Laminate

Abstract

Provided is a laminate in which a lower layer (base material layer), an intermediate layer, and an upper layer can be reliably bonded during use, water resistance is good, and after use, a primer layer for detachment formed from a primer composition for detachment containing a titanium-modified polyethyleneimine-based compound can easily separate and detach the lower layer (base material layer) and / or the upper layer from the intermediate layer more easily under mild conditions (a detachment liquid which is hot water).SOLUTION: The laminate is constituted by laminating a base material layer, a primer layer A for desorption, an intermediate layer, a primer layer B for desorption and an upper layer in this order. Wherein one of the primer layer A for detachment and the primer layer B for detachment is a primer layer for detachment formed from a primer composition for detachment containing a titanium-modified polyethyleneimine-based compound having an amine value of 5.0 to 25. 0mmol / g, and the other has a detachment layer not containing a titanium-modified polyethyleneimine-based compound.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminate. [Background technology]

[0002] Packaging materials made from various plastic films are used for food, confectionery, household goods, pet food, etc., from the viewpoints of design, economy, content protection, transportability, etc. Furthermore, gravure printing or flexographic printing is applied to many packaging materials with the intention of adding designs and messages that will appeal to consumers. To obtain these packaging materials, printing is performed by printing directly onto the surface of the base layer film of the packaging material, or by applying an adhesive or anchor agent to the printed surface of the base layer film of the packaging material as needed, and then laminating the film. In printing for laminating films, a colored ink composition and a white ink composition are printed in sequence on various films such as polyester, nylon, and aluminum foil, and then a polyethylene film or polypropylene film for heat sealing is laminated on the printed layer of the white ink composition by dry lamination using an adhesive or extrusion lamination using an anchor coating agent (see Patent Document 1).

[0003] In recent years, packaging, plastic bottles, and other plastic products made from plastic film have been discarded and dumped into the ocean as litter, causing environmental pollution problems. These plastic products break down in seawater, turning into submicron-sized fragments (microplastics), which float in the water. When these plastics are ingested by marine organisms such as fish, they become concentrated in their bodies. This raises concerns about the health of seabirds and humans who consume these marine organisms as food.

[0004] As one of various efforts to reduce microplastics in order to alleviate such problems, a recycling method has been proposed in which the plastic substrate layer of a laminate is removed from a laminate to which a printing ink composition has been laminated. As methods for removing the plastic substrate layer of a laminate, methods have been proposed using a removing ink composition (see, for example, Patent Document 2), a removing adhesive (see, for example, Patent Document 3), a removing anchor coating agent (see, for example, Patent Documents 4 to 6), and a removing liquid (see, for example, Patent Document 7). However, in these methods, when there are two removable primer layers, it is not sufficient to remove one of the removable primer layers using hot water as a remover liquid, and there are problems with the waterproofness of the layer that is removed using hot water, and with the inability to recover the base layer and the sealant layer separately. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 5-97959 [Patent Document 2] Patent No. 6631964 [Patent Document 3] Patent No. 6642688 [Patent Document 4] Patent No. 6388131 [Patent Document 5] Japanese Patent Publication No. 2020-175620 [Patent Document 6] International Publication No. 2021 / 090690 [Patent Document 7] Patent No. 6690806 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention provides a detachable primer layer formed from a detachable primer composition containing a titanium-modified polyethyleneimine compound that can reliably bond the lower layer (substrate layer), intermediate layer, and upper layer, and also other layers, if any, during use, and that has good water resistance. Furthermore, after use, the detachable primer layer can be easily separated and detached from the intermediate layer under mild conditions (hot water as a detachment liquid). Another objective is to adjust the order of detachment by providing detachable primer layers that separate and detach under different conditions. [Means for solving the problem]

[0007] The present inventors have found that the above problems can be solved by forming the following laminate, and have arrived at the present invention. That is, the present invention provides a laminate comprising a substrate layer, a removable primer layer A, an intermediate layer, a removable primer layer B, and an upper layer laminated in this order. The present invention relates to a laminate in which one of the detachable primer layer A and the detachable primer layer B is a detachable primer layer formed from a detachable primer composition containing a titanium-modified polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g, and the other is a detachable layer that does not contain a titanium-modified polyethyleneimine-based compound. [Effects of the Invention]

