Laminate and PTP packaging sheet

Abstract

To provide laminates and PTP packages that offer reduced environmental load and exhibit superior heat resistance, rub resistance, adhesive strength, blocking resistance and rubbing strength.SOLUTION: A laminate includes a metal foil, a first ink layer provided on the metal foil and a varnish layer provided on the first ink layer. As a binder resin component (1) in the first ink layer, a butyral resin is contained. As a binder resin component (2) in the varnish layer, a butyral resin is contained.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a laminate and a PTP packaging sheet. [Background technology]

[0002] A PTP (press-through pack) package used for packaging medicines such as tablets or capsules is composed of a container having a pocket-shaped recess for accommodating the contents of the medicine and a flange provided at the end of the recess, and the lid. The lid (i.e., PTP lid) comprises a metal foil (e.g., hard aluminum foil (also called hard aluminum foil)) as a base material, an ink layer and a varnish layer formed in sequence on one side of the metal foil, and a printing layer and a heat seal layer formed in sequence on the other side of the metal foil as necessary. After accommodating the contents of the medicine in the recess of the container, the heat seal layer of the lid is brought into contact with the flange of the container and heat-sealed to perform normal packaging. As for the materials of such PTP packages, vinyl chloride resin is generally used for the container, nitrocellulose-based resin for the ink layer, epoxy-melamine-based resin for the varnish layer, and vinyl chloride-vinyl acetate copolymer for the heat seal layer.

[0003] However, since carcinogenic NDMA (dimethylamine) has been detected in products that use soluble nitrocellulose resins in the ink layer, particularly in pharmaceutical PTP packaging, it is suspected that the NDMA detected in these products is caused by the soluble nitrocellulose resins used as a raw material in the ink layer, and there is a growing demand for ink layers that are free of soluble nitrocellulose resins. Furthermore, from the perspective of controlling and preventing the emission of environmental hormones such as dioxins, the use of chlorine-based resins (including vinyl chloride-vinyl acetate copolymers) is restricted overseas (in some regions such as the EU), and interest in chlorine-based resin-free PTP packaging is growing.

[0004] An example of a technology for low environmental load, such as building a recycling-oriented society that reduces substances that may have adverse effects on the human body or the environment, is Patent Document 1. Patent Document 1 describes a composition containing an epoxy resin, a polyvinyl butyral resin, and a formaldehyde absorbent, and a technology having a heat-resistant coating layer made of the composition. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2018-2922 A Summary of the Invention [Problem to be solved by the invention]

[0006] According to the above-mentioned Patent Document 1, the amount of formaldehyde generated during heat curing can be suppressed by absorbing the formaldehyde generated by the heat curing with a formaldehyde absorbent. However, the Patent Document 1 also states that butylated melamine resin is preferable for the first printed layer. Therefore, it is questionable to what extent this technology can actually suppress the amount of formaldehyde generated, for reasons such as the fact that unreacted formaldehyde remains in the melamine resin that is usually produced by reacting melamine with formaldehyde.

[0007] In addition, since the cited document 1 also describes that the ink composition for the printing layer contains a vinyl chloride-vinyl acetate copolymer resin, it is insufficient as a technology for low environmental impact. Furthermore, when used as a PTP lid material, high levels of heat resistance to withstand the heating temperature during heat sealing, abrasion resistance and rubbing strength of the surface layer, adhesion between adjacent layers, etc. are required to be sufficient for practical use.

[0008] Therefore, the present disclosure provides a laminate that reduces the environmental load and has excellent heat resistance, abrasion resistance, adhesion, blocking resistance and rubbing strength, as well as a PTP packaging body having the laminate. [Means for solving the problem]

[0009] Therefore, the inventors conducted extensive research to solve the above problems and discovered that by using a laminate containing a butyral resin as the binder resin component in the ink layer and varnish layer, the environmental impact can be reduced and excellent heat resistance, abrasion resistance, adhesion, blocking resistance and rubbing strength can be achieved, thereby completing the present invention.

[0010] [1] A laminate having a metal foil, a first ink layer provided on the metal foil, and a varnish layer provided on the first ink layer, wherein the first ink layer contains a butyral-based resin and the varnish layer contains a butyral-based resin.

[0011] [2] The laminate according to [1], wherein the butyral-based resin is the component contained most abundantly in the resin components of the first ink layer.

[0012] [3] The laminate described in [1] or [2], wherein the varnish layer contains the butyral resin and a polyisocyanate compound.

[0013] [4] A laminate according to any one of [1] to [3], comprising the metal foil, a first ink layer provided on one side of the metal foil, the varnish layer provided on the first ink layer, and a heat seal layer provided on the other side of the metal foil, wherein the heat seal layer contains an α-olefin-(meth)acrylic acid ester copolymer.

[0014] [5] A second ink layer is provided between the metal foil and the heat seal layer, The laminate according to any one of [1] to [4], wherein the second ink layer contains a butyral resin.

[0015] [6] The laminate described in [5], wherein the first ink layer and / or the second ink layer is a multilayer printed layer composed of multilayer printing including a solid color display ink layer and an information display ink layer that displays letters and / or patterns.

[0016] [7] The laminate according to any one of [1] to [6], which is used as a lid material for PTP packaging.

[0017] [8] A PTP packaging sheet comprising: a container sheet having a plurality of recesses capable of accommodating medicines; and the laminate described in any one of [1] to [6], which is a lid material covering the recesses. Effect of the Invention

[0018] According to the present disclosure, it is possible to provide a laminate which reduces the environmental load and is excellent in heat resistance, abrasion resistance, adhesion, blocking resistance and rubbing strength. According to the present disclosure, it is possible to provide a PTP lid material and a PTP package that reduce the environmental impact and have excellent heat resistance, abrasion resistance, adhesion, blocking resistance and rubbing strength. [Brief description of the drawings]

[0019] [Figure 1] FIG. 2 is a cross-sectional view of an example of a laminate according to the present embodiment. [Diagram 2] FIG. 2 is a cross-sectional view of an example of a PTP package of the present embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail, but the present invention is not limited to the following description and can be practiced with various modifications within the scope of the gist. In addition, in this embodiment, A (number) to B (number) means A or more and B or less. [Definition] In this specification, the term "ink composition" refers to a liquid printing ink, such as gravure ink or flexographic ink, that is applied to a printing method using a printing plate, and is preferably gravure ink or flexographic ink. The term "ink composition" is a general term that includes a first ink composition used to form a first ink layer and a second ink composition used to form a second ink layer. Similarly, the term "ink layer" is a general term that includes a first ink layer and a second ink layer. In addition, all "ink" used in the following description refers to "printing ink". In this specification, all "parts" refer to "parts by mass," "total amount of ink" refers to the total amount of ink including all volatile components such as solvent, and "total amount of ink solids" refers to the total amount of only non-volatile components, excluding volatile components. In this specification, "on" includes a case where the reference element is in direct contact with the reference element and is located above the reference element, and a case where the reference element is not in direct contact with the reference element and is located above the reference element. Thus, for example, "on a surface" includes a case where the surface is in direct contact with the surface and a case where the surface is not in direct contact with the surface and is located above the surface.

[0021] [Laminate] The present disclosure relates to a laminate having a metal foil, a first ink layer provided on the metal foil, and a varnish layer provided on the first ink layer, wherein the first ink layer contains a butyral-based resin, and the varnish layer contains a butyral-based resin. This makes it possible to provide a laminate that reduces the environmental load and is excellent in heat resistance, abrasion resistance, adhesion, blocking resistance and rubbing strength. The laminate of the present disclosure has a metal foil, an ink layer provided on at least one side of the metal foil, and a varnish layer provided on the ink layer. It is also preferable to have a heat seal layer on the other side of the metal foil. And, it is preferable to have an ink layer between the heat seal layer and the metal foil. In this specification, for convenience, the ink layer between the varnish layer and the metal foil is called the first ink layer, and the ink layer between the metal foil and the optional heat seal layer is called the second ink layer. The first ink layer and the second ink layer may have the same composition or different compositions. It is preferable that the first ink layer and the second ink layer have the same composition. This further reduces the environmental load and is more excellent in heat resistance, abrasion resistance, adhesion, blocking resistance, and rubbing strength. Thus, a preferred laminate of the present disclosure comprises a metal foil, a first ink layer provided on one side of the metal foil, a varnish layer provided on the first ink layer, a second ink layer provided on the other side of the metal foil, and the heat seal layer provided on the second ink layer. In the laminate of this embodiment, the average thickness of the part excluding the metal foil is preferably 0.1 to 10 μm for the combined thickness of the first ink layer and varnish layer, and 1 to 10 μm for the combined thickness of the second ink layer and heat layer.

[0022] Hereinafter, preferred examples of the laminate of the present embodiment will be described in detail with reference to the drawings. Fig. 1 is a cross-sectional view of an example of the laminate of this embodiment. The laminate 10 shown in Fig. 1 comprises a metal foil 1, ink layers (first ink layer 2, second ink layer 3) 2, 3 provided on both sides of the metal foil 1, a varnish layer 4 provided on the first ink layer 2, and an optional heat seal layer 5 provided on the optional second ink layer 3. In other words, the laminate 10 shown in Fig. 1 is laminated in the order of the varnish layer 4, the first ink layer 2, the metal foil 1, the second ink layer 3, and the heat seal layer 5. In addition, an anchor coat layer (not shown) may be further provided between the second ink layer 3 and the heat seal layer 5 as necessary. The metal foil 1, the first ink layer 2, the varnish layer 4, the second ink layer 3, the heat seal layer 5 and the anchor coat layer (not shown) which constitute the laminate 10 of this embodiment will be described in detail below.

[0023] (Metal foil) The metal foil 1 of this embodiment can be made of various metals, and among them, aluminum foil is preferable, and aluminum foil with an aluminum purity of 98.0 to 99.9% by weight is more preferable. Specifically, according to the JIS H4160 standard, aluminum materials such as 1000 series (1N30, 1070, etc.), 3000 series, or 8000 series (8021, 8079, etc.) can be used. For tempering, any of hard materials (H materials (JISH0001)), semi-hard materials, and soft materials (O materials (JISH0001)) can be used, but hard aluminum foil is more preferable. Here, the hard aluminum foil is a foil obtained by rolling raw aluminum, for example, to about 200 μm to 5 μm by a roll or the like and stretching it thinly. It is distinguished from soft aluminum foil, which is obtained by rolling raw aluminum, stretching it thin, and then heating it at about 400 ° C. to soften it. The average thickness of the metal foil 1 is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 5 μm to 100 μm, more preferably 5 μm to 50 μm. In addition, a sheet having a metal layer may be used as the metal foil 1 of this embodiment. Specifically, a sheet-like base material such as a plastic film provided with, for example, a metal foil, a metal vapor deposition film, a metal plating film, etc. can be used.

[0024] In this embodiment, a method of laminating desired layers such as ink layers (corresponding to the first ink layer 2 and / or the second ink layer 3 described below) 2, 3 on the metal foil 1 is preferably a method of coating a liquid ink composition. Coating the metal foil can be performed using, for example, a bar coater, a gravure coat method, a roll coat method, a knife coat method, a kiss coat method, or other methods. To maximize the effect of this embodiment, the coating amount of the liquid ink composition on the metal foil 1 is 0.5 to 5 g / m. 2The drying conditions are preferably within a range of 120 to 200° C. for 5 to 100 seconds.

[0025] (First ink layer) The first ink layer 2 of this embodiment is provided on one side of the metal foil 1. The first ink layer can display information such as characters, figures, or symbols, and / or colors. More specifically, when the laminate 10 is used as a lid material for a PTP package, the first ink layer 2 can be printed with invariable information such as the name of the content, the price, the dosage of the content, and the efficacy and effect of the content, or variable information such as the date of manufacture, lot number, and expiration date. In particular, the first ink layer 2 preferably displays a one-dimensional code (e.g., a barcode) or a two-dimensional code (e.g., a QR code (registered trademark)) including variable information such as the date of manufacture and lot number, which is individual information of the product of the content. For example, when the content is a medicine, the first ink layer 2 can display GS1 (old RSS code), GS1-RSS Limited composite symbol CC-A, and GS1-RSS14 stack composite symbol CC-A, which are barcodes for the medicine. The color displayed by the first ink layer 2 of this embodiment is not particularly limited, and it may be uncolored, or may display colors such as black, blue, green, red, yellow, etc. The first ink layer 2 can be formed by a conventionally known method, and for example, the first ink layer 2 can be formed by a conventionally known material and printing method using various printing inks such as gravure ink, flexo ink, offset ink, stencil ink, inkjet ink, etc.

[0026] In this embodiment, in order to print information such as a barcode, it is preferable to provide a color indicating ink layer that displays a predetermined solid color on the metal foil 1, and / or to provide an information indicating ink layer that displays information such as letters, figures or symbols; it is even more preferable to provide a color indicating ink layer that displays a predetermined solid color on the metal foil 1, in order to print information such as a barcode, and to further provide an information indicating ink layer on top of that that displays information such as letters, figures or symbols. That is, the first ink layer 2 in this embodiment preferably includes a solid color indicating ink layer or an information indicating ink layer displaying letters and / or patterns, and it is more preferable that the first ink layer 2 is a multilayer printed layer composed of multilayer printing including a solid color indicating ink layer and an information indicating ink layer displaying letters and / or patterns. In particular, when the laminate 10 is used as a lid material for PTP for pharmaceuticals, it may be necessary to display a barcode or QR code to prevent misidentification of the contents, etc., and a barcode or QR code (information display ink layer) may be difficult to read even if it is formed by directly printing on the metal foil 1. In response to this, a color display ink layer may be provided on the metal foil 1 by solid printing, and then a barcode or QR code (information display ink layer) may be printed on top of that to make the information display ink layer such as a barcode easier to read. The solid color indicating ink layer and the information indicating ink layer can be formed using the first ink composition and / or the second ink composition described below. The color indicating ink layer is a layer formed by printing the entire surface with one color (including transparent), and a light color such as white is preferable from the viewpoint of making the information indicating ink layer clear. The color indicating ink layer can be formed using the ink composition described below in which a light color pigment such as a white pigment is blended as a colorant. The color indicating ink layer can be formed by solid printing with the first ink composition or the second ink composition. As will be described later, for reasons similar to those of the first ink layer 2, the second ink layer 3, which is provided if necessary, is preferably a multilayer printed layer composed of multilayer printing including a solid color display ink layer and an information display ink layer displaying letters and / or patterns. In addition, the information-displaying ink layer is usually a layer formed by printing characters, but in this specification, layers on which bar codes, QR codes, patterns, pictures, etc. are printed instead of characters depending on the purpose of the printing are also included in the information-displaying ink layer.

