Transfer film and barrier laminate

Abstract

A transfer film, which is a transfer film provided with a support substrate, a heat-seal layer, and an inorganic vapor deposition film in this order in a thickness direction, wherein the inorganic vapor deposition film is in contact with the heat-seal layer, or the transfer film is further provided with an anchor coat layer between the inorganic vapor deposition film and the heat-seal layer, and the inorganic vapor deposition film is in contact with the anchor coat layer.

Description

Technical Field

[0001] This invention relates to transfer films and barrier laminates. Background Technology

[0002] In recent years, environmental problems caused by microplastics have been raised. In order to reduce the environmental burden, it is also required to improve recyclability by making products composed of paper as much as possible in the paper-using industries.

[0003] Previously, packaging materials with high gas barrier properties were used to prevent the degradation of contents (e.g., food, medical products, synthetic chemicals, and cosmetics) caused by moisture or oxygen. Here, paper-based packaging materials have attracted attention considering the recycling or incineration of used packaging materials. However, paper-based materials typically lack sufficient gas barrier properties. Therefore, to improve the gas barrier properties of paper-based packaging materials, studies have been conducted on coating paper-based materials with resin or laminating resin films with inorganic vapor-deposited coatings onto paper-based materials.

[0004] Patent Document 1 discloses a laminate in which a thin film layer with gas barrier properties based on plasma polymerization is deposited on a substrate made of paper or pulp mold, which has a filler layer on its surface composed of a condensation polymer of polysaccharides and silicon compounds. In Patent Document 1, because the substrate made of paper or pulp mold is arranged within the plasma polymerization apparatus during the formation of the gas barrier film layer, paper dust or pulp dust generated by the paper or pulp mold easily hinders the depressurization of 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 filler layer and the thin film layer easily becomes insufficient, and the gas barrier properties easily become unstable. While Patent Document 1 involves chemical vapor deposition (CVD) for the formation of the gas barrier film layer, the same problem exists in physical vapor deposition (PVD).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent No. 4622201 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] It is desirable to provide a barrier laminate that has a substrate that is difficult to directly vapor deposit, not limited to paper substrates, and exhibits excellent interlayer adhesion. Furthermore, packaging materials typically have a heat-sealable layer to seal the packaging material. Therefore, barrier laminates such as barrier papers suitable for packaging material applications preferably have a heat-sealable layer.

[0010] One object of the present invention is to provide a barrier laminate comprising a substrate, an inorganic vapor-deposited film, and a heat-sealing layer, exhibiting excellent interlayer adhesion and suppressed interlayer delamination. Another object of the present invention is to provide a transfer film suitable for manufacturing such a barrier laminate.

[0011] Methods for solving problems

[0012] The transfer film of the present invention comprises, in the thickness direction, a supporting substrate, a heat-sealing layer and an inorganic vapor-deposited film, wherein the inorganic vapor-deposited film is in contact with the heat-sealing layer, or the transfer film further comprises an anchor coating layer between the inorganic vapor-deposited film and the heat-sealing layer, wherein the inorganic vapor-deposited film is in contact with the anchor coating layer.

[0013] In one embodiment, the barrier laminate of the present invention comprises, in the thickness direction, a substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-sealing layer, wherein the inorganic vapor-deposited film is in contact with the heat-sealing layer; or, the barrier laminate further comprises an anchor coating layer between the inorganic vapor-deposited film and the heat-sealing layer, wherein the inorganic vapor-deposited film is in contact with the anchor coating layer.

[0014] In one embodiment, the barrier laminate of the present invention comprises, in the thickness direction, a substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-sealing layer, wherein no release layer is provided between the inorganic vapor-deposited film and the heat-sealing layer.

[0015] The effects of the invention

[0016] According to the present invention, a barrier laminate comprising a substrate, an inorganic vapor-deposited film, and a heat-sealing layer can be provided, exhibiting excellent interlayer adhesion and suppressed interlayer delamination. According to the present invention, a transfer film suitable for manufacturing such a barrier laminate can be provided. Attached Figure Description

[0017] Figure 1 This is a cross-sectional view illustrating an example of the layer structure of the transfer film of the present invention.

[0018] Figure 2 This is a cross-sectional view illustrating an example of the layer structure of the transfer film of the present invention.

[0019] Figure 3 This is a cross-sectional view illustrating an example of the layer structure of the barrier laminate of the present invention.

[0020] Figure 4 This is a cross-sectional view illustrating an example of the layer structure of the barrier laminate of the present invention.

[0021] Figure 5 This is a process diagram illustrating an example of a method for manufacturing the barrier paper of the present invention.

[0022] Figure 6 This is an example of a curve obtained from a TOF-SIMS measurement before standardization. Detailed Implementation

[0023] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings and other accompanying text. The present invention can be implemented in many different ways and is not limited to the description of the embodiments illustrated below.

[0024] To make the description clearer, the accompanying drawings sometimes schematically show the width, thickness, angle, and shape of various parts compared to the actual representation. However, the drawings are merely examples and do not limit the interpretation of the invention. In this specification and the drawings, the same reference numerals are used for elements that are the same as those described with respect to the figures, and detailed descriptions are sometimes appropriately omitted. For ease of explanation, terms such as "up" or "down" are sometimes used, but the up / down direction can be reversed. The same applies to the left / right direction.

[0025] In the following description, each component (e.g., additives, resin components such as various resins, colorants and curing agents) may be used in one or more forms.

[0026] [Transfer film]

[0027] The transfer film of the present invention comprises, in the thickness direction, a supporting substrate, a heat-sealing layer, and an inorganic vapor-deposited film. An anchor coating layer may also be provided between the heat-sealing layer and the inorganic vapor-deposited film. The heat-sealing layer, the anchor coating layer as needed, and the inorganic vapor-deposited film constitute the transfer layer. In one embodiment, the transfer film and the transfer layer may further include functional layers such as a protective layer.

[0028] That is, the transfer film of the present invention comprises a support substrate and a transfer layer disposed on the support substrate, wherein the transfer layer comprises a heat-sealing layer and an inorganic vapor-deposited film sequentially in the thickness direction. In one embodiment, the transfer layer may further comprise an anchor coating layer between the heat-sealing layer and the inorganic vapor-deposited film. The heat-sealing layer is in contact with the support substrate and is disposed in a manner that allows it to be peeled off from the support substrate.

[0029] Here, in the above-mentioned transfer layer, the inorganic vapor-deposited film is in contact with the heat-sealing layer (or the anchor coating layer if an anchor coating layer is provided), or the above-mentioned transfer layer does not have a release layer between the inorganic vapor-deposited film and the heat-sealing layer.

[0030] In one embodiment, the transfer film has a protective layer on the inorganic vapor-deposited film.

[0031] In one embodiment, when the inorganic vapor-deposited film is composed of metal oxides such as aluminum oxide and silicon oxide, the transfer film has a barrier coating on the inorganic vapor-deposited film.

[0032] As a supporting substrate for transfer printing, the transfer film can be a single sheet or a continuous film wound into a roll.

[0033] Figure 1 An embodiment of the transfer film of the present invention is shown in the figure. Figure 1 The transfer film 2 has a supporting substrate 50, a heat-sealing layer 40 and an inorganic vapor-deposited film 30 in sequence in the thickness direction.

[0034] Figure 2 Another embodiment of the transfer film of the present invention is shown in the figure. Figure 2 The transfer film 2 has, in the thickness direction, a supporting substrate 50, a heat-sealing layer 40, an anchor coating 32, and an inorganic vapor-deposited film 30.

[0035] <Supporting substrate>

[0036] The transfer film of the present invention includes a support substrate that serves as a substrate for transfer.

[0037] As the supporting substrate, a film made of resin (hereinafter also referred to as "resin film") is preferred. Examples of the resins mentioned above 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 homopolymers, acrylonitrile-styrene copolymers (AS resin), and acrylonitrile-butadiene-styrene copolymers (ABS resin); (meth)acrylic resins, polycarbonate, polyimide, diaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyethersulfone resins, polyurethane, cellulose resins, and fluorine resins.

[0038] Resin films can consist of a single layer or multiple layers consisting of two or more layers with the same or different compositions. Resin films can be unstretched films, or stretched films such as uniaxially stretched films and biaxially stretched films.

[0039] 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.

[0040] The support substrate preferably has the property of being able to form a heat-sealable layer on the substrate and to easily peel off the substrate from the heat-sealable layer during a peeling process. From this perspective, polyester films and polyamide films are preferred among resin films, polyester films are more preferred, and polyethylene terephthalate films are even more preferred.

[0041] The supporting substrate possesses excellent mechanical, physical, and chemical properties that can withstand the formation process of inorganic vapor deposition films, and is particularly preferably characterized by strength and heat resistance. From this perspective, polyethylene terephthalate films are also preferred.

[0042] Preferably, the resin film does not undergo the known easy-adhesion treatment on the surface in contact with the heat-sealing layer. Furthermore, it is preferable that the surface in contact with the heat-sealing layer does not have a known easy-adhesion layer. With this configuration, for example, the peelability between the support substrate and the heat-sealing layer during the peeling process can be improved.

[0043] <Heat-sealing layer>

[0044] The transfer film of the present invention includes a heat-sealing layer. The heat-sealing layer functions as a heat-sealing sealant layer, for example, when using a barrier laminate such as barrier paper as a packaging material. Furthermore, when the barrier laminate such as barrier paper is manufactured using the transfer method described later, the heat-sealing layer also functions as a release layer that peels off from the supporting substrate.

[0045] A heat-sealable layer refers to a layer with heat-sealing properties. Specifically, it is a layer that can be bonded to an object by heat pressing, or a layer that can be bonded to itself by heat pressing. It should be noted that the transfer film of the present invention can also be used for applications that do not require heat sealing.

[0046] In the transfer film of the present invention, the heat-sealing layer is preferably in contact with the support substrate. This configuration allows the support substrate to be easily peeled off from the heat-sealing layer. For example, since the heat-sealing layer is less likely to remain on the peeled support substrate, the support substrate can be easily recycled or reused.

[0047] A heat-sealable layer that can be peeled off from a 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.

[0048] In one embodiment, the heat-sealing layer contains an olefin-based polymer. With this configuration, for example, a heat-sealing layer with excellent heat-sealing and peelability can be obtained; in addition, a barrier laminate for packaging materials with sufficient rigidity, strength and heat resistance, and excellent recyclability can be obtained.

[0049] Examples of olefin-based polymers include ethylene-based polymers and propylene-based polymers. Among these, ethylene-based polymers are preferred from the perspective of balancing heat-sealing and peelability.

[0050] Examples of ethylene-based polymers include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. From a heat-sealing perspective, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene are preferred. From an environmental reduction perspective, polyethylene derived from biomass and / or recycled polyethylene can be used.

[0051] The density of high-density polyethylene is preferably greater than 0.945 g / cm³.3 The upper limit of the density of high-density polyethylene is, for example, 0.965 g / cm³. 3 The density of medium-density polyethylene is preferably greater than 0.925 g / cm³. 3 And it is 0.945 g / cm³ 3 The density of low-density polyethylene is preferably greater than 0.900 g / cm³. 3 And it is 0.925 g / cm³ 3 The density of linear low-density polyethylene is preferably greater than 0.900 g / cm³. 3 And it is 0.925 g / cm³ 3 The density of ultra-low density polyethylene is preferably 0.900 g / cm³. 3 The lower limit of the density of ultra-low density polyethylene is, for example, 0.860 g / cm³. 3 The density of polyethylene was determined according to JIS K7112 (1999).

[0052] Examples of ethylene-based polymers 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 (e.g., ethylene-ethyl acrylate copolymers).

[0053] Examples of propylene-based polymers include propylene homopolymers, propylene random copolymers, and propylene block copolymers. Propylene homopolymers are polymers consisting solely of propylene. Propylene random copolymers are random copolymers of propylene with olefinically unsaturated monomers other than propylene (e.g., α-olefins such as ethylene, 1-butene, and 4-methyl-1-pentene). Propylene block copolymers are copolymers having polymer blocks composed of propylene and polymer blocks composed of olefinically unsaturated monomers other than propylene (e.g., α-olefins such as ethylene, 1-butene, and 4-methyl-1-pentene). From an environmental perspective, polypropylene derived from biomass and / or recycled polypropylene can be used. Propylene-maleic anhydride copolymers are also an example of propylene-based polymers.

[0054] As described below, the barrier laminate of the present invention is preferably manufactured by a transfer printing method. In the transfer printing method, a heat-sealing layer is formed on a support substrate, and then an inorganic vapor-deposited film is formed on the heat-sealing layer. The heat-sealing layer and the inorganic vapor-deposited film are then transferred to a substrate such as a paper substrate. Therefore, it is preferable to use a coating liquid capable of forming a coating film on a support substrate and capable of forming a coating film with excellent peelability and heat-sealing properties from the support substrate to form the heat-sealing layer.

[0055] Such a heat-sealing layer is preferably formed using a heat-sealing coating liquid containing an ionomer of olefin-based polymers. Ionomers are a general term for synthetic resins that utilize the cohesive force of metal ions to form polymer aggregates.

[0056] Examples of such metal ions include alkali metal ions and alkaline earth metal ions, specifically sodium, potassium, calcium, magnesium, and zinc.

[0057] Examples of ionomers of olefin-based polymers include metal salts of olefin-unsaturated carboxylic acid copolymers, metal salts of olefin-(meth)acrylic acid copolymers, metal salts of olefin-urethane copolymers, and metal salts of olefin-fluorinated polymer copolymers.

[0058] Examples of the aforementioned olefins include α-olefins with 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, and ethylene is more preferred.

[0059] Examples of unsaturated carboxylic acids mentioned above include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and β-carboxyethyl (meth)acrylic acid; and unsaturated dicarboxylic acids such as maleic acid, itaconic acid, fumaric acid, and citraconic acid.

[0060] Among the above-mentioned ionomers, ionomers of ethylene-based polymers are preferred, metal salts of ethylene-(meth)acrylic acid copolymers, metal salts of ethylene-(meth)acrylic acid copolymers, metal salts of ethylene-carbamate 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.

[0061] The content of olefin-based polymer in the heat-sealing 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-sealing properties of the barrier laminate.

[0062] The heat-sealing layer may contain a rubber-based material together with the aforementioned thermoplastic resin. Examples of rubber-based materials include thermoplastic rubber, natural rubber, butyl rubber, nitrile rubber, and chloroprene rubber. The rubber-based material may be used in combination with the aforementioned thermoplastic resin.

