 5 μm or more and 25 μm or less. The thickness of the heat seal layer is preferably changed as appropriate depending on the strength of the heat seal layer, the processability of the transfer film, and the mass of the contents filled into the packaging material manufactured using the barrier laminate of this disclosure.

[0054] The indentation hardness of the heat seal layer is preferably 0.15 GPa or less, more preferably 0.10 GPa or less, and even more preferably 0.08 GPa or less, with a lower limit of, for example, 0.01 GPa or 0.02 GPa. When the indentation hardness is 0.15 GPa or less, for example, the flexibility and gas barrier properties of the barrier laminate tend to be further improved.

[0055] The composite modulus of the heat seal layer is preferably 2.0 GPa or less, more preferably 1.5 GPa or less, and even more preferably 1.0 GPa or less, with a lower limit of, for example, 0.1 GPa or 0.2 GPa. When the composite modulus is 2.0 GPa or less, for example, the bending resistance and gas barrier properties of the barrier laminate tend to be further improved.

[0056] In this disclosure, the indentation hardness and composite modulus of the heat seal layer can be adjusted, for example, by appropriately selecting the components contained in the heat seal layer.

[0057] In this disclosure, the indentation hardness and composite modulus of the heat seal layer are measured by the nanoindentation method. Specifically, the indentation hardness and composite modulus of the heat seal layer of the transfer film are measured using a nanoindenter, with the cross-section of the heat seal layer of the transfer film as the measurement surface. The above cross-section is obtained by cutting in the thickness direction perpendicular to the main surface of the transfer film. The indenter is pressed into the area near the center in the thickness direction of the heat seal layer, where the cross-section of the heat seal layer is exposed. The measurement conditions are as follows: A Berkovich indenter (triangular pyramidal indenter) is used as the indenter for the nanoindenter. The indenter is pressed into the heat seal layer from the cross-section of the heat seal layer to an indentation depth of 100 nm over 10 seconds, held in that position for 5 seconds, and then unloaded over 10 seconds until the maximum load P is reached. max Contact projected area A at maximum depth p And obtain the load-displacement curve. From the obtained load-displacement curve, P max / A p The indentation hardness is calculated using the formula shown, and the composite modulus is calculated using the formula (1) below.

[0058]

number

[0059] Measurements are performed at room temperature (23°C). Measurements are taken at 10 or more locations on the same cross-section, and the indentation hardness and composite modulus are recorded as the arithmetic mean of the 10 values ​​measured with good reproducibility. Details of the measurement conditions are described in the Examples section.

[0060] <Anchor Coat Layer> The transfer film of this disclosure may further include an anchor coat layer between the heat seal layer and the inorganic vapor-deposited film. By providing the anchor coat layer, the adhesion between the heat seal layer and the inorganic vapor-deposited film can be improved, and the occurrence of delamination between these layers can be suppressed. The anchor coat layer may, for example, be in contact with the inorganic vapor-deposited film on one side and in contact with the heat seal layer on the other side.

[0061] In one embodiment, the anchor coat layer contains a resin component. Examples of the resin component include thermoplastic resins such as polyolefins (e.g., polyethylene and polypropylene), vinyl resins, styrene resins, (meth)acrylic resins, polyesters, polyurethanes, and polyamides; and cured products of thermosetting resins such as phenolic resins, melamine resins, epoxy resins, alkyd resins, thermosetting (meth)acrylic resins, unsaturated polyesters, and thermosetting polyurethanes. When using a thermosetting resin, it is preferable to use a curing agent such as an amine compound, phenolic compound, isocyanate compound, or carboxylic acid compound in combination. From the viewpoint of adhesion, polyester is preferred as the resin component.

[0062] Examples of polyesters include polymers synthesized by polycondensation of acidic components such as polycarboxylic acids, their esters and acid anhydrides with polyhydric alcohols, lactone ring-opening polymers, polyhydroxycarboxylic acid polymers, urea-modified polyesters, and urethane-modified polyesters. Urethane-modified polyesters are polyesters that have urethane bonds.

[0063] Urethane-modified polyester is a resin in which, for example, two or more polyesters are bonded together by structural units derived from polyvalent isocyanates. Such a resin can be obtained, for example, by reacting the terminal hydroxyl groups of polyester with the isocyanate groups of polyvalent isocyanates.

[0064] The glass transition temperature (Tg) of urethane-modified polyester may be 50°C or higher, 60°C or higher, 70°C or higher, 120°C or lower, or 110°C or lower. Tg is the intermediate glass transition temperature obtained by differential scanning calorimetry (DSC) in accordance with JIS K7121.

[0065] The hydroxyl value of urethane-modified polyester may be, for example, 1 mg KOH / g or more, 3 mg KOH / g or more, 5 mg KOH / g or more, 90 mg KOH / g or less, or 70 mg KOH / g or less. The hydroxyl value is expressed as the number of milligrams of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when 1 g of the sample is acetylated. The hydroxyl value is determined in accordance with JIS K0070-1992.

[0066] The number-average molecular weight (Mn) of urethane-modified polyester may be 500 or more, 1,000 or more, 50,000 or less, 30,000 or less, or 10,000 or less. Mn is measured by gel permeation chromatography (GPC) using polystyrene as the standard substance, in accordance with JIS K7252-1.

[0067] Urethane-modified polyesters can be obtained, for example, by reacting a polyester polyol with a polyvalent isocyanate. It is preferable that the urethane-modified polyester has two or more hydroxyl groups per molecule, obtained by reacting a polyester polyol with a polyvalent isocyanate in a ratio of excess hydroxyl groups to isocyanate groups. The reaction conditions for conventional urethane formation reactions can be broadly applied to the reaction between the polyester polyol and the polyvalent isocyanate.

[0068] Polyester polyols are resins having two or more hydroxyl groups in one molecule, obtained by esterifying an acidic component such as a polycarboxylic acid, its ester, or its acid anhydride with a polyhydric alcohol. Polyester polyols may also be polyesters obtained by the ring-opening reaction of caprolactone.

[0069] Examples of polycarboxylic acids include aliphatic polycarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, and dodecanedicarboxylic acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid; and aliphatic polycarboxylic acids such as butanetricarboxylic acid, tricarbaryl acid, and citric acid.

[0070] Examples of polyhydric alcohols include compounds having two or more hydroxyl groups in one molecule, and include dihydric alcohols such as aliphatic glycols and polyhydric alcohols of three or more hydroxyl groups. Examples of dihydric alcohols include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, and 2,2,4-trimethyl-1,3-pentanediol. Examples of polyhydric alcohols with a valency of 3 or higher include aliphatic glycols, glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol.

[0071] Examples of polyvalent isocyanates include compounds having two or more isocyanate groups in one molecule, specifically aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and trimethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, methylenebis(cyclohexyl isocyanate), and cyclohexane diisocyanate; and aromatic diisocyanates such as xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, and biphenylene diisocyanate.

[0072] Urethane-modified polyesters can also be obtained by simultaneously reacting an acid component such as a polycarboxylic acid, its ester, and its acid anhydride with a polyhydric alcohol and a polyhydric isocyanate.

[0073] In one embodiment, the anchor coat layer may contain a cured resin formed from a resin having reactive functional groups and a curing agent as the resin component. Examples of reactive functional groups include hydroxyl groups, carboxyl groups, and amino groups. Examples of resins having reactive functional groups include urethane-modified polyesters.

[0074] Examples of curing agents include isocyanate compounds such as aromatic isocyanate compounds and aliphatic isocyanate compounds. Specifically, examples of curing agents include aromatic isocyanate compounds such as tolylene diisocyanate (TDI-type isocyanate) and xylylene diisocyanate (XDI-type isocyanate); aliphatic isocyanate compounds such as hexamethylene diisocyanate (HDI-type isocyanate) and isophorone diisocyanate (IPDI-type isocyanate); modified products of these isocyanate compounds, as well as polyfunctionalized dimers, adducts, allophanates, trimers, carbodiimide adducts, biuretes, polymers thereof, and polymers to which polyhydric alcohols have been added. From the viewpoint of adhesion between the heat seal layer and the inorganic vapor-deposited film, aromatic isocyanate compounds are preferred as curing agents, and xylylene diisocyanate (XDI) is more preferred.

[0075] The amount of curing agent used may be 10 parts by mass or more, 20 parts by mass or more, 200 parts by mass or less, or 150 parts by mass or less, per 100 parts by mass of the resin having the above-mentioned reactive functional group. This can, for example, further improve the adhesion between the heat seal layer and the inorganic vapor-deposited film.

[0076] The resin component content in the anchor coat layer may be 30% by mass or more, 50% by mass or more, 60% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more. The resin component also includes the cured resin mentioned above.

[0077] The anchor coat layer may contain additives. Examples of additives include lubricants, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, dyes, and silane coupling agents.

[0078] The anchor coat layer may further contain compounds having a glucose ring. Examples of compounds having a glucose ring include polysaccharides such as cellulose and pullulan, and their derivatives. Examples of derivatives include methylated, nitrated, acetylated, carboxymethylated, and cyanoethylated compounds. Specifically, examples of derivatives include cellulose acetate butyrate, cellulose acetate, and methylcellulose; as well as compounds having a nitro group and a glucose ring, such as nitrocellulose.

[0079] By adding a compound having a glucose ring to the anchor coat layer, for example, the adhesion can be further improved. Furthermore, by adding a compound having a glucose ring to the anchor coat layer, the heat resistance of the anchor coat layer can be improved, and deterioration of the anchor coat layer due to heat when forming an inorganic vapor-deposited film on the anchor coat layer can be suppressed, and therefore the formed inorganic vapor-deposited film can easily exhibit the desired gas barrier properties.

[0080] The content of the glucose ring compound in the anchor coat layer may be 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 200 parts by mass or less, or 100 parts by mass or less, per 100 parts by mass of the resin component. When the content of the glucose ring compound is 20 parts by mass or more and 100 parts by mass or less, for example, adhesion and gas barrier properties can be further improved.

[0081] NO in the anchor coat layer, measured using time-of-flight secondary ion mass spectrometry (TOF-SIMS). 2- In one embodiment, the normalized strength of the ions may be 0.5 or higher, 1.0 or higher, or 2.0 or higher, but is preferably 3.0 or higher, more preferably 3.2 or higher, and even more preferably 3.5 or higher. NO in the anchor coat layer 2- In one embodiment, the normalized ion strength may be 5.0 or less, 4.5 or less, preferably 4.2 or less, and more preferably 4.0 or less. 2-When the ion normalization strength is 3.0 or higher, the gas barrier properties and the appearance of the anchor coat layer tend to be superior. 2- When the ion normalization strength is 4.2 or less, the gas barrier properties and the adhesion between the anchor coat layer and the inorganic vapor-deposited film tend to be superior.

[0082] NO 2- The normalized intensity of ions is calculated as follows: NO 2- The detection intensity of the ion (mass number 45.992) is CN - Normalization is performed by dividing by the detection intensity of the ion (mass number 26.002) and multiplying by 100,000. NO in the central region in the thickness direction of the anchor coat layer. 2- The common logarithm of the average detection intensity after normalization of ions is used to determine NO in the anchor coat layer. 2- The ion strength is normalized. Here, the central region of the anchor coat layer refers to the area near the center of the anchor coat layer, with a thickness of 50% of the total thickness of the anchor coat layer.

[0083] NO 2- Normalized intensity of ions = log 10 {(NO 2- Ion detection intensity / CN - (Ion detection intensity) × 100,000

[0084] The intensity of each ion is measured as follows: Using a time-of-flight secondary ion mass spectrometer (ION TOF, TOF.SIMS5), soft etching is repeatedly performed from the outside of the transfer film at a constant rate using a Cs (cesium) ion gun, and ions in each layer are detected. The specific measurement conditions are described in the Examples section.

[0085] The thickness of the anchor coat layer is measured as follows: In the graph obtained from the TOF-SIMS measurement before normalization, the interface between the inorganic vapor-deposited film and the anchor coat layer is defined as the position where the intensity of ions originating from the inorganic vapor-deposited film is 50% of the maximum intensity of ions originating from the inorganic vapor-deposited film. The ions originating from the inorganic vapor-deposited film are, for example, SiO2 (mass number 59.96) in the case of a silica vapor-deposited film. In the above graph obtained from TOF-SIMS measurement before normalization, CN - Ion intensity is CN - The interface between the anchor coat layer and the heat seal layer is defined as the position where the maximum ion intensity reaches 50%. The distance in the thickness direction between the two interfaces described above is defined as the thickness of the anchor coat layer.

[0086] In one embodiment, the transition temperature of the anchor coat layer may be 70°C to 140°C. The transition temperature is preferably 90°C or higher, more preferably 95°C or higher, even more preferably 100°C or higher, and particularly preferably 105°C or higher. The transition temperature may be, for example, 135°C or lower, 130°C or lower, 125°C or lower, or 120°C or lower. When the transition temperature is 90°C or higher, the gas barrier properties tend to be better. When the transition temperature is 125°C or lower, the gas barrier properties tend to be better.