[0008] According to the present invention, it is possible to reliably obtain a laminate having a lower layer (substrate layer), a removable primer layer A, an intermediate layer, a removable primer layer B, and an upper layer. This provides improved water resistance compared to conventional removable primer layers. Furthermore, after use, the lower layer (substrate layer) and / or upper layer can be more easily separated and removed from the intermediate layer under milder conditions, i.e., with a release liquid that is hot water of 20°C or higher, preferably hot water at 40 to 80°C. Furthermore, by providing a release layer that can be separated and removed with a release liquid other than hot water, the order in which the lower layer (substrate layer), intermediate layer, and upper layer are removed from the laminate can be adjusted. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a diagram showing an example of a laminate of the present invention; [Figure 2] 1 is a diagram showing an example of a laminate of the present invention; DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention is a laminate invention based on the following items, and can be used for printed matter and laminates formed by various printing methods and laminating methods, and for various uses. [Laminate of the present invention] The laminate of the present invention is a laminate comprising a lower layer (substrate layer), a detachable primer layer A, an intermediate layer, a detachable primer layer B, and an upper layer, wherein one of the detachable primer layer A and the detachable primer layer B is a detachable primer layer formed from a detachable primer composition containing a titanium-modified polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g, and the other is a detachable layer formed from a detachable primer composition containing a compound that is not a titanium-modified polyethyleneimine-based compound. In this specification, the amine value is the equivalent weight of amino groups per 1 g of solid content, and is calculated as a value converted into the equivalent weight of potassium hydroxide after measuring by potentiometric titration (e.g., COMTITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATION K-900), manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1 N aqueous hydrochloric acid solution.

[0011] (Overview of each layer) In the present invention, each of the lower layer (substrate layer), removable primer layer A, intermediate layer, removable primer layer B, and upper layer can be independently formed from a single layer or multiple layers. One of the detachment primer layer A and the detachment primer layer B is a layer made of a detachment primer composition containing a titanium-modified polyethyleneimine compound. This detachment primer composition containing the titanium-modified polyethyleneimine compound is sometimes referred to as a "detachment primer composition," and a layer made of this "detachment primer composition" is sometimes referred to as a "detachment primer layer."

[0012] The other layer of the detachable primer layer A and the detachable primer layer B is a primer composition that does not contain a titanium-modified polyethyleneimine compound, or a layer that contains a titanium-modified polyethyleneimine compound and contains a non-negligible amount of a compound that inhibits the effect of the titanium-modified polyethyleneimine compound. This primer composition that does not contain a titanium-modified polyethyleneimine compound is called the "detachable composition," and the layer formed from this "detachable composition" is called the "detachable layer." The present invention requires that at least one layer be a layer made of a detachment primer composition containing a titanium-modified polyethyleneimine compound, and that at least one other layer be a layer made of a primer composition that does not contain a titanium-modified polyethyleneimine compound, or a layer containing a titanium-modified polyethyleneimine compound that contains a non-negligible amount of a compound that inhibits the effect of the titanium-modified polyethyleneimine compound. In this way, in the present invention, at least two different layers for detachment are provided, and in order to distinguish between them, one is referred to as the above-mentioned "detachment primer layer" and the other as the above-mentioned "detachment layer."

[0013] In the present invention, a release primer layer is provided between the lower layer (substrate layer) and the intermediate layer, and a release layer is provided between the intermediate layer and the upper layer, thereby integrating the lower layer (substrate layer), the intermediate layer, and the upper layer into a laminate. Alternatively, a release layer is provided between the lower layer (substrate layer) and the intermediate layer, and a release primer layer is provided between the intermediate layer and the upper layer, thereby integrating the lower layer (substrate layer), the intermediate layer, and the upper layer into a laminate. After use, the lower layer (substrate layer) and / or the upper layer can be separated and detached from the intermediate layer with a detachment liquid. For example, when a laminate is reused after use, the resin film or the like, which is the lower layer (substrate layer) of the laminate, the intermediate layer containing the printed layer or the like, the printed layer-containing layer or the like, and the sealant layer or the like, which is the upper layer formed thereon, are separated. In this way, the constituent lower layer (substrate layer) and upper layer or the like can be removed from the laminate.

[0014] The laminates shown in Figures 1 and 2 are examples of the laminate of the present invention. The laminate in Figure 1 has a "detachable primer layer" provided between the lower layer (substrate layer) and the intermediate layer, and a "detachable layer" provided between the intermediate layer and the upper layer. The laminate in Figure 2 is an example in which the positions of the "detachable primer layer" and the "detachable layer" are swapped in the laminate in Figure 1. In the present invention, the terms "lower layer (substrate layer)" and "upper layer" are used to indicate the top-bottom orientation, but they refer to the positional relationship between both sides of the laminate and the "detachment primer layer" and "detachment layer" within the laminate. Therefore, the lower layer (substrate layer) and the upper layer may be interchanged, as shown in Figures 1 and 2 above. The laminate of the present invention is not limited to these examples. In Figures 1 and 2, at least one of the lower layer (substrate layer), intermediate layer, and upper layer may have a structure in which multiple layers are laminated via a "detachable primer layer" and / or a "detachable layer."

[0015] Since the laminate of the present invention has a "detachable primer layer" and a "detachable layer" as described above, when the layers constituting the laminate are recovered separately, detachment conditions are selected to dissolve either the "detachable primer layer" or the "detachable layer," and the laminate is separated into multiple layers at that layer. Subsequently, for the laminate obtained by separation that is made up of an undissolved primer layer, different detachment conditions are selected to dissolve the remaining primer layer, i.e., the "detachable primer layer" and the "detachable layer," and the laminate is further separated into multiple layers at that layer. The removable primer layer can also be dissolved in non-alkaline hot water to separate the layers constituting the composition from each other.