[0063] The heat-sealable layer is typically an unstretched layer. For example, a heat-sealable layer can be formed by coating a heat-sealable layer containing an olefin polymer onto a support substrate with a coating liquid and then drying it, or by melt-extruding a resin composition containing an olefin polymer onto a support substrate. For the above reasons, the heat-sealable layer is preferably a cast coating formed using a coating liquid containing an olefin polymer.

[0064] Examples of solvents that can be used as coating solutions for heat-sealing layers 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 dichloromethane 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.

[0065] In the preparation of the coating liquid for the heat-sealing layer, an emulsion of an ionomer of an olefin polymer is preferred, a self-emulsifying emulsion is more preferred, and a self-emulsifying emulsion of a metal salt of an ethylene-(meth)acrylic acid copolymer is even more preferred. Such a coating liquid can, for example, form a coating film well on a support substrate, and can form a coating film with excellent peelability from the support substrate, and the heat-sealing properties of the coating film are also excellent.

[0066] As the aforementioned emulsion, an aqueous ionomer emulsion is preferred. Such an emulsion allows for lower coating weight control, and since there are no VOC emissions, it results in packaging materials with a lower environmental impact.

[0067] The coating liquid for heat-sealing layers 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.

[0068] The thickness of the heat-sealing 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-sealing layer is 5 μm or more and 25 μm or less. The thickness of the heat-sealing layer is preferably varied appropriately based on the strength of the heat-sealing layer, the processing adaptability of the transfer film, and the quality of the contents filled in the packaging material manufactured using the barrier laminate of the present invention.

[0069] The indentation hardness of the heat-sealing layer is preferably 0.15 GPa or less, more preferably 0.10 GPa or less, and even more preferably 0.08 GPa or less. The lower limit can be, for example, 0.01 GPa or 0.02 GPa. When the indentation hardness is 0.15 GPa or less, for example, there is a tendency to further improve the bending resistance and gas barrier properties of the barrier laminate.

[0070] The composite elastic modulus of the heat-sealing layer is preferably 2.0 GPa or less, more preferably 1.5 GPa or less, and even more preferably 1.0 GPa or less. The lower limit can be, for example, 0.1 GPa or 0.2 GPa. When the composite elastic modulus is 2.0 GPa or less, for example, there is a tendency to further improve the bending resistance and gas barrier properties of the barrier laminate.

[0071] In this invention, the indentation hardness and composite elastic modulus of the heat-sealing layer can be adjusted, for example, by appropriately selecting the components contained in the heat-sealing layer.

[0072] In this invention, the indentation hardness and composite elastic modulus of the heat-sealing layer are determined by nanoindentation. Specifically, a nanoindenter is used, and the cross-section of the heat-sealing layer of the transfer film is used as the measurement surface to measure the indentation hardness and composite elastic modulus. The cross-section is obtained by cutting along the thickness direction perpendicular to the main surface of the transfer film. The indenter is inserted near the center of the heat-sealing layer in the thickness direction of the exposed portion of the cross-section. The measurement conditions are as follows. A Berkovich indenter (triangular pyramid indenter) is used as the indenter for the nanoindenter. The indenter is pressed into the heat-sealing layer from the cross-section for 10 seconds until the indentation depth reaches 100 nm, held in this state for 5 seconds, and then unloaded for 10 seconds to obtain the maximum load P. max The contact projected area A at maximum depth p and load-displacement curves. Based on the obtained load-displacement curves, using equation P... max / A p The indentation hardness is calculated, and the composite elastic modulus is calculated using the following formula (1).

[0073] [Number 1]

[0074]

[0075] In equation (1), A p Let S be the contact projected area, S be the contact rigidity, and E be the contact area. r The composite elastic modulus of the heat-sealing layer.

[0076] The measurements were performed at room temperature (23°C). Measurements were taken at more than 10 locations within the same cross-section, and the indentation hardness and composite elastic modulus were recorded as the arithmetic mean of the 10 reproducible measurements. Detailed descriptions of the measurement conditions are provided in the Examples section.

[0077] <Anchor Coating>

[0078] The transfer film of the present invention may further include an anchor coating layer between the heat-sealing layer and the inorganic vapor-deposited film. By providing the anchor coating layer, the adhesion between the heat-sealing layer and the inorganic vapor-deposited film can be improved, and peeling between these layers can be suppressed. For example, the anchor coating layer is in contact with the inorganic vapor-deposited film on one side and with the heat-sealing layer on the other side.

[0079] In one embodiment, the anchor coating contains a resin component. Examples of resin components include thermoplastic resins such as polyolefins (e.g., polyethylene and polypropylene), vinyl resins, styrene-based 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 thermosetting resins, curing agents such as amine compounds, phenolic compounds, isocyanate compounds, and carboxylic acid compounds are preferred. For example, from the perspective of adhesion, polyester is preferred as a resin component.

[0080] Examples of polyesters include polymers synthesized by polycondensation of polycarboxylic acids, their esters, and their anhydrides with polyols, lactone ring-opening polymers, polyhydroxycarboxylic acid polymers, urea-modified polyesters, and urethane-modified polyesters. Uramate-modified polyesters refer to polyesters containing urethane bonds.

[0081] A urethane-modified polyester is, for example, a resin in which two or more polyesters are bonded together by structural units derived from a polyisocyanate. Such a resin can be obtained, for example, by reacting the terminal hydroxyl groups of the polyester with the isocyanate groups of the polyisocyanate.

[0082] The glass transition temperature (Tg) of urethane-modified polyester can be above 50℃, above 60℃, above 70℃, below 120℃, or below 110℃. Tg is the midpoint glass transition temperature obtained by differential scanning calorimetry (DSC) according to JIS K7121.

[0083] The hydroxyl value of urethane-modified polyesters can be, for example, above 1 mg KOH / g, above 3 mg KOH / g, above 5 mg KOH / g, below 90 mg KOH / g, or below 70 mg KOH / g. Regarding the hydroxyl value, it is expressed as the number of mg of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when 1 g of sample is acetylated. The hydroxyl value is determined according to JIS K0070-1992.

[0084] The number average molecular weight (Mn) of urethane-modified polyester can be above 500, above 1,000, below 50,000, below 30,000, or below 10,000. Mn is determined by gel permeation chromatography (GPC) using polystyrene as a standard substance according to JIS K7252-1.

[0085] Carbamate-modified polyesters are obtained, for example, by reacting a polyester polyol with a polyisocyanate. Carbamate-modified polyesters are obtained, for example, by reacting a polyester polyol with a polyisocyanate in an excess of hydroxyl groups relative to isocyanate groups, preferably having two or more hydroxyl groups per molecule. In the reaction of the polyester polyol with the polyisocyanate, the reaction conditions of conventional carbamate reactions can be widely used.

[0086] Polyester polyols are resins with two or more hydroxyl groups per molecule, obtained by esterification of polycarboxylic acids, their esters, and their anhydrides with a polyol. Polyester polyols can also be polyesters obtained through the ring-opening reaction of caprolactone.

[0087] 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, propylenetricarboxylic acid, and citric acid.

[0088] Examples of polyols include compounds having two or more hydroxyl groups in one molecule, such as aliphatic diols and polyols with three or more hydroxyl groups. Examples of diols 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 polyols with three or more hydroxyl groups include aliphatic diols, glycerol, trimethylolpropane, trimethylolethane, and pentaerythritol.

[0089] Examples of polyisocyanates 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, methylene bis(cyclohexyl isocyanate), and cyclohexane diisocyanate; and aromatic diisocyanates such as phenyl diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, and biphenyl diisocyanate.

[0090] Carbamate-modified polyesters can also be obtained by simultaneously reacting polycarboxylic acids, their esters and their anhydrides, polyols and polyisocyanates.

[0091] In one embodiment, the anchor coating may contain a cured resin as a resin component, formed from a resin having reactive functional groups and a curing agent. Examples of reactive functional groups include hydroxyl, carboxyl, and amino groups. Examples of resins having reactive functional groups include, for example, urethane-modified polyesters.

[0092] 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 toluene diisocyanate (TDI-based isocyanate) and diphenylmethylene diisocyanate (XDI-based isocyanate); aliphatic isocyanate compounds such as hexamethylene diisocyanate (HDI-based isocyanate) and isophorone diisocyanate (IPDI-based isocyanate); modified forms of these isocyanate compounds; and multifunctional dimers, adducts, urea esters, trimers, carbodiimide adducts, biuret esters, and their polymers, as well as polymers containing addition polyols. From the perspective of the adhesion between the heat-sealing layer and the inorganic vapor-deposited film, aromatic isocyanate compounds are preferred as curing agents, and diphenylmethylene diisocyanate (XDI) is more preferred.

[0093] The amount of curing agent used relative to 100 parts by mass of the aforementioned resin with reactive functional groups can 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. This, for example, can further improve the adhesion between the heat-sealing layer and the inorganic vapor-deposited film.

[0094] The resin content in the anchor coating can be 30% or more by mass, 50% or more by mass, 60% or more by mass, 80% or more by mass, 90% or more by mass, or 95% or more by mass. The resin composition also includes the aforementioned cured resin.

[0095] Anchor coatings may contain additives. Examples of additives include lubricants, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, dyes, and silane coupling agents.

[0096] The anchor coating may also contain compounds with glucose rings. Examples of compounds with glucose rings include polysaccharides such as cellulose and pullulan, and their derivatives. Examples of derivatives include methylates, nitro compounds, acetylates, carboxymethylates, and cyanoethylates. Specifically, examples of derivatives include cellulose acetate butyrate, cellulose acetate, and methylcellulose; and compounds with nitro groups and glucose rings, such as nitrocellulose.

[0097] The aforementioned adhesion can be further improved by adding compounds with glucose rings to the anchor coating. Furthermore, adding compounds with glucose rings to the anchor coating can improve its heat resistance and suppress heat-induced degradation of the anchor coating during the formation of the inorganic vapor-deposited film. Therefore, the formed inorganic vapor-deposited film can readily achieve the desired gas barrier properties.

[0098] The content of the glucose ring-containing compound in the anchor coating relative to 100 parts by mass of the above-mentioned resin component can 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. When the content of the glucose ring-containing compound is 20 parts by mass or more but less than 100 parts by mass, for example, the sealing and gas barrier properties can be further improved.

[0099] In one embodiment, the NO2 in the anchor coating is measured using time-of-flight secondary ion mass spectrometry (TOF-SIMS). - The normalized strength of the ions can be 0.5 or higher, 1.0 or higher, or 2.0 or higher, preferably 3.0 or higher, more preferably 3.2 or higher, and even more preferably 3.5 or higher. In one embodiment, NO2 in the anchor coating - The normalized strength of the ions can be 5.0 or less, 4.5 or less, preferably 4.2 or less, and more preferably 4.0 or less. NO2 - When the normalized strength of the ions is above 3.0, there is a tendency for the coating to exhibit superior gas barrier properties and an attractive appearance. NO2 - When the normalized strength of the ions is below 4.2, it tends to have better gas barrier properties and better adhesion between the anchor coating and the inorganic vapor-deposited film.

[0100] NO2 - The normalized strength of the ions is calculated as follows. (The text then abruptly shifts to a seemingly unrelated topic: NO2.) - The detection intensity of the ion (mass number 45.992) divided by CN - The detection intensity of the ion (mass number 26.002) was normalized by multiplying it by 100,000. The NO2 concentration in the central region along the thickness direction of the anchor coating was then normalized. - The logarithm of the average value of the normalized detection intensity of ions is commonly used as the NO2 in the anchor coating. - Normalized intensity of ions. Here, the central region of the anchor coating refers to the area near the center of the anchor coating and with a thickness of 50% relative to the thickness of the anchor coating.

[0101] NO2 - Normalized intensity of ions = log 10 {(NO2 - Detection intensity of ions / CN - (Ion detection intensity) × 100000

[0102] The intensities of each ion were measured as follows. A time-of-flight secondary ion mass spectrometer (ION TOF, TOF.SIMS5) was used to repeatedly perform soft etching at a constant speed from the outside of the transfer film using a Cs (cesium) ion gun, and the ions in each layer were detected. Specific measurement conditions are described in the Examples section.

[0103] The thickness of the anchor coating was measured as follows.

[0104] In the unnormalized curve obtained by TOF-SIMS measurement, the interface between the inorganic vapor deposition film and the anchor coating is defined as the position where the intensity of ions from the inorganic vapor deposition film is 50% of the maximum intensity of ions from the inorganic vapor deposition film. For example, in the case of a silicon dioxide vapor deposition film, the ions from the inorganic vapor deposition film are SiO2 (mass number 59.96).

[0105] In the unstandardized curve obtained by TOF-SIMS measurement, CN - The strength of the ions is called CN. - The location at 50% of the maximum ion strength serves as the interface between the anchor coating and the heat seal layer.

[0106] The thickness of the anchor coating is defined as the distance in the thickness direction between the two interfaces.

[0107] In one embodiment, the transition temperature of the anchor coating can be 70°C or higher and 140°C or lower. The transition temperature is preferably 90°C or higher, more preferably 95°C or higher, further preferably 100°C or higher, and particularly preferably 105°C or higher. The transition temperature can, for example, be 135°C or lower, 130°C or lower, 125°C or lower, or 120°C or lower. If the transition temperature is 90°C or higher, there is a tendency for better gas barrier properties. If the transition temperature is 125°C or lower, there is a tendency for better gas barrier properties.

[0108] The transition temperature of the anchor coating is determined using localized thermal analysis with a thermal probe. In this analysis, the thermal probe is brought into contact with the cross-section of the anchor coating, and the temperature is increased while the displacement of the thermal probe along the normal direction of the anchor coating cross-section from before heating is measured, thus obtaining the thermal expansion curve.

[0109] The aforementioned cross-section was obtained by cutting along the thickness direction perpendicular to the main surface of the transfer film. The thermal probe contacts the portion of the exposed portion of the anchor coating in the thickness direction near the center of the anchor coating. Measurements were performed at five or more locations within the same cross-section, and the transition temperature was recorded as the arithmetic mean of the five reproducible measurements.

[0110] In localized thermal analysis, the resin contained in the anchor coating expands upon heating, thus pushing up the thermal probe. Due to structural changes in the resin of the anchor coating, the slope (displacement / temperature) of the thermal expansion curve changes. During the structural transformation of the resin in the anchor coating, especially from expansion to softening, the tip of the thermal probe enters the resin, causing the 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 temperature of the anchor coating is obtained.