[0027] The average thickness of the first ink layer 2 in this embodiment is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.1 μm to 5 μm, and more preferably 0.1 μm to 3 μm. The first ink layer 2 of this embodiment contains a butyral resin as the binder resin component (1), and, if necessary, preferably further contains one or more selected from the group consisting of colorants, curing agents, waxes, and additives. In addition, in the first ink layer of this embodiment, the content of the butyral resin is preferably 50 mass% or more, more preferably 60 mass% or more, and even more preferably 70 mass% or more, relative to the total amount of the first ink layer, and may be 100 mass% (i.e., all of the binder resin component (1) may be a butyral resin). It is preferable that the butyral resin is the component with the highest content among the resin components (so-called binder resin component (1)) contained in the first ink layer. This makes it possible to suppress the generation of carcinogenic NDMA (dimethylamine) because no soluble nitrocellulose resin such as nitrocellulose is used, and therefore a more excellent effect of reducing the environmental load can be expected. The components that can constitute the first ink layer, that is, butyral resin, binder resin component (1), colorant, curing agent, and additives, are described below. For convenience of explanation, the binder resin component contained in the first ink layer is referred to as binder resin component (1), the binder resin component contained in the varnish layer is referred to as binder resin component (2), and the binder resin component contained in the second ink layer is referred to as binder resin component (3). The binder resin component (1) and the binder resin component (3) may have the same composition or different compositions. Furthermore, since no nitrocellulose or other soluble nitrocellulose resin or vinyl chloride is used in any of the binder resin components (1) to (3), the environmental load is further reduced, and excellent effects can be exhibited in heat resistance, abrasion resistance, adhesion, blocking resistance, and rubbing strength.

[0028] <Butyral resin> The butyral resin is excellent in improving adhesion to the metal foil 1. In addition, the butyral resin is environmentally friendly since its constituent elements are only carbon atoms, hydrogen atoms, and oxygen atoms. As the butyral resin of this embodiment, any known resin can be used without any particular limitation. In general, as the butyral resin, a reaction product obtained by acetalizing polyvinyl alcohol with an aldehyde compound such as butyraldehyde by a known reaction can be used. The butyral resin of this embodiment is represented by the following general formula (1): [ka] (In the above general formula (1), n1 and n2 each independently represent an integer of 1 or more; R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. It is preferable that the compound has a partial structure represented by the following formula: In the above general formula (1), R 1 preferably represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, and even more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. The hydrocarbon group may be an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, and may be linear, branched, or cyclic. Among these, an alkyl group is preferred. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, a (n-)heptyl group, a (n-)octyl group, a (n-)nonyl group, a (n-)decyl group, a (n-)undecyl group, a (n-)dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a cyclononyl group. Among these, R 1 is more preferably a propyl group or an isopropyl group. As described above, the butyral resin of the present embodiment is a resin made by reacting polyvinyl alcohol and an aldehyde compound. 1 When represented as -C(=O)H, R in the general formula (1) 1 is a hydrocarbon group derived from an aldehyde compound used in synthesizing butyral resins.

[0029] A butyral-based resin suitable in this embodiment is preferably a resin having a partial structure represented by the above general formula (1), a partial structure represented by the following general formula (2), and a partial structure represented by the following general formula (3). [ka] (In the above general formula (2), n3 is independently an integer of 1 or more, and R 2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. [ka] (In the above general formula (3), each n4 is independently an integer of 1 or more.)

[0030] In the above general formula (2), R 2 preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In addition, the above R 2 As the alkyl group, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group is more preferable. Furthermore, when the butyral-based resin of this embodiment is represented by a resin having a partial structure represented by the above general formula (1), a partial structure represented by the following general formula (2), and a partial structure represented by the following general formula (3), the content of the partial structure represented by the above general formula (2) relative to the total amount of the butyral-based resin is preferably 12 mass% or less, more preferably 8 mass% or less, and even more preferably 5 mass% or less. Thus, by setting the content of the partial structure represented by the above general formula (2) in the butyral-based resin within the above range, an ink layer with an excellent balance between fluidity and dispersibility can be obtained.

[0031] The weight-average molecular weight of the butyral resin in this embodiment is preferably 5,000 to 150,000, more preferably 6,000 to 100,000, and even more preferably 7,000 to 50,000. By setting the weight-average molecular weight of the butyral resin within the above range, excellent curability can be achieved, and both strength and appropriate flexibility of the coating film can be achieved. In addition, butyral resins having a weight-average molecular weight of 5,000 to 150,000 are easy to obtain, and by using such a butyral resin, an ink layer having an excellent balance between fluidity and dispersibility can be obtained.

[0032] The butyral resin of the present embodiment preferably has a glass transition temperature (hereinafter sometimes referred to as Tg) in the range of 50° C. to 120° C., more preferably in the range of 55° C. to 115° C., and more preferably in the range of 60° C. to 110° C. In the present invention, the glass transition temperature is obtained by measurement using a differential scanning calorimeter.

[0033] The hydroxyl value of the butyral resin in this embodiment is preferably in the range of 10 to 40% by mass, and more preferably 15 to 30% by mass. By setting the hydroxyl value of the butyral resin in the above range, an ink layer with an excellent balance between fluidity and dispersibility can be obtained. The amount of hydroxyl groups refers to the amount of the partial structure represented by the above general formula (3) relative to the total amount of the butyral resin.

[0034] The amount of acetyl groups in the butyral resin is preferably 8% by mass or less, and more preferably 5% by mass or less. By setting the amount of acetyl groups in the butyral resin within the above range, an ink layer having an excellent balance between fluidity and dispersibility can be obtained. The amount of acetyl groups refers to the amount of acetyl groups in the partial structure represented by the general formula (2) above. 2 When the partial structure is a methyl group, it is called an acetyl group, and the amount of the acetyl group is expressed as the content relative to the total amount of the butyral resin.

[0035] The butyral resin in the ink layer (corresponding to the first ink layer and / or the second ink layer) may be a resin constituting a resin component (e.g., a binder resin component (corresponding to the binder resin component (1) and / or the binder resin component (3) described below)) having the highest content (solid content) among the resin components in the ink layer (e.g., a binder resin component (corresponding to the binder resin component (1) and / or the binder resin component (3) described below)). This makes it possible to obtain an ink layer with an excellent balance between fluidity and dispersibility. More specifically, the proportion of the butyral-based resin in the total amount of the resin components (for example, the binder resin components (corresponding to binder resin component (1) and / or binder resin component (3) described below)) is preferably greater than 50 mass %. Here, this proportion refers to the proportion in terms of solid content. When the proportion of the butyral-based resin in the total amount of the resin components (for example, the binder resin components (corresponding to binder resin component (1) and / or binder resin component (3) described below))) is greater than 50 mass %, the adhesion of the ink composition to the metal foil is further improved. The proportion of the butyral-based resin in the total amount of the resin components (for example, binder resin components (corresponding to binder resin component (1) and / or binder resin component (3) described below)) is more preferably 60 mass% or more, even more preferably 70 mass% or more, particularly preferably 80 mass% or more, and may be 100 mass% (i.e., all of the binder resin components may be butyral-based resins).

[0036] -Resin component- The butyral-based resin of this embodiment is preferably the component with the largest content among the resin components contained in the first ink layer. In other words, the first ink layer 2 of this embodiment preferably contains a binder resin component (1). In the binder resin component (1), the component with the largest content is preferably a butyral-based resin (also called a "main resin"), and the binder resin component (1) may further contain another binder resin (also called an "auxiliary resin"). In this specification, the term "resin component" refers to components other than colorants. Also, the term "binder resin component" refers to a resin component contained in an organic solvent-based gravure ink, such as a resin having a binding effect, excluding wax and additives described below. The first ink layer of this embodiment and the first ink composition described below may contain a binder resin other than a butyral-based resin as the binder resin component (1). In other words, the binder resin component (1) essentially contains a butyral-based resin, and may contain a binder resin (auxiliary resin) other than the butyral-based resin (main resin) as necessary. Examples of the other binder resin (auxiliary resin) include ketone resin, rosin resin, polyurethane resin, acrylic resin, cellulose resin, polyester resin, etc., and further include polyamide resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, alkyd resin, cyclized rubber, butyral, petroleum resin, etc. Among these, the other binder resin (auxiliary resin) is preferably ketone resin, rosin resin, polyurethane resin, acrylic resin, or cellulose resin (excluding nitrocellulose resin).

[0037] The content of the other binder resin (auxiliary resin) is preferably in the range of 0.1 to 49% by mass based on the total amount of the binder resin component (1). When the content of the other binder resin (auxiliary resin) is 0.1% by mass or more based on the total amount of the binder resin component (1), the physical properties of the ink are improved and the printability is improved. When the content of the other binder resin (auxiliary resin) is 49% by mass or less based on the total amount of the binder resin component (1), the proportion of the butyral resin (main resin) can be increased, and even when baking is performed at a low temperature of about 150°C, the adhesion to the metal foil 1 is easily improved. The upper limit of the content of the other binder resin (auxiliary resin) is more preferably 45% by mass or less, even more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less based on the total amount of the binder resin component (1).

[0038] -Ketone resin- The ketone resin may be any known one, and for example, a formaldehyde resin, a cyclohexanone-formaldehyde resin, a ketone aldehyde condensation resin, or the like may be suitably used.

[0039] -Rosin-based resin- The rosin resin is not particularly limited as long as it is a resin having a rosin skeleton, but is preferably a rosin-modified maleic acid resin, a rosin ester, a rosin phenol, a polymerized rosin, etc. The rosin resin preferably has a softening point (by the ring and ball method) of 90 to 200°C.

[0040] -Polyurethane resin- The polyurethane resin is not particularly limited as long as it is a polyurethane resin obtained by reacting a polyol with a polyisocyanate.

[0041] As the polyol, for example, various known polyols generally used in the production of polyurethane resins can be used, and one or more of them may be used in combination. Specific examples of the polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, ... Saturated or unsaturated low molecular weight polyols (1), such as ethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, and pentaerythritol; these low molecular weight polyols (1) and sebacic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, tetrahydrofuran ... polyester polyols (2) obtained by dehydration condensation or polymerization of polycarboxylic acids such as trimellitic acid and pyromellitic acid, or their anhydrides; polyester polyols (3) obtained by ring-opening polymerization of cyclic ester compounds, such as lactones such as polycaprolactone, polyvalerolactone, and poly(β-methyl-γ-valerolactone); polycarbonate polyols (4) obtained by reacting the low molecular weight polyols (1) or the like with, for example, dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, or the like; polybutadiene glycols (5); glycols (6) obtained by adding ethylene oxide or propylene oxide to bisphenol A; and acrylic polyols (7) obtained by copolymerizing, in one molecule, one or more hydroxyethyl groups, hydroxypropyl acrylate, hydroxybutyl acrylate, or the like, or the corresponding methacrylic acid derivatives, with, for example, acrylic acid, methacrylic acid, or an ester thereof. In addition, various known polyether polyols that are generally used in the production of polyurethane resins can be used, and one or more of them may be used in combination. For example, polyether polyols of polymers or copolymers of methylene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, etc. can be mentioned. Specifically, known general-purpose ones such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can be used. In the polyurethane resin of the present invention, as the polyol, it is preferable to use a polyester polyol, and it is more preferable to use the polyester polyols (2) and polyether polyols.

[0042] Examples of the polyisocyanate include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins. Specific examples of the polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2,5-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3, 5-Diethylbenzene diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1-methyl-naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate aromatic polyisocyanates such as 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, and diphenylmethane-2,4-diisocyanate;Aliphatic or alicyclic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-di(isocyanatemethyl)cyclohexane, 1,4-di(isocyanatemethyl)cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more.;

[0043] A chain extender can also be used for the polyurethane resin. Examples of the chain extender include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, and the like, as well as amines having a hydroxyl group in the molecule, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. These chain extenders can be used alone or in combination of two or more.

[0044] In addition, a monovalent active hydrogen compound can be used as a terminal blocking agent for the purpose of stopping the reaction in the polyurethane resin. Examples of such compounds include dialkylamines such as di-n-butylamine, and alcohols such as ethanol and isopropyl alcohol. Furthermore, when it is particularly desired to introduce a carboxyl group into the polyurethane resin, amino acids such as glycine and L-alanine can be used as a reaction stopper. These terminal blocking agents can be used alone or in combination of two or more.

[0045] The polyurethane resin preferably has a weight average molecular weight of 10,000 to 100,000, and more preferably in the range of 15,000 to 80,000. In the present invention, the number average and weight average molecular weights are values ​​measured by gel permeation chromatography (GPC) under the following conditions.