[0087] The transition point of the anchor coat layer is a value measured by local thermal analysis using a thermal probe. In local thermal analysis using a thermal probe, the thermal probe is brought into contact with the cross-section of the anchor coat layer, and the displacement in the direction normal to the cross-section of the anchor coat layer is measured while the temperature of the thermal probe is increased, thereby obtaining a thermal expansion curve.

[0088] The above cross-section is obtained by cutting the transfer film in the thickness direction perpendicular to the main surface. The area where the thermal probe makes contact is near the center in the thickness direction of the anchor coat layer, within the portion where the cross-section of the anchor coat layer is exposed. Measurements are performed at five or more locations on the same cross-section, and the transition point is recorded as the arithmetic mean of the five values ​​measured with good reproducibility.

[0089] In local thermal analysis, heating causes the resin contained in the anchor coat layer to expand, pushing up the thermal probe. The slope of the thermal expansion curve (displacement / temperature) changes due to structural transitions in the resin of the anchor coat layer. In particular, when the structural transition of the resin in the anchor coat layer changes from expansion to softening, the tip of the thermal probe penetrates into the resin, causing the thermal probe to descend. The point where the displacement of the thermal probe changes from rising to falling corresponds to the peak of the thermal expansion curve and is called the softening point. By reading the temperature of the peak of the thermal expansion curve, the transition point of the anchor coat layer can be obtained.

[0090] A "shoulder peak" may appear on a thermal expansion curve as its slope (displacement / temperature) changes. A "shoulder peak" is defined as a point where the slope (displacement / temperature) of the thermal expansion curve changes and becomes close to zero, even though it is not a clearly convex shape. By drawing tangents to the thermal expansion curve in the temperature range before and after the change in the slope of the thermal expansion curve and calculating the temperature at the intersection, an inflection point can be obtained. This temperature at the inflection point is defined as the temperature of the "shoulder peak".

[0091] If a peak is obtained in the thermal expansion curve, the temperature at the peak of the thermal expansion curve is defined as the transition point. However, if a peak is not obtained in the thermal expansion curve and a "shoulder peak" is obtained, or if a "shoulder peak" is observed at a temperature lower than the temperature at which a peak can be obtained, the temperature of the "shoulder peak" is defined as the transition point. The transition point that appears at the lowest temperature after the start of measurement is defined as the transition point of the anchor coat layer. Details of the measurement conditions are described in the Examples section.

[0092] The thickness of the anchor coat layer is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. If the thickness is above the lower limit, for example, sufficient adhesion strength can be obtained between the heat seal layer and the inorganic vapor-deposited film. If the thickness is below the upper limit, for example, the anchor coat layer can be formed well on the heat seal layer.

[0093] <Inorganic vapor-deposited film> The transfer film of this disclosure comprises an inorganic vapor-deposited film. Preferably, the inorganic vapor-deposited film is a layer that is directly vapor-deposited onto one side of the heat seal layer, or, if an anchor coat layer is provided, onto one side of the anchor coat layer.

[0094] The inorganic vapor-deposited film is a layer that suppresses the permeation of gases such as oxygen and water vapor. Therefore, for example, a gas barrier laminate obtained by transferring a transfer layer from the transfer film of this disclosure to a transfer target has excellent gas barrier properties. If the inorganic vapor-deposited film is an opaque layer, the inorganic vapor-deposited film may also have light-shielding properties against sunlight and other light sources, and may also have aroma-retaining properties for the contents.

[0095] The inorganic vapor-deposited film may be a metal vapor-deposited film composed of a metal, or it may be a vapor-deposited film composed of an inorganic compound.

[0096] Examples of metals that can be used to make up a metal vapor-deposited film include aluminum, chromium, tin, nickel, copper, silver, gold, and platinum. Among these, aluminum is preferred. In other words, an aluminum vapor-deposited film is preferred.

[0097] Examples of inorganic compounds constituting the above-mentioned deposited film include metal oxides, metal nitrides and metal carbides, indium tin oxide (ITO), and SiO2. X C Y Examples of complex inorganic compounds include those listed above. Among these, metal oxides are preferred.

[0098] Examples of metallic elements that make up inorganic compounds include aluminum (Al), silicon (Si), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), zinc (Zn), vanadium (V), barium (Ba), and chromium (Cr).

[0099] The average composition of inorganic compounds is, for example, AlO x SiO x SiOx C y For example, MO x or MO x C y This is expressed as follows: In the formula, M represents the metal element mentioned above, and the values ​​of x and y differ in range depending on the metal element.

[0100] For metal oxides, x can take values ​​in the following ranges: greater than 0 and less than or equal to 1.5 for aluminum, greater than 0 and less than or equal to 2 for silicon, greater than 0 and less than or equal to 1 for magnesium, greater than 0 and less than or equal to 1 for calcium, greater than 0 and less than or equal to 0.5 for potassium, greater than 0 and less than or equal to 2 for tin, greater than 0 and less than or equal to 0.5 for sodium, greater than 0 and less than or equal to 1.5 for boron, greater than 0 and less than or equal to 2 for titanium, greater than 0 and less than or equal to 1 for lead, greater than 0 and less than or equal to 2 for zirconium, and greater than 0 and less than or equal to 1.5 for yttrium.

[0101] MO x In this case, the upper limit of the range of x is the value when it is completely oxidized. For aluminum oxide, a range of x from 0.5 to 1.5 is preferred, and for silicon oxide, a range of x from 1.0 to 2.0 is preferred.

[0102] Among metal oxides, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, boron oxide, titanium oxide, zirconium oxide, and barium oxide are preferred, with aluminum oxide and silicon oxide being more preferred.

[0103] The inorganic vapor-deposited film may be formed from one metal or inorganic compound, or from a combination of two or more metals or inorganic compounds. The inorganic vapor-deposited film may consist of a single layer, or from two or more layers of the same or different compositions.

[0104] When an inorganic vapor-deposited film is multilayered, each layer can be deposited to have high gas barrier properties, thus achieving even higher gas barrier properties than a single-layered film. Furthermore, if the composition of each layer is different in a multilayered inorganic vapor-deposited film, the inorganic vapor-deposited film consists of distinct, discontinuous layers, which allows for more efficient suppression of the permeation of oxygen gas, water vapor, and other gases.

[0105] The thickness of the inorganic vapor-deposited film is preferably 3 nm or more, more preferably 4 nm or more, even more preferably 5 nm or more, preferably 300 nm or less, more preferably 250 nm or less, even more preferably 200 nm or less, and particularly preferably 80 nm or less or 60 nm or less. If the thickness is above the lower limit, for example, sufficient oxygen barrier properties and water vapor barrier properties can be obtained. If the thickness is below the upper limit, for example, the occurrence of cracks in the inorganic vapor-deposited film can be suppressed.

[0106] In one embodiment, the thickness of the inorganic vapor-deposited film composed of aluminum oxide is preferably 3 nm or more, more preferably 5 nm or more, preferably 100 nm or less, and more preferably 50 nm or less. In one embodiment, the thickness of the inorganic vapor-deposited film composed of silicon oxide is preferably 3 nm or more, more preferably 10 nm or more, preferably 300 nm or less, and more preferably 50 nm or less. The thickness of the inorganic vapor-deposited film composed of silicon oxide is preferably 20 nm or more and 40 nm or less.

[0107] The inorganic vapor-deposited film may be subjected to surface treatment. This can improve the adhesion between the inorganic vapor-deposited film and adjacent layers (e.g., adhesive layers). Examples of surface treatment methods include physical surface treatments such as corona discharge treatment, ozone treatment, plasma treatment, glow discharge treatment, and sandblasting, as well as chemical surface treatments such as oxidation treatment using chemicals.

[0108] <Protective layer> The transfer film of this disclosure may further include a protective layer on the surface opposite to the heat-sealing layer side of the inorganic vapor-deposited film. This can, for example, suppress damage to the inorganic vapor-deposited film.

[0109] In one embodiment, the protective layer contains a resin component. Examples of resin components include polyethylene, polypropylene, polystyrene, vinyl chloride resin, polyester, (meth)acrylic resin, urethane resin, melamine resin, and epoxy resin. For example, urethane resin is preferred as the resin component.

[0110] The resin component content in the protective layer may be 50% by mass or more, 75% by mass or more, 95% by mass or less, or 90% by mass or less.

[0111] The protective layer may contain additives. Examples of additives include curing agents, antistatic agents, ultraviolet absorbers, colorants, heat stabilizers, and silane coupling agents. Examples of silane coupling agents include vinyl-based, epoxy-based, styryl-based, methacrylic-based, acrylic-based, amino-based, isocyanurate-based, ureido-based, mercapto-based, sulfide-based, or isocyanate-based silane coupling agents.

[0112] The thickness of the protective layer is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less.

[0113] For example, if the inorganic vapor-deposited film is composed of metal oxides such as aluminum oxide and silicon oxide, the transfer film of this disclosure may include a barrier coat layer as a protective layer on the inorganic vapor-deposited film. This can, for example, further improve the gas barrier properties of a barrier laminate.

[0114] In one embodiment, the barrier coating layer contains a gas barrier resin. Examples of gas barrier resins include ethylene-vinyl alcohol copolymer, polyvinyl alcohol, poly(meth)acrylonitrile; polyamides such as nylon 6, nylon 6,6 and polymethaxylylene adipamide (MXD6); polyester; polyurethane; and (meth)acrylic resin.

[0115] The content of the gas barrier resin in the barrier coat layer is preferably 50% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, preferably 95% by mass or less, and more preferably 90% by mass or less. If the content is above the lower limit, for example, the gas barrier properties of the barrier laminate can be further improved.

[0116] The barrier coating layer may contain the above-mentioned additives.

[0117] The thickness of the barrier coating layer is preferably 0.01 μm or more, more preferably 0.1 μm or more, preferably 10 μm or less, and more preferably 5 μm or less. If the thickness is above the lower limit, for example, the gas barrier properties of the barrier laminate can be further improved. If the thickness is below the upper limit, for example, the processability of the barrier laminate can be improved.

[0118] In another embodiment, the barrier coat layer is a gas barrier coating film formed by polycondensation treatment of a composition containing a metal alkoxide and a water-soluble polymer using a sol-gel method in the presence of a sol-gel catalyst, water, and an organic solvent. By providing such a barrier coat layer on an inorganic vapor-deposited film, the gas barrier properties can be improved.

[0119] In one embodiment, the metal alkoxide is represented by the following general formula. R 1 n M(OR 2 ) m

[0120] In the formula, R 1 and R 2Each of these is an organic group with 1 to 8 carbon atoms, M is a metal atom, n is a non-negative integer, m is a non-negative integer, and n+m represents the valence of M.

[0121] R 1 and R 2 Examples of organic groups represented by include alkyl groups having 1 to 8 carbon atoms, specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups. Examples of metal atoms M include silicon, zirconium, titanium, and aluminum.

[0122] Examples of metal alkoxides that satisfy the above general formula include tetramethoxysilane (Si(OCH3)4), tetraethoxysilane (Si(OC2H5)4), tetrapropoxysilane (Si(OC3H7)4), and tetrabutoxysilane (Si(OC4H9)4).

[0123] It is preferable to use a silane coupling agent together with the above-mentioned metal alkoxide. As the silane coupling agent, known organic reactive group-containing organoalkoxysilanes can be used, and organoalkoxysilanes having an epoxy group are preferred. Examples of organoalkoxysilanes having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. It is preferable to use the silane coupling agent in an amount of 1 to 20 parts by mass per 100 parts by mass of the metal alkoxide.

[0124] Preferred water-soluble polymers are polyvinyl alcohol and ethylene-vinyl alcohol copolymer. Depending on the desired physical properties such as oxygen barrier properties, water vapor barrier properties, water resistance, and weather resistance, either polyvinyl alcohol or ethylene-vinyl alcohol copolymer may be used, or both may be used in combination. Alternatively, a gas barrier coating film obtained using polyvinyl alcohol and a gas barrier coating film obtained using ethylene-vinyl alcohol copolymer may be laminated.

[0125] The content of the water-soluble polymer in the above composition is preferably 5 parts by mass or more and 500 parts by mass or less per 100 parts by mass of metal alkoxide. If the content is above the lower limit, for example, the gas barrier properties of the barrier laminate can be further improved. If the content is below the upper limit, for example, the film-forming properties of the above composition can be further improved.

[0126] Acids or amine compounds are preferred as catalysts for the sol-gel method. As amine compounds, tertiary amines that are substantially insoluble in water and soluble in organic solvents are preferred, such as N,N-dimethylbenzylamine, tripropylamine, tributylamine, and tripentylamine. Among these, N,N-dimethylbenzylamine is preferred.

[0127] The amount of amine compound used is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, preferably 1.0 part by mass or less, and more preferably 0.3 parts by mass or less, per 100 parts by mass of metal alkoxide. If the amount used is above the lower limit, for example, the catalytic effect can be improved. If the amount used is below the upper limit, for example, the thickness of the gas barrier coating film can be made uniform.