[0111] As the slope (displacement / temperature) of the thermal expansion curve changes, a "shoulder" is sometimes observed. A "shoulder" is defined as a point where the slope of the thermal expansion curve decreases to near zero, even though it is not a clearly defined convex shape. By plotting the tangent lines to the thermal expansion curves before and after this slope change, and calculating the temperature at the intersection, we obtain the inflection point. This inflection point temperature is taken as the temperature of the "shoulder."

[0112] If a peak in the thermal expansion curve is obtained, the temperature of the peak is taken as the transition temperature. However, if a "shoulder peak" is obtained instead of a peak in the thermal expansion curve, or if a "shoulder peak" is observed at a temperature lower than the temperature at which the peak was obtained, the temperature of the "shoulder peak" is taken as the transition temperature. After the measurement begins, the transition temperature exhibited at the lowest temperature is defined as the transition temperature of the anchor coating.

[0113] Detailed information about the measurement conditions is provided in the Examples section.

[0114] The thickness of the anchor coating 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 at or above the lower limit, sufficient adhesion strength between the heat-sealing layer and the inorganic vapor-deposited film can be obtained, for example. If the thickness is below the upper limit, the anchor coating can be well formed on the heat-sealing layer, for example.

[0115] Inorganic vapor deposition film

[0116] The transfer film of the present invention comprises an inorganic vapor-deposited film. The inorganic vapor-deposited film is preferably a layer formed by direct vapor deposition on one side of the heat-sealing layer, or on one side of the anchor coating layer when an anchor coating layer is provided.

[0117] Inorganic vapor-deposited films are layers that inhibit the permeation of gases such as oxygen and water vapor. Therefore, for example, gas-barrier laminates obtained by transferring a transfer layer from the transfer film of the present invention to a transfer substrate exhibit excellent gas barrier properties. When the inorganic vapor-deposited film is an opaque layer, it possesses light-blocking properties against sunlight and can also retain the aroma of its contents.

[0118] Inorganic vapor-deposited films can be metal vapor-deposited films made of metal or vapor-deposited films made of inorganic compounds.

[0119] Examples of metals that can constitute a metal vapor-deposited film include aluminum, chromium, tin, nickel, copper, silver, gold, and platinum. Among these, aluminum is preferred. That is, aluminum vapor-deposited films are preferred.

[0120] Examples of inorganic compounds constituting the aforementioned vapor-deposited films include metal oxides, metal nitrides and metal carbides, indium tin oxide (ITO), and SiO₂. X C Y Complex inorganic compounds, etc. Among these, metal oxides are preferred.

[0121] Examples of metallic elements that constitute 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).

[0122] The average composition of inorganic compounds, such as AlO x SiO x SiO x C y Wait until that, by MO x or MO x C y The formula is given by M, where M represents the aforementioned metallic element, and the values ​​of x and y vary depending on the metallic element.

[0123] In the case of metal oxides, x can take values ​​in the following ranges: aluminum greater than 0 and less than 1.5, silicon greater than 0 and less than 2, magnesium greater than 0 and less than 1, calcium greater than 0 and less than 1, potassium greater than 0 and less than 0.5, tin greater than 0 and less than 2, sodium greater than 0 and less than 0.5, boron greater than 0 and less than 1.5, titanium greater than 0 and less than 2, lead greater than 0 and less than 1, zirconium greater than 0 and less than 2, and yttrium greater than 0 and less than 1.5.

[0124] in MO x In this context, the upper limit of the range of x is the value when fully oxidized. For alumina, x is preferably in the range of 0.5 to 1.5, and for silicon oxide, x is preferably in the range of 1.0 to 2.0.

[0125] Among the 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.

[0126] Inorganic vapor-deposited films can be formed from one type of metal or inorganic compound, or from a combination of two or more types of metal or inorganic compounds. Inorganic vapor-deposited films can consist of a single layer, or multiple layers consisting of two or more layers with the same or different compositions.

[0127] When an inorganic vapor-deposited film is multilayered, vapor deposition can be performed with each layer possessing high gas barrier properties, thus achieving higher gas barrier properties than a single layer. Furthermore, if the composition of each layer is different, the inorganic vapor-deposited film becomes a series of discontinuous layers, which can more effectively suppress the permeation of oxygen and water vapor.

[0128] The thickness of the inorganic vapor-deposited film is preferably 3 nm or more, more preferably 4 nm or more, further preferably 5 nm or more, preferably 300 nm or less, more preferably 250 nm or less, further 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, sufficient oxygen barrier and water vapor barrier properties can be obtained, for example. If the thickness is below the upper limit, for example, the generation of cracks in the inorganic vapor-deposited film can be suppressed.

[0129] In one embodiment, the thickness of the inorganic vapor-deposited film made of alumina is preferably 3 nm or more, more preferably 5 nm or more, preferably 100 nm or less, more preferably 50 nm or less. In one embodiment, the thickness of the inorganic vapor-deposited film made of silicon oxide is preferably 3 nm or more, more preferably 10 nm or more, preferably 300 nm or less, more preferably 50 nm or less. The thickness of the inorganic vapor-deposited film made of silicon oxide is preferably 20 nm or more and 40 nm or less.

[0130] Surface treatment can also be applied to inorganic vapor-deposited films. This improves 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; and chemical surface treatments such as oxidation treatment using chemicals.

[0131] <Protective Layer>

[0132] The transfer film of the present invention may also have a protective layer on the side of the inorganic vapor-deposited film opposite to the heat-sealing layer side. This, for example, can suppress damage to the inorganic vapor-deposited film.

[0133] In one embodiment, the protective layer contains a resin component.

[0134] Examples of resin components include polyethylene, polypropylene, polystyrene, vinyl chloride resins, polyesters, (meth)acrylic resins, urethane resins, melamine resins, and epoxy resins. Uramate resins are preferred as a resin component, for example.

[0135] The resin content in the protective layer can be above 50% by mass, above 75% by mass, below 95% by mass, or below 90% by mass.

[0136] The protective layer may contain additives. Examples of additives include curing agents, antistatic agents, UV absorbers, colorants, heat stabilizers, and silane coupling agents. Examples of silane coupling agents include vinyl-based, epoxy-based, styrene-based, methacryl-based, acryloyl-based, amino-based, isocyanurate-based, acrylamide-based, mercapto-based, thioether-based, or isocyanate-based silane coupling agents.

[0137] 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.

[0138] For example, when the inorganic vapor-deposited film is composed of metal oxides such as aluminum oxide and silicon oxide, the transfer film of the present invention can have a barrier coating as a protective layer on the inorganic vapor-deposited film. This, for example, can further improve the gas barrier properties of the barrier laminate.

[0139] In one embodiment, the barrier coating contains a gas-barrier resin. Examples of gas-barrier resins include ethylene-vinyl alcohol copolymers, polyvinyl alcohol, poly(meth)acrylonitrile; polyamides such as nylon 6, nylon 6,6 and poly(m-phenylene adipamide) (MXD6); polyesters; polyurethanes; and (meth)acrylic resins.

[0140] The content of the gas barrier resin in the barrier coating 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 at or above the lower limit, the gas barrier properties of the barrier laminate can be further improved, for example.

[0141] The barrier coating may contain the above-mentioned additives.

[0142] The thickness of the barrier coating is preferably 0.01 μm or more, more preferably 0.1 μm or more, preferably 10 μm or less, more preferably 5 μm or less. If the thickness is at or above the lower limit, the gas barrier properties of the barrier laminate can be further improved, for example. If the thickness is at or below the upper limit, the processability of the barrier laminate can be improved, for example.

[0143] In another embodiment, the barrier coating is a gas-barrier coating film formed by polycondensation treatment of a composition containing metal alkoxides and water-soluble polymers using a sol-gel method in the presence of a sol-gel catalyst, water, and organic solvent. By applying such a barrier coating to an inorganic vapor-deposited film, gas barrier properties can be improved.

[0144] In one embodiment, the metal alkoxide is represented by the following general formula.

[0145] R 1 n M(OR 2 ) m

[0146] In the formula, R 1 and R 2 Each is an organic group with 1 to 8 carbon atoms, M is a metal atom, n is an integer greater than or equal to 0, m is an integer greater than or equal to 1, and n+m represents the valence of M.

[0147] As R 1 and R 2 Examples of organic groups that can be represented include alkyl groups with 1 to 8 carbon atoms, specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. Examples of metal atoms M include silicon, zirconium, titanium, and aluminum.

[0148] 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).

[0149] It is preferred to use a silane coupling agent in conjunction with the aforementioned metal alkoxide. Known organoalkoxysilanes containing organic reactive groups can be used as silane coupling agents, with organoalkoxysilanes having an epoxy group being preferred. Examples of organoalkoxysilanes having an epoxy group include, for instance, γ-epoxypropoxypropyltrimethoxysilane, γ-epoxypropoxypropylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The silane coupling agent is preferably used at a concentration of 1 to 20 parts by mass relative to 100 parts by mass of the metal alkoxide.

[0150] As a water-soluble polymer, polyvinyl alcohol and ethylene-vinyl alcohol copolymers are preferred. 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 can be used, or both can be used together. Alternatively, a gas barrier coating film obtained using polyvinyl alcohol and a gas barrier coating film obtained using ethylene-vinyl alcohol copolymer can be laminated.

[0151] 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 relative to 100 parts by mass of the metal alkoxide. If the content is at or above the lower limit, the gas barrier properties of the barrier laminate can be further improved, for example. If the content is at or below the upper limit, the film-forming properties of the above composition can be further improved, for example.

[0152] Acid or amine compounds are preferred as catalysts for the sol-gel method.

[0153] As amine compounds, tertiary amines that are substantially insoluble in water but soluble in organic solvents are preferred, such as N,N-dimethylbenzylamine, tripropylamine, tributylamine, and tripentylamine. Among these, N,N-dimethylbenzylamine is preferred.

[0154] The amount of the amine compound relative to 100 parts by mass of the metal alkoxide is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, preferably 1.0 parts by mass or less, more preferably 0.3 parts by mass or less. If the amount is at or above the lower limit, the catalytic effect can be improved, for example. If the amount is at or below the upper limit, the thickness of the gas barrier coating film can be made uniform, for example.

[0155] Acids are suitable as catalysts for sol-gel processes, primarily for the hydrolysis of metal alkoxides and silane coupling agents. Examples of acids include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, as well as organic acids such as acetic acid and tartaric acid.

[0156] The amount of acid used is preferably 0.001 mol or more and 0.05 mol or less, relative to the total amount of alkoxide components (e.g., silicate portion) of the metal alkoxide and silane coupling agent. If the amount of acid used is above the lower limit, the catalytic effect can be improved, for example. If the amount of acid used is below the upper limit, the thickness of the gas barrier coating film can be made uniform, for example.

[0157] Relative to the total amount of 1 mole of alkoxide, the above composition preferably contains at least 0.1 moles, more preferably at least 0.8 moles, more preferably at least 100 moles, and more preferably at least 2 moles of water. If the water content is at or above the lower limit, the gas barrier properties of the barrier laminate can be further improved, for example. If the water content is below the upper limit, the hydrolysis reaction can be carried out rapidly, for example.

[0158] The above composition may contain an organic solvent. Examples of organic solvents include methanol, ethanol, n-propanol, isopropanol, and n-butanol.

[0159] 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, more preferably 50 μm or less. This further improves the gas barrier properties of the barrier laminate. If the thickness is at or above the lower limit, the gas barrier properties of the barrier laminate can be further improved, and the generation of cracks in the inorganic vapor-deposited film can be suppressed. If the thickness is below the upper limit, a barrier laminate suitable for manufacturing single-material packaging containers can be produced.

[0160] <Adhesive layer>

[0161] The transfer film of the present invention may have an adhesive layer on the surface opposite to the heat-sealing layer side of the inorganic vapor-deposited film. In the transfer method described later, the adhesive layer is used to bond the transfer body (e.g., a paper component having a paper substrate) to the transfer film having a support substrate, a heat-sealing layer, and an inorganic vapor-deposited film. The transfer film may not have an adhesive layer; for example, an adhesive layer may be provided on the transfer body.

[0162] 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 inhibits the formation of cracks in the inorganic vapor-deposited film, and even when the inorganic vapor-deposited film begins to develop tiny cracks after the bending load, it also inhibits the reduction of gas barrier properties.

[0163] Details of the adhesive layer are described later; the description in this section is omitted.

[0164] <Layer Structure of Transfer Film>

[0165] Regarding the layer structure of the transfer film of the present invention, several examples are given below.

[0166] Inorganic vapor deposition film / HS layer / supporting substrate

[0167] Inorganic vapor deposition film / AC layer / HS layer / support substrate

[0168] • Protective layer / Inorganic vapor deposition film / HS layer / Supporting substrate

[0169] • Protective layer / Inorganic vapor deposition film / AC layer / HS layer / Supporting substrate

[0170] • Protective layer / Protective layer / Inorganic vapor deposition film / HS layer / Supporting substrate

[0171] • Protective layer / Protective layer / Inorganic vapor deposition film / AC layer / HS layer / Supporting substrate

[0172] "HS layer" refers to the heat-sealing layer, "AC layer" refers to the anchor coating layer, and " / " refers to the interlayer.

[0173] [Manufacturing method of transfer film]

[0174] The method for manufacturing the transfer film of the present invention may include: a step of forming a heat-sealing layer on a support substrate (hereinafter also referred to as the "heat-sealing layer forming step"); a step of forming an anchor coating on the heat-sealing layer as needed (hereinafter also referred to as the "anchor coating forming step"); and a step of forming an inorganic vapor-deposited film on the heat-sealing layer or the anchor coating (hereinafter also referred to as the "vapor-deposited film forming step"). The above manufacturing method may include a step of forming a protective layer on the inorganic vapor-deposited film (hereinafter also referred to as the "protective layer forming step").

[0175] <Heat-sealing layer formation process>

[0176] A heat-sealing layer can be formed, for example, by applying a heat-sealing coating liquid to one side of a support substrate and then drying it. The heat-sealing layer is preferably located on the side of the support substrate where no easy-to-bond treatment has been performed, or on the side where no easy-to-bond layer has been formed.

[0177] As a coating liquid for heat-sealing layers, a coating liquid that can form a coating film on a support substrate and has excellent peelability from the support substrate and heat-sealing properties is preferred. Details of the coating liquid for heat-sealing layers are as described above.