[0046] Measurement equipment: High-speed GPC equipment (Tosoh Corporation "HLC-8220GPC") Column: The following columns manufactured by Tosoh Corporation were used, connected in series. "TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 "TSKgel G2000" (7.8mmI.D. x 30cm) x 1 Detector: RI (differential refractometer) Column temperature: 40℃ Eluent: tetrahydrofuran (THF) Flow rate: 1.0mL / min Injection volume: 100 μL (sample concentration 0.4% by mass in tetrahydrofuran solution) Standard sample: A calibration curve was prepared using the following standard polystyrene. [Standard polystyrene] "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0047] -Acrylic resin- The acrylic resin is not particularly limited as long as it is a copolymer of a polymerizable monomer having a (meth)acrylic acid ester as a main component. Examples of the polymerizable monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, iso-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, iso-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and phenoxyethyl (meth)acrylate. Here, "(meth)acrylate" refers to both acrylate and methacrylate. The polymerization method is not particularly limited, and those obtained by known methods such as bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used. The acrylic resin preferably has a weight average molecular weight of 5,000 to 200,000, and more preferably has a weight average molecular weight in the range of 10,000 to 100,000.

[0048] -Cellulose resin- Examples of the cellulose resin (cellulose resin) include cellulose ester resins such as cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB), soluble cellulose resin (also called "nitrocellulose"), hydroxyalkyl cellulose, and carboxyalkyl cellulose, but from the viewpoint of the environment and health, resins other than soluble cellulose resin are preferred. The cellulose ester resin preferably has an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group, and the alkyl group may further have a substituent. The cellulose resin is preferably cellulose acetate propionate or cellulose acetate butyrate.

[0049] The cellulose resin preferably has a weight average molecular weight of 5,000 to 200,000, and more preferably 10,000 to 50,000. The cellulose resin preferably has a glass transition temperature of 120° C. to 180° C. Use of the cellulose resin is expected to improve the blocking resistance, scratch resistance, and other physical properties of the ink film.

[0050] -Polyester resin- The polyester resin is not particularly limited as long as it is a polyester resin obtained by reacting an alcohol with a carboxylic acid using a known esterification polymerization reaction. Examples of the alcohol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,2-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, and 1,4-butynediol. Examples of the alcohols include diol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaerythritol, 1,4-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, spiroglycol, and isosorbide. These may be used alone or in combination of two or more. Among these, polyfunctional alcohols are preferred.

[0051] Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, linoleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, and 1,4-cyclohexanedicarboxylic acid. These can be used alone or in combination of two or more. Among them, polyfunctional carboxylic acids are preferred. The polyester resin preferably has a weight average molecular weight of 500 to 6,000, and more preferably 1,400 to 5,500.

[0052] <Coloring agent> The ink layer (corresponding to the first ink layer and / or the second ink layer described below) and the ink composition (corresponding to the first ink composition and / or the second ink composition described below) of this embodiment preferably contain a colorant. The colorant may be either a color pigment or a white pigment. The colorant is preferably a pigment, and examples of the colorant include organic pigments and inorganic pigments that are commonly used in inks, paints, recording materials, and the like.

[0053] Examples of the organic pigment include soluble azo pigments, insoluble azo pigments, azo pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, anthraquinone pigments, anthanthrone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, flavanthrone pigments, diketopyrrolopyrrole pigments, isoindoline pigments, indanthrone pigments, and carbon black pigments. In addition, for example, carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, chromophthal yellow, chromophthal red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigments, etc. can be mentioned. In addition, both non-acid-treated pigments and acid-treated pigments can be used. In addition, examples of the organic pigments include black pigments, indigo pigments, green pigments, red pigments, purple pigments, yellow pigments, orange pigments, and brown pigments. Preferred specific examples of each organic pigment are given below.

[0054] Examples of black pigments include CI Pigment Black 1, CI Pigment Black 6, CI Pigment Black 7, CI Pigment Black 9, and CI Pigment Black 20.

[0055] Examples of indigo pigments include CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:5, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 17:1, CI Pigment Blue 22, CI Pigment Blue 24:1, CI Pigment Blue 25, CI Pigment Blue 26, CI Pigment Blue 60, CI Pigment Blue 61, CI Pigment Blue 62, CI Pigment Blue 63, CI Pigment Blue 64, CI Pigment Blue 75, CI Pigment Blue 79, and CI Pigment Blue 80.

[0056] Examples of green pigments include CI Pigment Green 1, CI Pigment Green 4, CI Pigment Green 7, CI Pigment Green 8, CI Pigment Green 10, and CI Pigment Green 36.

[0057] Examples of red pigments include CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 20, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 24, CI Pigment Red 25, CI Pigment Red 26, CI Pigment Red 27, CI Pigment Red 28, CI Pigment Red 29, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 33, CI Pigment Red 34, CI Pigment Red 35, CI Pigment Red 36, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 39, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 43, CI Pigment Red 44, CI Pigment Red 45, CI Pigment Red 46, CI Pigment Red 47, CI Pigment Red 48, CI Pigment Red 49, CI Pigment Red 50, CI Pigment Red 51, CI Pigment Red 52, CI Pigment Red 53, CI Pig Tread 19, CI Pigment Red 20, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 38, CI Pigment Red 41, CI Pigment Red 43, CI Pigment Red 46, CI Pigment Red 48, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red CI Pigment Red 48:5, CI Pigment Red 48:6, CI Pigment Red 49, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 49:3, CI Pigment Red 52, CI Pigment Red 52:1, CI Pigment Red 52:2, CI Pigment Red 53, CI Pigment Red 53:1, CI Pigment Red 53:2, CI Pigment Red 53:3, CI Pigment Red 54, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 58, CI Pigment Red 58:1, CI Pigment Red 58:2, CI Pigment Red 58:3, CI Pigment Red 58:4, CI Pigment Red 60:1, CI Pigment Red 63, CI Pigment Red 63:1, CI Pigment Red 63:2, CI Pigment Red 63:3, CI Pigment Red 64:1, CI Pigment Red 68, CI Pigment Red 68, CI Pigment Red 81:1, CI Pigment Red 83, C.I. Pigment Red 88, CI Pigment Red 89, CI Pigment Red 95, CI Pigment Red 112, CI Pigment Red 114, CI Pigment Red 119, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 136, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 147, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 164, CI Pigment Red Pigment Red 166, CI Pigment Red 168, CI Pigment Red 169, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 181, CI Pigment Red 182, CI Pigment Red 183, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 192, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 200, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 210, CI Pigment Red 211, CI Pigment Red Pigment Red 213, CI Pigment Red 214, CI Pigment Red 216, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 223, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 237, CI Pigment Red 238, CI Pigment Red 239, CI Pigment Red 240, CI Pigment Red 242, CI Pigment Red 245, CIPigment Red 247, CI Pigment Red 248, CI Pigment Red 251, CI Pigment Red 253, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 256, CI Pigment Red 257, CI Pigment Red 258, CI Pigment Red 260, CI Pigment Red 262, CI Pigment Red 263, CI Pigment Red 264, CI Pigment Red 266, CI Pigment Red 268, CI Pigment Red 269, CI Pigment Red 270, CI Pigment Red 271, CI Pigment Red 272, CI Pigment Red 279, etc.

[0058] Examples of purple pigments include CI Pigment Violet 1, CI Pigment Violet 2, CI Pigment Violet 3, CI Pigment Violet 3:1, CI Pigment Violet 3:3, CI Pigment Violet 5:1, CI Pigment Violet 13, CI Pigment Violet 19 (γ type, β type), CI Pigment Violet 23, CI Pigment Violet 25, CI Pigment Violet 27, CI Pigment Violet 29, CI Pigment Violet 31, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 37, CI Pigment Violet 38, CI Pigment Violet 42, and CI Pigment Violet 50.

[0059] Examples of yellow pigments include CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, Pigment Yellow 17, CI Pigment Yellow 24, CI Pigment Yellow 42, CI Pigment Yellow 55, CI Pigment Yellow 62, CI Pigment Yellow 65, CI Pigment Yellow 74, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 95, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 117, CI Pigment Yellow 120, CI Pigment Yellow 122, CI Pigment Yellow 124, CI Pigment Yellow 126, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 130, CI Pigment Yellow 131, CI Pigment Yellow 132, CI Pigment Yellow 133, CI Pigment Yellow 134, CI Pigment Yellow 135, CI Pigment Yellow 136, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 140, CI Pigment Yellow 141, CI Pigment Yellow 142, CI Pigment Yellow 143, CI Pigment Yellow 144, CI Pigment Yellow 145, CI Pigment Yellow 146, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 149, CI Pigment Yellow 150, CI Pigment Yellow 15 Yellow 120, Pigment Yellow 125, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 174, CI Pigment Yellow 180, CI Pigment Yellow 185 and CI Pigment Yellow 213.

[0060] Examples of orange pigments include CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 37, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Range 55, CI Pigment Orange 59, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 71, and CI Pigment Orange 74.

[0061] Examples of brown pigments include CI Pigment Brown 23, CI Pigment Brown 25, and CI Pigment Brown 26.

[0062] Among them, preferred pigments include CI Pigment Black 7 as a black pigment, CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6 as indigo pigments, CI Pigment Green 7 as a green pigment, and CI Pigment Red 57:1, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 146, CI Pigment Red 242, CI Pigment Red 185, CI Pigment Red 1 as red pigments. Examples of pigments that can be used include CI Pigment Red 22, CI Pigment Red 178, CI Pigment Red 149, CI Pigment Red 144, CI Pigment Red 166, purple pigments such as CI Pigment Violet 23 and CI Pigment Violet 37, yellow pigments such as CI Pigment Yellow 83, CI Pigment Yellow 14, CI Pigment Yellow 180, and CI Pigment Yellow 139, and orange pigments such as CI Pigment Orange 38, CI Pigment Orange 13, CI Pigment Orange 34, and CI Pigment Orange 64. It is preferable to use at least one or more pigments selected from these groups.

[0063] Examples of the inorganic pigment include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, litbones, antimony white, and gypsum. Among the inorganic pigments, titanium oxide is particularly preferred. Titanium oxide is white and is preferred in terms of coloring power, hiding power, chemical resistance, and weather resistance, and from the viewpoint of printing performance, the titanium oxide is preferably treated with silica and / or alumina.

[0064] Examples of inorganic pigments other than white include carbon black, aluminum particles, mica, bronze powder, chrome vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine, Prussian blue, red iron oxide, yellow iron oxide, zircon, and the like. Aluminum is in powder or paste form, but it is preferable to use it in paste form from the standpoint of handleability and safety. Whether leafing or non-leafing aluminum is used is appropriately selected from the standpoint of brightness and concentration.

[0065] In the ink layer of this embodiment (which corresponds to the first ink layer and the second ink layer described below), the content of the colorant relative to the total amount of the ink layer is preferably 1.0 to 90.0 mass %, and more preferably 1.0 to 60 mass %.

[0066] <Additives, etc.> The ink layer (corresponding to the first ink layer and the second ink layer described below) of this embodiment and the ink composition (including the first ink composition and the second ink composition) described below may further contain additives as necessary. The additives are preferably selected from the group consisting of extender pigments, pigment dispersants, dispersants, leveling agents, defoamers, plasticizers, infrared absorbing agents, ultraviolet absorbing agents, aromatics, and flame retardants. In the ink layer of this embodiment (corresponding to the first ink layer and the second ink layer described below), the content of the additive is preferably 0.1 to 20.0% by mass with respect to the total amount of the ink layer. The ink layer (corresponding to the first ink layer and the second ink layer described below) of this embodiment and the ink composition (including the first ink composition and the second ink composition) described below may further contain one or more types selected from the group consisting of a curing agent and a wax, as necessary. The curing agent may be an isocyanate-based curing agent. The wax may preferably be a polyolefin wax or a fatty acid amide wax known in the field of liquid ink. The polyolefin wax may be oxidized polyethylene wax or oxidized polypropylene wax. The fatty acid amide wax may be saturated fatty acid amide such as stearic acid amide or palmitic acid amide, unsaturated fatty acid amide such as erucic acid amide, substituted amide, or aromatic amide. In the ink layer of this embodiment (corresponding to the first ink layer and the second ink layer described below), the wax content is preferably 0.1 to 20.0% by mass with respect to the total amount of the ink layer.

[0067] In addition, the first ink layer 2 of this embodiment and the first ink composition described below preferably do not contain either soluble nitrocellulose resin or chlorine-based resin. The first ink layer that does not contain either soluble nitrocellulose resin or chlorine-based resin is preferable from the viewpoints of environment and health. Carcinogenic NDMA (N-nitrosodimethylamine) has been detected in products that use soluble nitrocellulose resin as ink for pharmaceutical PTP packaging, and the soluble nitrocellulose, an ink raw material, is suspected to be the cause of the NDMA. However, the first ink layer 2 and the first ink composition described below do not contain soluble nitrocellulose resin as a binder resin, thereby eliminating such concerns. Furthermore, overseas (some regions, such as the EU) have restrictions on the use of chlorine-based resins (vinyl chloride-vinyl acetate copolymer resins, etc.), and as the ink layer (the first ink layer and / or the second ink layer described below) and the ink composition (the first ink composition and / or the second ink composition described below) do not contain chlorine-based resins as binder resins, export to the entire world will be possible.

[0068] <Ink composition> The first ink layer 2 of the present embodiment is preferably formed from a first ink composition. Moreover, the first ink composition is preferably a liquid composition, that is, a so-called liquid ink composition. Similarly, when an optional second ink layer 3 is further provided on the metal foil 1, the second ink layer 3 is preferably formed from a second ink composition. Moreover, the second ink composition is preferably a liquid composition, that is, a so-called liquid ink composition. The ink composition of the present embodiment (corresponding to the first ink composition and / or the second ink composition described below) contains a resin component (for example, a binder resin component (corresponding to the binder resin component (1) and / or the binder resin component (3) described below))), and the binder resin component has the effect of improving adhesion to an adjacent layer (for example, a metal foil, etc.). In the ink composition, it is preferable that the component with the largest content of the binder resin component (i.e., the main component of the binder resin component) is a butyral resin.