[0128] Acids are suitably used as catalysts for the hydrolysis of sol-gel catalysts, mainly metal alkoxides and silane coupling agents. Examples of acids include mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, as well as organic acids such as acetic acid and tartaric acid.

[0129] The amount of acid used is preferably 0.001 moles or more and 0.05 moles or less per mole of the total amount of the metal alkoxide and the alkoxide portion (e.g., silicate portion) of the silane coupling agent. If the amount of acid used is above the lower limit, for example, the catalytic effect can be improved. If the amount of acid used is below the upper limit, for example, the thickness of the gas barrier coating film can be made uniform.

[0130] The above composition preferably contains water in an amount of 0.1 moles or more, more preferably 0.8 moles or more, preferably 100 moles or less, and more preferably 2 moles or less, per mole of the total amount of alkoxide. If the water content is above the lower limit, for example, the gas barrier properties of the barrier laminate can be further improved. If the water content is below the upper limit, for example, the hydrolysis reaction can be carried out rapidly.

[0131] The above composition may contain an organic solvent. Examples of organic solvents include alcoholic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butanol.

[0132] The thickness of the gas barrier coating film is preferably 0.01 μm or more, more preferably 0.1 μm or more, preferably 100 μm or less, and more preferably 50 μm or less. This further improves the gas barrier properties of the barrier laminate. If the thickness is above the lower limit, for example, the gas barrier properties of the barrier laminate can be further improved, and the occurrence of cracks in the inorganic vapor-deposited film can be suppressed. If the thickness is below the upper limit, for example, a barrier laminate suitable for use in the manufacture of monomaterial packaging containers can be obtained.

[0133] <Adhesive layer> The transfer film of this disclosure may have an adhesive layer on the surface opposite to the heat-seal layer side of the inorganic vapor-deposited film. In the transfer method described later, the adhesive layer is a layer for bonding the transfer object (for example, a paper member having a paper substrate) with the transfer film comprising the support substrate, the heat-seal layer, and the inorganic vapor-deposited film. The transfer film does not have to have an adhesive layer; for example, an adhesive layer may be provided on the transfer object.

[0134] In one embodiment, the adhesive layer is a layer in contact with the inorganic vapor-deposited film. In this embodiment, the adhesive layer protects the inorganic vapor-deposited film. For example, when a bending load is applied to the transfer film, the adhesive layer suppresses the occurrence of cracks in the inorganic vapor-deposited film, and even if minute cracks begin to appear in the inorganic vapor-deposited film after the bending load, it suppresses a decrease in gas barrier properties. Details of the adhesive layer will be described later, and will not be explained here.

[0135] <Layer structure of transfer film> Several examples of the layer structure of the transfer film disclosed herein are given below. ·Inorganic vapor deposition film / HS layer / supporting base material ·Inorganic vapor deposition film / AC layer / HS layer / support base material • Protective layer / Inorganic vapor-deposited film / HS layer / Support substrate ·Protective layer / Inorganic vapor deposition film / AC layer / HS layer / Support base material • Protective layer / Inorganic vapor-deposited film / HS layer / Support substrate • Protective layer / Inorganic vapor-deposited film / AC layer / HS layer / Support substrate

[0136] "HS layer" refers to the heat seal layer, "AC layer" refers to the anchor coat layer, and " / " indicates the space between layers.

[0137] [Method for manufacturing transfer film] The method for manufacturing the transfer film of this disclosure may include a step of forming a heat seal layer on a support substrate (hereinafter also referred to as the "heat seal layer formation step"), a step of forming an anchor coat layer on the heat seal layer as needed (hereinafter also referred to as the "anchor coat layer formation step"), and a step of forming an inorganic vapor-deposited film on the heat seal layer or the anchor coat layer (hereinafter also referred to as the "vapor-deposited film formation step"). The above manufacturing method may also include a step of forming a protective layer on the inorganic vapor-deposited film (hereinafter also referred to as the "protective layer formation step").

[0138] <Heat seal layer formation process> The heat seal layer can be formed, for example, by applying a heat seal coating liquid to one surface of the support substrate and drying it. It is preferable to provide the heat seal layer on a surface of the support substrate that has not been treated for easy adhesion, or on a surface where an easy adhesion layer has not been formed.

[0139] The coating liquid for the heat seal layer is preferably one that can form a coating film on a support substrate and that has excellent peelability from the support substrate as well as heat sealability. Details of the coating liquid for the heat seal layer are as described above.

[0140] In one embodiment, a coating liquid for the heat seal layer is applied to a support substrate and dried. Examples of known coating methods for the heat seal layer coating liquid include gravure coating, reverse coating, air knife coating, comma coating, die coating, blade coating, roll coating, bar coating, curtain coating, spray coating, lip coating, and dipping.

[0141] Methods for drying the applied heat seal coating include, for example, hot air drying, hot roll drying, and methods involving the application of heat such as infrared irradiation. The drying temperature is preferably 50°C to 150°C.

[0142] <Anchor coat layer formation process> By providing an anchor coat layer on the heat seal layer, the adhesion of the inorganic vapor-deposited film can be improved, and the vapor-deposited surface can be smoothed. Depending on the required degree of gas barrier properties and interlayer strength, the anchor coat layer may not be necessary.

[0143] The anchor coating agent can be prepared, for example, by mixing the resin component or its precursor resin (e.g., thermosetting resin) described above with a curing agent as needed, an additive as needed, and a solvent. The details of these components are as described above, and the solvent can be the same as the solvent used for the heat seal layer coating liquid.

[0144] The anchor coat layer can be formed, for example, by applying an anchor coat agent onto a heat seal layer and drying it. Methods for applying the anchor coat agent include the known application methods described above. Methods for drying the applied anchor coat agent include, for example, applying heat such as hot air drying, hot roll drying, and infrared irradiation. The drying temperature is preferably 50°C to 150°C.

[0145] <Deposited film formation process> The inorganic vapor-deposited film is preferably a layer directly deposited onto one side of the heat seal layer or anchor coat layer. Examples of methods for forming the inorganic vapor-deposited film include physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, ion plating, and cluster ion beam deposition, as well as chemical vapor deposition (CVD) methods such as plasma chemical vapor deposition, thermochemical vapor deposition, and photochemical vapor deposition. The inorganic vapor-deposited film may also be a composite film comprising two or more different layers formed by using both physical vapor deposition and chemical vapor deposition methods in combination. Examples of heating means include resistance heating, induction heating, and electron beam heating.

[0146] The gas pressure in the deposition chamber is 10 -8 mbar or more (10) -2A pressure of mbar or less is preferred. When forming an inorganic vapor-deposited film composed of an inorganic compound, for example, oxygen gas, nitrogen gas, or carbon dioxide gas is introduced as the reaction gas. When forming an inorganic vapor-deposited film composed of a metal oxide, the gas pressure after the introduction of oxygen gas is 10 -6 mbar or more (10) -1 mbar or less is preferable.

[0147] The amount of reaction gas introduced varies depending on the size of the deposition machine, etc. Inert gases such as argon, helium, and nitrogen may be used as carrier gases for the reaction gases, such as oxygen, to the extent that they do not cause problems.

[0148] When using a roll-shaped transfer substrate and continuously forming an inorganic vapor-deposited film, the transport speed of the transfer substrate, on which the heat seal layer and, if necessary, the anchor coat layer are formed, is, for example, 10 m / min or more and 800 m / min or less.

[0149] During the formation of an inorganic vapor-deposited film, pretreatment using Ar gas, O2, or N2 can be used to clean the surface of the layer on which the inorganic vapor-deposited film will be deposited. By generating polar groups or free radicals on the surface of the layer, the adhesion between the inorganic vapor-deposited film and the layer can be improved.

[0150] In one embodiment, the PVD method uses, for example, a winding type deposition machine, where a substrate unwound from an unwinding roll is placed in a deposition chamber, where a deposition source heated in a crucible is evaporated, and an inorganic deposition film is formed on the substrate on a cooled coating drum while oxygen gas or the like is blown out from an oxygen gas outlet as needed, and then the substrate is wound onto a winding roll.

[0151] In one embodiment, the PE-CVD method involves introducing a mixed gas containing, for example, an organosilicon compound as a monomer gas, oxygen gas, and an inert gas into a deposition chamber, generating a plasma, and forming an inorganic deposition film composed of silicon oxide or the like on a substrate.

[0152] The above substrate comprises a transfer substrate, a heat seal layer, and optionally an anchor coat layer. In this way, a transfer film is obtained that comprises a transfer substrate, a heat seal layer, optionally an anchor coat layer, and an inorganic vapor-deposited film in this order in the thickness direction.

[0153] <Protective layer formation process> The protective layer can be formed, for example, by applying a protective coating solution onto an inorganic vapor-deposited film and drying it. Methods for applying the protective coating solution include the known methods described above. Methods for drying the applied protective coating solution include, for example, applying heat such as hot air drying, hot roll drying, and infrared irradiation. The drying temperature is preferably 50°C to 150°C.

[0154] The protective layer coating liquid can be prepared, for example, by mixing the resin components described above with a curing agent as needed, an additive as needed, and a solvent. The details of these components are as described above, and the solvent can be the same as the solvent used for the heat seal layer coating liquid.

[0155] A barrier coating layer, serving as a protective layer, can be formed, for example, by dissolving or dispersing a material such as a gas barrier resin in water or a suitable organic solvent, and then applying and drying the resulting coating solution onto an inorganic vapor-deposited film. Alternatively, a barrier coating layer can also be formed, for example, by applying and drying a commercially available barrier coating agent.

[0156] In one embodiment, the barrier coat layer is the gas barrier coating film described above. The gas barrier coating film can be formed, for example, by applying the above composition containing a metal alkoxide and a water-soluble polymer by a conventionally known coating method, and then polycondensing the composition by a sol-gel method.

[0157] The following describes one embodiment of a method for forming a gas barrier coating film. First, a metal alkoxide, a water-soluble polymer, a sol-gel catalyst, water, an organic solvent, and optionally a silane coupling agent are mixed to prepare a composition. A polycondensation reaction gradually proceeds within this composition.

[0158] Next, the composition is applied to the inorganic vapor-deposited film and dried using a conventionally known coating method. This drying further promotes the polycondensation reaction between the metal alkoxide and the water-soluble polymer (and the silane coupling agent if the composition contains one), forming a layer of composite polymer.

[0159] Finally, the above composition is heated at a temperature preferably between 20°C and 250°C, more preferably between 50°C and 220°C, for a period of preferably 1 second to 10 minutes. This allows a gas barrier coating film to be formed.

[0160] [Barrier laminate] In one embodiment, the barrier laminate of the present disclosure comprises a substrate such as a paper substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-seal layer in this order in the thickness direction. In one embodiment, the barrier laminate of the present disclosure further comprises an anchor coat layer between the inorganic vapor-deposited film and the heat-seal layer. Here, the inorganic vapor-deposited film and the heat-seal layer or the anchor coat layer (if an anchor coat layer is provided) are in contact.

[0161] In one embodiment, the barrier laminate of the present disclosure comprises a substrate such as a paper substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-seal layer in this order in the thickness direction. In one embodiment, the barrier laminate of the present disclosure further comprises an anchor coat layer between the inorganic vapor-deposited film and the heat-seal layer. The barrier laminate of this embodiment does not have a release layer between the inorganic vapor-deposited film and the heat-seal layer.

[0162] Figure 3 shows one embodiment of the barrier laminate of the present disclosure. The barrier laminate 1 in Figure 3 comprises a substrate 10, an adhesive layer 20, an inorganic vapor-deposited film 30, and a heat-seal layer 40 in this order in the thickness direction.

[0163] Figure 4 shows another embodiment of the barrier laminate of the present disclosure. The barrier laminate 1 in Figure 4 comprises a printed layer 12, a substrate 10, an adhesive layer 20, an inorganic vapor-deposited film 30, an anchor coat layer 32, and a heat seal layer 40 in this order in the thickness direction.

[0164] The barrier laminate of this disclosure does not have a release layer between the heat seal layer and the inorganic vapor-deposited film, resulting in high adhesion strength between these layers. Therefore, the barrier laminate of this disclosure suppresses the occurrence of delamination during the manufacturing process and during use.

[0165] A release layer is typically a layer provided as the surface layer on the transfer support side of a transfer film, in a conventional transfer film comprising a transfer support and a transfer layer, in order to improve the peelability of the transfer layer from the transfer support. In other words, the transfer layer includes a release layer as the surface layer on the transfer support side.

[0166] A release layer is typically a layer containing a release agent. Examples of release agents include waxes such as silicone wax, silicone oil, silicone resin, fluororesin, and phosphate ester. In one embodiment, the release layer contains a resin component. Examples of resin components include polyolefin, vinyl resin, styrene resin, (meth)acrylic resin, polyester, polyurethane, polycarbonate, polyamide, polyimide, and cellulose resin.

[0167] <Base material> The barrier laminate of this disclosure comprises a substrate.