[0016] For example, the laminate of the present invention is immersed in hot water at a temperature of 20° C. or higher, preferably about 40 to 80° C., to dissolve only the "detachable primer layer" in the laminate. As a result, the two layers adjacent to both sides of the "detachable primer layer" and bound by the primer layer are separated from each other. Thereafter, at least the layer having the "detachment layer" of the laminate separated into two layers is immersed in, for example, alkaline water or water containing a surfactant, to dissolve the detachment layer, which is insoluble in water at a temperature of about 40°C to 80°C, thereby further peeling the layers of the laminate. As a result, both the "detachment primer layer" and the "detachment layer" that originally constituted the laminate can be dissolved, and at least the lower layer (substrate layer), middle layer, and upper layer can be separated and recovered. Here, the "detachment layer" is a layer that does not dissolve in hot water. Furthermore, the order of layers to be recovered can be determined by substantially specifying the dissolution order of the release primer layers. In particular, when a part of the initial laminate before treatment includes a layer that particularly needs to be recovered selectively, it is useful to prepare the structure of that layer in advance as the laminate of the present invention.

[0017] [Lower layer (base material layer)] The lower layer (substrate layer) in the present invention may be a resin layer, a paper layer, a metal layer, or any of these layers on which a printed layer or the like is formed. It may consist of one of these layers, or may consist of multiple layers. Among these, the lower layer (substrate layer) may be a resin film made of only resin, a resin film obtained by laminating a resin to a paper substrate, or a substrate layer on which one or more layers selected from a plasma-treated layer, a corona-discharge-treated layer, an adhesive layer, an anchor coat layer, or other pretreatment layer are formed on the surface of the substrate layer on which the detachable primer layer A is located or on the opposite surface. Also, a laminate having a thermoplastic resin layer and a polyethylene-based resin layer may be used, or a laminate formed of any resin may be used, or these may not be used.

[0018] Such a lower layer (substrate layer) contains a known resin and is, for example, a resin substrate layer that can be laminated on the surface, and a resin film for laminate printing can also be used. Examples of such a lower layer (substrate layer) include resin films of polyesters such as polyethylene terephthalate (PET), polyolefins such as polyethylene (PE) and polypropylene (PP), and polyamides such as nylon (NY), as well as the above-mentioned resin films having a metal layer such as aluminum, and the above-mentioned resin films having a transparent vapor deposition layer. Specifically, biaxially oriented polypropylene, polyester, oriented nylon, transparent vapor deposition films, and the like, which are water-resistant, heat-resistant, and impact-resistant and also have excellent moisture resistance and gas barrier properties, are preferred. Furthermore, the lower layer (substrate layer) may be in the form of a plate rather than a film. Furthermore, a laminate of these lower layers (base layers) may also be used as a new lower layer (base layer). The lamination means may be a known adhesive or the like, or at least one of the removable primer layer A and the removable primer layer B of the present invention may be used.

[0019] [Removable primer layer] The detachable primer composition of the present invention is a composition containing a titanium-modified polyethyleneimine compound having an amine value of 5.0 to 25.0 mmol / g, and the detachable primer layer is a layer formed from this detachable primer composition. This release primer composition has the property of being soluble in water at a temperature of 20°C or higher, preferably 40 to 80°C. By providing a release primer layer between the lower layer (substrate layer) and the intermediate layer, the lower layer (substrate layer) and the intermediate layer are integrated to form a laminate, which can be separated from the intermediate layer with a release liquid after use. Furthermore, by providing a release primer layer between the intermediate layer and the upper layer, the intermediate layer and the upper layer are integrated. After use, the obtained laminate can be separated into the intermediate layer and the upper layer with a release liquid.

[0020] When used for lamination, the titanium-modified polyethyleneimine compound contained in the release primer composition of the present invention preferably has a number-average molecular weight of 1,000 to 200,000 from the viewpoint of strength. Of these, a number-average molecular weight of 2,000 or more is preferred, and a number-average molecular weight of 5,000 or more is more preferred. A number-average molecular weight of 200,000 or less is also preferred. The mass average molecular weight of the titanium-modified polyethyleneimine compound is preferably 4,000 to 800,000. As such titanium-modified polyethyleneimine compounds, Orgatix WS-700 and Titabond T-100 can be used. The more within these ranges, the easier the desorption can be achieved.

[0021] In addition to the titanium-modified polyethyleneimine compound, this detachment primer composition may contain, as necessary, one or more other compounds selected from polyethyleneimine compounds, polybutadiene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer resins, silane coupling agents containing epoxy groups, silane coupling agents containing isocyanate groups, and other optional additives, within the scope of not impairing the effects of the present invention. As these other compounds, the compounds described below in the desorption composition may be used. The release primer composition can be obtained by adding a solvent to the titanium-modified polyethyleneimine compound and stirring the mixture. The solvent can be a mixture of water and one or more alcohols such as methanol, ethanol, and isopropyl alcohol. In addition, when the detachment primer composition of the present invention contains a titanium-modified polyethyleneimine compound and a silane coupling agent containing an epoxy group and / or a silane coupling agent containing an isocyanate group, within a range that does not impair the effects of the present invention, it can be obtained by adding a solvent to the titanium-modified polyethyleneimine compound and stirring, and then further adding a silane coupling agent containing an epoxy group and / or a silane coupling agent containing an isocyanate group and stirring the mixture.