[0069] In the ink composition used in the ink layer of the conventional PTP lid material, the main component of the binder resin is nitrocellulose resin or the like, and when baking is performed at a low temperature of about 150°C, the adhesion to the metal foil is low. Therefore, with the conventional liquid ink composition, baking must be performed at a high temperature of about 200°C, which reduces the work efficiency and damages the metal foil from the heat. In contrast, the ink composition of this embodiment (corresponding to the first ink composition and / or the second ink composition described below) has a resin component (for example, a binder resin component (corresponding to the binder resin component (1) and / or the binder resin component (3) described below)) mainly composed of a butyral resin, so that the adhesion to the metal foil is good even when baking is performed at a low temperature of about 150°C. Therefore, the ink composition of this embodiment, the first ink composition and / or the second ink composition, is corresponding. ) makes it possible to perform baking at low temperatures of around 150°C, improving the efficiency of the baking process and reducing damage to the metal foil from heat.

[0070] The first ink composition of this embodiment can be produced by dissolving and / or dispersing in a solvent a butyral resin and, if necessary, one or more selected from the group consisting of a binder resin component (1) other than the butyral resin, a colorant, an additive, a curing agent, and a wax. For example, the first ink composition can be produced by dispersing a pigment as a colorant in an organic solvent with a butyral resin or the binder resin component (1) to produce a pigment dispersion, and then adding other compounds, etc., to the resulting pigment dispersion as necessary. The particle size distribution of the pigment in the pigment dispersion can be adjusted by appropriately adjusting the size of the grinding media of the dispersing machine, the packing rate of the grinding media, the dispersion treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, etc. As the dispersing machine, a commonly used machine, such as a roller mill, a ball mill, a pebble mill, an attritor, a sand mill, etc. can be used. When air bubbles or unexpectedly large particles are contained in the ink composition, they deteriorate the quality of the printed matter, so that it is preferable to remove them by filtration, etc. As the filter, a conventionally known filter can be used.

[0071] The viscosity of the ink composition produced by the above method (this corresponds to the first ink composition and / or the second ink composition described below) is preferably in the range of 10 mPa s or more from the viewpoint of preventing sedimentation of the pigment and adequately dispersing it, and 1000 mPa s or less from the viewpoint of workability during ink production and printing. The above viscosity is measured at 25°C using a Tokimec B-type viscometer. The viscosity of the ink composition of this embodiment (corresponding to the first ink composition and / or the second ink composition described below) can be adjusted by appropriately selecting the types and amounts of raw materials used, for example, the binder resin component (corresponding to the binder resin component (1) and / or the binder resin component (3) described below), colorant, solvent, additive, hardener, wax, etc. In addition, the viscosity of the ink composition can also be adjusted by adjusting the particle size and particle size distribution of the pigment in the ink composition.

[0072] -Binder resin component (1) in the first ink composition- The first ink composition of the present embodiment preferably contains a binder resin component (1) containing a butyral resin. The total content of the binder resin component (1) containing the butyral resin is preferably 10 to 80 mass %, more preferably 20 to 70 mass %, based on the total amount of the first ink composition. When the first ink composition contains the binder resin component (1) containing a butyral resin in the above range, the adhesion is further improved. In the first ink composition of this embodiment, the butyral-based resin is preferably the component with the highest content in the binder resin component (1). The proportion of the butyral-based resin in the total amount of the binder resin component (1) is more preferably more than 50% by mass. Here, the proportion refers to the proportion in terms of solid content. When the proportion of the butyral-based resin in the total amount of the binder resin component (1) is more than 50% by mass, the adhesion of the first ink composition to the metal foil is further improved. The proportion of the butyral-based resin in the total amount of the binder resin component (1) is more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, and may be 100% by mass (i.e., the entire binder resin component (1) may be a butyral-based resin).

[0073] -Butyral resin- The ink composition of the present embodiment (corresponding to the first ink composition and / or the second ink composition described below) contains a butyral resin. The content of the butyral resin is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, based on the total amount of the ink composition. A preferred ink composition of this embodiment (corresponding to the first ink composition and / or the second ink composition described below) preferably has a butyral resin (main resin) content of 5 to 30 mass %, a binder resin component (1) other than the butyral resin (auxiliary resin) content of 0 to 10 mass %, a colorant content of 0 to 45 mass %, a solvent content of 10 to 90 mass %, and an additive (wax, etc.) content of 0 to 10 mass %, relative to the total amount of the ink composition.

[0074] -solvent- The ink composition of this embodiment (corresponding to the first ink composition and / or the second ink composition described below) may contain a solvent (preferably an organic solvent), and preferably contains at least one solvent selected from the group consisting of aromatic solvents, ketone solvents, ester solvents, and alcohol solvents. Aromatic solvents, ketone solvents, ester solvents, and alcohol solvents have good solubility for the above-mentioned butyral resin (main resin) and the above-mentioned other binder resins (auxiliary resins). The content of the solvent in the ink composition is preferably in the range of 10 to 90% by mass with respect to the total amount of the ink composition. Examples of the aromatic solvent include toluene, xylene, Solvesso #100, Solvesso #150, etc. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Examples of the ester solvent include methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, propylene glycol monomethyl ether acetate, etc. Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, propylene glycol monomethyl ether, etc. These can be used alone or in a mixture of two or more. In recent years, from the viewpoint of the working environment, it is more preferable not to use aromatic solvents such as toluene and xylene or ketone solvents. The ink composition of the present embodiment (corresponding to the first ink composition and / or the second ink composition described below) may contain water as a volatile component together with the organic solvent. The content of water is preferably less than 10% by mass of the total amount of the ink composition. By adding water, the drying property of the ink can be controlled, and in particular, in gravure printing, the gradation part with a small amount of ink transfer, which is a characteristic of gravure printing, can be beautifully reproduced. Furthermore, it is particularly preferable that the content of water is in the range of 1 to 5% by mass of the total amount of the ink composition, since this improves the printability. In addition, the organic solvent component used can be reduced by adding water in this way. Water may be added to the organic solvent in advance to form a water-containing organic solvent, or a specific amount of water may be added separately.

[0075] -Coloring agent- In the ink composition of this embodiment (corresponding to the first ink composition and / or the second ink composition described below), the content of the colorant is preferably an amount sufficient to ensure the concentration and coloring power of the ink composition, i.e., 1 to 60 mass% of the total amount of the ink composition, and 10 to 90 mass% of the total amount of solids in the ink layer (corresponding to the first ink layer and / or the second ink layer). The colorant may be used alone or in combination of two or more kinds. In order to stably disperse the colorant such as the pigment in the solvent, the binder resin component alone can be used, but in order to further stably disperse the colorant such as the pigment, a pigment dispersant can be used in combination. As the pigment dispersant, anionic, nonionic, cationic, amphoteric, or other surfactants can be used. For example, a comb-shaped polymer compound in which a polyester is added to polyethyleneimine, or an alkylamine derivative of an α-olefin maleic acid polymer can be used. Specific examples of pigment dispersants include the Solsperse series (ZENECA), Ajisper series (Ajinomoto), and Homogenol series (Kao). In addition, the BYK series (BYK-Chemie), EFKA series (EFKA), and the like can also be used as appropriate. The pigment dispersant is preferably contained in the ink composition in an amount of 0.05 mass % or more relative to the total mass of the ink composition (this applies to the first ink composition and / or the second ink composition described below) from the viewpoint of storage stability of the ink composition, and 5 mass % or less from the viewpoint of lamination suitability, and more preferably in the range of 0.1 to 2 mass %.

[0076] -Additives- In the ink composition of this embodiment (which corresponds to the first ink composition and / or the second ink composition described below), the content of the above-mentioned additives is preferably 0 to 30 mass %, more preferably 0 to 20 mass %, and even more preferably 0 to 10 mass %, relative to the total amount of the ink composition.

[0077] - Hardener - A curing agent may be used in the ink composition of this embodiment (this corresponds to the first ink composition and / or the second ink composition described below). The ink composition of this embodiment (corresponding to the first ink composition and / or the second ink composition described below) can be applied to printing even if it is a one-liquid composition, and has excellent workability in printing. That is, the first ink composition of this embodiment has excellent ink dispersibility, flowability, etc., whether it is a one-liquid type that does not use a curing agent or a two-liquid type that does use a curing agent. The curing agent may be any of the curing agents commonly used in organic solvent-based gravure inks, such as isocyanate-based curing agents. It is preferable that the ink composition of this embodiment (corresponding to the first ink composition and / or the second ink composition described below) does not use a melamine resin as a curing agent. By not using a melamine resin as a curing agent in the ink composition, the generation of formaldehyde can be suppressed. In the ink composition of this embodiment (which corresponds to the first ink composition and / or the second ink composition described below), the content of the curing agent is preferably in the range of 0.3 mass % to 10.0 mass % relative to the total solid content of the ink composition, from the viewpoint of curing efficiency, and more preferably in the range of 1.0 mass % to 7.0 mass %.

[0078] -wax- The ink composition of the present embodiment (corresponding to the first ink composition and / or the second ink composition described below) preferably contains the above-mentioned wax. The ink composition containing wax can prevent blocking during winding and is easy to process. The content of the wax is not particularly limited and may be within a known range, but is usually preferably in the range of 0.1 to 20 mass % based on the total solid content of the ink composition (this corresponds to the first ink composition and / or the second ink composition described below).

[0079] (varnish layer) The laminate 10 of this embodiment has a varnish layer 4 provided on the first ink layer 2. The varnish layer 4 is also called an "overprint varnish layer," an "overcoat layer," or a "topcoat layer," and can be a layer that protects the first ink layer 2. This can provide a laminate with excellent heat resistance and abrasion resistance. The varnish layer 4 of this embodiment contains a butyral resin as the binder resin component (2). This can provide a laminate that reduces the environmental load and has excellent heat resistance, abrasion resistance, adhesion, blocking resistance, and rubbing strength, as well as a PTP package having the laminate. The average thickness of the varnish layer 4 in this embodiment is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.1 μm to 10 μm, and more preferably 1 μm to 5 μm. The varnish layer 4 may be colored or may not be colored. To color the varnish layer, a colorant may be added to the resin, and the colorant may be any of those described above in the section on ink compositions.

[0080] The varnish layer 4 of this embodiment preferably contains a polyisocyanate compound and a butyral resin, and more specifically, the varnish layer 4 more preferably contains a resin made of a butyral resin and a polyisocyanate compound as reaction raw materials. The varnish layer 4 may further contain a butyral resin and, if necessary, one or more selected from the group consisting of a binder resin component (2) other than the butyral resin (hereinafter also referred to as other resins), a colorant, and an additive. In other words, the binder resin component (2) includes a butyral resin and other resins. It is preferable that melamine resin is not used in the varnish layer 4. By not using melamine resin, the generation of formaldehyde can be suppressed, and therefore a more excellent effect of reducing the environmental load can be expected. The butyral resin or a structural unit derived from a butyral resin (=butyral resin residue, for example, a partial structure represented by the above general formula (1)) is preferably the structural component with the highest content in the varnish layer, and more preferably the butyral resin or a structural unit derived from a butyral resin is the structural component with the highest content in the binder resin component (2). As a result, since the amount of butyral resin used is large, the generation of formaldehyde can be suppressed, and therefore a more excellent effect of reducing environmental load can be expected. The varnish layer 4 of this embodiment can be formed by applying a coating agent, which will be described later, by gravure coating or the like. The coating amount of the varnish layer 4 is not particularly limited, but is preferably 0.5 g / m per unit area. 2 ~5g / m 2 It can be formed with. Below, we will explain the polyisocyanate compound, butyral resin, and binder resin component (2), which are the components that make up the varnish layer 4. Note that for the colorants and additives that are optional components of the varnish layer 4, the contents of the colorants and additives in the section (first ink layer) above are incorporated by reference.

[0081] <Polyisocyanate compounds> The varnish layer 4 of the present embodiment and the coating agent forming the varnish layer 4 described later contain a butyral resin and a polyisocyanate compound, and can form a crosslinked resin by the curing reaction between them. This improves adhesion, abrasion resistance, and heat resistance.

[0082] The polyisocyanate compound used in the present embodiment is not particularly limited as long as it is a polyisocyanate compound having a plurality of isocyanate groups so as to be capable of reacting with a butyral-based resin. Specific examples of the polyisocyanate compound include polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3-(isocyanatomethyl)cyclohexane, 1,5-naphthalene diisocyanate, and triphenylmethane triisocyanate; and derivatives (modified products) of polyisocyanates such as adducts of these polyisocyanates, biuret forms of these polyisocyanates, and isocyanurates of these polyisocyanates.

[0083] The polyisocyanate compound used in the present disclosure acts as a so-called curing agent and can be appropriately selected for use, but may be aromatic or aliphatic. That is, the polyisocyanate compound of the present embodiment is preferably an aliphatic or aromatic polyisocyanate. Examples of polyisocyanate compounds preferably used in this embodiment include polyisocyanates such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), tolylene diisocyanate (TDI), and diphenylmethane diisocyanate (MDI). Among them, xylylene diisocyanate (XDI) and tolylene diisocyanate (TDI) is preferred.