[0178] In one embodiment, a heat-sealing coating liquid is applied to a support substrate and then dried. Examples of coating methods for the heat-sealing coating liquid include, for instance, gravure coating, reverse coating, air knife coating, comma coating, mold coating, doctor blade coating, roller coating, bar coating, curtain coating, spray coating, lip coating, and dipping.

[0179] Methods for drying the coating liquid used in the heat-sealing layer include, for example, hot air drying, hot roller drying, and infrared irradiation. The drying temperature is preferably 50°C to 150°C.

[0180] <Anchor Coating Formation Process>

[0181] By applying an anchor coating to the heat-sealing layer, the adhesion of the inorganic vapor-deposited film can be improved, and the vapor-deposited surface can be smoothed. Depending on the required level of gas barrier properties and the required interlayer strength, an anchor coating may not be necessary.

[0182] Anchoring agents can be prepared, for example, by mixing the above-mentioned resin components or their precursor resins (e.g., thermosetting resins), a curing agent as needed, additives as needed, and a solvent. Details of these components are as described above. Additionally, solvents similar to those used in heat-sealing coating solutions can be cited as examples.

[0183] An anchor coating can be formed, for example, by applying an anchoring agent to a heat-sealing layer and then drying it. Examples of methods for applying the anchoring agent include the well-known methods described above. Examples of methods for drying the applied anchoring agent include applying heat, such as hot air drying, hot roller drying, and infrared irradiation. The drying temperature is preferably 50°C to 150°C.

[0184] <Evaporation film formation process>

[0185] The inorganic vapor-deposited film is preferably formed by direct vapor deposition on one side of the heat-sealing layer or anchor coating. Examples of methods for forming the inorganic vapor-deposited film include physical vapor deposition (PVD) methods such as vacuum evaporation, sputtering, ion plating, and cluster ion beam deposition; and chemical vapor deposition (CVD) methods such as plasma chemical vapor deposition, thermochemical vapor deposition, and photochemical vapor deposition. The inorganic vapor-deposited film can also be a composite film consisting of two or more different types of layers formed by combining physical vapor deposition and chemical vapor deposition. Examples of heating units include resistance heating units, induction heating units, and electron beam heating units.

[0186] The preferred gas pressure for the vapor deposition chamber is 10. -8 mbar and above 10 -2 Below mbar. In the case of forming an inorganic vapor-deposited film composed of inorganic compounds, oxygen, nitrogen, or carbon dioxide are introduced as the reaction gas. In the case of forming an inorganic vapor-deposited film composed of metal oxides, after introducing oxygen, the gas pressure is preferably 10 mbar. -6 mbar and above 10 -1 Below mbar.

[0187] The amount of reactive gas introduced varies depending on the size of the vapor deposition machine. Among the introduced reactive gases such as oxygen, inert gases such as argon, helium, and nitrogen can be used as carrier gases without obstruction.

[0188] When using a roll-shaped transfer substrate and continuously forming an inorganic vapor-deposited film, the conveying speed of the transfer substrate, which forms a heat-sealing layer and an anchor coating as required, is, for example, 10 m / min or more and 800 m / min or less.

[0189] When forming an inorganic vapor deposition film, the surface of the layer to be formed by vapor deposition is cleaned by using pretreatment with Ar gas, O2 or N2, etc., and polar groups or free radicals are generated on the surface of the layer, thereby improving the adhesion between the inorganic vapor deposition film and the layer.

[0190] In one embodiment, in the PVD process, for example, a roll-up vapor deposition machine is used to place the substrate released from the unwinding roller into the vapor deposition chamber, where the vapor deposition source heated by the crucible evaporates, and as needed, oxygen is ejected from the oxygen outlet, while an inorganic vapor deposition film is formed on the substrate on the cooled coating drum. The substrate is then wound up onto the take-up roller.

[0191] In one embodiment, in the PE-CVD method, for example, a mixed gas containing, for example, an organosilicon compound as a monomer gas, oxygen and inactive gas is introduced into the evaporation chamber to generate plasma, thereby forming an inorganic evaporation film made of silicon oxide or the like on a substrate.

[0192] The aforementioned substrate comprises a transfer substrate, a heat-sealing layer, and an anchor coating as required. Thus, a transfer film is obtained having, in the thickness direction, a transfer substrate, a heat-sealing layer, an anchor coating as required, and an inorganic vapor-deposited film in sequence.

[0193] <Protective Layer Formation Process>

[0194] The protective layer can be formed, for example, by applying a protective coating liquid onto an inorganic vapor-deposited film and then drying it. The coating method for the protective coating liquid can be any of the known methods described above. The drying method for the applied protective coating liquid can be, for example, hot air drying, hot roller drying, or infrared irradiation. The drying temperature is preferably 50°C to 150°C.

[0195] The protective coating liquid can be prepared, for example, by mixing the above-mentioned resin components, a curing agent as needed, additives as needed, and a solvent. Details of these components are as described above. Furthermore, the same solvents used in the heat-sealing coating liquid can be cited as examples.

[0196] Barrier coatings, serving as protective layers, can be formed, for example, by dissolving or dispersing materials such as gas barrier resins in water or a suitable organic solvent, applying the resulting coating solution onto an inorganic vapor-deposited film, and then drying it. Alternatively, barrier coatings can be formed, for example, by applying commercially available barrier coating agents and then drying them.

[0197] In one embodiment, the barrier coating is the aforementioned gas barrier coating film. The gas barrier coating film can be formed, for example, by coating the aforementioned composition containing metal alkoxides and water-soluble polymers using a known coating method, and then subjecting the composition to polycondensation treatment using a sol-gel method.

[0198] The following describes one embodiment of a method for forming a gas barrier coating film.

[0199] First, a composition is prepared by mixing a metal alkoxide, a water-soluble polymer, a sol-gel catalyst, water, an organic solvent, and a silane coupling agent as needed. In this composition, the polycondensation reaction proceeds gradually.

[0200] Next, the above composition is coated onto an inorganic vapor-deposited film using a known coating method and then dried. During this drying process, the polycondensation reaction of the metal alkoxide and the water-soluble polymer (including the silane coupling agent if the composition contains such an agent) proceeds further, forming a layer of composite polymer.

[0201] Finally, the above composition is heated at a temperature preferably 20°C to 250°C, more preferably 50°C to 220°C, for at least 1 second to 10 minutes. This allows the formation of a gas barrier coating film.

[0202] [Barrier laminates]

[0203] In one embodiment, the barrier laminate of the present invention comprises, in the thickness direction, a substrate such as a paper substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-sealing layer. In another embodiment, the barrier laminate of the present invention further comprises an anchor coating layer between the inorganic vapor-deposited film and the heat-sealing layer. Here, the inorganic vapor-deposited film is in contact with the heat-sealing layer or the anchor coating layer (if the anchor coating layer is provided).

[0204] In one embodiment, the barrier laminate of the present invention comprises, in the thickness direction, a substrate such as a paper substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-sealing layer. In another embodiment, the barrier laminate of the present invention further comprises an anchor coating layer between the inorganic vapor-deposited film and the heat-sealing layer. The barrier laminate of this embodiment does not have a release layer between the inorganic vapor-deposited film and the heat-sealing layer.

[0205] Figure 3 The diagram illustrates one embodiment of the barrier laminate of the present invention. Figure 3 The barrier laminate 1 has, in the thickness direction, a substrate 10, an adhesive layer 20, an inorganic vapor-deposited film 30, and a heat-sealing layer 40.

[0206] Figure 4 Another embodiment of the barrier laminate of the present invention is shown in the figure. Figure 4The barrier laminate 1 has, in the thickness direction, a printed layer 12, a substrate 10, an adhesive layer 20, an inorganic vapor-deposited film 30, an anchor coating 32, and a heat-sealing layer 40.

[0207] The barrier laminate of the present invention does not have a release layer between the heat-sealing layer and the inorganic vapor-deposited film, thus resulting in high interlayer adhesion strength. Therefore, the barrier laminate of the present invention suppresses interlayer delamination during its manufacturing process and use.

[0208] A release layer typically refers to a layer provided on the surface of a transfer layer on the transfer support side in an existing transfer film that includes 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 has a release layer as the surface layer on the transfer support side.

[0209] The release layer is typically a layer containing a release agent. Examples of release agents include waxes such as silicone waxes, silicone oils, silicone resins, fluoropolymers, and phosphate esters. In one embodiment, the release layer contains a resin component. Examples of resin components include polyolefins, vinyl resins, styrene resins, (meth)acrylic resins, polyesters, polyurethanes, polycarbonates, polyamides, polyimides, and cellulose resins.

[0210] <Substrate>

[0211] The barrier laminate of the present invention comprises a substrate.

[0212] Examples of substrates include paper substrates and resin films as support substrates, as described above. Among these, paper substrates are preferred. Barrier laminates having a paper substrate as a base material are also referred to as "barrier paper".

[0213] Examples of paper substrates include kraft paper, plain white toilet paper, high-grade paper, ordinary paper, cellophane, drawing paper, processed base paper, cardboard, and synthetic paper. Paper substrates with filler or resin layers formed on one or both sides of the paper can also be used, such as clay-coated paper, micro-coated printing paper, coated printing paper (e.g., coated paper, cast-coated paper, and art paper), resin-coated paper, release base paper, and double-sided coated release base paper.

[0214] Paper substrates may contain additives. Examples of additives include sizing agents, lubricants, antioxidants, UV absorbers, light stabilizers, antistatic agents, optical brighteners, optical decolorizing agents, fillers, reinforcing agents, pigments, and dyes. Additives may be added in any amount as needed, provided they do not adversely affect other properties.

[0215] Physical surface treatments such as corona discharge treatment, ozone treatment, plasma treatment, glow discharge treatment, and sandblasting can also be applied to the surface of the adhesive layer side of the substrate; as well as chemical surface treatments such as oxidation treatment using chemicals.

[0216] In one embodiment, the paper substrate includes the aforementioned paper material and a filler layer or resin layer formed on the surface of the paper material on the side of the adhesive layer. The filler layer has the function of inhibiting the penetration of the adhesive constituting the adhesive layer into the paper material and stabilizing the adhesive force of the adhesive layer.

[0217] In one embodiment, the filler 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, (meth)acrylic resins, polyesters, polyamides, polyurethanes, and cellulose resins, as well as cured thermosetting resins.

[0218] In one embodiment, the filler 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 filler layer or resin layer preferably contains fillers. Examples of fillers include clay, silica, calcium carbonate, titanium dioxide, and zinc oxide.

[0219] The filler layer or resin layer can be formed, for example, by coating or extrusion coating. The thickness of the filler layer or resin layer is, for example, 0.1 μm or more and 30 μm or less.

[0220] It should be noted that, generally speaking, the surface of paper is porous and uneven. Therefore, when forming an inorganic vapor-deposited film directly on paper, it is sometimes preferable to pre-form a filler layer with a thickness of 20 μm or more on the paper surface. However, in this invention, since barrier paper can be manufactured by the transfer method described later, it is not necessary to form an inorganic vapor-deposited film directly on the paper. Therefore, it is not necessary to form such a thick filler coating on the paper surface.

[0221] Furthermore, generally speaking, when paper is placed in a vapor deposition apparatus and an inorganic vapor deposition film is formed under reduced pressure, paper dust generated from the paper can sometimes hinder the reduction of pressure within the vapor deposition apparatus to a suitable vapor deposition pressure. In such cases, it is difficult to form a stable inorganic vapor deposition film, and therefore the adhesion between the formed inorganic vapor deposition film and the paper is prone to become insufficient, and the gas barrier properties sometimes become unstable. However, in this invention, since the barrier paper can be manufactured by the transfer method described later, it is not necessary to place the paper in a vapor deposition apparatus and instead form the inorganic vapor deposition film directly on the paper. Therefore, the above-mentioned problems can be avoided.

[0222] Thus, in this invention, a paper substrate can be used as the paper substrate, which is composed of paper and is not impregnated with resin components, clay materials, etc. Furthermore, in this invention, a paper substrate can be used as the paper substrate, which is composed of paper and does not have a filler layer, resin layer, or clay coating.

[0223] Paper-based substrates and other substrates can consist of a single layer or multiple layers comprising two or more layers containing the same or different substrates. The substrates can be laminated together using any known lamination method with existing adhesive layers.

[0224] The thickness of the paper substrate or other substrate is preferably 10 μm or more, more preferably 30 μm or more, further preferably 40 μm or more, preferably 1,500 μm or less, more preferably 500 μm or less, and further preferably 300 μm or less. The basis weight of the paper substrate is preferably 30 g / m³. 2 The above, and more preferably 50g / m 2 The above is preferably 600g / m 2 The following, or more preferably, is 450g / m 2 Below. When the substrate is composed of multiple layers, the thickness of the substrate refers to the total thickness of the multiple substrate layers. This also applies to the basis weight.

[0225] Such thickness and / or basis weight, for example, can impart appropriate strength and rigidity to the barrier laminate. If the thickness and / or basis weight is above the lower limit, for example, curling and undulation can be suppressed during the manufacture of the barrier laminate. If the thickness and / or basis weight is below the upper limit, the strength and rigidity are within an appropriate range, and the reduction in work efficiency can be suppressed.

[0226] <Printed Layer>

[0227] In one embodiment, the barrier laminate of the present invention has a printed layer on a substrate such as a paper substrate. The barrier laminate of the present invention can have a 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, preferably on the surface of the substrate opposite to the adhesive layer side.

[0228] Printed layers may include, for example, images. Examples of images include text, graphics, symbols, patterns, designs, and combinations thereof. Printed layers are provided, for example, to display the contents of the packaging material, to display the expiration date, to display information to the manufacturer and seller, for decoration, and to enhance aesthetics.

[0229] 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-curable resin composition, each containing a colorant. Specifically, the printed layer contains a cured thermoplastic resin, a cured thermosetting resin or a cured energy-curable resin, and a colorant.

[0230] The thermoplastic resin composition contains a thermoplastic resin and a colorant.

[0231] Examples of thermoplastic resins include polyolefins, vinyl resins, styrene resins, (meth)acrylic resins, polyesters, polyurethanes, polycarbonates, polyamides, polyimides, cellulose resins, petroleum resins, and fluoropolymers.

[0232] 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.

[0233] A thermosetting resin composition is a composition containing a thermosetting resin and a colorant, a curing agent as needed, and cured by heating. In one embodiment, the thermosetting resin composition is a so-called thermosetting ink.

[0234] 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.

[0235] Thermosetting resin compositions may contain the above-mentioned additives.