[0022] The detachable primer layer in the present invention can be formed by applying, printing, or the like on the lower substrate layer and / or the intermediate layer so as to be positioned between the lower layer (substrate layer) and the intermediate layer. Alternatively, the detachable primer composition can be formed by applying, printing, or the like on the intermediate layer and / or the upper layer. The removable primer layer of the present invention has a solid density of 0.003 g / m 2 More than 0.005 g / m is preferable. 2 More preferably, 0.600 g / m or more is used. 2 Preferably less than 0.500 g / m 2 The following is more preferable: Too little may not be effective enough, and too much may not be effective enough. The detachment primer composition may or may not contain polyolefin resin particles, inorganic metal salts, or organic metal salts.

[0023] [Detachment layer] The release layer in the present invention is formed from a release composition that does not contain a titanium-modified polyethyleneimine compound. This desorption composition has the property of being soluble in basic water at a temperature of about 40°C to 80°C, but is insoluble in non-basic water in the same temperature range. In order to consider the detachment properties of the entire laminate, the detachment composition is preferably one containing one or more compounds selected from the following compounds A to D. The following compound E may also be used as the detachment layer. A. Polyethyleneimine-based compounds B. Polybutadiene compounds C. Polyvinyl alcohol D. Ethylene vinyl alcohol copolymer resin (EVOH) This desorption composition may contain a titanium-modified polyethyleneimine compound or any additives as needed, provided that the effect of the present invention is not impaired.

[0024] (A. Polyethyleneimine-based compounds) The polyethyleneimine compounds used in the releasing composition can be further classified into A-1 to A-3, namely, A-1. polyethyleneimine compound, A-2. mixture containing a polyethyleneimine compound and an epoxy group-containing silane coupling agent and / or an isocyanate group-containing silane coupling agent, and A-3. siloxane-modified polyethyleneimine compound. These compounds A-1 to A-3 are different from each other and do not overlap. A. The polyethyleneimine compound preferably has an amine value of 5.0 to 25.0 mmol / g.

[0025] (A-1. Polyethyleneimine Compounds) A-1. The polyethyleneimine compound is preferably one having an amine value of 15.0 to 25.0 mmol / g, more preferably 16.0 mmol / g or more, and more preferably 20.0 mmol / g or less. In addition, polyethyleneimine compounds having all of the amino groups in the molecule, from primary to tertiary amino groups, are preferred. Furthermore, it is preferable that the number of secondary amino groups is greater than the number of primary and tertiary amino groups, and more preferably the number of secondary amino groups relative to the total number of all amino groups, from primary to tertiary, is 40% or more. The more within these ranges, the easier the elimination can be performed. The polyethyleneimine compound-containing desorption composition can be obtained by adding a solvent to the polyethyleneimine compound and stirring the mixture. The solvent can be, in particular, a mixture of water and one or more alcohols such as methanol, ethanol, and isopropyl alcohol. It should be noted that A-1. polyethyleneimine compound does not include A-3. siloxane-modified polyethyleneimine compound, and A-3. siloxane-modified polyethyleneimine compound is a compound different from A-1. polyethyleneimine compound.

[0026] (A-2. Mixture containing a polyethyleneimine compound and one or more selected from epoxy group-containing silane coupling agents and / or isocyanate group-containing silane coupling agents) In order to further improve the lamination suitability of the laminate compared to when the above A-1. polyethyleneimine compound is used, it is preferable to further contain a silane coupling agent containing an epoxy group and / or an isocyanate group in the above polyethyleneimine compound. As the polyethyleneimine compound, the above A-1. polyethyleneimine compound can be used, and this polyethyleneimine compound does not include A-3. siloxane-modified polyethyleneimine compound.

[0027] Examples of silane coupling agents containing an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethoxydimethoxysilane, 3-glycidyloxypropylmethoxydiethoxysilane, and 3-glycidyloxypropyltriethoxysilane.

[0028] Examples of silane coupling agents containing an isocyanate group include 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 2-isocyanateethyltriethoxysilane, and 2-isocyanateethyltrimethoxysilane. From the viewpoint of lamination suitability after retort, it is preferable to blend the silane coupling agent containing an epoxy group and the silane coupling agent containing an isocyanate group so that the ratio of (number of epoxy groups in the silane coupling agent + number of isocyanate groups) to (number of amino groups in the polyethyleneimine compound) ((number of epoxy groups in the silane coupling agent + number of isocyanate groups in the silane coupling agent) / total number of primary amino groups and secondary amino groups in the polyethyleneimine compound) is 0.20 to 2.50. It is more preferably 0.30 or more, more preferably 2.20 or less, and even more preferably 1.90 or less. The number of amino groups is the sum of the number of primary amino groups and the number of secondary amino groups.