[0084] -Isocyanate group content (equivalent)- In this embodiment, the isocyanate group content (equivalent) of the polyisocyanate compound relative to the hydroxyl value of the butyral resin is preferably in the range of 0.1 to 5.0, more preferably in the range of 0.2 to 4.0, and even more preferably in the range of 0.3 to 3.0. By setting it in this range, it is possible to achieve both adhesion to the metal foil and abrasion resistance. In this embodiment, the isocyanate group content (equivalent) of the polyisocyanate compound relative to the hydroxyl value of the butyral resin was calculated by the following method. Hydroxyl value of butyral resin: A (mgKOH / g) Mass of butyral resin: B(g) Proportion (%) of isocyanate groups (-N=C=O) in polyisocyanate compounds: C (%) Mass of polyisocyanate compound: D(g) The ratio (isocyanate group / hydroxyl group) = C x D x 561 / (A x B x 42) D(g) = ((A x B) / C) x (42 / 561) x (isocyanate group / hydroxyl group) (equivalent ratio)

[0085] <Butyral resin> The butyral-based resin in the varnish layer 4 of this embodiment may be the same as the butyral-based resin described above in the section (first ink layer). That is, the butyral resin in the varnish layer 4 can generally be a reaction product obtained by acetalizing polyvinyl alcohol with an aldehyde compound such as butyraldehyde by a known reaction. It is preferable that the butyral resin has a partial structure represented by the above general formula (1), and more preferably, the butyral resin has a partial structure represented by the above general formula (1), a partial structure represented by the above general formula (2), and a partial structure represented by the above general formula (3). The polyvinyl butyral resin contained in the varnish layer 4 of this embodiment may be of one type or of two or more types in combination.

[0086] The weight-average molecular weight of the butyral resin used in the varnish layer 4 is preferably 5,000 to 150,000, more preferably 6,000 to 100,000, and even more preferably 7,000 to 50,000. By setting the weight-average molecular weight of the polyvinyl butyral resin within the above range, it is possible to provide a varnish layer that has an excellent balance between strength and dispersibility.

[0087] The glass transition temperature (hereinafter sometimes referred to as Tg) of the butyral resin used in the varnish layer 4 is preferably in the range of 50° C. to 120° C., more preferably in the range of 55° C. to 115° C., and more preferably in the range of 60 to 90° C. In the present invention, the glass transition temperature is obtained by measurement with a differential scanning calorimeter.

[0088] The hydroxyl value of the butyral resin used in the varnish layer 4 is preferably in the range of 10 to 50 mol / %, and more preferably 30 to 40 mol / %. By setting the hydroxyl value of the polyvinyl butyral resin in the above range, it is possible to achieve excellent curing properties when reacted with a crosslinking agent, and to achieve both strength and appropriate flexibility of the coating film. The amount of hydroxyl groups refers to the amount of the partial structure represented by the above general formula (3) relative to the total amount of the butyral resin.

[0089] <Binder resin component (2)> The varnish layer 4 of the present embodiment preferably contains a binder resin component (2). In the binder resin component (2), the component with the largest content is preferably a butyral resin, and other resins may also be contained. Examples of the other resins include epoxy resins, cellulose resins, polyamide resins, rosin resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, acrylic resins, styrene resins, dammar resins, styrene-maleic acid copolymer resins, polyester resins, alkyd resins, terpene resins, phenol-modified terpene resins, ketone resins, cyclized rubbers, polyacetal resins, petroleum resins, and modified resins thereof. These other resins can be used alone or in combination of two or more. In the case of pharmaceutical or food applications, it is preferable not to use epoxy resins or chlorine-based resins from the viewpoint of safety and hygiene.

[0090] <Coating agent> The varnish layer 4 of the present embodiment is preferably formed from a liquid coating agent. More specifically, the varnish layer 4 is preferably formed by applying a coating agent onto the first ink layer 2 by a known method. The coating agent preferably contains a polyisocyanate compound and a butyral resin. In order to achieve the effects of the present invention, the lower limit of the total amount of the butyral resin and the polyisocyanate compound relative to the total amount of resin contained in the coating agent of the present embodiment is preferably 50% by mass or more, preferably 70% by mass or more, preferably 80% by mass or more, preferably 90% by mass or more, and preferably 95% by mass or more. The upper limit of the total amount of the butyral resin and the polyisocyanate compound is preferably 100% by mass or less. In addition, it is particularly preferable that the total amount of the butyral resin and the polyisocyanate compound is substantially 100% by mass (excluding unavoidable impurities) relative to the total amount of resin contained in the coating agent. The above upper and lower limits can be combined arbitrarily. In order to improve the abrasion resistance, the coating agent may contain an anti-abrasion agent, a slip agent, etc., if necessary. Fatty acid amide, silicone, polyethylene, polypropylene, PTFE, etc. may be used alone or in combination of two or more kinds. In order to improve the curing property, a catalyst may be added to the coating agent, if necessary. Examples of the catalyst include organic tin compounds, tertiary amine compounds, organic titanium compounds, and organic zirconium compounds.

[0091] In the coating agent of the present embodiment, the content of the butyral resin is preferably 10 to 50 mass % relative to the total amount (solid content) of the coating agent, more preferably 15 to 40 mass %, and most preferably 20 to 30 mass %.

[0092] The coating agent of the present embodiment preferably contains an organic compound-based antiblocking agent other than those mentioned above, such as fatty acid amide, fatty acid ester, higher fatty acid, etc., as necessary. These organic compound-based antiblocking agents prevent blocking by bleeding out onto the ink layer surface. For this reason, a particle-based antiblocking agent and an organic compound-based antiblocking agent may be used in combination. If a large amount of an organic compound-based antiblocking agent is added, it inhibits adhesion and is likely to cause poor adhesion, so it is preferable to limit the addition to a small amount.

[0093] When actually applying the coating agent of this embodiment onto the first ink layer 2, in order to improve the application performance, it can be dissolved in various organic solvents to a solid content of 20% by mass. The organic solvent that can be used for dilution is not particularly limited, and examples thereof include various organic solvents based on aromatic hydrocarbons such as toluene, xylene, Solvesso #100, Solvesso #150, etc.; aliphatic hydrocarbons such as hexane, heptane, octane, decane, etc.; and esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, etc. Examples of water-miscible organic solvents include alcohols such as methanol, ethanol, propanol, and butanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and glycol ethers such as ethylene glycol (mono, di) methyl ether, ethylene glycol (mono, di) ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) methyl ether, propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono, di) methyl ether. Among these, it is preferable to use alcohols, ketones such as methyl ethyl ketone, and mixtures thereof. In recent years, from the viewpoint of the working environment, it is more preferable not to use aromatic solvents such as toluene and xylene, or ketone solvents.

[0094] The above is the content regarding the metal foil 1, the first ink layer 2, and the varnish layer 4, which are essential components of the laminate 10 of this embodiment. Below, the second ink layer 3 and the heat seal layer 5, which are optional elements of this embodiment, will be described.

[0095] (Second ink layer) The second ink layer 3 of this embodiment may be provided on the other surface of the metal foil 1. More specifically, in the laminate 10 of this embodiment, the second ink layer 3 may be provided on the surface of the metal foil 1 opposite to the surface on which the first ink layer is provided. The second ink layer 3 may display information such as characters, figures or symbols, and / or colors, as in the case of the first ink layer 2. More specifically, when the laminate 10 is used as a lid material for a PTP package, invariable information such as the name of the content, the price, the dosage of the content, and the efficacy and effect of the content, or variable information such as the date of manufacture, lot number, and expiration date may be printed as the first ink layer 2 and / or the second ink layer 3. Among these, it is preferable that the first ink layer 2 and / or the second ink layer 3 display a one-dimensional code (e.g., a barcode) or a two-dimensional code (e.g., a QR code (registered trademark)) including variable information such as the date of manufacture and lot number, which is individual information of the product of the content. For example, if the contents are pharmaceutical products, the barcode for the pharmaceutical product, such as GS1 (old RSS code), GS1-RSS Limited composite symbol CC-A, or GS1-RSS14 stacked composite symbol CC-A, may be displayed as the first ink layer 2 and / or the second ink layer 3. The color displayed by the second ink layer 3 of this embodiment is not particularly limited, and it may be uncolored, or may display colors such as black, blue, green, red, yellow, etc. The second ink layer 3 can be formed by a conventionally known method, for example, inkjet printing, gravure printing, etc. The second ink layer of the present embodiment is preferably a multi-layer printed layer formed by multi-layer printing including a solid color indicating ink layer and an information indicating ink layer that displays characters and / or patterns. When the second ink layer is a multi-layer printed layer, particularly when the laminate 10 is used as a lid material for PTP for pharmaceuticals, it may be necessary to display a barcode or QR code to prevent misidentification of the contents, etc., and the barcode or QR code (information display ink layer) may be difficult to read even if it is formed by directly printing on the metal foil 1. In response to this, the information display ink layer such as a barcode can be made easier to read by first providing a color display ink layer on the metal foil 1 by solid printing, and then printing and forming a barcode or QR code (information display ink layer) on top of that.

[0096] The average thickness of the second ink layer 3 in this embodiment is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.1 μm to 5 μm, and more preferably 0.1 μm to 3 μm. The second ink layer 3 of this embodiment contains a butyral resin, and preferably further contains one or more kinds selected from the group consisting of a binder resin component (3) other than the butyral resin, a colorant, a curing agent, a wax, and an additive, if necessary. The binder resin component (3) essentially contains a butyral resin. The composition of the second ink layer in this embodiment is preferably the same as that of the first ink layer. In this case, the contents of the binder resin component (3) and the butyral resin in the second ink layer refer to the preferred ranges of the content of the binder resin component (1) in the first ink layer. The butyral-based resin of this embodiment is preferably the component with the highest content among the resin components contained in the second ink layer. In other words, the butyral-based resin is preferably the component with the highest content among the binder resin components (3). This makes it possible to suppress the generation of carcinogenic NDMA (dimethylamine) since no soluble nitrocellulose-based resin such as nitrocellulose is used, and therefore a more excellent effect of reducing environmental impact can be expected. The components that can be used to form the second ink layer, that is, the butyral resin, the binder resin component (3), the colorant, the hardener, the wax, and the additives, are the same as the components that can be used to form the first ink layer, that is, the butyral resin, the binder resin component (1), the colorant, the hardener, the wax, and the additives. Therefore, the contents of the above (first ink layer) section are incorporated by reference for the contents of the butyral resin, the colorant, the hardener, the wax, and the additives, which are the components that can be used to form the second ink layer.

[0097] <Binder resin component (3)> The second ink layer 3 of this embodiment preferably contains a binder resin component (3). In the binder resin component (3), the component with the largest content is preferably a butyral-based resin (also called a "main resin"), and may further contain a binder resin (also called an "auxiliary resin") other than the butyral-based resin (main resin). The second ink layer 3 of this embodiment and the second ink composition described below may contain not only a butyral-based resin but also a binder resin component (3) other than the butyral-based resin. In other words, the binder resin component (3) contains a butyral-based resin as an essential component, and may contain other binder resins (auxiliary resins) other than the butyral-based resin (main resin) as necessary. The resins of the other binder resins (auxiliary resins) are the same as the binder resin component (1), and therefore will not be described here.

[0098] The content of the other binder resin (auxiliary resin) that can be contained in the binder resin component (3) is preferably in the range of 0.1 to 49% by mass based on the total amount of the binder resin component (3). When the content of the other binder resin (auxiliary resin) is 0.1% by mass or more based on the total amount of the binder resin component (3), the physical properties of the ink are improved and the printability is improved. When the content of the other binder resin (auxiliary resin) is 49% by mass or less based on the total amount of the binder resin component (3), the proportion of the butyral resin (main resin) can be increased, and even when baking is performed at a low temperature of about 150°C, the adhesion to the metal foil 1 is easily improved. The upper limit of the content of the other binder resin (auxiliary resin) is more preferably 45% by mass or less, even more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less based on the total amount of the binder resin component (3).

[0099] In addition, the second ink layer 3 of this embodiment and the second ink composition described later preferably do not contain either soluble nitrocellulose resin or chlorine-based resin. The first ink layer containing neither soluble nitrocellulose resin nor chlorine-based resin is preferable from the viewpoint of environment and health. Carcinogenic NDMA (N-nitrosodimethylamine) has been detected in products that use soluble nitrocellulose resin as ink for pharmaceutical PTP packaging, and the soluble nitrocellulose, an ink raw material, is suspected to be the cause of the NDMA. However, the second ink layer 3 and the second ink composition described below do not contain soluble nitrocellulose resin as a binder resin, thereby eliminating such concerns.

[0100] <Second ink composition> In the laminate 10 of the present embodiment, when an optional second ink layer 3 is further provided on the metal foil 1, the second ink layer 3 is preferably formed from a second ink composition. In addition, the second ink composition is preferably a liquid composition, that is, a so-called liquid ink composition. The second ink composition of this embodiment can be produced by dissolving and / or dispersing in a solvent a butyral resin and, if necessary, one or more selected from the group consisting of a binder resin component (3) other than the butyral resin, a colorant, an additive, a curing agent, and a wax. For example, the second ink composition can be produced by dispersing a pigment as a colorant in an organic solvent with the binder resin component (3) to produce a pigment dispersion, and then adding other compounds, etc., to the obtained pigment dispersion as necessary. The particle size distribution of the pigment in the pigment dispersion can be adjusted by the same method and means as the pigment dispersion in the first ink composition. The second ink composition has the same composition as the first ink composition. In this case, the contents of the binder resin component (3) and the butyral-based resin in the second ink layer refer to the preferred ranges of the binder resin component (1) in the first ink layer.

[0101] In the second ink composition of this embodiment, the butyral-based resin is preferably the component with the highest content in the binder resin component (3). The proportion of the butyral-based resin in the total amount of the binder resin component (3) is more preferably more than 50% by mass. Here, the proportion refers to the proportion in terms of solid content. When the proportion of the butyral-based resin in the total amount of the binder resin component (3) is more than 50% by mass, the adhesion of the second ink composition to the metal foil is further improved. The proportion of the butyral-based resin in the total amount of the binder resin component (3) is more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, and may be 100% by mass (i.e., the entire binder resin component (3) may be a butyral-based resin).