[0168] Examples of substrates include paper substrates and the aforementioned resin films as support substrates. Among these, paper substrates are preferred. A barrier laminate comprising a paper substrate as the base material is also called "barrier paper".

[0169] Examples of paper substrates include kraft paper, pure white roll paper, fine paper, medium-quality paper, glassine paper, Bristol board, processed paper, cardboard, and synthetic paper. Alternatively, paper substrates may be used in which a sealing layer or resin layer is formed on one or both sides of the paper material, such as clay-coated paper, lightly coated printing paper, coated printing paper (e.g., coated paper, cast-coated paper, and art paper), resin-coated paper, release paper, and double-sided coated release paper.

[0170] The paper substrate may contain additives. Examples of additives include sizing agents, lubricants, antioxidants, UV absorbers, light stabilizers, antistatic agents, fluorescent whitening agents, fluorescent decolorizing agents, fillers, reinforcing agents, pigments, and dyes. Additives can be added in any amount as needed, as long as they do not adversely affect other properties.

[0171] The adhesive layer side of the substrate may be pre-treated with physical surface treatments such as corona discharge treatment, ozone treatment, plasma treatment, glow discharge treatment, and sandblasting, as well as chemical surface treatments such as oxidation treatment using chemicals.

[0172] In one embodiment, the paper substrate comprises the paper material described above and a sealing layer or resin layer formed on the surface of the paper material facing the adhesive layer. The sealing layer has the function of suppressing the penetration of the adhesive constituting the adhesive layer into the paper material and stabilizing the adhesive strength of the adhesive layer.

[0173] In one embodiment, the sealing layer or resin layer contains a resin component. Examples of resin components include polyolefins such as polyethylene and polypropylene, vinyl resins such as vinyl chloride resins and vinyl acetate resins, styrene resins such as styrene-butadiene copolymers, thermoplastic resins such as (meth)acrylic resins, polyesters, polyamides, polyurethanes, and cellulose resins; and cured products of thermosetting resins.

[0174] In one embodiment, the sealing layer or resin layer contains additives. Examples of additives include lubricants, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fluorescent whitening agents, fluorescent decolorizing agents, fillers, reinforcing agents, pigments, and dyes. The sealing layer or resin layer preferably contains fillers. Examples of fillers include clay, silica, calcium carbonate, titanium dioxide, and zinc oxide.

[0175] The sealing layer or resin layer can be formed, for example, by a coating method or an extrusion coating method. The thickness of the sealing layer or resin layer is, for example, 0.1 μm or more and 30 μm or less.

[0176] Generally, since the surface of paper materials is porous and uneven, it is sometimes preferable to form a sealing layer of 20 μm or more on the surface of the paper material when directly forming an inorganic vapor-deposited film on the paper material. However, in this disclosure, since barrier paper can be manufactured by the transfer method described later, it is not necessary to directly form an inorganic vapor-deposited film on the paper material. Therefore, it is not necessary to form such a thick sealing coat layer on the surface of the paper material.

[0177] Furthermore, when forming an inorganic vapor-deposited film in a reduced pressure environment by placing paper material inside a vapor deposition apparatus, paper dust generated from the paper material can hinder the reduction of pressure inside the vapor deposition apparatus to a suitable atmospheric pressure for vapor deposition. In such cases, it becomes difficult to form a stable inorganic vapor-deposited film, which can easily result in insufficient adhesion between the formed inorganic vapor-deposited film and the paper material, leading to unstable gas barrier properties. However, in this disclosure, since barrier paper can be manufactured by the transfer method described later, it is not necessary to place the paper material inside the vapor deposition apparatus and directly form an inorganic vapor-deposited film on the paper material. Therefore, the above-mentioned problems can be avoided.

[0178] Thus, in this disclosure, a paper substrate can be made of paper material and not impregnated with resin components, clay materials, etc. Furthermore, in this disclosure, a paper substrate can be made of paper material and not have a sealing layer, a resin layer, or a clay coat layer.

[0179] The substrate, such as a paper substrate, may consist of a single layer, or it may consist of two or more layers made of the same or different substrates. The substrates can be laminated together using any lamination method via conventionally known adhesive layers.

[0180] The thickness of the substrate, such as paper substrate, is preferably 10 μm or more, more preferably 30 μm or more, even more preferably 40 μm or more, preferably 1,500 μm or less, more preferably 500 μm or less, and even more preferably 300 μm or less. The basis weight of the paper substrate is preferably 30 g / m². 2 Above, a comfortable 50g / m 2 The above is preferable, preferably 600 g / m² 2 More preferably, 450 g / m² 2 The following applies: If the substrate is composed of multiple layers, the thickness of the substrate refers to the total thickness of the multiple layers of substrate. The same applies to basis weight.

[0181] With such thickness and / or basis weight, for example, appropriate strength and rigidity can be imparted to a barrier laminate. If the thickness and / or basis weight is above the lower limit, for example, curling and warping can be suppressed during the manufacturing of the barrier laminate. If the thickness and / or basis weight is below the upper limit, the strength and rigidity will be within an appropriate range, and a decrease in work efficiency can be suppressed.

[0182] <Print layer> In one embodiment, the barrier laminate of the present disclosure comprises a printed layer on a substrate such as a paper substrate. The barrier laminate of the present disclosure may have the printed layer on the surface of the substrate opposite to the adhesive layer side and / or on the surface of the substrate on the adhesive layer side, and it is preferable that the printed layer be on the surface of the substrate opposite to the adhesive layer side.

[0183] The printed layer includes, for example, an image. Examples of images include letters, figures, symbols, pictures, patterns, and combinations thereof. The printed layer is provided, for example, for indicating the contents of packaging materials, indicating the expiration date, indicating the manufacturer and seller, for decoration, and for adding aesthetic appeal.

[0184] In one embodiment, the printed layer is formed using a printing layer composition such as a thermoplastic resin composition, a thermosetting resin composition, and an energy-ray curable resin composition, each containing a colorant. Specifically, the printed layer contains a thermoplastic resin, a cured product of a thermosetting resin, or a cured product of an energy-ray curable resin, and a colorant.

[0185] The thermoplastic resin composition contains a thermoplastic resin and a coloring agent. Examples of thermoplastic resins include polyolefins, vinyl resins, styrene resins, (meth)acrylic resins, polyesters, polyurethanes, polycarbonates, polyamides, polyimides, cellulose resins, petroleum resins, and fluororesins.

[0186] Thermoplastic resin compositions may contain additives. Examples of additives include lubricants, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fluorescent whitening agents, fluorescent decolorizing agents, fillers, reinforcing agents, pigments, and dyes.

[0187] A thermosetting resin composition is a composition that contains a thermosetting resin, a colorant, and optionally a curing agent, and hardens upon heating. In one embodiment, the thermosetting resin composition is a so-called thermosetting ink.

[0188] Examples of thermosetting resins include phenolic resins, melamine resins, urea resins, epoxy resins, unsaturated polyesters, thermosetting polyurethanes, silicone resins, and (meth)acrylic thermosetting resins. Examples of curing agents include epoxy curing agents and isocyanate curing agents. The thermosetting resin composition may contain the above-mentioned additives.

[0189] An energy-ray curable resin composition is a composition that contains a compound having an energy-ray curable functional group (hereinafter also referred to as "energy-ray curable compound") and a colorant, and is cured by energy-ray irradiation. In one embodiment, the energy-ray curable resin composition is a so-called ultraviolet-curable ink, and preferably a (meth)acrylic ultraviolet-curable ink.

[0190] Examples of energy rays include electromagnetic waves such as ultraviolet rays, infrared rays, X-rays, and gamma rays; and charged particle beams such as electron beams, proton beams, and neutron beams. Among these, ultraviolet rays are preferred from the viewpoint of curing speed, ease of obtaining irradiation sources, and cost.

[0191] Examples of energy-ray curable functional groups include ethylenically unsaturated groups such as (meth)acryloyl groups, vinyl groups, and allyl groups; as well as epoxy groups and oxetanyl groups. Examples of energy-ray curable compounds include compounds having ethylenically unsaturated groups, with compounds having two or more ethylenically unsaturated groups being preferred, and polyfunctional (meth)acrylate compounds being more preferred. Both monomers and oligomers can be used as polyfunctional (meth)acrylate compounds.

[0192] When the energy ray-curable compound is an ultraviolet-curable compound, it is preferable that the energy ray-curable composition (ultraviolet-curable resin composition) contains at least one selected from a photopolymerization initiator and a photopolymerization accelerator. The energy ray curable resin composition may contain the above-mentioned additives.

[0193] Examples of colorants include pigments and dyes. Specific examples of pigments include titanium dioxide, zinc oxide, carbon black, iron oxide, iron yellow, ultramarine, metallic pigments, pearl pigments, and fluorescent pigments. The printed layer may also be a high-luminosity layer with a high metallic sheen.

[0194] Compositions for printing layers may contain organic solvents and / or water from the viewpoint of improving coatability and other properties. Examples of organic solvents include hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate, cellosolve acetate and butyl cellosolve acetate; and alcohol solvents such as propanol.

[0195] For example, a printing layer can be formed by applying and drying a printing layer composition onto a substrate such as a paper substrate, and then, in the case of a thermosetting resin composition, heating it to the temperature required for curing, or in the case of an energy-ray curable resin composition, irradiating it with energy rays. If the printing layer composition does not contain organic solvents and / or water, drying is not necessary.

[0196] Methods for forming the printed layer include, for example, letterpress printing, flexographic printing, gravure printing, offset printing, screen printing, inkjet printing, and thermal transfer printing. The printed layer may be applied to the entire surface of the substrate or to only a portion of it.

[0197] In one embodiment, the printed layer contains a sublimation dye. The printed layer in this embodiment can be formed, for example, by sublimation transfer printing using a thermal transfer sheet.

[0198] The thickness of the printed layer is preferably 0.01 μm or more, more preferably 0.5 μm or more, even more preferably 1 μm or more, preferably 30 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less.

[0199] <Adhesive layer> The barrier laminate of this disclosure comprises an adhesive layer between the substrate and the inorganic vapor-deposited film. In the transfer method described later, the adhesive layer is a layer for bonding a transfer subject, such as a paper member comprising a paper substrate, with a transfer film comprising a support substrate, a heat seal layer, and an inorganic vapor-deposited film.

[0200] In one embodiment, the adhesive layer is a layer in contact with the inorganic vapor-deposited film. In this embodiment, the adhesive layer protects the inorganic vapor-deposited film. For example, when a bending load is applied to the barrier laminate, the adhesive layer suppresses the occurrence of cracks in the inorganic vapor-deposited film, and even if minute cracks begin to appear in the inorganic vapor-deposited film after the bending load, it suppresses a decrease in gas barrier properties.

[0201] The thickness of the adhesive layer is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 20 μm or less, and more preferably 10 μm or less. The basis weight of the adhesive layer is preferably 1 g / m². 2 More than 2g / m 2 The above is preferable, preferably 20 g / m² 2 More preferably 10 g / m 2 The following applies:

[0202] The adhesive layer can be formed using conventionally known adhesives. The adhesive may be a one-component curing type, a two-component curing type, or a non-curing type adhesive. The adhesive may be a solvent-free type or a solvent-type adhesive. The adhesive layer may be formed, for example, by a non-solvent lamination method using a non-solvent adhesive, or by a dry lamination method using a dry lamination adhesive. An anchor coat layer may be formed first on the layer on which the adhesive layer will be formed, and then the adhesive layer may be formed.

[0203] The anchor coat layer can be formed using, for example, an anchor coat agent such as isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, or organotitanium-based; or an anchor coat agent such as (meth)acrylic resin-based, polyurethane-based, polyester-based, epoxy-based, polyvinyl acetate-based, polyvinyl chloride-based, or cellulose resin-based.

[0204] Examples of adhesives include two-component curing urethane adhesives, polyester polyurethane adhesives, polyether polyurethane adhesives, (meth)acrylic adhesives, polyester adhesives, polyether adhesives, polyamide adhesives, epoxy adhesives, rubber adhesives, polyolefin adhesives, acid-modified polyolefin adhesives, polyvinyl acetate adhesives, and polyvinyl chloride adhesives. Acid-modified polyolefin resins are resins obtained by acid-modifying polyolefin resins using unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid, or their anhydrides, by graft polymerization or copolymerization.

[0205] A urethane-based resin composition is preferred as the adhesive for forming an adhesive layer between a transfer target, such as a paper substrate, and an inorganic vapor-deposited film. This allows for the formation of, for example, a gas barrier adhesive layer. In other words, the adhesive layer is preferably a layer formed using a urethane-based resin composition. The urethane-based resin composition preferably contains a polyol having two or more hydroxyl groups in one molecule and an isocyanate compound having two or more isocyanate groups in one molecule. The urethane-based resin composition may further contain a phosphoric acid compound and may further contain an inorganic compound. The urethane resin composition may be solvent-free or solvent-based.

[0206] Examples of commercially available adhesives include the dry laminate adhesives (main component RU-40 / hardener H-1, and main component RU-77T / hardener H-7) manufactured by Rock Paint Co., Ltd.