[0029] The ratio of (the number of epoxy groups in the silane coupling agent + the number of isocyanate groups) to (the number of amino groups in the polyethyleneimine compound) ((the number of epoxy groups in the silane coupling agent + the number of isocyanate groups) / (the total number of primary amino groups and secondary amino groups in the polyethyleneimine compound)) can be calculated using the following formula: [(Coating amount of epoxy group-containing silane coupling agent (g / m 2 ) × average number of epoxy groups in one molecule) / average molecular weight of epoxy group-containing silane coupling agent (g / mmol)] + [(coating amount of isocyanate group-containing silane coupling agent (g / m 2 ) × average number of isocyanate groups in one molecule / average molecular weight of isocyanate group-containing silane coupling agent (g / mmol)], [(coating amount of polyethyleneimine compound (g / m 2 ) × amine value (mmol / g) × (average number of primary amino groups + number of secondary amino groups per molecule) / (average number of primary amino groups + number of secondary amino groups + number of tertiary amino groups per molecule)).

[0030] In addition, when the desorption composition of the present invention selectively contains both A-1. polyethyleneimine compound and A-2. a mixture containing a polyethyleneimine compound and an epoxy group-containing silane coupling agent and / or an isocyanate group-containing silane coupling agent, these overlap in that they contain a polyethyleneimine compound, and therefore, in essence, a mixture containing A-2. polyethyleneimine compound and an epoxy group-containing silane coupling agent and / or an isocyanate group-containing silane coupling agent has been selected. A detachment composition containing a mixture of a polyethyleneimine compound and one or more selected from an epoxy group-containing silane coupling agent and an isocyanate group-containing silane coupling agent can be obtained by adding a solvent to the polyethyleneimine compound and stirring, and then further adding an epoxy group-containing silane coupling agent and / or an isocyanate group-containing silane coupling agent and stirring. The solvent can be a mixture of water and one or more alcohols such as methanol, ethanol, and isopropyl alcohol.

[0031] (A-3. Siloxane-modified polyethyleneimine compounds) To improve the lamination suitability of the laminate, a siloxane-modified polyethyleneimine compound can be used. The amine value of the siloxane-modified polyethyleneimine compound is preferably 5.0 mmol / g or more and 15.0 mmol / g or less. A-3. Siloxane-modified polyethyleneimine compounds include polyethyleneimine and a compound of the formula: RZ-SiY3 and a silane coupling agent which is at least one amine-reactive hydrolyzable organosilane represented by the formula: [wherein R represents an amine-reactive group selected from the group consisting of an isocyanate group, an oxiranyl group, a glycidoxy group, an acryloxy group, a carbethoxy group, a carbomethoxy group, a vinylsulfonyl group, and an acrylamide group; Z represents a divalent organic group containing carbon atoms; and each Y independently represents a hydrolyzable group].

[0032] This siloxane-modified polyethyleneimine compound has a structure in which the group R of the silane coupling agent reacts with the amino group of polyethyleneimine to bond the silane coupling agent to the polyethyleneimine. However, as described above, it is preferable that the siloxane-modified polyethyleneimine compound has a predetermined amine value. A-3. A desorption composition containing a siloxane-modified polyethyleneimine compound can be obtained by adding a solvent to the siloxane-modified polyethyleneimine and stirring. The solvent can be a mixture of water and one or more alcohols such as methanol, ethanol, and isopropyl alcohol.

[0033] The molecular weights of the polyethyleneimine compounds in A-1 and A-2 and the siloxane-modified polyethyleneimine compound in A-3 that may be contained in the primer composition of the present invention are preferably each independently a number-average molecular weight of 1,000 to 200,000, from the viewpoint of lamination suitability, and each independently a mass-average molecular weight of 4,000 to 800,000. It should be noted that A-3. siloxane-modified polyethyleneimine compound is not included in the polyethyleneimine compound a. and the polyethyleneimine compound A-2., and is a compound different from the polyethyleneimine compound.

[0034] (B. Polybutadiene Compounds) The polybutadiene compound contained in the detachment composition is preferably an aqueous compound. To make it aqueous and improve adhesion, a hydroxyl group-containing polybutadiene compound or a carboxyl group-containing polybutadiene compound, in which a hydroxyl group or a carboxyl group is introduced into a polybutadiene compound, is preferred. Note that it is preferable that the polybutadiene compound is not crosslinked in order to exhibit detachment properties. Specific examples include EL-451 (Toyo-Morton Co., Ltd.) and T-180E (Nippon Soda Co., Ltd.). The polybutadiene-based compound-containing desorption composition can be obtained by adding a solvent to the polybutadiene-based compound and stirring the mixture. The solvent can be a mixture of water and one or more alcohols such as methanol, ethanol, and isopropyl alcohol.