[0102] (Heat seal layer) The laminate 10 of this embodiment may further include a heat seal layer 5 on the second ink layer 3. The heat seal layer 5 of this embodiment is a layer used when the laminate 10 is thermally bonded to another member. For example, when the laminate 10 is used as a lid material for a PTP package, the heat seal layer 5 is a layer that is welded to the flange of the container when the laminate 10 is thermally bonded to another member such as a container, and it is preferable to select a material that can satisfactorily bond the container and the laminate 10. Therefore, the heat seal layer 5 contains a known thermoplastic resin that imparts heat sealability as a main resin component, and may further contain other components as necessary. The heat seal layer 5 of the present embodiment contains a known thermoplastic resin that imparts heat sealability as a main resin component, and may further contain other components as necessary. The thermoplastic resin is not particularly limited, and known thermoplastic resins may be appropriately selected depending on the purpose. The thermoplastic resin used in the heat seal layer 5 is preferably a copolymer having an olefin monomer unit (also referred to as a constituent unit) and an unsaturated carboxylic acid monomer unit (e.g., a monomer unit such as (meth)acrylic acid, (meth)acrylic acid ester, maleic acid, fumaric acid, or itaconic acid), and an α-olefin-(meth)acrylic acid ester copolymer is particularly preferred. Therefore, the heat seal layer 5 of this embodiment is preferably provided by applying a heat seal agent containing an α-olefin-(meth)acrylic acid ester copolymer onto a substrate such as a metal foil 1 or onto the second ink layer 3. In this specification, "(meth)acrylic acid ester" is a general term for acrylic acid ester and methacrylic acid ester. In the specification, the term "α-olefin-(meth)acrylic acid ester copolymer" refers to a copolymer in which an α-olefin and a (meth)acrylic acid ester are copolymerized. The α-olefin may be any known α-olefin without any particular limitation, and examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, butadiene, etc., and one or more of these may be used. Among these, α-olefins mainly composed of ethylene or propylene are preferred.

[0103] The (meth)acrylic acid ester can be any known (meth)acrylic acid ester without any particular limitation. The (meth)acrylic acid ester can be, for example, an alkyl ester, a hydroxyalkyl ester, or an alkoxyalkyl ester of acrylic acid or methacrylic acid. Specific examples of the (meth)acrylic acid ester include acrylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, n-octyl acrylate, 2-hydroxyethyl acrylate, and 2-methoxyethyl acrylate, and methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, 2-hydroxyethyl methacrylate, and 2-ethoxyethyl methacrylate. These can be used alone or in combination of two or more. Among them, it is preferable to use one or more of methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate as the (meth)acrylic acid ester, and it is preferable to use methyl (meth)acrylate as the main component in combination with n-butyl (meth)acrylate and isobutyl (meth)acrylate. For example, it is preferable that methyl (meth)acrylate is 60 mass% or more, and more preferably 70 mass% or more, of the total amount of (meth)acrylic acid esters.

[0104] In addition, the α-olefin-(meth)acrylic acid ester copolymer of this embodiment may further comprise other monomers copolymerized therein besides the α-olefin monomer units and the (meth)acrylic acid ester monomer units, but the content of monomer units derived from other monomers is preferably 30 mass% or less, more preferably 10 mass% or less, even more preferably 3 mass% or less, and even more preferably 1 mass% or less of the entire copolymer.

[0105] The proportion of ethylene in the α-olefin-(meth)acrylic acid ester copolymer of this embodiment is not particularly limited, but the proportion of ethylene in the copolymer is preferably 50% by mass or more, more preferably 60% by mass or more. On the other hand, the proportion of the (meth)acrylic acid ester copolymer in the copolymer is preferably 20% by mass or more, more preferably 30% by mass or more.

[0106] The weight average molecular weight of the α-olefin-(meth)acrylic acid ester copolymer of the present embodiment is not particularly limited, but is preferably 200,000 or more from the viewpoint of blocking resistance, while the weight average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less from the viewpoint of adhesion and low-temperature heat sealability.

[0107] In addition, the glass transition temperature of the α-olefin-(meth)acrylic acid ester copolymer is preferably 20° C. or lower, more preferably 10° C. or lower, and even more preferably 0° C. or lower, since the heat sealability at low temperatures is good. On the other hand, the lower limit of the glass transition temperature is preferably −70° C. or higher, more preferably −60° C. or higher, and even more preferably −50° C. or higher. The α-olefin-(meth)acrylic acid ester copolymer used in the present embodiment may be a known one, and a commercially available product may be used.

[0108] The heat seal layer 5 may also contain a resin other than the α-olefin-(meth)acrylic acid ester copolymer, for example, a thermoplastic resin other than the α-olefin-(meth)acrylic acid ester copolymer. The thermoplastic resin is not particularly limited and may be appropriately selected from known thermoplastic resins depending on the purpose, and examples thereof include α-olefin resins, styrene resins, ester resins, acrylic resins, cyclic olefin resins, acrylic / olefin resins, polyester resins, ethylene-vinyl acetate copolymer resins (EVA), ethylene-vinyl alcohol copolymer resins, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, cyclized rubber, polyamide resins, ketone resins, butyral resins, polyurethane resins, styrene-maleic acid resins, casein, and alkyd resins. These may be used alone or in combination of two or more. Among these, α-olefin resins are preferred because they can provide good heat sealability. The average thickness of the heat seal layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably from 1 μm to 10 μm, and more preferably from 3 μm to 5 μm.

[0109] The heat seal layer 5 is disposed on the metal foil 1 directly or via an optional layer (for example, a second ink layer). The heat seal layer can be formed by applying a heat seal agent in which the resin or the like is dispersed or dissolved in a solvent. As such a heat seal agent, a commercially available hot melt seal agent can also be used. The heat seal agent can be applied entirely or partially to the desired outermost surface of the PTP lid material.

[0110] <Heat sealant> The heat seal layer 5 of the present embodiment can be formed by applying a heat sealant onto a desired layer or metal foil. The heat sealant is not particularly limited, and may be in any form, such as a type in which a thermoplastic resin having heat sealability is dissolved in an organic solvent, a type in which the thermoplastic resin is dissolved in water or an aqueous organic solvent, or an emulsion type in which the thermoplastic resin is dispersed in water or an aqueous organic solvent. Among them, the heat sealant of the present embodiment preferably contains an α-olefin-(meth)acrylic acid ester copolymer and an organic solvent, and may further contain the thermoplastic resin as necessary. In the heat sealant, the α-olefin-(meth)acrylic acid ester copolymer is preferably adjusted to have a solid content concentration of 20 to 70% by weight.

[0111] The organic solvent that can be used is not particularly limited, but examples thereof include various organic solvents such as aromatic hydrocarbons, such as toluene, xylene, Solvesso #100, Solvesso #150, etc.; aliphatic hydrocarbons, such as hexane, heptane, octane, decane, etc.; and esters, such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, etc. Examples of water-miscible organic solvents include alcohols such as methanol, ethanol, propanol, and butanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and glycol ethers such as ethylene glycol (mono, di) methyl ether, ethylene glycol (mono, di) ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) methyl ether, propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono, di) methyl ether. Among these, it is preferable to use alcohols, ketones such as methyl ethyl ketone, and mixtures thereof. In recent years, from the viewpoint of the working environment, it is more preferable not to use aromatic solvents such as toluene and xylene, or ketone solvents.

[0112] The heat sealant of the present embodiment may contain optional additives in addition to the thermoplastic resin and the organic solvent. Examples of the optional additives include wax, filler, viscosity modifier, preservative, antibacterial agent, rust inhibitor, antioxidant, crosslinking agent, curing agent, curing catalyst, light stabilizer, ultraviolet absorber, photocatalytic compound, dye, inorganic pigment, organic pigment, extender pigment, plasticizer, antistatic agent, etc. Among them, it is preferable to contain a filler such as silica and an antiblocking agent such as wax in order to prevent blocking.

[0113] On the other hand, the heat-sealing agent of the present embodiment does not substantially contain any other resin than the α-olefin-(meth)acrylic acid ester copolymer, and the resin component contained in the heat-sealing agent is preferably made of the α-olefin-(meth)acrylic acid ester copolymer. That is, the heat-sealing agent of the present invention preferably has a simple structure made of the α-olefin-(meth)acrylic acid ester copolymer. The term "substantially free" means that no resin other than the α-olefin-(meth)acrylic acid ester copolymer is intentionally contained.

[0114] (Anchor coat layer) The laminate 10 of the present embodiment may further include an anchor coat layer between the ink layer (including the first ink layer 2 and the second ink layer 3) and the heat seal layer 5, if necessary. When the laminate 10 is used as a lid material for PTPs for pharmaceutical products, the heat seal layer 5 preferably does not contain a colorant since it comes into direct contact with the pharmaceutical product in the content portion. Therefore, when it is desired to provide a colored layer on the ink layer (including the first ink layer 2 and the second ink layer 3) (for example, the above-mentioned information display ink layer), it is preferable to provide an anchor coat layer between the heat seal layer and the heat seal layer and color the anchor coat layer. For the anchor coat layer, the same resin as the above-described heat seal layer can be used, and it is preferable to add a colorant. As the colorant used for the anchor coat layer, the colorants described in the section of the first ink composition above can be used. Further, the anchor coat layer can be formed, for example, by applying a coating solution of the raw material in a solid coating manner. The average thickness of the anchor coat layer is not particularly limited and can be appropriately selected according to the purpose, but is preferably 1 μm to 10 μm, more preferably 1 μm to 5 μm.

[0115] (Preferred form of the laminate) In the present embodiment, specific uses of the laminate 10 include lid materials for medical PTP packages (Press Through Packages) filled with tablets or capsules, lid materials for yogurt packs, lid materials for jelly packs, lid materials for coffee packs, lid materials for milk beverage packs, sheets having a metal foil such as electromagnetic shielding, and the like. Among them, the laminate 10 of the present embodiment is preferably used as a lid material (referred to as a PTP lid material) used for a PTP package. That is, the laminate 10 of the present embodiment is preferably a PTP lid material. Hereinafter, a preferred form when the laminate 10 is used as a PTP lid material will be described.

[0116] <Preferred embodiment of the PTP lid material> Preferred embodiments when the laminate 10 of the present embodiment is used as the PTP lid material include those having the following configurations. In the following notations, each layer is described in the lamination order. Further, for the varnish layer, in order to distinguish between the case with coloring and the case without coloring, they are respectively denoted as "varnish layer (without coloring)" and "varnish layer (with coloring)".

[0117] First embodiment: Varnish layer (without coloring) / Information display ink layer / Hard aluminum foil / Information display ink layer / Heat seal layer (without coloring) Second embodiment: Varnish layer (without coloring) / Information display ink layer / Color display ink layer / Hard aluminum foil / Information display ink layer / Heat seal layer (without coloring) Third embodiment: Varnish layer (uncolored) / information display ink layer / color display ink layer / hard aluminum foil / color display ink layer / information display ink layer / heat seal layer (uncolored) Fourth embodiment: Varnish layer (uncolored) / information display ink layer / hard aluminum foil / color display ink layer / information display ink layer / heat seal layer (uncolored)

[0118] In the PTP covering materials of the first to fourth embodiment modes described above, neither the varnish layer nor the heat seal layer is colored, and the information display ink layer can be seen as it is. In the first embodiment, the "information display ink layer" on the varnish layer side corresponds to the first ink layer, and the "information display ink layer" on the heat seal layer side corresponds to the second ink layer. In the second embodiment, a color indicating ink layer is provided between the information indicating ink layer on the varnish layer side and the hard aluminum foil in order to make the information indicating ink layer on the varnish layer side more easily visible. Also, in the second embodiment, the "information indicating ink layer / color indicating ink layer" on the varnish layer side (the above multilayer printed layer) corresponds to the first ink layer, and the "information indicating ink layer" on the heat seal layer side corresponds to the second ink layer. In the third embodiment, the "information display ink layer / color display ink layer" (the multilayer printed layer) on the varnish layer side corresponds to the first ink layer, and the "color display ink layer / information display ink layer" (the multilayer printed layer) on the heat seal layer side corresponds to the second ink layer. In the third embodiment, color display ink layers are provided on both sides of the hard aluminum foil to make the information display ink layers on both the varnish layer side and the heat seal layer side more easily visible. In the fourth embodiment, a color indicating ink layer is provided between the information indicating ink layer on the heat seal layer side and the hard aluminum foil in order to make the information indicating ink layer on the heat seal layer side more visible. In the fourth embodiment, the "information indicating ink layer" on the varnish layer side corresponds to the first ink layer, and the "color indicating ink layer / information indicating ink layer" on the heat seal layer side corresponds to the second ink layer.