[0207] The adhesive layer and the urethane resin composition may contain additives. Examples of additives include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fluorescent whitening agents, fluorescent decolorizing agents, fillers, reinforcing agents, antiblocking agents, flame retardants, crosslinking agents, pigments, and dyes.

[0208] In one embodiment, the adhesive layer has a glass transition temperature (Tg) in the range of preferably -30°C or higher, more preferably 0°C or higher, even more preferably 25°C or higher, preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 70°C or lower. If the Tg is below the upper limit, the adhesive layer tends to have excellent flexibility at room temperature and excellent adhesion to adjacent layers. If the Tg is above the lower limit, the adhesive layer tends to have excellent cohesive force and therefore excellent adhesion.

[0209] The adhesive layer can be formed by applying the adhesive to a substrate and / or an inorganic vapor-deposited film and optionally drying it, for example, by methods such as the direct gravure roll coating method, gravure roll coating method, kiss coating method, reverse roll coating method, fontein method, and transfer roll coating method.

[0210] <Polyols containing two or more hydroxyl groups in a single molecule> Examples of polyols having two or more hydroxyl groups in one molecule include polyols having two or more hydroxyl groups in one molecule and having at least one selected from polyester structural components, polyester polyurethane structural components, polyether structural components, and polyether polyurethane structural components as the main skeleton. Polyols having two or more hydroxyl groups in one molecule and having at least one selected from polyester structural components and polyester polyurethane structural components as the main skeleton are preferred, and polyols having two or more hydroxyl groups in one molecule and having a polyester structural component as the main skeleton are more preferred. The polyester structural component can be obtained, for example, by polycondensation reaction of polycarboxylic acids and polyhydroxy compounds.

[0211] Polycarboxylic acids refer to polycarboxylic acids, as well as their anhydrides and ester-forming derivatives. Examples of polycarboxylic acids include aliphatic polycarboxylic acids and aromatic polycarboxylic acids.

[0212] Examples of aliphatic polycarboxylic acids include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

[0213] Examples of aromatic polycarboxylic acids include dicarboxylic acids such as o-phthalic acid, isophthalic acid, terephthalic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, and 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; as well as trivalent or higher carboxylic acids such as trimellitic acid and pyromellitic acid. Among these, o-aromatic dicarboxylic acids are preferred. Examples of o-aromatic dicarboxylic acids include o-phthalic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid.

[0214] Examples of polyvalent hydroxy compounds include, Aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol; Aromatic polyhydric phenols such as hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, and tetramethylbiphenol, and their alkylene oxide adducts; and Hydrogenated alicyclic compounds of the above aromatic polyvalent phenols; These are some examples.

[0215] The polycarboxylic acid-derived structural portion constituting the polyester structural portion or polyester polyurethane structural portion preferably has a structural portion derived from o-aromatic dicarboxylic acids. It is preferable that 70% to 100% by mass of the polycarboxylic acid-derived structural portion constituting the polyester structural portion or polyester polyurethane structural portion is the structural portion derived from o-aromatic dicarboxylic acids. o-aromatic dicarboxylic acids refer to o-aromatic dicarboxylic acids, as well as their anhydrides and ester-forming derivatives.

[0216] <Isocyanate compounds having two or more isocyanate groups in one molecule> The isocyanate compounds having two or more isocyanate groups in one molecule may be aromatic compounds or aliphatic compounds, and may be low-molecular-weight compounds or high-molecular-weight compounds, as long as they have two or more isocyanate groups in one molecule. Examples include diisocyanate compounds having two isocyanate groups and polyisocyanate compounds having three or more isocyanate groups. Blocked isocyanate compounds obtained by addition reaction using a known isocyanate blocking agent by a known and conventional method may also be used.

[0217] The above isocyanate compound is preferably a compound having an aromatic ring in its main skeleton, and more preferably a compound having a polyurethane structure portion containing an aromatic ring in its main skeleton.

[0218] From the viewpoint of adhesion, polyisocyanate compounds are preferred, and from the viewpoint of gas barrier properties, polyisocyanate compounds having aromatic rings are more preferred. Isocyanate compounds containing a metaxylene skeleton are more preferred because they are expected to improve gas barrier properties not only through hydrogen bonding of urethane groups but also through π-π stacking between aromatic rings.

[0219] Examples of the above-mentioned isocyanate compounds include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, metaxylylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate. Trimers of these isocyanate compounds are also included. Adducts, burettes, or allophanates obtained by reacting an excess amount of these isocyanate compounds with an active hydrogen-containing low-molecular-weight compound or an active hydrogen-containing high-molecular-weight compound are also included.

[0220] Examples of low molecular weight compounds containing active hydrogen include ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, and metaxylylenediamine, as well as their alkylene oxide adducts. Examples of high molecular weight compounds containing active hydrogen include polyesters, polyether polyols, and polyamides.

[0221] <Inorganic vapor-deposited film> The barrier laminate of this disclosure comprises an inorganic vapor-deposited film. The inorganic vapor-deposited film is preferably a layer that is directly vapor-deposited on one side of the heat seal layer, or, if an anchor coat layer is provided, on one side of the anchor coat layer. Details of the inorganic vapor-deposited film are as described above and will not be explained further in this section.

[0222] <Protective layer> The barrier laminate of this disclosure may include a protective layer on the surface of the inorganic vapor-deposited film opposite to the heat-sealing layer side. This can, for example, suppress damage to the inorganic vapor-deposited film. Details of the protective layer are as described above and will not be explained further in this section.

[0223] <Anchor Coat Layer> The barrier laminate of this disclosure may further include an anchor coat layer between the heat seal layer and the inorganic vapor-deposited film. By providing the anchor coat layer, the adhesion between the heat seal layer and the inorganic vapor-deposited film can be improved, and the occurrence of delamination between these layers can be suppressed. The anchor coat layer, for example, is in contact with the inorganic vapor-deposited film on one side and in contact with the heat seal layer on the other side. Details of the anchor coat layer are as described above and will not be explained further in this section.

[0224] <Heat seal layer> The barrier laminate of this disclosure includes a heat-seal layer as a surface layer on one side. In one embodiment, the heat-seal layer functions as a heat-seal layer. For example, when the barrier laminate is used as a packaging material, the heat-seal layer functions as a heat-sealable sealant layer. Furthermore, when the barrier laminate is manufactured by a transfer method described later, the heat-seal layer also functions as a release layer from the support substrate. Details of the heat-seal layer are as described above and will not be explained further in this section.

[0225] <Functional layer> The barrier laminate of this disclosure may include a functional layer in addition to the layers described above. The functional layer is a layer that imparts to the barrier laminate functions such as light shielding, mechanical strength, deformation resistance, impact resistance, pinhole resistance, heat resistance, sealing, quality preservation, workability, and hygiene.

[0226] In one embodiment, the functional layer contains a resin component. Examples of resin components include polyolefins, vinyl resins, styrene resins, (meth)acrylic resins, polyesters, polyurethanes, polycarbonates, polyamides, polyimides, fluororesins, cellulose resins, and ionomer resins.

[0227] The functional layer may contain the above-mentioned additives according to its function. The thickness of the functional layer is, for example, between 1 μm and 300 μm.

[0228] <Layer structure and uses of barrier paper> Regarding the layer structure of the barrier paper of the present disclosure, several examples are given below. ·Paper substrate / Adhesive layer / Inorganic vapor deposition film / HS layer ·Paper substrate / Adhesive layer / Inorganic vapor deposition film / AC layer / HS layer ·Paper substrate / Adhesive layer / Protective layer / Inorganic vapor deposition film / HS layer ·Paper substrate / Adhesive layer / Protective layer / Inorganic vapor deposition film / AC layer / HS layer ·Printing layer / Paper substrate / Adhesive layer / Inorganic vapor deposition film / HS layer ·Printing layer / Paper substrate / Adhesive layer / Inorganic vapor deposition film / AC layer / HS layer ·Printing layer / Paper substrate / Adhesive layer / Protective layer / Inorganic vapor deposition film / HS layer ·Printing layer / Paper substrate / Adhesive layer / Protective layer / Inorganic vapor deposition film / AC layer / HS layer ·Paper substrate / Adhesive layer / Protective layer / Protective layer / Inorganic vapor deposition film / HS layer ·Paper substrate / Adhesive layer / Protective layer / Protective layer / Inorganic vapor deposition film / AC layer / HS layer ·Printing layer / Paper substrate / Adhesive layer / Protective layer / Protective layer / Inorganic vapor deposition film / HS layer ·Printing layer / Paper substrate / Adhesive layer / Protective layer / Protective layer / Inorganic vapor deposition film / AC layer / HS layer

[0229] The "HS layer" means a heat seal layer, the "AC layer" means an anchor coat layer, and " / " means between layers. The paper substrate may be a paper material / sealing layer (or resin layer). In this case, for example, the part of "paper substrate / adhesive layer" in the above layer structure becomes "paper material / sealing layer (or resin layer) / adhesive layer". Instead of the paper substrate, a resin film may be used, or a substrate that is difficult to directly vapor-deposit (such as wood, etc.) may be used.

[0230] Compared with a gas barrier plastic film, the barrier paper of the present disclosure has a paper substrate, so the content of paper material is high and the content of plastic is low, which can contribute to the reduction of plastic waste, and also makes recycling and biodegradation easier, does not damage the incinerator, and can reduce the incineration residue.

[0231] The oxygen permeability of the barrier laminate such as barrier paper of the present disclosure is preferably 10 cc / m 2 / 24hr / atm or less, more preferably 5 cc / m 2 / 24hr / atm or less, still more preferably 3 cc / m 2 / 24hr / atm or less, particularly preferably 1.5 cc / m 2 / 24hr / atm or less. The lower limit value of the oxygen permeability may be, for example, 0.01 cc / m 2 / 24hr / atm. The oxygen permeability is measured in accordance with JIS K7126 under the conditions of 23°C and 90%RH.

[0232] The water vapor permeability of the barrier laminate such as barrier paper of the present disclosure is preferably 20 g / m 2 / 24hr or less, more preferably 10 g / m 2 / 24hr or less, still more preferably 5 g / m 2 / 24hr or less, particularly preferably 1.5 g / m 2 / 24hr or less. The lower limit value of the water vapor permeability may be, for example, 0.01 g / m 2 / 24hr. The water vapor permeability is measured in accordance with JIS K7129 under the conditions of 40°C and 90%RH.

[0233] The barrier laminate of the present disclosure can be suitably used for packaging material applications such as packaging bags. As described above, since the barrier laminate of the present disclosure has excellent interlayer adhesion and interlayer peeling is suppressed, the packaging material provided with the barrier laminate suppresses the occurrence of so-called delamination during its use.

[0234] The packaging material of the present disclosure includes the barrier laminate of the present disclosure. The packaging material of the present disclosure may further include layers having various functions together with the above-mentioned barrier laminate as required.

[0235] For example, a packaging material can be manufactured by folding the barrier laminate in half so that the base material, such as a paper substrate, is on the outside and the heat-seal layer is on the inside, overlapping the layers, and then heat-sealing the edges. Alternatively, a packaging material can be manufactured by overlapping multiple barrier laminates so that their heat-seal layers face each other, and then heat-sealing the edges. The entire packaging material may be composed of the barrier laminate, or only a portion of the packaging material may be composed of the barrier laminate.

[0236] Examples of heat sealing forms for packaging materials include side seals, two-side seals, three-side seals, four-side seals, envelope seals, gusset seals (pillow seals), pleated seals, flat-bottom seals, square-bottom seals, and gusset seals. Stand-up pouches are also possible. Examples of heat sealing methods include bar seals, rotary roll seals, belt seals, impulse seals, high-frequency seals, and ultrasonic seals.

[0237] Examples of contents to be filled into the packaging material include liquids, powders, and gels, and may be food or non-food items. After filling the packaging material with contents, the opening of the packaging material is heat-sealed to obtain the package.

[0238] The contents specifically include coffee beans, tea leaves; cheese, snacks, rice crackers, fresh and semi-fresh confectionery, nuts, vegetables, fruits, fish and meat products, processed fish products, dried fish, smoked foods, preserved foods, raw rice, cooked rice dishes, mochi, baby food, jam, mayonnaise, ketchup, cooking oil, dressings, sauces, spices, dairy products, and pet food; beverages such as beer, wine, fruit juice, green tea, and coffee; pharmaceuticals; cosmetics, shampoo, conditioner, and detergents; and metal and electronic components.

[0239] [Method for manufacturing barrier laminates] The barrier laminate of this disclosure can be obtained, for example, by the transfer method described below. The method for producing a barrier laminate by the above transfer method is as follows: A step of preparing a transfer object such as a paper component having a paper substrate and the transfer film of this disclosure (hereinafter also referred to as the "preparation step"), The process involves bonding the object to be transferred and the transfer film via an adhesive layer, with the support substrate of the transfer film facing outwards and the inorganic vapor-deposited film facing inwards (towards the object to be transferred), to obtain an intermediate laminate (hereinafter also referred to as the "bonding process"). The process includes a step of peeling the support substrate from the heat seal layer of the intermediate laminate (hereinafter also referred to as the "peeling step").