[0035] (C. Polyvinyl alcohol) Polyvinyl alcohol is a water-soluble resin obtained by saponifying polyvinyl acetate. It is used in water-soluble packaging materials, adhesives, emulsifiers, etc., and is the raw material for the synthetic fiber vinylon. It is commonly abbreviated as poval or PVA. Commercially available products include Kuraray's Poval, Elvanol, and Exeval, Mitsubishi Chemical's Gohsenol, and Nippon Vinyl Acetate & Poval. The degree of saponification of polyvinyl alcohol is determined by the ratio of acetoxy groups in polyvinyl acetate replaced with hydroxyl groups, and a degree of saponification of 90% or more is preferable. Examples of polyvinyl alcohols with a degree of saponification of 90% or more include, but are not limited to, the following commercially available products: Kuraray Co., Ltd. Poval "3-98, 5-98, 28-98, 60-98, 27-96," Kuraray Co., Ltd. Elvanol "71-30, 90-50, T-25, T-66," Kuraray Co., Ltd. Exeval "AQ-4104, HR-3010, RS-2117, RS-1717," Mitsubishi Chemical Co., Ltd. Gohsenol "N-300, NL-05" ,A-300,AL-06R", and Nippon Vinyl Acetate & Poval Co., Ltd.'s "JC-25, JC-33, JC-40, JF-02, JF-03, JF-04, JF-05, JF-10, JF-17, JF-17L, JF-22, JM-17, JM-17L, JM-23, JM-26, JM-33, JT-05, JT-13Y", etc.

[0036] An inorganic layered compound can be contained within a range that does not decrease the adhesiveness to the layer to be bonded and / or does not decrease the suitability for lamination. The inorganic layered compound may be any inorganic layered compound that swells and cleaves in the dispersion medium, such as the kaolinite group, which has a 1:1 structure of phyllosilicate, the antigorite group, which belongs to the jamonite group, the smectite group, which has a number of interlayer cations, the vermiculite group, which is a hydrous silicate mineral, and the mica group. Specific examples of inorganic layered compounds include kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, hectorite, saponite, sauconite, stevensite, tetrasilylic mica, sodium taeniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, and chlorite, which may be natural or synthetic. Furthermore, scaly silica and the like can also be used. These may be used alone or in combination of two or more. Among these, montmorillonite is preferred from the viewpoint of coating properties and gas barrier properties. The polyvinyl alcohol-containing desorption composition can be obtained by adding a solvent to polyvinyl alcohol and stirring the mixture. The solvent can be a mixture of water and one or more alcohols such as methanol, ethanol, and isopropyl alcohol.

[0037] (D. Ethylene vinyl alcohol resin) Ethylene vinyl alcohol resins are obtained by saponifying ethylene-vinyl acetate copolymers, and have the properties of excellent moisture barrier properties and high transparency. The ethylene-vinyl alcohol-based resin may contain copolymerized units of vinyl acetate and its saponification product, and copolymerized units derived from ethylene, as well as other copolymerizable monomer units. Furthermore, the ethylene-vinyl alcohol-based resin has copolymerized units derived from ethylene and units derived from a vinyl alcohol structure as copolymerized components. The ethylene content is a value obtained by dividing the number of moles of ethylene by the total number of moles of all copolymerizable components, where ethylene constituting the ethylene-vinyl alcohol resin is one copolymerizable component and another component having an unsaturated double bond is the other copolymerizable component.

[0038] The ethylene content of the ethylene-vinyl alcohol resin is preferably 1 mol % or more, more preferably 4 mol % or more, and is preferably 35 mol % or less, more preferably 30 mol % or less. If the ethylene content is less than 1 mol %, the gas barrier properties at high temperatures and high humidity tend to decrease, and if the ethylene content is more than 35 mol %, the viscosity tends to increase. The ethylene vinyl alcohol resin preferably has a degree of saponification of 95% or more, more preferably 96% or more. If the degree of saponification is less than 95%, the gas barrier properties and oil resistance may decrease.

[0039] The desorption composition can be obtained by adding an ethylene vinyl alcohol resin to a mixed solvent of lower alcohols as needed, and dissolving the resin with stirring. The detachment composition containing an ethylene vinyl alcohol-based resin may contain an inorganic layered compound within a range that does not reduce the adhesion to adjacent layers such as the surface of the resin substrate layer or the printed layer, and / or does not reduce the suitability for lamination. As the inorganic layered compound, the same inorganic layered compounds as those described above in C. Polyvinyl alcohol can be used.

[0040] The dispersion medium contained in the desorption composition containing an ethylene-vinyl alcohol-based resin can be either an aqueous dispersion medium or an organic dispersion medium. The aqueous dispersion medium may be water alone, or a dispersion medium obtained by mixing water with a water-miscible organic solvent such as an alcohol such as methanol, ethanol, or propanol, a polyhydric alcohol such as ethylene glycol or propylene glycol, an alkyl ether derivative thereof, an ester such as ethyl formate, methyl acetate, or ethyl acetate, or a ketone such as acetone. As the dispersion medium, from the viewpoint of maintaining an appropriate solid content, it is preferable to use a mixture containing 50 to 95 mass% of water and 5 to 50 mass% of at least one of ethyl alcohol, propyl alcohol, and butyl alcohol, which are lower alcohols having 2 to 4 carbon atoms.