[0119] Fifth embodiment: Varnish layer (colored) / information display ink layer / hard aluminum foil / information display ink layer / anchor coat layer (colored) / heat seal layer (uncolored) Sixth embodiment: Varnish layer (colored) / information display ink layer / color display ink layer / hard aluminum foil / information display ink layer / anchor coat layer (colored) / heat seal layer (uncolored) Seventh embodiment: Varnish layer (colored) / information display ink layer / color display ink layer / hard aluminum foil / color display ink layer / information display ink layer / anchor coat layer (colored) / heat seal layer (uncolored) Eighth embodiment: Varnish layer (colored) / information display ink layer / hard aluminum foil / color display ink layer / information display ink layer / anchor coat layer (colored) / heat seal layer (not colored)

[0120] In the PTP covering materials of the fifth to eighth embodiment forms, the varnish layer is colored, but the heat seal layer is not colored. Also, in order to provide a colored layer on the information-displaying ink layer on the content side, a colored anchor coat layer is provided between the information-displaying ink layer and the heat seal layer. In the sixth embodiment, in order to make the information indicating ink layer on the varnish layer side more easily visible, a color indicating ink layer is provided between the information indicating ink layer on the varnish layer side and the hard aluminum foil. In the eighth embodiment, in order to make the information indicating ink layer on the heat seal layer side more easily visible, a color indicating ink layer is provided between the information indicating ink layer on the heat seal layer side and the hard aluminum foil. In the seventh embodiment, in order to make the information indicating ink layers on both the varnish layer side and the heat seal layer side more easily visible, color indicating ink layers are provided on both sides of the hard aluminum foil. In the fifth to eighth embodiments, like the first to fourth embodiments, the "information display ink layer / color display ink layer" or "information display ink layer" on the varnish layer side corresponds to the first ink layer, and the "color display ink layer / information display ink layer" or "information display ink layer" on the heat seal layer side corresponds to the second ink layer.

[0121] Ninth embodiment: Varnish layer (not colored) / information display ink layer / hard aluminum foil / information display ink layer / anchor coat layer (colored) / heat seal layer (not colored) Tenth embodiment: Varnish layer (not colored) / information display ink layer / color display ink layer / hard aluminum foil / information display ink layer / anchor coat layer (colored) / heat seal layer (not colored) Eleventh embodiment: Varnish layer (not colored) / information display ink layer / color display ink layer / hard aluminum foil / color display ink layer / information display ink layer / anchor coat layer (colored) / heat seal layer (not colored) Twelfth embodiment: Varnish layer (not colored) / information display ink layer / hard aluminum foil / color display ink layer / information display ink layer / anchor coat layer (colored) / heat seal layer (not colored)

[0122] In the PTP covering materials of the ninth to twelfth embodiment, neither the varnish layer nor the heat seal layer is colored. However, in order to provide a colored layer on the information-displaying ink layer on the content side, a colored anchor coat layer is provided between the information-displaying ink layer and the heat seal layer. In the tenth embodiment, in order to make the information indicating ink layer on the varnish layer side easier to see, a color indicating ink layer is provided between the information indicating ink layer on the varnish layer side and the hard aluminum foil. In the twelfth embodiment, in order to make the information indicating ink layer on the heat seal layer side more easily visible, a color indicating ink layer is provided between the information indicating ink layer on the heat seal layer side and the hard aluminum foil. In the eleventh embodiment, in order to make the information indicating ink layers on both the varnish layer side and the heat seal layer side more easily visible, color indicating ink layers are provided on both sides of the hard aluminum foil. In the ninth to twelfth embodiments, like the first to fourth embodiments, the "information display ink layer / color display ink layer" or "information display ink layer" on the varnish layer side corresponds to the first ink layer, and the "color display ink layer / information display ink layer" or "information display ink layer" on the heat seal layer side corresponds to the second ink layer.

[0123] Thirteenth embodiment: Varnish layer (colored) / information display ink layer / hard aluminum foil / information display ink layer / heat seal layer (uncolored) 14th embodiment: Varnish layer (colored) / information display ink layer / color display ink layer / hard aluminum foil / information display ink layer / heat seal layer (uncolored) Fifteenth embodiment: Varnish layer (colored) / information display ink layer / color display ink layer / hard aluminum foil / color display ink layer / information display ink layer / heat seal layer (uncolored) 16th embodiment: Varnish layer (colored) / information display ink layer / hard aluminum foil / color display ink layer / information display ink layer / heat seal layer (uncolored)

[0124] In the PTP covering materials of the thirteenth to sixteenth embodiment forms, the varnish layer is colored, but the heat seal layer is not colored. However, in order to provide a colored layer on the information-displaying ink layer on the content side, a colored anchor coat layer is provided between the information-displaying ink layer and the heat seal layer. In the fourteenth embodiment, in order to make the information indicating ink layer on the varnish layer side easier to see, a color indicating ink layer is provided between the information indicating ink layer on the varnish layer side and the hard aluminum foil. In the sixteenth embodiment, in order to make the information indicating ink layer on the heat seal layer side more easily visible, a color indicating ink layer is provided between the information indicating ink layer on the heat seal layer side and the hard aluminum foil. In the fifteenth embodiment, in order to make the information indicating ink layers on both the varnish layer side and the heat seal layer side more easily visible, color indicating ink layers are provided on both sides of the hard aluminum foil. In the ninth to twelfth embodiments, like the first to fourth embodiments, the "information display ink layer / color display ink layer" or "information display ink layer" on the varnish layer side corresponds to the first ink layer, and the "color display ink layer / information display ink layer" or "information display ink layer" on the heat seal layer side corresponds to the second ink layer.

[0125] In the first to sixteenth embodiments, the ink composition of the present embodiment (including the first ink composition and the second ink composition) can be used as at least one layer of the information indicating ink layer and the color indicating ink layer. Note that these embodiments are some of the preferred examples of the PTP covering material of the present invention, and various configurations can be adopted for the PTP covering material of the present invention. It is preferable that none of the components of the PTP lid material of the present embodiment contain soluble nitrocellulose resin or chlorine-based resin. A PTP lid material that does not contain soluble nitrocellulose resin or chlorine-based resin is preferable from the viewpoint of the environment and health. More specifically, the PTP lid material does not contain soluble nitrocellulose resin, which can eliminate concerns about the generation of NDMA (N-nitrosodimethylamine). In addition, the PTP lid material does not contain chlorine-based resin, which can be exported worldwide. Moreover, it is preferable that none of the components of the PTP lid material of this embodiment contain melamine resin. When the PTP lid material does not contain melamine resin, the generation of formaldehyde can be suppressed.

[0126] [PTP packaging] The PTP package of this embodiment is characterized by having a laminate 10 as a PTP lid material. That is, the PTP package of this embodiment is composed of a container having a pocket-shaped recess for accommodating contents such as medicines and a flange portion provided at the end of the recess, and the laminate 10 as a PTP lid material. Then, after the contents such as medicines are accommodated in the recess of the container, the opening of the recess is covered and sealed with the laminate 10 as the PTP lid material. At this time, when the laminate 10 has a heat seal layer 5 on the surface thereof, it is preferable to bring the heat seal layer of the laminate 10 into contact with the flange portion of the container and heat seal the contents. Hereinafter, the PTP packaging body (press-through package) of this embodiment will be described in further detail with reference to the drawings. Fig. 2 is a cross-sectional view of an example of a PTP package of this embodiment. The PTP package 100 shown in Fig. 2 is composed of a container 20 for accommodating contents such as a medicine, and a PTP lid material 10 (=laminate 10) bonded to the container 20. The container 20 has a pocket-shaped recess 21 for accommodating contents 30, and a flange portion 22 provided at an end of the recess 21. The contents 30 such as a medicine (tablets) are directly accommodated in the recess 21, and the PTP lid material 10 (more specifically, the heat seal layer 5 of the PTP lid material 10) is directly bonded to the flange portion 22.

[0127] The PTP lid material 10 may be the laminate 10 described above, which is the PTP lid material of this embodiment. The container 20 can be made of a thermoplastic resin sheet made of polyester resin, polyolefin resin, or fluorine resin. Examples of the polyester resin include polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, and polybutylene terephthalate. Examples of the polyolefin resin include polyethylene resin, polypropylene resin, ethylene-vinyl alcohol copolymer resin, and resin made of cyclic olefin. Examples of the fluorine resin include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (EPA), tetrafluoroethylene-ethylene copolymer (ETFE), and polyvinylidene fluoride (PVDF).

[0128] The PTP package 100 of this embodiment is used by bonding the above-mentioned PTP lid material 10 and container 20 with a heat seal layer. That is, the PTP package 100 can be manufactured by a method in which contents 30 such as medicines (tablets) are placed in the recess 21 of the container 20, and the PTP lid material 10 is placed on the container 20 with the heat seal layer facing the container 20 and thermally bonded. The PTP package of this embodiment can be used as a packaging material for medicines, tablets, and foods such as candy and chocolate, etc. It can also be used as a packaging material for blister packs of toothbrushes, dry batteries, toys, etc.

[0129] It is preferable that none of the components of the PTP package of the present embodiment contain soluble nitrocellulose resin or chlorine-based resin. A PTP package that does not contain either soluble nitrocellulose resin or chlorine-based resin is preferable from the viewpoint of the environment and health. More specifically, the PTP package does not contain soluble nitrocellulose resin, which can eliminate concerns about the generation of NDMA (N-nitrosodimethylamine). In addition, the PTP package does not contain chlorine-based resin, which can enable export to the whole world. Moreover, it is preferable that none of the components of the PTP packaging body of this embodiment contain melamine resin. When the PTP packaging body does not contain melamine resin, the generation of formaldehyde can be suppressed. EXAMPLES

[0130] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the following, "parts" and "%" are all based on mass unless otherwise specified. [Measurement or evaluation methods used in the examples and comparative examples] (1) Measurement of weight average molecular weight The weight average molecular weight (polystyrene equivalent) was measured by GPC using an HLC8220 system manufactured by Tosoh Corporation under the following conditions. Separation column: Four TSKgel GMHHR-N columns manufactured by Tosoh Corporation were used. Column temperature: 40℃ Mobile phase: Tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) Flow rate: 1.0mL / min Sample concentration: 1.0% by weight Sample injection volume: 100 microliters Detector: Differential refractometer

[0131] (2) Evaluation of the physical properties of the varnish layer (2-0) Preparation of test specimen As described in the columns of Example 5, Reference Example, Comparative Example 3, and Comparative Example 4 described later, the laminates of Example 5, Reference Example, Comparative Example 3, and Comparative Example 4 were each prepared. Then, the laminate immediately after preparation of each laminate was used as test specimen (1), the laminate left at room temperature (23°C) for one day after preparation of the laminate was used as test specimen (2), the laminate left at room temperature (23°C) for two days after preparation of the laminate was used as test specimen (3), the laminate left at 40°C for one day after preparation of the laminate was used as test specimen (4), and the laminate left at 40°C for two days after preparation of the laminate was used as test specimen (5), and each was prepared as a measurement or evaluation object. The evaluations of "(2-1) Adhesion, (2-2) Heat resistance (ink bleeding), (2-3) Abrasion resistance, (2-4) MEK rubbing characteristics, and (2-5) Blocking resistance" described below were performed on a laminate (a laminate having a metal foil, a first ink layer, and a varnish layer) that did not have a heat seal layer and a second ink layer containing the second ink composition.

[0132] (2-1) Adhesion Nichiban cellophane tape (18 mm wide) was applied to the varnish layer on the surface of the above test specimens (1), (2) and (4), and the cellophane tape was peeled off at an angle of 90°. The peeling of the varnish coating was visually judged and rated from 1 to 5. The rating is in increments of 1, with 1 being poor and 5 being good, and the higher the rating, the better the adhesion of the varnish coating to the hard aluminum base material or the ink layer. The experimental results are shown in Table 2. Details of the ratings are shown below. 5: No peeling at all 4: Approximately 25% peeled off 3: Approximately 50% peeled off 2: Approximately 75% peeled off 1: Completely peeled off (about 100% peeled off)

[0133] (2-2) Heat resistance (ink bleeding) The above test specimens (1) to (5) were prepared and pressed with a heat seal bar at each temperature (230°C, 250°C, or 270°C) with 0.3 N for 2 seconds, and the coating film condition or bleeding (running) of the lettering ink was visually judged and rated from 1 to 5. The rating is in increments of 1, with 1 being poor and 5 being good, and the higher the rating, the less the ink bleeding and the more excellent the heat resistance. The experimental results are shown in Table 2.

[0134] (2-3) Abrasion resistance The above test specimen (2) was prepared and cut to an appropriate size, then set in a Gakushin type friction tester (RT-100, Daiei Scientific Instruments Manufacturing Co., Ltd., curved surface radius 200 mm). Gauze was attached to the tip of the abrasive, and after 100 reciprocations with a test load of 500 (g), scratches and abrasion of the coating surface were visually evaluated. The experimental results are shown in Table 2. (Evaluation Criteria) 5: The surface of the coating is scratched or worn at 0%. 4: The coating surface is scratched or worn down by less than 10% 3: The coating surface is scratched or worn down by 10% or more but less than 30% 2: The coating surface is scratched or worn down by 30% or more but less than 50% 1: The coating surface is scratched or worn down by 50% or more.

[0135] (2-4) MEK rubbing characteristics The above test specimens (3) and (5) were prepared, and absorbent cotton soaked in MEK (methyl ethyl ketone) was placed on the coating surface of each of the test specimens (3) and (5) with a load of 500 g. The number of times the absorbent cotton was rubbed back and forth until the coating on the surface of the test specimens (3) and (5) peeled off was counted. One reciprocation was counted as one rub. The experimental results are shown in Table 2.