[0236] The energy-curable resin composition is a composition containing a compound having energy-curable functional groups (hereinafter also referred to as "energy-curable compound") and a colorant, which is cured by irradiation with energy rays. In one embodiment, the energy-curable resin composition is a so-called ultraviolet-curable ink, preferably a (meth)acrylic-based ultraviolet-curable ink.

[0237] 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 in terms of curing speed, ease of obtaining the irradiation source, and cost.

[0238] Examples of energy-curable functional groups include olefinically unsaturated groups such as (meth)acryloyl, vinyl, and allyl; as well as epoxy and oxetyl groups. Examples of energy-curable compounds include compounds having olefinically unsaturated groups, preferably compounds having two or more olefinically unsaturated groups, and more preferably polyfunctional (meth)acrylate compounds. As polyfunctional (meth)acrylate compounds, either monomers or oligomers can be used.

[0239] When the energy-curable compound is an ultraviolet-curable compound, the energy-curable composition (ultraviolet-curable resin composition) preferably contains at least one selected from photopolymerization initiator and photopolymerization accelerator.

[0240] Energy-curable resin compositions may contain the above-mentioned additives.

[0241] Examples of colorants include pigments and dyes. Specifically, examples of pigments include titanium dioxide, zinc white, carbon black, iron oxide, iron oxide yellow, ultramarine, metallic pigments, pearlescent pigments, and fluorescent pigments. The printing layer can be a high-gloss layer with a high metallic sheen.

[0242] From the perspective of improving coatability, the composition for the printing layer may contain organic solvents and / or water. 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, acetic acid cellosolve, and butyl cellosolve acetate; and alcohol solvents such as propanol.

[0243] For example, a printing layer can be formed by coating a printing layer composition onto a substrate such as a paper substrate and drying it, followed by heating at the required curing temperature in the case of a thermosetting resin composition, or by irradiating with energy rays in the case of an energy-curable resin composition. If the printing layer composition does not contain organic solvents and / or water, drying is not required.

[0244] Examples of methods for forming a printed layer include letterpress printing, flexographic printing, gravure printing, offset printing, screen printing, inkjet printing, and thermal transfer printing. The printed layer can be applied to the entire surface of the substrate or to a portion thereof.

[0245] In one embodiment, the printed layer comprises a sublimable dye. This printed layer can be formed, for example, by sublimation transfer printing using a heat transfer sheet.

[0246] 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.

[0247] <Adhesive layer>

[0248] The barrier laminate of the present invention has an adhesive layer between the substrate and the inorganic vapor-deposited film. In the transfer method described later, the adhesive layer is a layer used to bond the transfer body, such as a paper component having a paper substrate, to the transfer film having a support substrate, a heat-sealing layer, and an inorganic vapor-deposited film.

[0249] In one embodiment, the adhesive layer is a layer bonded to 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 inhibits the formation of cracks in the inorganic vapor-deposited film, and even when the inorganic vapor-deposited film begins to develop microcracks after the bending load, it also inhibits the reduction of gas barrier properties.

[0250] The thickness of the adhesive layer is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 20 μm or less, more preferably 10 μm or less. The basis weight of the adhesive layer is preferably 1 g / m³. 2 The above, and more preferably 2g / m 2 The above is preferably 20g / m 2 The following, or more preferably, is 10g / m 2 the following.

[0251] The adhesive layer can be formed using existing, known adhesives. The adhesive can be any of the following: single-component curing, two-component curing, or non-curing adhesives. The adhesive can be a solvent-free adhesive or a solvent-based adhesive. The adhesive layer can be formed, for example, by a solvent-free lamination method using a solvent-free adhesive, or by a dry lamination method using a dry-laminated adhesive. Alternatively, an anchor coating can be formed first on the layer forming the adhesive layer, and then the adhesive layer can be formed.

[0252] Anchor coatings can be formed using, for example, isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, or organotitanium-based anchor coatings; or (meth)acrylic resin-based, polyurethane-based, polyester-based, epoxy-based, polyvinyl acetate-based, polyvinyl chloride-based, or cellulose resin-based anchor coatings.

[0253] Examples of adhesives include two-component curing urethane adhesives, polyester-based polyurethane adhesives, polyether-based polyurethane adhesives, (meth)acrylic adhesives, polyester-based adhesives, polyether-based adhesives, polyamide-based adhesives, epoxy adhesives, rubber-based adhesives, polyolefin-based adhesives, acid-modified polyolefin-based adhesives, polyvinyl acetate-based adhesives, and polyvinyl chloride-based adhesives. Acid-modified polyolefin resins are obtained by acid modification of polyolefin resins using unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid, or their anhydrides, through graft polymerization or copolymerization.

[0254] As an adhesive for forming an adhesive layer between a transfer substrate such as paper and an inorganic vapor-deposited film, a urethane-based resin composition is preferred. This allows, for example, the formation of a gas-barrier adhesive layer. Specifically, the adhesive layer is preferably formed using a urethane-based resin composition. The urethane-based resin composition preferably contains a polyol having two or more hydroxyl groups per molecule and an isocyanate compound having two or more isocyanate groups per molecule. The urethane-based resin composition may further contain a phosphoric acid compound, and may also further contain an inorganic compound.

[0255] The urethane resin composition can be either solvent-free or solvent-based.

[0256] Commercially available products of the aforementioned adhesives include, for example, dry lamination adhesives (base agent RU-40 / curing agent H-1 and base agent RU-77T / curing agent H-7) manufactured by Rock Paint Co., Ltd.

[0257] The adhesive layer and the urethane resin composition may contain additives. Examples of additives include, for instance, 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.

[0258] In one embodiment, the adhesive layer has a glass transition temperature (Tg) in a range preferably above -30°C, more preferably above 0°C, further preferably above 25°C, preferably below 80°C, more preferably below 70°C, and even more preferably below 70°C. If Tg is below the upper limit, it tends to have excellent flexibility near room temperature and excellent adhesion to layers adjacent to the adhesive layer. If Tg is above the lower limit, it tends to have excellent cohesion and thus excellent adhesion.

[0259] The adhesive layer can be formed by applying the adhesive to a substrate and / or an inorganic vapor-deposited film and then drying it arbitrarily, for example, by methods such as direct gravure roller coating, gravure roller coating, kiss coating, reverse roller coating, futon coating and transfer roller coating.

[0260] Polyols having two or more hydroxyl groups within a single molecule

[0261] Examples of polyols having two or more hydroxyl groups per molecule include polyols having two or more hydroxyl groups per molecule and having at least one selected from polyester, polyester-polyurethane, polyether, and polyether-polyurethane structural portions as their main backbone. More preferably, polyols having two or more hydroxyl groups per molecule and having at least one selected from polyester and polyester-polyurethane structural portions as their main backbone are preferred. More preferably, polyols having two or more hydroxyl groups per molecule and having a polyester structural portion as their main backbone are preferred. The polyester structural portion can be obtained, for example, by polycondensation reaction of a polycarboxylic acid with a polyhydroxy compound.

[0262] 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.

[0263] Examples of aliphatic polycarboxylic acids include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

[0264] Examples of aromatic polycarboxylic acids include, for example, 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, naphthalenedicarboxylic acid, biphenyl dicarboxylic acid, and 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; as well as trimethylbenzene and pyromellitic acid, and other trivalent or higher carboxylic acids. Among these, ortho-aromatic dicarboxylic acids are preferred. Examples of ortho-aromatic dicarboxylic acids include, for example, phthalic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid.

[0265] Examples of polyhydroxy compounds include:

[0266] Ethylene glycol, propylene glycol, butanediol, neopentyl glycol, cyclohexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butyl ethyl propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol, etc., are aliphatic diols and other aliphatic polyols.

[0267] Aromatic polyphenols such as hydroquinone, resorcinol, catechol, naphthol, biphenol, bisphenol A, bisphenol F, and tetramethylbiphenol, and their epoxide adducts; and

[0268] The above-mentioned hydrogenated alicyclic compounds of aromatic polyphenols.

[0269] The structural portion derived from the polycarboxylic acid constituting the polyester or polyester polyurethane structural portion preferably includes a structural portion derived from an ortho-aromatic dicarboxylic acid. Preferably, 70% to 100% by mass of the structural portion derived from the polycarboxylic acid constituting the polyester or polyester polyurethane structural portion is derived from an ortho-aromatic dicarboxylic acid. Ortho-aromatic dicarboxylic acids refer to ortho-aromatic dicarboxylic acids, as well as their anhydrides and ester-forming derivatives.

[0270] Isocyanate compounds having two or more isocyanate groups within a single molecule

[0271] The isocyanate compounds having two or more isocyanate groups within one molecule can be either aromatic or aliphatic compounds, or low-molecular-weight or high-molecular-weight compounds, as long as they have two or more isocyanate groups within one molecule. Examples include diisocyanate compounds having two isocyanate groups and polyisocyanate compounds having three or more isocyanate groups. Examples also include end-capped isocyanate compounds obtained by addition reactions using known isocyanate end-capping agents through appropriate, commonly used methods.

[0272] As the aforementioned isocyanate compound, compounds having an aromatic ring in the main skeleton are preferred, and compounds having a polyurethane structural portion containing an aromatic ring in the main skeleton are more preferred.

[0273] From the perspective of adhesiveness, polyisocyanate compounds are preferred; from the perspective of gas barrier properties, polyisocyanate compounds having aromatic rings are more preferred. Isocyanate compounds containing a m-xylene skeleton are expected to improve gas barrier properties not only through hydrogen bonding of carbamate groups but also through π-π stacking of aromatic rings, and are therefore more preferred.

[0274] Specifically, examples of the aforementioned isocyanate compounds include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, isophenyl dimethyl diisocyanate, hydrogenated phenyl dimethyl diisocyanate, and isophorone diisocyanate. Trimers of these isocyanate compounds may also be cited. Furthermore, adducts, biuret forms, or ureocarbamate forms obtained by reacting excess of these isocyanate compounds with low-molecular-weight compounds or high-molecular-weight compounds containing active hydrogen may also be cited.

[0275] Examples of low-molecular-weight compounds containing active hydrogen include ethylene glycol, propylene glycol, isophthalic acid, 1,3-dihydroxyethylbenzene, 1,4-dihydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, and m-phenylenediamine, as well as their alkyl oxide adducts. Examples of high-molecular-weight compounds containing active hydrogen include polyesters, polyether polyols, and polyamides.

[0276] Inorganic vapor deposition film

[0277] The barrier laminate of the present invention comprises an inorganic vapor-deposited film. The inorganic vapor-deposited film is preferably formed by direct vapor deposition on one side of the heat-sealing layer, or, in the case of an anchor coating, on one side of the anchor coating. Details of the inorganic vapor-deposited film are as described above, and further explanation in this section is omitted.

[0278] <Protective Layer>

[0279] The barrier laminate of the present invention can have a protective layer on the surface of the inorganic vapor-deposited film opposite to the heat-sealing layer side. This, for example, can suppress damage to the inorganic vapor-deposited film. Details of the protective layer are as described above, and are omitted in this section.

[0280] <Anchor Coating>

[0281] The barrier laminate of the present invention may further include an anchor coating layer between the heat-sealing layer and the inorganic vapor-deposited film. By providing the anchor coating layer, the adhesion between the heat-sealing layer and the inorganic vapor-deposited film can be improved, and delamination between these layers can be suppressed. The anchor coating layer, for example, is in contact with the inorganic vapor-deposited film on one side and with the heat-sealing layer on the other side. Details of the anchor coating layer are as described above, and further explanation in this section is omitted.

[0282] <Heat-sealing layer>

[0283] The barrier laminate of the present invention has a heat-sealing layer as one side surface layer. In one embodiment, the heat-sealing layer functions as a heat-sealing layer. For example, when the barrier laminate is used as a packaging material, the heat-sealing layer functions as a heat-sealing sealant layer. Furthermore, when the barrier laminate is manufactured using the transfer printing method described later, the heat-sealing layer also functions as a release layer from the supporting substrate. Details of the heat-sealing layer are as described above, and the description in this section is omitted.

[0284] <Functional Layer>

[0285] The barrier laminate of the present invention may include a functional layer in addition to the aforementioned layers. The functional layer imparts functions such as light-shielding, mechanical strength, deformation resistance, impact resistance, pinhole resistance, heat resistance, sealing, quality preservation, workability, and hygiene to the barrier laminate.

[0286] 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, fluorinated resins, cellulose resins, and ionomer resins.

[0287] The functional layer may contain the aforementioned additives corresponding to its function.

[0288] The thickness of the functional layer is, for example, between 1 μm and 300 μm.

[0289] <Layer structure and applications of barrier paper>

[0290] Regarding the layer structure of the barrier paper of the present invention, several examples are given below.

[0291] • Paper substrate / adhesive layer / inorganic vapor deposition film / HS layer

[0292] • Paper substrate / adhesive layer / inorganic vapor deposition film / AC layer / HS layer

[0293] • Paper substrate / adhesive layer / protective layer / inorganic vapor deposition film / HS layer

[0294] • Paper substrate / adhesive layer / protective layer / inorganic vapor deposition film / AC layer / HS layer

[0295] • Printed layer / Paper substrate / Adhesive layer / Inorganic vapor deposition film / HS layer

[0296] • Printed layer / Paper substrate / Adhesive layer / Inorganic vapor deposition film / AC layer / HS layer

[0297] • Printed layer / Paper substrate / Adhesive layer / Protective layer / Inorganic vapor deposition film / HS layer

[0298] • Printed layer / Paper substrate / Adhesive layer / Protective layer / Inorganic vapor deposition film / AC layer / HS layer

[0299] • Paper substrate / adhesive layer / protective layer / protective layer / inorganic vapor deposition film / HS layer

[0300] • Paper substrate / adhesive layer / protective layer / protective layer / inorganic vapor deposition film / AC layer / HS layer

[0301] • Printed layer / Paper substrate / Adhesive layer / Protective layer / Protective layer / Inorganic vapor deposition film / HS layer

[0302] • Printed layer / Paper substrate / Adhesive layer / Protective layer / Protective layer / Inorganic vapor deposition film / AC layer / HS layer

[0303] "HS layer" refers to the heat-sealing layer, "AC layer" refers to the anchor coating layer, and " / " refers to the interlayer.

[0304] The paper substrate can be a paper / filler layer (or resin layer). In this case, for example, the portion of the "paper substrate / adhesive layer" in the above layer structure becomes a "paper / filler layer (or resin layer) / adhesive layer". Instead of a paper substrate, a resin film can be used, or a substrate that is difficult to directly vapor deposit (such as wood) can be used.