[0240] Figure 5 is a process diagram showing an example of a method for manufacturing the barrier laminate according to this disclosure.

[0241] Through the aforementioned bonding and peeling processes, a transfer layer comprising an inorganic vapor-deposited film and a heat-seal layer in that order in the thickness direction can be transferred onto a transfer target such as a paper member. The inorganic vapor-deposited film transferred onto the paper substrate by the transfer method is less contaminated, has higher adhesion between the inorganic vapor-deposited film and the adhesive layer, is more homogeneous and stable, and has superior gas barrier properties compared to an inorganic vapor-deposited film directly vapor-deposited onto the paper substrate.

[0242] The manufacturing method of this disclosure makes it possible to provide an inorganic vapor-deposited film on a paper substrate in the same way as when using a resin substrate, thereby obtaining a barrier paper that has excellent gas barrier properties and is environmentally friendly.

[0243] Furthermore, in a method for forming a heat-seal layer by forming an inorganic vapor-deposited film on a paper substrate and then applying a heat-seal coating solution onto the inorganic vapor-deposited film, the gas barrier properties of the inorganic vapor-deposited film may decrease due to cracks or thermal damage caused by tension or drying during the formation of the heat-seal layer. The manufacturing method of this disclosure can avoid such a decrease. In addition, the heat-seal layer can suppress the deterioration of the inorganic vapor-deposited film during the application process and during the peeling process when the supporting substrate is peeled off.

[0244] The manufacturing method of the present disclosure can suppress the degradation of the inorganic vapor-deposited film, and therefore, for example, when a barrier laminate is used as a packaging material, the degree of degradation due to bending, folding, and heat seal damage can be reduced.

[0245] It should be noted that a reference barrier paper (hereinafter also referred to as "reference barrier paper") with a different layer structure from the barrier paper disclosed herein may also be considered, having a layer structure of paper substrate / adhesive layer / inorganic vapor-deposited film / release layer / primer layer / heat seal layer if necessary.

[0246] One example of a method for manufacturing the reference barrier paper is to bond a paper substrate and a transfer film comprising a transfer substrate, a release layer, and an inorganic vapor-deposited film via an adhesive layer to form a laminate (1) having a layer structure of paper substrate / adhesive layer / inorganic vapor-deposited film / release layer / transfer substrate; peel off the transfer substrate from the laminate (1) to form a laminate (2) having a layer structure of paper substrate / adhesive layer / inorganic vapor-deposited film / release layer; and, if necessary, form a primer layer and a heat seal layer on the release layer of the laminate (2) to obtain the reference barrier paper. Hereinafter, this manufacturing method will also be referred to as the "reference transfer method".

[0247] The reference transfer method has several advantages over inorganic vapor-deposited films that are transferred onto a paper substrate by the transfer method. These films result in less contamination, higher adhesion between the inorganic vapor-deposited film and the adhesive layer, greater homogeneity and stability, and superior gas barrier properties compared to inorganic vapor-deposited films directly deposited onto the paper substrate.

[0248] However, since the reference barrier paper has a release layer between the heat seal layer and the inorganic vapor-deposited film, the adhesion strength between these layers may not be sufficient. In addition, in the reference transfer method, after peeling off the transfer substrate, it is necessary to separately form a heat seal layer (heat-sealable sealant layer) on the release layer, for example, when manufacturing packaging materials, which increases the number of manufacturing steps.

[0249] In contrast, since the barrier paper of the present disclosure does not include a release layer between the heat seal layer and the inorganic vapor deposition film, the adhesion strength between these layers is sufficiently high. Further, in the manufacturing method of the present disclosure, the heat seal layer also serves as a release layer from the support substrate, and after peeling the support substrate, there is no need to separately form the heat seal layer (heat sealant layer), so the number of manufacturing steps can be reduced.

[0250] Further, in the manufacturing method of the present disclosure, in one embodiment, the heat seal layer and the inorganic vapor deposition film are pre-formed on a thin film support substrate. In the production of the transfer film, since processing can be performed in a wider width and longer length than that of a paper substrate, the cost per unit area of the barrier paper can be reduced.

[0251] Thus, although both the reference barrier paper and the reference transfer method have excellent advantages, the barrier paper of the present disclosure and its manufacturing method are further excellent in the above-mentioned points and can be said to have advantageous effects.

[0252] <Preparation step> In the preparation step, a transfer body such as a paper member and a transfer film are prepared.

[0253] Examples of the transfer body include a paper member. The paper member includes a paper substrate. The paper member may be a single sheet or a continuous sheet wound in a roll shape.

[0254] The paper member may include only the paper substrate, or may include the paper substrate and a printing layer provided on the paper substrate. The paper member preferably has a printing layer on the surface opposite to the surface on which the adhesive layer of the paper substrate is provided. In the preparation step, a printing layer may be formed on the paper substrate to produce a paper member, or a paper member having a printing layer provided on the paper substrate in advance may be used. The printing layer may be formed between the sticking step and the peeling step, or after the peeling step, but from the viewpoint of suppressing a decrease in gas barrier properties, it is preferable to form the printing layer before the sticking step.

[0255] The paper substrate may consist only of paper material, or it may consist of paper material and a sealing layer or resin layer formed on the paper material. By using a paper substrate with a sealing layer or resin layer on the paper material, the penetration of the adhesive into the paper material can be suppressed, and the adhesive strength of the adhesive layer can be stabilized. In the preparation step, the paper substrate may be made by forming the sealing layer or resin layer on the paper material, or a paper substrate that already has a sealing layer or resin layer on it, such as coated paper, may be used.

[0256] In addition to forming the printing layer described above, the paper substrate may be decorated on the side opposite to the side where the adhesive layer is applied, for example, by foil stamping, embossing, and shaping. The paper member obtained in this way may be used. Decoration may be performed between the bonding and peeling steps, or after the peeling step, but from the viewpoint of suppressing a decrease in gas barrier properties, it is preferable to perform the decoration before the bonding step. Details of each element are as described above and will not be described here.

[0257] The resin film described above may be used as the transfer target and supporting substrate. Alternatively, substrates that are difficult to directly deposit (e.g., wood) may be used.

[0258] In the preparation step, the transfer film of this disclosure, which has been prepared in advance, is prepared.

[0259] <Pasting process> In the bonding process, the transfer object, such as a paper component, and the transfer film are bonded together via an adhesive layer, with the support substrate of the transfer film facing outwards and the inorganic vapor-deposited film facing inwards (towards the transfer object), to obtain an intermediate laminate (see Figures 5(A) and (B)). In one embodiment, by providing an adhesive layer between the paper substrate and the inorganic vapor-deposited film, the inorganic vapor-deposited film can be stably bonded even if the surface of the paper substrate is rough.

[0260] In the application process, the adhesive layer may be formed on either the object to be transferred or the transfer film, or on both. Adhesive may also be supplied between the object to be transferred and the transfer film to simultaneously form the adhesive layer and bond the object to be transferred and the transfer film.

[0261] In the application process, in one embodiment, an adhesive layer is formed on the transfer object, and the transfer film is bonded to the adhesive layer. In one embodiment, it is preferable to form the adhesive layer on the sealing layer or resin layer of the paper member.

[0262] In the application process, in one embodiment, an adhesive layer is formed on the transfer film, and the object to be transferred is bonded to the adhesive layer. The adhesive layer is formed on the side of the transfer film opposite to the support substrate. In one embodiment, it is preferable to form the adhesive layer on the inorganic vapor-deposited film of the transfer film.

[0263] In the bonding process, in one embodiment, an adhesive layer is formed on the object to be transferred, an adhesive layer is formed on the transfer film, and the object to be transferred and the transfer film are bonded together so that their adhesive layers are in contact.

[0264] Specific methods for forming the adhesive layer include, for example, a method of forming a coating layer by applying a liquid adhesive composition, a dry lamination method using a dry laminating adhesive, and a non-solvent lamination method using a non-solvent adhesive.

[0265] Prior to forming the adhesive layer, an anchor coat layer may be formed before forming the adhesive layer to improve its adhesion. The anchor coat agent is preferably formed by application and drying.

[0266] The bonding process can be carried out using generally known equipment, temperature, and pressure, depending on the type and characteristics of the adhesive and the method of forming the adhesive layer. For example, when forming the adhesive layer by a dry lamination method, in one embodiment, a dry lamination adhesive is applied to the transfer object and / or transfer film to form an adhesive layer, the transfer object and transfer film are overlapped with the adhesive layer in between, and then pressurized to obtain an intermediate laminate. Heating may be used as needed.

[0267] The method and pressure of pressing the intermediate laminate during the bonding process should preferably be selected and set in a way that minimizes damage to the inorganic vapor-deposited film. The pressure during pressing is preferably between 0.1 MPa and 10 MPa. For example, the adhesive layer may be softened by heating before bonding. Depending on the composition of the adhesive, the adhesive layer may be cured by heating after bonding.

[0268] <Peeling process> In the peeling process, the support substrate is peeled from the heat-sealed layer of the intermediate laminate (see Figure 5(C)). For example, after sufficient adhesive strength has been achieved by the adhesive layer between the object to be transferred and the transfer film, the support substrate is peeled from the intermediate laminate. Peeling can be performed using known apparatus and temperature, depending on the type and characteristics of the adhesive layer and the method of forming the adhesive layer.

[0269] In one embodiment, the support substrate of the transfer film may be peeled off while the object to be transferred and the transfer film are bonded together via an adhesive layer. In this way, a barrier laminate such as the barrier paper of this disclosure can be obtained.

[0270] For example, if the intermediate laminate is a continuous sheet wound in a roll shape, a release roll may be used to continuously peel the support substrate from the heat seal layer of the intermediate laminate, and the barrier laminate and the support substrate may be wound up separately.

[0271] This disclosure relates, for example, to the following [1] to

[19] . [1] A transfer film comprising a support substrate, a heat seal layer, and an inorganic vapor-deposited film in this order in the thickness direction, wherein the inorganic vapor-deposited film and the heat seal layer are in contact, or the transfer film further comprises an anchor coat layer between the inorganic vapor-deposited film and the heat seal layer, wherein the inorganic vapor-deposited film and the anchor coat layer are in contact. [2] The transfer film according to [1], wherein the inorganic vapor-deposited film is directly vapor-deposited onto one side surface of the heat seal layer. [3] The transfer film according to [1], wherein the inorganic vapor-deposited film is directly vapor-deposited onto one side surface of the anchor coat layer. [4] The transfer film according to any one of the above [1] to [3], further comprising a protective layer on the inorganic vapor-deposited film. [5] The transfer film according to any one of [1] to [4], wherein the inorganic vapor-deposited film contains at least one selected from aluminum, aluminum oxide, and silicon oxide. [6] The transfer film according to any one of the above [1] to [5], wherein the indentation hardness of the heat-seal layer by nanoindentation method is 0.15 GPa or less and the composite modulus is 2.0 GPa or less. [7] The transfer film according to any one of the above [1] to [6], wherein the transition point of the anchor coat layer, as measured by local thermal analysis using a thermal probe, is 90°C or higher and 140°C or lower. [8] NO in the anchor coat layer is measured while etching the transfer film using time-of-flight secondary ion mass spectrometry (TOF-SIMS). 2- A transfer film according to any one of the above [1] to [7], wherein the normalized ion strength is 3.0 or more and 4.2 or less. [The above normalized strength is determined by NO using TOF-SIMS.] 2- Ion detection intensity CN - The NO is normalized by dividing it by the detection intensity of the ions and multiplying by 100,000. 2- This refers to the common logarithm of the average value of the normalized detection intensity of ions. [9] A barrier laminate comprising a substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-seal layer in this order in the thickness direction, wherein the inorganic vapor-deposited film and the heat-seal layer are in contact, or the barrier laminate further comprises an anchor coat layer between the inorganic vapor-deposited film and the heat-seal layer, wherein the inorganic vapor-deposited film and the anchor coat layer are in contact.

[10] The barrier laminate according to [9], wherein the inorganic vapor-deposited film is directly vapor-deposited and formed on one side surface of the heat seal layer.

[11] The barrier laminate according to [9], wherein the inorganic vapor-deposited film is directly vapor-deposited and formed on one side surface of the anchor coat layer.

[12] A barrier laminate comprising a substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-seal layer in this order in the thickness direction, wherein there is no release layer between the inorganic vapor-deposited film and the heat-seal layer.

[13] The barrier laminate according to

[12] , further comprising an anchor coat layer between the inorganic vapor-deposited film and the heat seal layer.

[14] The barrier laminate according to any one of the above [9] to

[13] , wherein the inorganic vapor-deposited film contains at least one selected from aluminum, aluminum oxide, and silicon oxide.

[15] The barrier laminate according to any one of the above [9] to

[14] , wherein the substrate is a paper substrate.