[0041] In the present invention, when a detachment primer layer is provided between a lower layer (substrate layer) and an intermediate layer, the detachment layer can be formed between the intermediate layer and an upper layer by applying, printing, or the like a detachment composition directly onto the surface of the intermediate layer. Also, when a detachment primer layer is provided between an intermediate layer and an upper layer, the detachment layer can be formed between the lower layer (substrate layer) and an intermediate layer by applying, printing, or the like a detachment composition directly onto the surface of the lower layer (substrate layer). The release layer in the present invention has a solid density of 0.003 g / m 2 More than 0.005 g / m is preferable. 2 More preferably, 0.600 g / m or more is used. 2 Preferably less than 0.500 g / m 2 The following is more preferable: Too little may not be effective enough, and too much may not be effective enough. The detaching composition may or may not contain polyolefin resin particles, inorganic metal salts, or organic metal salts.

[0042] [Middle layer] The intermediate layer that may be used in the present invention may be a resin layer, a paper layer, a metal layer, or a layer formed by forming a printed layer or the like on any of these layers. It may also be a printed layer alone. It may consist of one of these layers or multiple layers. Furthermore, the pretreatment layer described above for the substrate layer may be provided on both sides. The intermediate layer can be arbitrarily selected from the layers that can be used as the lower layer (base layer) described above. When the intermediate layer is made up of multiple layers, the multiple layers may be formed by using the same layer as the lower layer (substrate layer) or a layer having the pretreatment layer on both sides, and the multiple layers may be laminated via the detachable primer layer and / or detachable layer of the present invention. When forming the print layer, it may be formed directly on the "detachable primer layer" and / or the "detachable layer", or it may be formed via a primer layer or the like.

[0043] The print layer and the resin layer will be specifically described. (Printing layer) The printing layer printed with the printing ink composition that may be provided in the present invention can be, for example, a known reverse printing ink composition or front printing ink composition for lamination applications, such as a gravure printing ink composition for lamination, an active energy ray-curable offset printing ink composition for lamination, or an active energy ray-curable inkjet composition for lamination.

[0044] In the laminate of the present invention, the above-mentioned detachable primer layer is formed on one side of the printed layer, which is an intermediate layer, and the above-mentioned detachable layer is formed on the other side. Furthermore, when the detachable primer composition is provided between the lower layer (substrate layer) and the printed layer, which is an intermediate layer, it is also possible to form an anchor coating agent layer on the surface of the lower layer (substrate layer), then form a detachable primer composition layer on these layers, and then form the printed layer, which is an intermediate layer, on top of that. In these cases, the lower layer (substrate layer) can be peeled off from the printed layer, which is an intermediate layer, together with the anchor coating agent layer. Furthermore, when a detachable primer composition is provided between a printed layer serving as an intermediate layer and an upper layer, it is also possible to (1) form an anchor coating agent layer or adhesive layer on the surface of the printed layer serving as an intermediate layer, then form a detachable primer composition layer on those layers, and then form an upper layer on top of that, or (2) form a detachable primer composition layer on the surface of the printed layer serving as an intermediate layer, then form an anchor coating agent layer or adhesive layer on the surface above that, and then form the upper layer. In the case of (1), the upper layer can be peeled off from the printed layer serving as an intermediate layer having the anchor coating agent layer or adhesive layer, and in the case of (2), the upper layer can be peeled off from the printed layer serving as an intermediate layer together with the anchor coating agent layer or adhesive layer.

[0045] <Gravure printing ink composition for lamination> The gravure printing ink for lamination is a gravure printing ink for reverse printing containing a binder resin, a colorant, a solvent such as an organic solvent or an aqueous medium, additives, etc., and is not particularly limited. Examples of binder resins that can be used include urethane resins (with or without biomass), (biomass) urethane resins, vinyl chloride / vinyl acetate copolymers, vinyl acetate / acrylic copolymers, and cellulose acetate propionate.

[0046] Examples of colorants include organic and inorganic pigments and dyes used in general gravure inks. Examples of organic pigments include azo-based, phthalocyanine-based, anthraquinone-based, perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethine azo-based, dictopyrrolopyrrole-based, and isoindoline-based pigments. Examples of inorganic pigments include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, red iron oxide, aluminum, and mica. Examples of other pigments include glittering pigments (Metashine; Nippon Sheet Glass Co., Ltd.) that are made of glass flakes or aggregate flakes as a base material and coated with a metal or metal oxide. Examples of organic solvents include aromatic organic solvents, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester solvents such as ethyl acetate, n-propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate, and alcohol solvents such as n-propanol, isopropanol, n-butanol, and propylene glycol monomethyl ether, and in recent years, the use of ester solvents and alcohol solvents has become more environmentally friendly. Examples of aqueous solvents include solvents in which a water-soluble alcohol solvent or the like is mixed with water as the main component. Examples of additives include extender pigments, pigment dispersants, antifoaming agents, waxes, plasticizers, antiblocking agents, adhesion improvers, infrared absorbers, ultraviolet absorbers, fragrances, and flame retardants.