[0305] Compared to gas barrier plastic films, the barrier paper of the present invention has a paper substrate, thus having a high paper content and a low plastic content, which can help reduce plastic waste. In addition, recycling and biodegradation become easier, it will not damage the incinerator, and can reduce incineration residue.

[0306] The oxygen permeability of the barrier paper or other barrier laminate of the present invention is preferably 10 cc / m 2 / 24hr / atm or less, preferably 5cc / m 2 / 24hr / atm or less, further preferred 3cc / m 2 / 24hr / atm or less, with 1.5cc / m being the preferred choice. 2 / 24hr / atm or less. The lower limit of oxygen permeability can be, for example, 0.01cc / m 2 / 24hr / atm. Oxygen permeability was determined according to JIS K7126 at 23°C and 90% RH.

[0307] The water vapor permeability of the barrier paper or other barrier laminate of the present invention is preferably 20 g / m³. 2 / 24hr or less, preferably 10g / m 2 / less than 24hr, further preferred 5g / m 2 / less than 24hr, with a preferred concentration of 1.5g / m 2 / 24hr or less. The lower limit for water vapor permeability can be, for example, 0.01 g / m 2 / 24hr. Water vapor transmission was determined according to JIS K7129 at 40°C and 90% RH.

[0308] The barrier laminate of the present invention is suitable for use in packaging materials such as packaging bags. As described above, the barrier laminate of the present invention has excellent interlayer adhesion and suppresses interlayer delamination. Therefore, packaging materials equipped with this barrier laminate suppress the occurrence of so-called delamination during their use.

[0309] The packaging material of the present invention comprises the barrier laminate of the present invention. The packaging material of the present invention may, as needed, also comprise layers with various functions together with the above-described barrier laminate.

[0310] For example, packaging materials can be manufactured by folding and overlapping the aforementioned barrier laminates with the paper substrate or other substrate on the outside and the heat-sealing layer on the inside, and then heat-sealing their ends. Alternatively, packaging materials can be manufactured by overlapping multiple of the aforementioned barrier laminates with their heat-sealing layers facing each other and then heat-sealing their ends. The packaging material may be entirely composed of the aforementioned barrier laminates, or only a portion of the packaging material may be composed of the aforementioned barrier laminates.

[0311] Examples of heat-sealing methods for packaging materials include side-sealed, two-sided-sealed, three-sided-sealed, four-sided-sealed, envelope-adhesive-sealed, butt-sealed (pillow-type), folded-sealed, flat-bottomed, square-bottomed, and corner-braced types. Additionally, stand-up pouches can also be used. Examples of heat-sealing methods include rod sealing, rotary roller sealing, belt sealing, pulse sealing, high-frequency sealing, and ultrasonic sealing.

[0312] Examples of contents that can be filled within packaging materials include liquids, powders, and gels, and can be either food or non-food products. After filling the packaging material with the contents, the opening of the packaging material is heat-sealed, thus obtaining the package.

[0313] Specifically, the contents include: coffee beans, tea leaves; cheese, snacks, roasted rice noodles, stuffed Japanese sweets / semi-dried sweets, nuts, vegetables, fruits, fish and meat products, porridge products, dried fish and shellfish, smoked products, salted seafood, raw rice, cooked rice, rice cakes, baby food, jam, mayonnaise, ketchup, cooking oil, sauces, sarsaparilla, spices, dairy products, and pet food; beverages such as beer, wine, fruit juice, green tea, and coffee; pharmaceuticals; cosmetics, shampoos, conditioners, and detergents; as well as metal and electronic components.

[0314] [Method for manufacturing barrier laminates]

[0315] The barrier laminate of the present invention is obtained, for example, by the transfer method described below.

[0316] The above-mentioned method for manufacturing barrier laminates using the transfer method comprises:

[0317] The process of preparing a paper component or other transferable object having a paper substrate and the transfer film of the present invention (hereinafter also referred to as the "preparation process");

[0318] The process of bonding the transfer substrate and the transfer film together with the support substrate of the transfer film facing outwards and the inorganic vapor-deposited film facing inwards (on the transfer substrate side) using an adhesive layer to obtain an intermediate laminate (hereinafter also referred to as the "bonding process"); and

[0319] The process of peeling the support substrate from the heat-sealing layer of the intermediate laminate (hereinafter also referred to as the "peeling process").

[0320] Figure 5 This is a process diagram illustrating an example of a method for manufacturing the barrier laminate of the present invention.

[0321] Through the aforementioned attachment and peeling processes, a transfer layer comprising an inorganic vapor-deposited film and a heat-sealing layer sequentially in the thickness direction can be transferred onto a substrate such as a paper component. Compared to inorganic vapor-deposited films formed directly on paper substrates, inorganic vapor-deposited films transferred to paper substrates via this method exhibit less contamination, higher adhesion between the inorganic vapor-deposited film and the adhesive layer, greater homogeneity and stability, and superior gas barrier properties.

[0322] According to the manufacturing method of the present invention, an inorganic vapor-deposited film can be formed on the substrate while using a paper substrate, just as in the case of using a resin substrate, thereby obtaining a barrier paper with excellent gas barrier properties and environmental friendliness.

[0323] Furthermore, in methods such as forming an inorganic vapor-deposited film on a paper substrate and then coating a heat-sealing layer onto the inorganic vapor-deposited film with a coating liquid to form a heat-sealing layer, the gas barrier properties of the inorganic vapor-deposited film may decrease due to cracking or thermal damage caused by tension, drying, etc., during the formation of the heat-sealing layer. The manufacturing method of the present invention can avoid such a decrease. In addition, the heat-sealing layer can suppress the deterioration of the inorganic vapor-deposited film during the bonding process and during the peeling process of the support substrate.

[0324] In the manufacturing method of the present invention, the deterioration of the inorganic vapor-deposited film can be suppressed in such a way that, for example, when using a barrier laminate as a packaging material, the degree of deterioration caused by bending, folding and heat-sealing damage can be reduced.

[0325] It should be noted that although the barrier paper with a different layer structure than the barrier paper of the present invention (hereinafter also referred to as "reference barrier paper"), a reference barrier paper with a layer structure such as paper substrate / adhesive layer / inorganic vapor-deposited film / release layer / undercoat layer as needed / heat-sealing layer can also be considered.

[0326] As a method for manufacturing reference barrier paper, one example is the following: A paper substrate is bonded to a transfer film having a transfer substrate, a release layer, and an inorganic vapor-deposited film by 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; the transfer substrate is peeled off from the laminate (1) to form a laminate (2) having a layer structure of paper substrate / adhesive layer / inorganic vapor-deposited film / release layer; a base coating layer and a heat-sealing layer are formed on the release layer of the laminate (2) as needed to obtain the aforementioned reference barrier paper. Hereinafter, this manufacturing method will also be referred to as the "reference transfer method".

[0327] The reference transfer method has the following advantages: compared with the inorganic vapor-deposited film formed directly on the paper substrate, the inorganic vapor-deposited film transferred to the paper substrate by the transfer method has less pollution, higher adhesion between the inorganic vapor-deposited film and the adhesive layer, is homogeneous and stable, and has excellent gas barrier properties.

[0328] However, because the reference barrier paper has a release layer between the heat-sealing layer and the inorganic vapor-deposited film, the adhesion strength between these layers is sometimes insufficient. In addition, in the reference transfer method, after peeling off the transfer substrate, a heat-sealing layer (heat-sealing sealant layer) required for manufacturing packaging materials needs to be formed on the release layer, thus increasing the number of manufacturing steps.

[0329] In contrast, the barrier paper of the present invention does not have a release layer between the heat-sealing layer and the inorganic vapor-deposited film, thus the adhesion strength between these layers is sufficiently high. Furthermore, in the manufacturing method of the present invention, the aforementioned heat-sealing layer also serves as a release layer from the support substrate. After peeling off the support substrate, there is no need to form a separate heat-sealing layer (heat-sealing sealant layer), thereby reducing the number of manufacturing steps.

[0330] Furthermore, in one embodiment of the manufacturing method of the present invention, a heat-sealing layer and an inorganic vapor-deposited film are pre-formed on a support substrate of the film. In the manufacturing of the transfer film, a wider and longer processing method than that for paper substrates is possible, thus reducing the cost per unit area of ​​the barrier paper.

[0331] Thus, both the reference barrier paper and the reference transfer method have excellent advantages, but the barrier paper and its manufacturing method of the present invention are superior in the above aspects, and can be said to have a beneficial effect.

[0332] <Preparation Process>

[0333] In the preparation process, paper components and other transfer materials and transfer film are prepared.

[0334] Examples of materials that can be transferred include paper components.

[0335] Paper components have a paper substrate. Paper components can be single sheets or continuous sheets wound into rolls.

[0336] The paper component may consist only of a paper substrate, or it may consist of a paper substrate and a printed layer disposed on the paper substrate. Preferably, the paper component has a printed layer on the side of the paper substrate opposite to the side where the adhesive layer is disposed. During the preparation process, the paper component can be manufactured by forming the printed layer on the paper substrate, or a paper component with a pre-existing printed layer on the paper substrate can be used. The printed layer can be formed between the bonding and peeling processes, or after the peeling process; however, from the perspective of suppressing a decrease in gas barrier properties, it is preferable to form the printed layer before the bonding process.

[0337] Paper substrates can consist of only paper, or they can consist of paper and a filler layer or resin layer formed on the paper. By using paper substrates with a filler layer or resin layer on the paper, it is possible to inhibit the penetration of adhesive into the paper and stabilize the adhesive strength of the adhesive layer. In the preparation process, the paper substrate can be made by forming a filler layer or resin layer on the paper, or a paper substrate with a filler layer or resin layer pre-formed on the paper, such as coated paper, can be used.

[0338] On the side of the paper substrate opposite to the side where the adhesive layer is applied, in addition to forming a printed layer as described above, decorative processes such as hot stamping, embossing, and shaping can also be performed. The paper component thus obtained can be used. Decoration can be performed between the application and peeling processes, or after the peeling process, but from the perspective of suppressing a decrease in gas barrier properties, it is preferable to perform decoration before the application process.

[0339] Details of each element are as described above and are omitted here.

[0340] As the substrate to be transferred, a resin film as described above can be used as the supporting substrate. Alternatively, substrates that are difficult to directly vapor deposit (such as wood) can also be used.

[0341] In the preparation process, a pre-made transfer film of the present invention is prepared.

[0342] <Attachment Process>

[0343] In the bonding process, the transfer substrate, such as a paper component, is bonded to the transfer film with the support substrate of the transfer film facing outwards and the inorganic vapor-deposited film facing inwards (towards the transfer substrate) using an adhesive layer to obtain an intermediate laminate (see reference). Figure 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 when the surface of the paper substrate is rough.

[0344] In the bonding process, the adhesive layer can be formed on either the substrate or the transfer film, or on both. Alternatively, adhesive can be supplied between the substrate and the transfer film while simultaneously forming the adhesive layer and bonding the substrate and the transfer film.

[0345] In the bonding process, in one embodiment, an adhesive layer is formed on the substrate to be transferred, and the transfer film is bonded to the adhesive layer. In one embodiment, the adhesive layer is preferably formed on a filler layer or a resin layer in the paper component.

[0346] In one embodiment, during the bonding process, 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 supporting substrate. In one embodiment, the adhesive layer is preferably formed on an inorganic vapor-deposited film within the transfer film.

[0347] In one embodiment of the bonding process, an adhesive layer is formed on the transfer body and an adhesive layer is formed on the transfer film, and the transfer body and the transfer film are bonded together by means of their adhesive layers being in contact.

[0348] Specific methods for forming the adhesive layer include, for example, methods for forming a coating layer by applying a liquid adhesive composition, dry lamination using a dry lamination adhesive, and solventless lamination using a solventless adhesive.

[0349] Alternatively, an anchor coating can be pre-formed before the adhesive layer is formed, thereby improving the adhesion of the adhesive layer. The anchor coating is preferably formed by application and drying.

[0350] The bonding process can be performed using generally known apparatus, temperature, and pressure, depending on the type and properties of the adhesive and the method of forming the adhesive layer. For example, in the case of forming the adhesive layer by dry lamination, in one embodiment, a dry lamination adhesive is applied to the substrate and / or transfer film and dried to form the adhesive layer. The substrate and transfer film are then overlapped by the adhesive layer, and pressure is applied to obtain an intermediate laminate. Heating may also be performed as needed.

[0351] The method and pressure for pressurizing the intermediate layer in the bonding process are preferably selected and set in a way that minimizes damage to the inorganic vapor-deposited film. The pressure applied during pressurization is preferably between 0.1 MPa and 10 MPa. For example, the adhesive layer can be softened by heating before bonding. Depending on the composition of the adhesive, the adhesive layer can also be cured by heating after bonding.

[0352] <Stripping Process>

[0353] In the peeling process, the support substrate is peeled off from the heat-sealing layer of the intermediate laminate (see reference). Figure 5 (C)). For example, after the adhesive layer between the transfer substrate and the transfer film has demonstrated sufficient adhesive strength, the supporting substrate is peeled off 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.

[0354] In one embodiment, the support substrate of the transfer film can be peeled off while the transfer body and the transfer film are bonded together by an adhesive layer.

[0355] Thus, the barrier laminate, such as the barrier paper of the present invention, is obtained.

[0356] For example, when the intermediate laminate is a continuous sheet wound into a roll, a release roller can be used to continuously peel the support substrate from the heat-sealing layer of the intermediate laminate, and then roll up the barrier laminate and the support substrate separately.

[0357] The present invention relates to, for example, the following [1] to

[19] .

[0358] [1] A transfer film having a supporting substrate, a heat-sealing layer and an inorganic vapor-deposited film sequentially in the thickness direction, wherein the inorganic vapor-deposited film is in contact with the heat-sealing layer, or the transfer film further has an anchor coating layer between the inorganic vapor-deposited film and the heat-sealing layer, wherein the inorganic vapor-deposited film is in contact with the anchor coating layer.

[0359] [2] As described in [1], the transfer film is formed by direct vapor deposition on one side of the heat-sealing layer.

[0360] [3] As described in [1], the transfer film is formed by direct vapor deposition on one side of the anchor coating.

[0361] [4] The transfer film as described in any one of [1] to [3], wherein the inorganic vapor-deposited film further comprises a protective layer.

[0362] [5] The transfer film as described in any one of [1] to [4], wherein the inorganic vapor-deposited film contains at least one selected from aluminum, alumina and silicon oxide.