[0136] (2-5) Blocking resistance A test specimen (1) was prepared, and the varnish layer was placed on a polyethylene terephthalate (PET) film so that the layer was in contact with the film, and then both sides were sandwiched between milky white PET films to prepare a sample to be measured. The sample to be measured was subjected to a load of 0.5 MPa using a blocking tester manufactured by Toyo Seiki Co., Ltd., and left to stand in a thermostatic chamber at 50°C for 24 hours. After 24 hours, the sample to be measured was removed and the PET film was peeled off. The degree to which the varnish layer or ink layer was transferred to the PET film that had been in contact with the varnish layer surface was sensorily evaluated on the following three-point scale. The experimental results are shown in Table 2. (Evaluation Criteria) 3: Peels off without resistance Between 2:3 and 1 1: Strong peel resistance

[0137] (3) Evaluation of the physical properties of the heat seal layer (3-0) Preparation of test pieces As described in the Examples, Reference Examples, and Comparative Examples below, laminates of the Examples, Reference Examples, and Comparative Examples were prepared. Then, a PVC sheet (made by Shohoku Aluminum Co., Ltd.) and the laminate were laminated via a heat seal layer to prepare test pieces. The prepared test pieces were then evaluated as follows. (3-1) Measurement of the strength of the heat seal layer (also called the HS layer) The above test pieces were heat sealed at a sealing temperature of 180°C and 0.3MPa / sec, and the adhesive strength was measured at a peel speed of 100mm / min, a peel direction of 180° (bottom: hard PVC sheet, top: hard aluminum), and a peel width of 15mm using a small tabletop tester EZ test manufactured by Shimadzu Corporation. The evaluation criteria were as follows: The experimental results are shown in Table 3. Note that the evaluation result of "3.5" in Table 3 is a case where, among multiple evaluations, evaluation results of 3 and 4 were mixed at the same level. (Evaluation Criteria) 5:10(N / 15mm) or more 4:3 (N / 15mm) or more and less than 10 (N / 15mm) 3:1 (N / 15mm) or more but less than 3 (N / 15mm) Less than 2:1 (N / 15mm) 1: No adhesion at all

[0138] [Preparation of laminate and PTP packaging] <Example 1> A laminate 10 of Example 1 was produced as follows (see, for example, FIG. 1). (Metal Foil 1) As the aluminum foil layer, a hard aluminum foil was used. (First ink layer 2 and second ink layer 3) As the first ink layer, the first ink composition having the composition shown in Table 1 below was applied to the entire surface (OP layer side) of the hard aluminum foil, and GS1 Data Bar Limited was printed thereon. In addition, the name of a drug or the like was printed in black, indigo, and red inks using the second ink composition having the composition shown in Table 1 below on the back side (HS layer side) of the hard aluminum foil.

[0139] (4 varnish layers) The varnish layer 4 was formed by gravure coating on the first ink layer 2 using a coating agent having the composition shown below. The coating amount after baking was 2 g / m 2 It was. Specifically, the following coating agent was used for the varnish layer 4. Polyvinyl butyral resin (weight average molecular weight 15,000, hydroxyl value approximately 35 mol / %, glass transition point 70°C) was dissolved in a mixed solvent of methyl ethyl ketone and isopropyl alcohol in a mass ratio of 45:55 to a solid content of 25% to prepare a polyvinyl butyral solution. Next, 12 parts of Takenate D-110NB (xylylene diisocyanate (XDI)) as a polyisocyanate were mixed and stirred with 100 parts of the polyvinyl butyral solution so that the NCO group content (equivalent) of the isocyanate was 0.5 to 2.5 relative to the hydroxyl value of the polyvinyl butyral resin, to prepare a coating agent for the varnish layer 4.

[0140] (Heat seal layer 5) The heat seal layer 5 was formed by applying the heat seal agent (1) having the composition shown below onto the second ink layer with a bar coater. The coating amount was 4 g / m 2 It is. Specifically, the following heat seal material (1) for the heat seal layer 5 was used. A commercially available ethylene-methacrylic acid copolymer resin (solid content 45%) was dissolved in a mixed solvent of methyl ethyl ketone and ethyl acetate to a solid content of 25%, to prepare a heat sealant (1). The mass ratio of methyl ethyl ketone and ethyl acetate in the mixed solvent was methyl ethyl ketone / ethyl acetate = 50 / 50.

[0141] <Example 2> The laminate of Example 2 was produced as follows. In Example 2, the following heat seal agent (2) was used as the heat seal layer 5. The rest was the same as in Example 1. A vinyl chloride-vinyl acetate copolymer resin (weight average molecular weight 50,000, vinyl chloride content 85%, glass transition point (Tg) 75°C, K value measured by ISO1628-2 45) was dissolved in a mixed solvent of methyl ethyl ketone and ethyl acetate to a solid content of 25%, to prepare a heat sealant (2). The mass ratio of methyl ethyl ketone and ethyl acetate in the mixed solvent was methyl ethyl ketone / ethyl acetate = 50 / 50.

[0142] <Example 3> The laminate 10 of Example 3 was produced as follows. In Example 3, the following heat seal agent (3) was used as the heat seal layer 5. The rest was the same as in Example 1. A vinyl chloride-vinyl acetate copolymer resin (weight average molecular weight 50,000, vinyl chloride ratio 85%, glass transition point (Tg) 75°C, K value 45 measured by ISO1628-2) and a polyester resin (number average molecular weight 30,000, glass transition point (Tg) -20°C) were dissolved in a mixed solvent of methyl ethyl ketone and ethyl acetate to a solid content of 16%, to prepare a heat sealant (3). The ratio of vinyl chloride-vinyl acetate copolymer resin to polyester resin was 1:1 by mass. The ratio of methyl ethyl ketone to ethyl acetate in the mixed solvent was methyl ethyl ketone / ethyl acetate = 60 / 40 by mass.

[0143] <Example 4> The laminate 10 of Example 4 was produced as follows. Example 4 was the same as Example 1, except that the following heat seal agent (4) was used as the heat seal layer 5. A commercially available water dispersion of ethylene-vinyl acetate copolymer resin (solid content 50%) and water were adjusted to a mass ratio of ethylene-vinyl acetate copolymer resin dispersion / water = 80 / 20 to prepare a heat sealing material (4). The laminates of Examples 1 to 4 and Comparative Examples 1 and 2 described below all have the same layer structure as the varnish layer of Example 1, and the second ink layer was provided using the second ink composition of Example 1 described in Table 1-2. Additionally, the laminates 10 produced in Examples 1 to 4 above can all be used as lid materials for PTP packages.

[0144] <Example 5> The laminate of Example 5 was prepared as follows. As in Example 1 above, a hard aluminum foil similar to that in Example 1 was prepared, and the first ink composition having the composition in Example 1 shown in Table 1 was applied to the entire surface (OP layer side) of the hard aluminum foil, and GS1 Data Bar Limited was printed thereon to prepare a first ink layer. Then, as a varnish layer, a coating agent having the composition used in Example 1 above was used and gravure-coated onto the first ink layer to prepare a laminate of Example 5 in which an ink layer was formed only on one side. The amount of coating was 2 g / m2 after baking. 2 It was.

[0145] <Comparative Example 1> The laminate of Comparative Example 1 was produced as follows. Comparative Example 1 was the same as Example 1, except that the first ink layer was formed using the first ink composition of Comparative Example 1 in Table 1-1.

[0146] <Comparative Example 2> The laminate of Comparative Example 2 was produced as follows. Comparative Example 2 was the same as Example 1, except that the first ink layer was formed using the first ink composition of Comparative Example 2 in Table 1-1.

[0147] <Comparative Example 3> The laminate of Comparative Example 3 was produced as follows. In Comparative Example 3, a laminate having the same layer structure as in Example 5 was prepared in the same manner as in Example 5, except that the first ink layer was made of the first ink composition of Comparative Example 1 in Table 1-1.

[0148] <Comparative Example 4> The laminate of Comparative Example 4 was produced as follows. In Comparative Example 4, a laminate having the same layer structure as in Example 5 was prepared in the same manner as in Example 5, except that the first ink layer was made of the first ink composition of Comparative Example 2 in Table 1-1.

[0149] <Reference example 1> As a control, a coating weight of 2 g / m was applied to a hard aluminum substrate after baking. 2 Each coating agent was applied directly to one side of a hard aluminum base sheet using a gravure coater so that the coating was as shown below, and then dried at 180°C for 10 seconds to prepare a control laminate (0) having a hard aluminum base sheet and a varnish layer.

[0150] [Table 1-1]

[0151] [Table 1-2]

[0152] [Table 2]

[0153] [Table 3]

[0154] *1 Pigment 1: White pigment, Ishihara Sangyo Kaisha, Ltd. product name "Tipaku A-220" *2 Vinyl chloride resin: "Solvine A" manufactured by Nissin Chemical Co., Ltd. *3 Acrylic resin: "Paraloid A-11" manufactured by DOW *4 Butyral resin: Polyvinyl butyral resin (weight average molecular weight 19,000, hydroxyl group amount 26 mass%, glass transition point 70°C, acetyl group amount 4 mass% or less) obtained by reacting polyvinyl alcohol with butyraldehyde was dissolved in methyl ethyl ketone (MEK) and ethyl acetate at 25% to prepare a butyral resin solution. This butyral resin solution was used to prepare the ink composition. Tables 1-1 and 1-2 show the content as solids.

[0155] *5 Polyurethane resin: 233.38 parts of neopentyl glycol adipate diol (hydroxyl value: 37.4 mg KOH / g), 2.36 parts of polyethylene glycol (hydroxyl value: 280.5 mg KOH / g), and 31.58 parts of isophorone diisocyanate were charged into a four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, and reacted at 90°C for 10 hours under a nitrogen stream to produce a urethane prepolymer with an isocyanate group content of 1.77% by mass, to which 66.8 parts of ethyl acetate were added to obtain a homogeneous solution of the urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture of 10.59 parts of isophorone diamine, 0.28 parts of cyclohexylamine, 387.6 parts of ethyl acetate, and 194.7 parts of isopropyl alcohol, and the mixture was stirred and reacted at 45°C for 5 hours to obtain a polyurethane resin solution. The obtained polyurethane resin solution had a resin solid concentration of 30.3% by mass, and the weight average molecular weight (Mw) of the resin solid was 58,000. The polyurethane resin solution was used to prepare an ink composition. Tables 1-1 and 1-2 show the content as solids.

[0156] *6 Ketone resin: "TEGO VARIPLUS SK" manufactured by Evonik Tego Chemie GmbH was added. The solid content is shown in Table 1. *7 PE wax: Gifu Shellac Co., Ltd.'s product name "X-7019" was added. Table 1 shows the solid content. *8 Plasticizer: DIC Corporation's product name "Monocizer ATBC" was added. Table 1 shows the content as solid content. *9 Solvent: The total amount of solvent in the ink composition, including methyl ethyl ketone / normal propyl acetate = 1 / 1 (mass ratio) in addition to the solvent used to dissolve the binder resin components mentioned above.

[0157] From the experimental results in Tables 2 and 3, it can be seen that the laminates of the examples according to the present disclosure have excellent adhesion (adhesion) to hard aluminum foil even when baked at a low temperature of about 150°C. For example, it is confirmed from Table 2 that the laminate in Example 5 in which the first ink layer is provided only on one side has high levels of heat resistance, friction resistance, adhesion, blocking resistance, and rubbing strength, and is superior to the laminates in the comparative examples. Therefore, it is considered that even if ink layers are provided on both sides like the laminates in Examples 1 to 4, excellent results can be obtained in terms of heat resistance, friction resistance, adhesion, blocking resistance, and rubbing strength. Next, from the experimental results shown in Table 3, it was confirmed that when the heat seal layer contains an α-olefin-(meth)acrylic acid ester copolymer, the strength is excellent. From the above, it was confirmed that the laminates of the examples according to the present disclosure have a reduced environmental impact and are excellent in heat resistance, abrasion resistance, adhesion, blocking resistance, and rubbing strength compared to the comparative examples.

[0158] <Example 6> The PTP package 100 of Example 6 was produced as follows. A container 20 having a cylindrical storage section and a structure shown in Fig. 2 was produced by vacuum molding using a transparent polypropylene film having a thickness of 250 μm. Then, the produced transparent polypropylene container 20 was filled with contents 30 (tablet-shaped medicine), and the laminate 10 (PTP packaging lid material) of the above-mentioned Example 1 and the flange portion 22 of the container 20 were heat-sealed to seal the opening of the container 20, producing a PTP package 100. When the upper surface of the container 20 was pressed with a finger, the laminate 10 was pressed by the contents 30 and broke, and the contents 30 could be taken out. [Industrial Applicability]

[0159] The laminate and PTP package of the present disclosure reduce the environmental impact and are excellent in heat resistance, abrasion resistance, adhesion, blocking resistance and rubbing strength. [Explanation of symbols]

[0160] 10: Lid material for PTP 1: Metal foil 2: First ink layer 3: Second ink layer 4: Varnish layer 5: Heat seal layer 100:PTP packaging 20: Container 21: Recess 22: Flange part 30:Contents

Claims

1. A laminate having a metal foil, a first ink layer provided on the metal foil, and a varnish layer provided on the first ink layer, A laminate, wherein the first ink layer contains a butyral-based resin, and the varnish layer contains a butyral-based resin.

2. The laminate according to claim 1 , wherein the butyral-based resin is a component contained in the first ink layer in the largest amount among the resin components contained in the first ink layer.

3. The laminate according to claim 1 or 2, wherein the varnish layer contains the butyral resin and a polyisocyanate compound.

4. 3. The laminate of claim 1 or 2, comprising the metal foil, a first ink layer provided on one side of the metal foil, the varnish layer provided on the first ink layer, and a heat seal layer provided on the other side of the metal foil.

5. The laminate according to claim 1 or 2, wherein the heat seal layer contains an α-olefin-(meth)acrylic acid ester copolymer.

6. A second ink layer is provided between the metal foil and the heat seal layer, The laminate according to claim 4 , wherein the second ink layer contains a butyral resin.

7. The laminate described in claim 5, wherein the first ink layer and / or the second ink layer is a multilayer printed layer composed of multilayer printing including a solid color display ink layer and an information display ink layer that displays letters and / or patterns.

8. The laminate according to claim 1 or 2, which is used as a lid material for PTP packaging.

9. 3. A PTP package comprising: a container sheet having a plurality of recesses capable of accommodating medicine; and the laminate of claim 1 or 2 which is a lid material covering the recesses.

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