[16] The barrier laminate according to

[15] , wherein the paper substrate comprises a paper material and a sealing layer or resin layer formed on the surface of the paper material on the side of the adhesive layer.

[17] A barrier laminate comprising a paper substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-seal layer in this order in the thickness direction, wherein the inorganic vapor-deposited film and the heat-seal layer are in contact, or the barrier laminate further comprises an anchor coat layer between the inorganic vapor-deposited film and the heat-seal layer, wherein the inorganic vapor-deposited film and the anchor coat layer are in contact, and the paper substrate is made of paper material and does not comprise a sealing layer, a resin layer, or a clay coat layer.

[18] The barrier laminate according to any one of the above [9] to

[17] , further comprising a printed layer on the surface of the substrate opposite to the adhesive layer side.

[19] The barrier laminate according to any one of the above [9] to

[18] , wherein the thickness of the adhesive layer is 0.5 μm or more and 20 μm or less. [Examples]

[0272] The transfer films and barrier laminates of this disclosure will be described in more detail based on the following examples, but the transfer films and barrier laminates of this disclosure are not limited to these examples.

[0273] The main products used in the examples are as follows: [Paper substrate] • Paper substrate A: Manufactured by Daio Paper Corporation, Ryuo Coat, sheet-fed Basis weight 55g / m 2 Single-sided coated product. • Paper base material B: Manufactured by Daio Paper Corporation, Ryuo Coat, sheet-fed. Basis weight 80g / m 2 Single-sided coated product. • Paper base material C: Manufactured by Daio Paper Corporation, Nagoya Sarashi Ryuo, sheet-fed. Basis weight 50g / m 2 , Single-glazed item.

[0274] [Adhesive] • Adhesive A: Manufactured by Rock Paint Co., Ltd., adhesive for dry lamination. RU-40 / H-1=15 / 2 mass ratio, When in use, it is bonded using the dry lamination method. • Adhesive B: Manufactured by Rock Paint Co., Ltd., adhesive for dry lamination. RU-77T / H-7=10 / 1 mass ratio, When in use, it is bonded using the dry lamination method.

[0275] [Examples] [Example 1A: Preparation of Transfer Film A] A heat-seal layer with a thickness of 5 μm was formed by applying a heat-seal coating solution having the following composition to the non-corona-treated side of a PET film (manufactured by Toyobo Co., Ltd., 12 μm thick, corona-treated on one side) using the gravure coating method and drying it. An anchor coating agent was prepared by mixing polyester (manufactured by Toyobo Co., Ltd., trade name: Byron® UR1700) as the main agent, XDI-based isocyanate (manufactured by Mitsui Chemicals, Inc., trade name: Takenate D110N) as the curing agent, and nitrocellulose as an additive, in a ratio of main agent:curing agent:nitrocellulose (solid content mass ratio) of 1:1:1. The anchor coating agent was applied to the heat-seal layer using the gravure coating method and dried to form an anchor coating layer with a thickness of 500 nm. An aluminum vapor-deposited film with a thickness of 45 nm was formed on the anchor coating layer as an inorganic vapor-deposited film by physical vapor phase growth. A protective coating solution containing urethane resin and a silane coupling agent was applied to an aluminum vapor-deposited film by gravure coating and dried to form a protective layer with a thickness of 750 nm. In this way, a transfer film A having a layer structure of PET film / heat seal layer / anchor coat layer / aluminum vapor-deposited film / protective layer was obtained.

[0276] (Coating liquid for heat seal layer) Chemipearl (registered trademark) S120 (Mitsui Chemicals, Inc., Aqueous ionomer emulsion, Composition: Metal salt of ethylene-methacrylic acid copolymer, Self-emulsifying emulsion)

[0277] [Example 1B: Preparation of Transfer Film B] Except for forming a 20 nm thick aluminum oxide vapor-deposited film as an inorganic vapor-deposited film, a transfer film B was obtained in the same manner as the preparation of transfer film A, having a layer structure of PET film / heat seal layer / anchor coat layer / aluminum oxide vapor-deposited film / protective layer.

[0278] [Example 1C: Preparation of Transfer Film C] Except for forming a 35 nm thick silicon oxide vapor-deposited film as an inorganic vapor-deposited film by physical vapor deposition, a transfer film C was obtained in the same manner as the preparation of transfer film A, having a layer structure of PET film / heat seal layer / anchor coat layer / silicon oxide vapor-deposited film / protective layer.

[0279] [Example 1] Adhesive A is applied to the coated surface of paper substrate A (A4 size), with a basis weight of 3.0 g / m² after drying. 2 The adhesive layer A was formed by applying and drying it in such a manner.

[0280] The adhesive layer A surface of paper substrate A and the protective layer surface of transfer film A (A4 size) were placed facing each other, bonded together, and then subjected to pressure of 0.5 MPa, followed by aging at 40°C for 3 days. In this way, an intermediate laminate having a layer structure of paper substrate A [paper material / coating layer] / adhesive A layer / protective layer / aluminum vapor-deposited film / anchor coat layer / heat seal layer / PET film was obtained. The PET film in the above-mentioned intermediate laminate was peeled off to obtain barrier paper.

[0281] [Examples 2 - 6] Barrier paper was obtained using the same procedure as in Example 1, except that the type of paper substrate, the type of adhesive, and the transfer film were changed as described in Table 1.

[0282] [Reference Examples] [Reference Example 1A: Preparation of Reference Transfer Film A] A diluted release agent solution (a mixture of release agent k-45-3 and ethyl acetate, manufactured by Showa Ink Co., Ltd., in a 1:1 mass ratio) was applied to the corona-treated surface of a PET film (manufactured by Toyobo Co., Ltd., 12 μm thick, corona-treated on one side) until the basis weight after drying was 1.0 g / m². 2The film was coated by bar coating and dried in an 80°C oven for 1 minute to form a release layer, thereby obtaining a release substrate comprising a PET film and a release layer. An aluminum vapor-deposited film with a thickness of 45 nm was formed on the release layer as an inorganic vapor-deposited film by physical vapor phase growth. A protective coating liquid containing urethane resin and a silane coupling agent was applied to the aluminum vapor-deposited film by gravure coating and dried to form a protective layer with a thickness of 750 nm. In this way, a reference transfer film A having a layer structure of PET film / release layer / aluminum vapor-deposited film / protective layer was obtained.

[0283] [Reference Example 1B: Preparation of Reference Transfer Film B] Except for forming a 20 nm thick aluminum oxide vapor-deposited film as an inorganic vapor-deposited film, a reference transfer film B was obtained in the same manner as the preparation of reference transfer film A, having a layer structure of PET film / release layer / aluminum oxide vapor-deposited film / protective layer.

[0284] [Reference Example 1C: Preparation of Reference Transfer Film C] Except for forming a silicon oxide vapor-deposited film with a thickness of 35 nm as an inorganic vapor-deposited film by physical vapor deposition, a reference transfer film C was obtained in the same manner as the preparation of reference transfer film A, having a layer structure of PET film / release layer / silicon oxide vapor-deposited film / protective layer.

[0285] [Reference Example 1] Adhesive A is applied to the coated surface of paper substrate A (A4 size), with a basis weight of 3.0 g / m² after drying. 2 The adhesive A layer was formed by applying and drying the adhesive A layer on the paper substrate A and the protective layer surface of the reference transfer film A (A4 size). The two were then bonded together, pressurized at 0.5 MPa, and then aged at 40°C for 3 days. In this way, a laminate was obtained having a layer structure of paper substrate A [paper material / coating layer] / adhesive A layer / protective layer / aluminum vapor-deposited film / release layer / PET film.

[0286] The PET film in the laminate was peeled off, and a primer layer coating solution was applied to the peeled layer and dried to form a primer layer. A heat seal layer with a thickness of 5 μm was then applied to the primer layer and dried to form a heat seal layer having the above composition. As described above, a reference barrier paper was obtained.

[0287] [Reference Examples 2 - 6] A reference barrier paper was obtained using the same procedure as in Reference Example 1, except that the type of paper substrate, the type of adhesive, and the reference transfer film were changed as described in Table 2.

[0288] [Evaluation 1] [Adhesion] A two-component polyurethane adhesive was applied to a 70 μm thick unoriented polypropylene film, dried, and then dry-laminated with a 15 μm thick stretched nylon film to obtain a laminated film. A two-component polyurethane adhesive was applied to the heat-seal layer side of barrier paper or reference barrier paper, dried, and then dry-laminated with the above laminated film to obtain a laminated composite film.

[0289] After aging the above laminated composite film for 48 hours, it was cut into 15 mm wide strips to obtain test specimens. The adhesion strength (peel strength) of the test specimens was measured using a tensile testing machine (manufactured by Orientec Co., Ltd. [Model name: Tensilon Universal Material Testing Machine]) in accordance with JIS K6854-2.

[0290] For the measurement, the polypropylene film side and the (reference) barrier paper side, which had been peeled off in advance for measurement, were each grasped with the grips of the measuring instrument. They were then pulled at a speed of 50 mm / min in opposite directions (180° peeling: T-peeling method) perpendicular to the surface direction of the portion where the polypropylene film and (reference) barrier paper were still laminated, and the average value of the tensile stress in the stable region was measured to obtain the adhesion strength (N / 15 mm). The (reference) barrier paper was evaluated according to the following evaluation criteria.

[0291] [Evaluation Criteria] • AA: High adhesion strength, suitable for practical applications such as packaging materials. • BB: Adhesion strength is moderate, There are no issues with its application to actual uses such as packaging materials. • CC: Very low adhesion strength, It is difficult to apply this to actual uses such as packaging materials.

[0292] [Table 1]

[0293] [Table 2]

[0294] The barrier paper obtained in the examples did not have a release layer between the inorganic vapor-deposited film and the heat-seal layer, and therefore showed better interlayer adhesion compared to the reference barrier paper which had a release layer between the inorganic vapor-deposited film and the heat-seal layer.

[0295] [Test Example 1A] A transfer film having a layer structure of PET film / heat seal layer / anchor coat layer / aluminum vapor-deposited film (thickness 40 nm) / protective layer was obtained using the same procedure as in Example 1A. Using this transfer film, a barrier paper having a layer structure of heat seal layer / anchor coat layer / aluminum vapor-deposited film (thickness 40 nm) / protective layer / adhesive layer / paper (general paper) was obtained using a procedure similar to that in Example 1.

[0296] [Test Example 2A] Except for forming the heat seal layer using a polyester-based release agent instead of Chemipearl (registered trademark) S120, a reference transfer film having a layer structure of PET film / polyester-based release layer / anchor coat layer / aluminum vapor-deposited film (thickness 40 nm) / protective layer, and a reference barrier paper having a layer structure of polyester-based release layer / anchor coat layer / aluminum vapor-deposited film (thickness 40 nm) / protective layer / adhesive layer / paper (general paper) were obtained using the same procedure as in Test Example 1A.

[0297] [Test Example 3A] Except for forming the heat seal layer using a polycarbonate-based release agent instead of Chemipearl (registered trademark) S120, a reference transfer film having a layer structure of PET film / polycarbonate-based release layer / anchor coat layer / aluminum vapor-deposited film (thickness 40 nm) / protective layer and a reference barrier paper having a layer structure of polycarbonate-based release layer / anchor coat layer / aluminum vapor-deposited film (thickness 40 nm) / protective layer / adhesive layer / paper (general paper) were obtained using the same procedure as in Test Example 1A.

[0298] [Evaluation 2] [Measurement of Indentation Hardness and Complex Elastic Modulus] For the transfer film of Test Example 1A and the reference transfer films of Test Examples 2A-3A, the indentation hardness (H) was measured using a nanoindenter (Bruker's "TI950 TriboIndenter") based on the nanoindentation method, with the cross-section of the heat seal layer or release layer as the measurement surface. IT ) and composite modulus (E r The indentation hardness H was determined for each of these measurements. A Berkovich indenter (triangular pyramidal indenter; Berkovich_TI0039) was used as the indenter for the nanoindenter. Measurements were performed at 10 or more locations on the same cross-section, and the indentation hardness H was determined. IT and composite modulus E r These values ​​are listed as the arithmetic mean of 10 values ​​that were measured with good reproducibility.

[0299] The measurement conditions adopted the indentation depth control method (constant indentation depth of 100 nm, load application for 10 seconds / holding for 5 seconds / unloading for 10 seconds). Specifically, it was as follows. The indenter was pushed into the heat-sealing layer or the release layer from the cross-section of the heat-sealing layer or the release layer to a depth of 100 nm over 10 seconds, and held in that state for 5 seconds. Subsequently, it was unloaded over 10 seconds. As a result, the maximum load P max , the contact projected area A at the maximum depth p and the load-displacement curve could be obtained. From the obtained load-displacement curve, the values of indentation hardness and composite elastic modulus were calculated. The measurement was carried out under a room temperature (23 °C) environment. The location where the indenter was pushed in was near the center in the thickness direction of the heat-sealing layer or the release layer among the exposed portions of the cross-section of the heat-sealing layer or the release layer. The above cross-section was obtained by cutting in the thickness direction perpendicular to the main surface of the (reference) transfer film. The cross-section preparation was carried out by preparing a block in which the (reference) transfer film was embedded with an embedding resin, and cutting the block using a commercially available rotary microtome under a room temperature (23 °C) environment. The finishing was carried out with a diamond knife. The thickness of each layer could also be measured by observing the above cross-section.