[0363] [6] The transfer film as described in any one of [1] to [5], wherein the indentation hardness of the heat-sealing layer based on nanoindentation method is less than 0.15 GPa and the composite elastic modulus is less than 2.0 GPa.

[0364] [7] The transfer film as described in any one of [1] to [6], wherein the transition temperature of the anchor coating, as determined by local thermal analysis using a thermal probe, is 90°C or higher and 140°C or lower.

[0365] [8] The transfer film as described in any one of [1] to [7], wherein the NO2 in the anchor coating is measured while the transfer film is being etched using time-of-flight secondary ion mass spectrometry (TOF-SIMS). - The normalized strength of the ions is above 3.0 and below 4.2.

[0366] Regarding the standardized intensity, NO2 based on TOF-SIMS will be used. - The detection intensity of ions divided by CN - The detection intensity of the ion is normalized by multiplying it by 100,000, which refers to NO2.- The commonly used logarithmic value of the average detected intensity of ions after standardization.

[0367] [9] A barrier laminate having a substrate, an adhesive layer, an inorganic vapor-deposited film and a heat-sealing layer sequentially in the thickness direction, wherein the inorganic vapor-deposited film is in contact with the heat-sealing layer, or the barrier laminate further has an anchor coating layer between the inorganic vapor-deposited film and the heat-sealing layer, wherein the inorganic vapor-deposited film is in contact with the anchor coating layer.

[0368]

[10] The barrier laminate as described in [9], wherein the inorganic vapor-deposited film is directly vapor-deposited on one side of the heat-sealing layer.

[0369]

[11] The barrier laminate as described in [9], wherein the inorganic vapor-deposited film is directly vapor-deposited on one side of the anchor coating.

[0370]

[12] A barrier laminate having a substrate, an adhesive layer, an inorganic vapor-deposited film and a heat-sealing layer sequentially in the thickness direction, wherein no release layer is provided between the inorganic vapor-deposited film and the heat-sealing layer.

[0371]

[13] The barrier laminate as described in

[12] further includes an anchor coating layer between the inorganic vapor-deposited film and the heat-sealing layer.

[0372]

[14] The barrier laminate as described in any one of [9] to

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

[0373]

[15] The barrier laminate as described in any one of [9] to

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

[0374]

[16] The barrier laminate as described in

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

[0375]

[17] A barrier laminate comprising, in the thickness direction, a paper substrate, an adhesive layer, an inorganic vapor-deposited film and a heat-sealing layer, wherein the inorganic vapor-deposited film is in contact with the heat-sealing layer, or the barrier laminate further comprises an anchor coating layer between the inorganic vapor-deposited film and the heat-sealing layer, wherein the inorganic vapor-deposited film is in contact with the anchor coating layer, and the paper substrate is composed of paper and does not have any of the layers in the filler layer, resin layer and clay coating layer.

[0376]

[18] The barrier laminate as described in any one of [9] to

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

[0377]

[19] The barrier laminate as described in any one of [9] to

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

[0378] Example

[0379] The transfer film and barrier laminate of the present invention will be described in more detail based on the following embodiments, but the transfer film and barrier laminate of the present invention are not limited to these embodiments.

[0380] The main products used in the embodiments are described below.

[0381] [Paper substrate]

[0382] • Paper substrate A: Made by Daio Paper Co., Ltd., Ryuokot, single sheet, 55g / m² 2 Single-sided coated products.

[0383] • Paper substrate B: Made by Daio Paper Co., Ltd., Ryuokot, single sheet, 80g / m² 2 Single-sided coated products.

[0384] • Paper substrate C: Made by Daio Paper Co., Ltd., Nagoya Sunrise Dragon King, single sheet, 50g / m² 2 Single-color products.

[0385] [Adhesive]

[0386] • Adhesive A: Made by Rock Paint Co., Ltd., dry lamination adhesive, RU-40 / H-1 ​​= 15 / 2 by weight, used for dry lamination bonding.

[0387] • Adhesive B: Made by Rock Paint Co., Ltd., dry lamination adhesive, RU-77T / H-7 = 10 / 1 by weight, used for dry lamination bonding.

[0388] [Example]

[0389] [Example 1A: Production of Transfer Film A]

[0390] On the non-corona-treated side of a PET film (manufactured by Toyobo Co., Ltd., 12 μm thick, single-sided corona-treated), a heat-sealing layer with the following composition is coated by gravure coating and dried to form a 5 μm thick heat-sealing layer. An anchoring agent is prepared by mixing polyester (manufactured by Toyobo Co., Ltd., trade name: Vylon (registered trademark) UR1700) as the main agent, XDI-based isocyanate (manufactured by Mitsui Chemicals Co., Ltd., trade name: TAKENATE D110N) as the curing agent, and nitrocellulose as the additive in a ratio of main agent: curing agent: nitrocellulose (solid component mass ratio) of 1:1:1. The anchoring agent is coated onto the heat-sealing layer by gravure coating and dried to form a 500 nm thick anchor coating. An aluminum vapor deposition film with a thickness of 45 nm is formed on the anchor coating as an inorganic vapor deposition film by physical vapor deposition. A protective layer containing urethane resin and silane coupling agent is coated onto an aluminum vapor-deposited film using a gravure coating method and then dried to form a protective layer with a thickness of 750 nm. This yields transfer film A with a layer structure of PET film / heat-sealing layer / anchor coating / aluminum vapor-deposited film / protective layer.

[0391] (Coating liquid for heat-sealing layer)

[0392] Chemipearl (registered trademark) S120

[0393] (Mitsui Chemicals, Inc., Aqueous Ionomer Emulsion, Composition: Metal salt of ethylene-methacrylic acid copolymer, Self-emulsifying emulsion)

[0394] [Example 1B: Production of Transfer Film B]

[0395] An alumina vapor-deposited film with a thickness of 20 nm is formed as an inorganic vapor-deposited film. In addition, a transfer film B with a layer structure of PET film / heat-sealing layer / anchor coating / alumina vapor-deposited film / protective layer is obtained in the same way as the transfer film A.

[0396] [Example 1C: Production of Transfer Film C]

[0397] As an inorganic vapor deposition film, a silicon oxide vapor deposition film with a thickness of 35 nm is formed by physical vapor deposition. In addition, a transfer film C with a layer structure of PET film / heat seal layer / anchor coating / silicon oxide vapor deposition film / protective layer is obtained in the same way as the transfer film A.

[0398] [Example 1]

[0399] On the coated surface of paper substrate A (A4 size), the dried basis weight is 3.0 g / m². 2 Adhesive A is applied and dried to form adhesive A layer.

[0400] The adhesive A layer of paper substrate A is placed face-to-face with the protective layer of transfer film A (A4 size), and the two are bonded together. Pressure is applied at 0.5 MPa, followed by curing at 40°C for 3 days. This results in an intermediate laminate with a layer structure of paper substrate A [paper / coating] / adhesive A layer / protective layer / aluminum vapor-deposited film / anchor coating / heat-sealing layer / PET film.

[0401] Peel off the PET film from the intermediate laminate to obtain the barrier paper.

[0402] [Examples 2 - 6]

[0403] According to Table 1, the type of paper substrate, the type of adhesive, and the transfer film were changed, but the barrier paper was obtained by following the same steps as in Example 1.

[0404] [Reference Example]

[0405] [Reference Example 1A: Production of Reference Transfer Film A]

[0406] On the corona-treated surface of a PET film (manufactured by Toyobo Co., Ltd., 12μm thick, single-sided corona-treated), the basis weight after drying is 1.0 g / m². 2 A release agent diluent (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 using a bar coating method and dried in an oven at 80°C for 1 minute to form a release layer, resulting in a release substrate having 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 using physical vapor deposition. A protective layer coating solution containing urethane resin and a silane coupling agent was applied to the aluminum vapor-deposited film using a gravure coating method and dried to form a protective layer with a thickness of 750 nm. Thus, a reference transfer film A with a layer structure of PET film / release layer / aluminum vapor-deposited film / protective layer was obtained.

[0407] [Reference Example 1B: Production of Reference Transfer Film B]

[0408] An alumina vapor-deposited film with a thickness of 20 nm was formed as an inorganic vapor-deposited film. Otherwise, a reference transfer film B with a layer structure of PET film / release layer / alumina vapor-deposited film / protective layer was obtained in the same manner as the preparation of reference transfer film A.

[0409] [Reference Example 1C: Production of Reference Transfer Film C]

[0410] A 35 nm thick silicon oxide vapor deposition film was formed as an inorganic vapor deposition film by physical vapor deposition. In addition, a reference transfer film C with a layer structure of PET film / release layer / silicon oxide vapor deposition film / protective layer was obtained in the same way as the preparation of reference transfer film A.

[0411] [Reference Example 1]

[0412] On the coated surface of paper substrate A (A4 size), the dried basis weight is 3.0 g / m². 2 Adhesive A is applied and dried to form adhesive A layer. The adhesive A layer of paper substrate A is then placed face-to-face with the protective layer of a reference transfer film A (A4 size), and the two are bonded together under pressure of 0.5 MPa, followed by curing at 40°C for 3 days. This results in a laminate with a layer structure of paper substrate A [paper / coating] / adhesive A layer / protective layer / aluminum vapor-deposited film / release layer / PET film.

[0413] The PET film in the above-described laminate is peeled off, a primer coating liquid is applied to the peeling layer and dried to form a primer layer. A heat-sealing layer coating liquid having the above-described composition is applied to the primer layer and dried to form a heat-sealing layer with a thickness of 5 μm.

[0414] The reference barrier paper is shown above.

[0415] [Reference Examples 2 - 6]

[0416] According to Table 2, the type of paper substrate, the type of adhesive, and the reference transfer film were changed, and the reference barrier paper was obtained by following the same steps as in Reference Example 1.

[0417] [Evaluation 1]

[0418] [Adhesion]

[0419] A two-component curable polyurethane adhesive is coated onto a 70 μm thick unstretched polypropylene film. After drying, a 15 μm thick stretched nylon film is dry-laminated to obtain a laminated film. A two-component curable polyurethane adhesive is coated onto the heat-sealable side of a barrier paper or a reference barrier paper. After drying, the above laminated film is dry-laminated to obtain a laminated composite film.

[0420] After the above-mentioned laminated composite film was cured for 48 hours, it was cut into strips 15 mm wide to obtain test pieces. For the test pieces, the adhesion strength (peel force) was determined using a tensile testing machine (manufactured by ORIENTEC CO.,LTD. [model name: Tensilon universal testing machine]) according to JIS K6854-2.

[0421] During the test, the polypropylene film side and the (reference) barrier paper side, which were pre-peeled for the test, were held in the clamps of the tester. The film was stretched in opposite directions (180° peel: T-shaped peel) at a speed of 50 mm / min in a direction orthogonal to the surface direction of the still-laminated portions of the polypropylene film and (reference) barrier paper. The average tensile stress in the stable region was measured to obtain the bonding strength (N / 15 mm). The (reference) barrier paper was evaluated according to the following evaluation criteria.

[0422] [Evaluation Criteria]

[0423] •AA: High sealing strength, suitable for practical applications such as packaging materials.

[0424] •BB: The sealing strength is moderate, but it is not a problem for practical applications such as packaging materials.

[0425] •CC: The sealing strength is very low, making it difficult to apply to practical uses such as packaging materials.

[0426] [Table 1]

[0427] Table 1

[0428]

[0429] [Table 2]

[0430] Table 2

[0431]

[0432] The barrier paper obtained in the embodiment does not have a release layer between the inorganic vapor-deposited film and the heat-sealing layer, and therefore exhibits better interlayer adhesion compared with the reference barrier paper that has a release layer between the inorganic vapor-deposited film and the heat-sealing layer.

[0433] [Test Example 1A]

[0434] Following the same steps as in Example 1A, a transfer film with a layer structure of PET film / heat-sealing layer / anchor coating / aluminum vapor-deposited film (40 nm thick) / protective layer was obtained. Using this transfer film, following steps similar to those in Example 1, a barrier paper with a layer structure of heat-sealing layer / anchor coating / aluminum vapor-deposited film (40 nm thick) / protective layer / adhesive layer / paper (ordinary paper) was obtained.

[0435] [Test Example 2A]

[0436] Instead of using Chemipearl (registered trademark) S120 to form the heat-sealing layer, a polyester-based release agent is used to form the release layer. Otherwise, a reference transfer film with a layer structure of PET film / polyester-based release layer / anchor coating / aluminum vapor-deposited film (thickness 40nm) / protective layer and a reference barrier paper with a layer structure of polyester-based release layer / anchor coating / aluminum vapor-deposited film (thickness 40nm) / protective layer / adhesive layer / paper (general paper) are obtained by the same steps as in Test Example 1A.

[0437] [Test Example 3A]

[0438] Instead of using Chemipearl (registered trademark) S120 to form the heat-sealing layer, a polycarbonate-based release agent is used to form the release layer. Otherwise, a reference transfer film with a layer structure of PET film / polycarbonate-based release layer / anchor coating / aluminum vapor-deposited film (thickness 40 nm) / protective layer and a reference barrier paper with a layer structure of polycarbonate-based release layer / anchor coating / aluminum vapor-deposited film (thickness 40 nm) / protective layer / adhesive layer / paper (general paper) are obtained by the same steps as in Test Example 1A.

[0439] [Evaluation 2]

[0440] [Measurement of Indentation Hardness and Complex Elastic Modulus]

[0441] For the transfer film of Test Example 1A and the reference transfer films of Test Examples 2A-3A, based on the nanoindentation method, a nanoindenter (Bruker's "TI950 TriboIndenter") was used, with the cross-section of the heat-sealing layer or release layer as the measurement surface, to determine the indentation hardness (H). IT ) and composite elastic modulus (E r The Berkovich indenter (triangular pyramid indenter; Berkovich_TI0039) was used as the indenter for the nanoindenter. Measurements were performed at more than 10 points on the same cross-section, and the indentation hardness H was determined. IT and composite elastic modulus E r The values ​​are recorded as the arithmetic mean of 10 measurements with good reproducibility.

[0442] The measurement conditions employed a depth-controlled indentation method (constant indentation depth of 100 nm, 10 seconds of load / 5 seconds of hold / 10 seconds of unload), as follows: The indenter was pressed into the heat-sealing or release layer from its cross-section to a depth of 100 nm over 10 seconds, and held at this depth for 5 seconds. Then, unloading was performed over 10 seconds. This allowed the maximum load P to be obtained. max The contact projected area A at maximum depth pThe indentation hardness and composite elastic modulus were calculated from the obtained load-displacement curves. Measurements were performed at room temperature (23°C). The indentation head was inserted near the center of the heat-sealing or release layer in the thickness direction of the exposed portion of the heat-sealing or release layer cross-section. The cross-section was obtained by cutting along the thickness direction perpendicular to the main surface of the (reference) transfer film. The cross-section was prepared by fabricating a block in which the (reference) transfer film was embedded in embedding resin, and then cutting the block using a commercially available rotary slicer at room temperature (23°C). Finishing was performed with a diamond scalpel. The thickness of each layer can also be determined by observing the cross-section.

[0443] [Gas Barrier Property Evaluation]

[0444] Cut out the barrier paper from Test Example 1A or the reference barrier paper from Test Examples 2A to 3A to obtain the test piece. Using this test piece, determine the oxygen permeability (cc / m) using the following method. 2 / 24hr / atm) and water vapor transmission rate (g / m 2 ( / 24hr). In addition, these properties were also measured for test pieces that were restored after being folded four times (reference) of the barrier paper.

[0445] Using an oxygen permeability measuring device (MOCON OX-TRAN2 / 20), with the paper substrate side of the test piece as the oxygen supply side, the oxygen permeability (OTR; unit: cc / m) was measured at 23°C and 90% RH according to JIS K7126. 2 ( / 24hr / atm). Cases with an OTR below 1.5 are rated AA, cases with an OTR above 1.5 but below 3.0 are rated BB, and cases with an OTR above 3.0 are rated CC.

[0446] A water vapor transmission rate measuring device (MOCON, PERMATRAN-w 3 / 33) was used, with the paper substrate side of the test piece as the water vapor supply side. The water vapor transmission rate (WVTR; unit: g / m²) was measured at 40°C and 90% RH according to JIS K7129. 2 / 24hr). Cases with a WVTR below 1.5 are rated AA, cases with a WVTR above 1.5 but below 5.0 are rated BB, and cases with a WVTR above 5.0 are rated CC.

[0447] [Table 3]

[0448] Table 3

[0449]

[0450] [Test Example 1B]

[0451] Following the same steps as in Example 1C, a transfer film with a layer structure of PET film / heat-sealing layer / anchor coating / silica vapor-deposited film / protective layer was obtained. However, in the anchor coating agent, the content of nitrocellulose was changed to 0 parts by mass relative to 100 parts by mass of the total amount of the main agent and curing agent.

[0452] [Test Examples 2B - 4B]

[0453] In the anchoring agent, the content of nitrocellulose was changed to 5 parts by mass (Example 2B), 50 parts by mass (Example 3B), and 200 parts by mass (Example 4B) relative to the total amount of the main agent and the curing agent of 100 parts by mass. Otherwise, the transfer film was obtained by following the same steps as in Example 1B.

[0454] [Evaluation 3]

[0455] [Measurement of Transition Temperature]

[0456] Similar to the above-mentioned determination of indentation hardness and composite elastic modulus, a block in which a transfer film was embedded in embedding resin was prepared, and the block was cut at room temperature (23°C) using a commercially available rotary slicer to obtain a cross-section of the transfer film. Finishing was performed using a diamond tool.

[0457] The ANASYS INSTRUMENT nanoTA was used as the measuring device, and the ANASYS INSTRUMENTS PR-EX-AN2-300-5 was used as the thermal probe.

[0458] Before measurement, perform the following calibration.

[0459] As standard samples, nanoTA Calibration Samples manufactured by BRUKER were prepared. Polycaprolactone (softening point: 55°C), polyethylene (softening point: 116°C), and polyethylene terephthalate (softening point: 235°C), all with known softening points, were placed on the stage of the standard samples. Heating was performed while keeping the thermal probe in contact with the surface of each standard sample. During heating, the thermal expansion directly below the thermal probe was measured, and a deflection (displacement) curve representing the voltage was obtained. The measurement conditions set in the apparatus are as follows.

[0460] Measurement start temperature: 0.1V

[0461] Measurement termination temperature: 10V

[0462] Heating rate: 0.2V / sec

[0463] Using the softening point of each standard sample, the graph representing the displacement of the thermal probe relative to potential is converted into a graph representing the displacement relative to temperature. Calibration is performed as described above.

[0464] After calibration, the transition temperature of the anchor coating was measured. The transition temperature was measured near the center of the exposed portion of the anchor coating in the thickness direction. Measurements were performed at least five locations on the same cross-section, and the transition temperature was recorded as the arithmetic mean of the five reproducible measurements.

[0465] During the measurement, the thermal probe is brought into contact with the cross section of the anchor coating. While the thermal probe is in contact, the coating is heated under the following conditions, and a curve (thermal expansion curve) representing the displacement of the thermal probe relative to the temperature is obtained.

[0466] Measurement start temperature: 40℃

[0467] Measurement termination temperature: 350℃

[0468] Heating rate: 5℃ / sec

[0469] In the obtained thermal expansion curve, the transition temperature that appears on the lowest temperature side is obtained.

[0470] If the peak of the thermal expansion curve is obtained, the temperature of the peak is taken as the transition temperature. A continuous decrease in displacement from the highest displacement of the thermal expansion curve, measured at 0.2V or higher, is considered a peak.

[0471] However, when a "shoulder peak" is obtained instead of a peak in the thermal expansion curve, or when a "shoulder peak" is observed at a temperature lower than the temperature at which the peak was obtained, the temperature of the "shoulder peak" is taken as the transition temperature. A "shoulder peak" is defined as a point where the slope (displacement / temperature) of the thermal expansion curve decreases to near zero, even if it is not a clearly convex shape. Specifically, it is the absolute value of the slope in the tangent at a lower temperature compared to the change in the slope of the thermal expansion curve (= slope). A The absolute value of the slope of the tangent on the higher temperature side compared to the slope change of the thermal expansion curve (= slope). B ) satisfies (slope) A )>{(slope) B The relationship between )×5} and (slope) B When V ≤ 0.02V / ℃, the thermal expansion curve is considered to have a "shoulder". The tangent is drawn on the part of the thermal expansion curve that is close to a relatively stable straight line. The temperature at which the tangents drawn before and after the change in the slope of the thermal expansion curve intersect is taken as the transition temperature for a thermal expansion curve considered to have a "shoulder".

[0472] [TOF-SIMS Measurement]

[0473] NO2 in the anchor coating was determined using time-of-flight secondary ion mass spectrometry (TOF-SIMS). - Normalized intensity of ions. Specifically, using a time-of-flight secondary ion mass spectrometer (ION TOF, TOF.SIMS5), the mass of various ions in each layer was analyzed while repeatedly soft etching from the protective layer surface of the transfer film to the PET film side at a certain speed using a Cs (cesium) ion gun. In the anchor coating, CN from the resin component was analyzed. - Ions (mass number 26.002) and NO2 from nitrocellulose - Mass analysis of ions (mass number 45.992).

[0474] The specific measurement conditions for TOF-SIMS are as follows.

[0475] Primary ion type: Bi3 ++ (0.2pA, 100μs)

[0476] • Measurement area: 150×150μm 2

[0477] • Types of etching guns: Cs (1keV, 60nA)

[0478] • Etching area: 600×600μm 2

[0479] • Etching rate: 10 sec / cycle

[0480] • Vacuuming time: 1×10 -6 Below mbar, more than 15 hours

[0481] • TOF-SIMS measurements were performed within 30 hours of the start of vacuuming.

[0482] Figure 6 Showing CN - An example of the ion detection intensity measured by TOF-SIMS before standardization. [[ID=4 For simplicity, only CN is shown. - Ions, NO2 - The detection intensity of ions and SiO2. The vertical axis of the graph represents the intensity of the detected ions (intensity), and the horizontal axis represents the etching time (in seconds).

[0483] ​

[0484] Using the transfer films from Examples 1B to 4B, barrier paper with a layered structure of heat-sealing layer / anchor coating / silica vapor-deposited film / protective layer / adhesive layer / paper (ordinary paper) was obtained following steps similar to those in Example 1. The barrier paper was cut out to obtain test pieces. Using these test pieces, the oxygen permeability (cc / m³) was measured in the same manner as described above. 2 / 24hr / atm) and water vapor transmission rate (g / m 2 / 24hr).

[0485] Cases with an OTR below 1.5 are rated AA, cases with an OTR above 1.5 but below 3.0 are rated BB, and cases with an OTR above 3.0 are rated CC.

[0486] Cases with WVTR below 0.6 are rated SSS, cases with WVTR above 0.6 but below 1.0 are rated SS, and cases with WVTR above 1.0 are rated S.

[0487] ​

[0488] Visually evaluate the appearance of the anchor coating during its formation.

[0489] AA: Good

[0490] ·BB: Some parts show signs of adhesion.

[0491] •CC: Partial film peeling

[0492] [Table 4]

[0493] Table 4

[0494]

[0495] The barrier papers of Test Examples 1B, 2B, and 4B have WVTR and OTR that pose no problems in practical use. The barrier paper of Test Example 3B has superior WVTR and OTR compared to the barrier papers of Test Examples 1B, 2B, and 4B. The anchor coatings in Test Examples 1B, 2B, and 4B have an appearance that poses no problems in practical use. The anchor coating in Test Example 3B has a superior appearance compared to the anchor coatings in Test Examples 1B, 2B, and 4B.

[0496] As those skilled in the art will understand, the transfer film and barrier laminate of the present invention are not limited to the embodiments described above. The embodiments and description are only for illustrating the principles of the present invention. Various changes or modifications can be made without departing from the spirit and scope of the present invention, and all such changes or modifications are included within the scope of the claimed invention. Furthermore, the scope of protection of the present invention includes not only the claims but also their equivalents.

[0497] Explanation of reference numerals in the attached figures

[0498] 1...Barrier laminates

[0499] 2... Transfer film

[0500] 10...substrate

[0501] 12...printed layers

[0502] 20... Adhesive layer

[0503] 30...Inorganic vapor deposition film

[0504] 32... Anchor Coating

[0505] 40...heat seal layer

[0506] 50... Support substrate (substrate for transfer printing)

Claims

1. A transfer film, comprising a supporting substrate, a heat-sealing layer, and an inorganic vapor-deposited film sequentially arranged in the thickness direction, wherein, The inorganic vapor-deposited film is in contact with the heat-sealing layer, or... The transfer film further comprises an anchor coating layer between the inorganic vapor-deposited film and the heat-sealing layer, and the inorganic vapor-deposited film is in contact with the anchor coating layer. The heat-sealing layer has an indentation hardness of less than 0.15 GPa and a composite elastic modulus of less than 2.0 GPa based on nanoindentation.

2. The transfer film as described in claim 1, wherein, The inorganic vapor-deposited film is directly vapor-deposited onto one side of the heat-sealing layer.

3. The transfer film as described in claim 1, wherein, The inorganic vapor-deposited film is directly vapor-deposited onto one side of the anchor coating.

4. The transfer film according to any one of claims 1 to 3, wherein, The inorganic vapor-deposited film also has a protective layer.

5. The transfer film according to any one of claims 1 to 4, wherein, The inorganic vapor-deposited film contains at least one of aluminum, alumina, and silicon oxide.

6. The transfer film according to any one of claims 1 to 5, wherein, The transition temperature of the anchor coating, as determined by local thermal analysis using a thermal probe, is above 90°C and below 140°C.

7. The transfer film according to any one of claims 1 to 6, wherein, NO2 in the anchor coating was measured while the transfer film was being etched using time-of-flight secondary ion mass spectrometry (TOF-SIMS). - The normalized strength of the ions is above 3.0 and below 4.

2. Regarding the standardized intensity, NO2 based on TOF-SIMS will be used. - The detection intensity of ions divided by CN - The detection intensity of the ion is normalized by multiplying it by 100,000, which refers to NO2. - The commonly used logarithm of the average value of the normalized detection intensity of ions.

8. A barrier laminate, comprising, sequentially comprising, a substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-sealing layer in the thickness direction, wherein, The inorganic vapor-deposited film is in contact with the heat-sealing layer, or... The barrier laminate further comprises an anchor coating layer between the inorganic vapor-deposited film and the heat-sealing layer, wherein the inorganic vapor-deposited film is in contact with the anchor coating layer. The heat-sealing layer has an indentation hardness of less than 0.15 GPa and a composite elastic modulus of less than 2.0 GPa based on nanoindentation.

9. The barrier laminate as claimed in claim 8, wherein, The inorganic vapor-deposited film is directly vapor-deposited onto one side of the heat-sealing layer.

10. The barrier laminate of claim 8, wherein, The inorganic vapor-deposited film is directly vapor-deposited onto one side of the anchor coating.

11. A barrier laminate, comprising, sequentially comprising, a substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-sealing layer in the thickness direction, wherein, There is no release layer between the inorganic vapor-deposited film and the heat-sealing layer. The heat-sealing layer has an indentation hardness of less than 0.15 GPa and a composite elastic modulus of less than 2.0 GPa based on nanoindentation.

12. The barrier laminate of claim 11, wherein, An anchor coating is also provided between the inorganic vapor-deposited film and the heat-sealing layer.

13. The barrier laminate as described in any one of claims 8 to 12, wherein, The inorganic vapor-deposited film contains at least one of aluminum, alumina, and silicon oxide.

14. The barrier laminate as described in any one of claims 8 to 13, wherein, The substrate is a paper substrate.

15. The barrier laminate of claim 14, wherein, The paper substrate includes paper and a filler layer or resin layer formed on the surface of the paper on the side of the adhesive layer.

16. A barrier laminate, comprising, sequentially comprising, a paper substrate, an adhesive layer, an inorganic vapor-deposited film, and a heat-sealing layer in the thickness direction, wherein, The inorganic vapor-deposited film is in contact with the heat-sealing layer, or... The barrier laminate further comprises an anchor coating layer between the inorganic vapor-deposited film and the heat-sealing layer, wherein the inorganic vapor-deposited film is in contact with the anchor coating layer. The heat-sealing layer has an indentation hardness of less than 0.15 GPa and a composite elastic modulus of less than 2.0 GPa based on nanoindentation. The paper substrate is made of paper and does not have any of the layers in the filler layer, resin layer, and clay coating.

17. The barrier laminate as described in any one of claims 8 to 16, wherein, A printing layer is also provided on the surface of the substrate opposite to the adhesive layer side.

18. The barrier laminate as described in any one of claims 8 to 17, wherein, The thickness of the adhesive layer is between 0.5 μm and 20 μm.

Images