[0300] [Gas Barrier Property Evaluation] The barrier paper of Test Example 1A or the reference barrier paper of Test Examples 2A to 3A was cut out to obtain test pieces. Using these test pieces, the oxygen permeability (cc / m 2 / 24hr / atm) and water vapor permeability (g / m 2 / 24hr) were measured by the following method. Also, for the test pieces obtained by folding the (reference) barrier paper into four and then returning it to its original state, these physical properties were measured.

[0301] Using an oxygen permeability measuring device (manufactured by MOCON, OX-TRAN2 / 20), the test piece was set so that the paper base material side was the oxygen supply side, and in accordance with JIS K7126, the oxygen permeability (OTR; unit: cc / m 2OTR (Occurring Tolerance Rate) was measured (24hr / atm). OTR was rated as AA if it was 1.5 or less, BB if it was between 1.5 and 3.0, and CC if it was greater than 3.0.

[0302] Using a water vapor transmission rate measuring device (MOCON, PERMATRAN-w 3 / 33), the test specimen was set so that the paper substrate side was facing the water vapor supply side, and the water vapor transmission rate (WVTR; unit: g / m³) was measured in accordance with JIS K7129 at 40°C and 90%RH. 2 The WVTR (Weat Wave Length) was measured (24 hours). A WVTR of 1.5 or less was rated as AA, a WVTR between 1.5 and 5.0 was rated as BB, and a WVTR greater than 5.0 was rated as CC.

[0303] [Table 3]

[0304] [Test Example 1B] A transfer film having a layer structure of PET film / heat seal layer / anchor coat layer / silicon oxide vapor-deposited film / protective layer was obtained using the same procedure as in Example 1C. However, in the anchor coat agent, the nitrocellulose content was changed to 0 parts by mass relative to 100 parts by mass of the total amount of the main agent and curing agent.

[0305] [Test Examples 2B - 4B] In the anchor coating agent, a transfer film was obtained using the same procedure as in Test Example 1B, except that the nitrocellulose content was changed to 5 parts by mass (Test Example 2B), 50 parts by mass (Test Example 3B), and 200 parts by mass (Test Example 4B) per 100 parts by mass of the total amount of the main agent and hardener.

[0306] [Evaluation 3] [Measurement of Transition Point] In the same manner as described above for the measurement of indentation hardness and composite modulus, a block was prepared by embedding the transfer film in embedding resin. The cross-section of the transfer film was then prepared by cutting the block using a commercially available rotary microtome at room temperature (23°C). Finishing was performed with a diamond knife.

[0307] The nanoTA measuring device manufactured by ANASYS INSTRUMENTS was used, and the PR-EX-AN2-300-5 thermal probe manufactured by ANASYS INSTRUMENTS was used.

[0308] The following calibrations were performed before measurement. As standard samples, BRUKER nanoTA Calibration Samples were prepared. The standard sample holder contained polycaprolactone (softening point: 55°C), polyethylene (softening point: 116°C), and polyethylene terephthalate (softening point: 235°C), all of which have known softening points. Each standard sample was heated while a thermal probe was in contact with its surface. During heating, the thermal expansion directly beneath the thermal probe was measured, and a graph representing the Deflection (displacement) against Voltage (potential) was obtained. The measurement conditions set on the instrument were as follows: Measurement start temperature: 0.1V Measurement end temperature: 10V Heating rate: 0.2V / sec

[0309] Using the softening points of each standard sample, the graph representing the displacement of the thermal probe against potential was converted into a graph representing the displacement against temperature. Calibration was performed in this manner.

[0310] After calibration, the transition point of the anchor coat layer was measured. The measurement location for the transition point was near the center in the thickness direction of the anchor coat layer, within the exposed cross-section of the anchor coat layer. Measurements were performed at five or more locations on the same cross-section, and the transition point was recorded as the arithmetic mean of the five values ​​measured with good reproducibility.

[0311] The measurement was carried out by contacting a thermal probe with the cross-section of the anchor coat layer, heating it under the following conditions while the thermal probe was in contact, and obtaining a graph (thermal expansion curve) representing the displacement of the thermal probe with respect to temperature. Measurement start temperature: 40 °C Measurement end temperature: 350 °C Temperature rising rate: 5 °C / sec

[0312] In the obtained thermal expansion curve, the transition point that appeared on the lowest temperature side was obtained. When a peak of the thermal expansion curve was obtained, the temperature of the peak of the thermal expansion curve was taken as the transition point. For the thermal expansion curve where a continuous decrease in displacement of 0.2 V or more was measured from the highest displacement of the thermal expansion curve, it was regarded as having a peak.

[0313] However, when a "shoulder peak" was obtained instead of a peak of the thermal expansion curve, or when a "shoulder peak" was observed on the lower temperature side than the temperature at which a peak was obtained, the temperature of the "shoulder peak" was taken as the transition point. A "shoulder peak" is defined as a point where, although not a clear convex shape, the slope (displacement / temperature) of the thermal expansion curve changes and the slope of the thermal expansion curve becomes small close to 0. Specifically, when the absolute value of the slope of the tangent line on the lower temperature side where the slope of the thermal expansion curve changes (= slope A ) and the absolute value of the slope of the tangent line on the higher temperature side where the slope of the thermal expansion curve changes (= slope B ) satisfy the relationship (slope A ) > {(slope B ) × 5} and (slope B ) ≤ 0.02 V / °C, the thermal expansion curve was regarded as having a "shoulder peak". The tangent line was drawn at a part where the thermal expansion curve is close to a relatively stable straight line. For the thermal expansion curve regarded as having a "shoulder peak", the temperature of the intersection point of the tangent lines drawn before and after the change in the slope of the thermal expansion curve was taken as the transition point.

[0314] [TOF - SIMS Measurement] NO in the anchor coat layer 2-The normalized ion intensity was measured using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Specifically, using a time-of-flight secondary ion mass spectrometer (ION TOF, TOF.SIMS5), the mass analysis of various ions in each layer was performed while repeatedly soft etching from the protective layer surface of the transfer film toward the PET film side with a Cs (cesium) ion gun at a constant rate. In the anchor coat layer, CN derived from the resin component was measured. - Ions (mass number 26.002) and NO derived from nitrocellulose. 2- Mass spectrometry was performed on the ion (mass number 45.992).

[0315] The specific measurement conditions for TOF-SIMS are as follows: • Primary ion type: Bi3 ++ (0.2 pA, 100 μs) ·Measurement area: 150×150μm 2 Etching gun type: Cs (1 keV, 60 nA) Etching area: 600 × 600 μm 2 Etching rate: 10 sec / cycle • Vacuuming time: 1 x 10 -6 Below mbar for more than 15 hours TOF-SIMS measurements were performed within 30 hours of the start of vacuuming.

[0316] Figure 6 shows CN - An example of TOF-SIMS measurement before the above normalization based on ion detection intensity is shown in Figure 6. For simplicity, CN - Aeon, NO2 - Only the detection intensities of ions and SiO2 are shown. The vertical axis of the graph (intensity) indicates the intensity of the detected ions, and the horizontal axis (s) indicates the etching time.

[0317] [Gas Barrier Property Evaluation] Using the transfer films of Test Examples 1B to 4B, barrier paper with a layer structure of heat seal layer / anchor coat layer / silicon oxide vapor deposition film / protective layer / adhesive layer / paper (general paper) was obtained using a procedure similar to that of Example 1. The barrier paper was cut to obtain test specimens. Using these test specimens, the oxygen permeability (cc / m³) was measured. 2 (24hr / atm) and water vapor transmission rate (g / m³) 2 The measurement (24hr) was taken in the same manner as described above.

[0318] A score of AA was given if the OTR was 1.5 or less, BB if the OTR was between 1.5 and 3.0, and CC if the OTR was greater than 3.0. A WVTR of 0.6 or less was rated as SSS, a WVTR between 0.6 and 1.0 was rated as SS, and a WVTR greater than 1.0 was rated as S.

[0319] [Appearance Evaluation] The appearance during the formation of the anchor coat layer was visually evaluated. ·AA: Good BB: Partially shows signs of blocking. • CC: Partial peeling of the film present.

[0320] [Table 4]

[0321] The barrier papers in Test Examples 1B, 2B, and 4B had WVTR and OTR that were acceptable for practical use. The barrier paper in Test Example 3B had even better WVTR and OTR compared to the barrier papers in Test Examples 1B, 2B, and 4B. The anchor coat layers in Test Examples 1B, 2B, and 4B had an appearance that was acceptable for practical use. The anchor coat layer in Test Example 3B had an even better appearance compared to the anchor coat layers in Test Examples 1B, 2B, and 4B.

[0322] As those skilled in the art will understand, the transfer films and barrier laminates of this disclosure are not limited by the descriptions in the above examples, and the above examples and specification are merely for illustrating the principles of this disclosure. Various modifications or improvements can be made as long as they do not deviate from the spirit and scope of this disclosure, and any such modifications or improvements will fall within the scope of the disclosure for which protection is claimed. Furthermore, the scope for which protection is claimed by this disclosure includes not only the claims themselves but also their equivalents. [Explanation of symbols]

[0323] 1. Barrier laminate 2. Transfer film 10...Base material 12...printing layer 20...Adhesive layer 30. Inorganic vapor-deposited film 32. Anchor Coat Layer 40... Heat seal layer 50...Support substrate (transfer substrate)

Claims

1. Substrate and Adhesive layer, Inorganic vapor-deposited film and Heat seal layer and A barrier laminate having these elements in this order in the thickness direction, The inorganic vapor-deposited film and the heat-seal layer are transferred onto the adhesive layer from a transfer film comprising a support substrate, the heat-seal layer, and the inorganic vapor-deposited film in this order in the thickness direction. The inorganic vapor-deposited film and the heat seal layer are in contact, or The barrier laminate further comprises an anchor coat layer between the inorganic vapor-deposited film and the heat seal layer, the inorganic vapor-deposited film and the anchor coat layer are in contact, and the transition temperature of the anchor coat layer, as measured by local thermal analysis using a thermal probe, is 90°C or higher and 120°C or lower. Barrier laminate.

2. The barrier laminate according to claim 1, wherein the inorganic vapor-deposited film is directly vapor-deposited and formed on one side surface of the heat seal layer.

3. The barrier laminate according to claim 1, wherein the inorganic vapor-deposited film is directly vapor-deposited and formed on one side surface of the anchor coat layer.

4. A barrier laminate comprising a substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-seal layer in this order in the thickness direction, The inorganic vapor-deposited film and the heat-seal layer are transferred onto the adhesive layer from a transfer film comprising a support substrate, the heat-seal layer, and the inorganic vapor-deposited film in this order in the thickness direction. A barrier laminate in which there is no release layer between the inorganic vapor-deposited film and the heat-seal layer.

5. The barrier laminate according to claim 4, further comprising an anchor coat layer between the inorganic vapor-deposited film and the heat seal layer.

6. The barrier laminate according to any one of claims 1 to 5, wherein the inorganic vapor-deposited film contains at least one selected from aluminum, aluminum oxide, and silicon oxide.

7. The barrier laminate according to any one of claims 1 to 6, wherein the substrate is a paper substrate.

8. The barrier laminate according to claim 7, wherein the paper substrate comprises a paper material and a sealing layer or resin layer formed on the surface of the paper material facing the adhesive layer.

9. Paper substrate and Adhesive layer, Inorganic vapor-deposited film and Heat seal layer and A barrier laminate having these elements in this order in the thickness direction, The inorganic vapor-deposited film and the heat-seal layer are transferred onto the adhesive layer from a transfer film comprising a support substrate, the heat-seal layer, and the inorganic vapor-deposited film in this order in the thickness direction. The inorganic vapor-deposited film and the heat seal layer are in contact, or The barrier laminate further comprises an anchor coat layer between the inorganic vapor-deposited film and the heat seal layer, the inorganic vapor-deposited film and the anchor coat layer are in contact, and the transition temperature of the anchor coat layer, as measured by local thermal analysis using a thermal probe, is 90°C or higher and 120°C or lower. The aforementioned paper substrate is made of paper material and does not include a sealing layer, a resin layer, or a clay coat layer. Barrier laminate.

10. The barrier laminate according to any one of claims 1 to 9, further comprising a printed layer on the surface of the substrate opposite to the adhesive layer side.

11. The barrier laminate according to any one of claims 1 to 10, wherein the thickness of the adhesive layer is 0.5 μm or more and 20 μm or less.

12. The indentation hardness of the heat seal layer, as measured by nanoindentation, is 0.15 GPa or less. The barrier laminate according to any one of claims 1 to 11, wherein the composite elastic modulus of the heat seal layer, as measured by nanoindentation, is 2.0 GPa or less.

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