[0047] <Actinic energy ray curable inkjet printing ink composition for lamination> Examples of active energy ray-curable inkjet printing ink compositions for lamination include: For example, photopolymerizable compounds containing colorants, hydroxyl groups, and amine-modified oligomers For lamination containing a polymerizable compound, and optionally a polymerization initiator, sensitizer, pigment dispersant, additives, etc. Examples of the active energy ray-curable ink jet printing ink composition include the above. For example, active energy laminations such as those described in WO 2023 / 276290 An energy-ray curable ink jet printing ink composition can be used.

[0048] <Active energy ray curable offset printing ink composition for lamination> As the active energy ray curable offset printing ink composition for lamination, photopolymerizable compounds including photopolymerizable compounds containing hydroxyl groups, oligomers, and These may include initiators, pigment dispersants, and additives as needed. For example, active energy ray curing for lamination as described in Patent No. 7110508 A variety of offset printing ink compositions are available.

[0049] [Upper layer] The upper layer may be a resin layer used as a sealant layer, a resin layer not used as a sealant layer, or the same resin as the above-mentioned base layer. (Resin layer used as a sealant layer) The surface of the detachable primer layer or the release layer is laminated by various methods to form a sealant layer, thereby obtaining a laminate for use in packaging bags, etc. Examples of lamination methods that can be used include extrusion lamination, in which a molten polymer is laminated on the surface of the detachable primer layer or the release layer, with or without applying an anchor coating agent, and dry lamination, in which an adhesive is applied to the surface of the detachable primer layer or the release layer, and then a film-like polymer is attached to the surface. In the case of the dry lamination method, it is also possible to apply an adhesive to the surface of the intermediate layer, and then to laminate a film-like polymer coated with a release primer layer or a release layer.

[0050] The extrusion lamination method is a method in which, after forming an anchor coating layer by applying an anchor coating agent such as a titanium-based, urethane-based, imine-based, or polybutadiene-based agent to the surface of the detachment primer layer or detachment layer as necessary, a molten resin is laminated using a known extrusion laminator, or without applying an anchor coating agent, and the molten resin can also be laminated in a sandwich shape with other materials as an intermediate layer. In this case, it is not necessary to use a polyethyleneimine-based anchor coating agent. As the molten resin used in the extrusion lamination method, conventionally used resins such as polyolefin resins such as polyethylene polypropylene, including low density polyethylene, and ethylene-vinyl acetate copolymers can be used.

[0051] The dry lamination method is a method in which an adhesive such as a urethane-based or isocyanate-based adhesive is applied to the surface of the detachable primer layer or the detachable layer, and a resin film is laminated onto the resulting adhesive layer using a known dry laminating machine; or a method in which an adhesive such as a urethane-based or isocyanate-based adhesive is applied to the surface of the intermediate layer, and a resin film coated with the detachable primer layer or the detachable layer is laminated onto the resulting adhesive layer using a known dry laminating machine. Examples of the resin film used in this case include unstretched polyethylene film, unstretched propylene film, unstretched propylene film having a metal vapor deposition layer, polyester film, nylon film, etc. Furthermore, with regard to these resin films, films obtained by processing in advance such as coating or kneading in an antifogging agent, or surface coating or kneading in a matting agent can also be used. Furthermore, as the resin film, films in which a barrier layer formed by metal deposition or coating a barrier resin on various printing plastic films can be used.

[0052] (Resin layer not used as a sealant layer) A resin layer not used as a sealant can also be formed by laminating the surface of the release layer or intermediate layer by various methods, as explained for the resin layer used as a sealant layer.

[0053] (Layer having the same structure as the lower layer (base layer)) Instead of the above sealant or laminate layer, a layer obtained in accordance with the explanation for the above lower layer (substrate layer) may be used as the upper layer. In this case, a laminated upper layer may also be used as the upper layer. In this case, a known adhesive or other laminating means may be used, and at least one of the removable primer layer A and the removable primer layer B of the present invention may be used.

[0054] (Printing layer) The layer that can be used as the upper layer can be the printed layer described above for the intermediate layer. In this case, a printed layer, optionally with another surface treatment agent layer or primer layer interposed therebetween, is formed immediately above the removable primer layer B.

[0055] [Method for producing the laminate of the present invention] An example of a method for producing the laminate of the present invention will be described below. If necessary, an anchor coating agent is applied to the lower layer (substrate layer) to form an anchor coating layer, and then a layer consisting of at least one of a detachable primer layer and a detachable layer is formed on this lower layer (substrate layer) or the anchor coating layer. Then, when the intermediate layer is a printing ink layer, a printed layer is formed on the layer consisting of at least one of the detachable primer layer and the detachable layer by printing or printing the above-mentioned printing ink composition, or when the intermediate layer is not a printed layer, a film-like material such as a resin layer is laminated by a known means to obtain the intermediate layer.

[0056] Subsequently, the other of the release primer layer and the release layer is formed on the surface of the intermediate layer. Thereafter, an adhesive layer is provided on the surface of the other of the detachable primer layer and the detachable layer, and a film-like material that will become the upper layer is further adhered using a dry laminator to provide an upper sealant layer. Alternatively, the laminate of the present invention can be obtained by providing an anchor coating agent layer on the surface of the other layer of the detachable primer layer and the detachable layer, and then laminating molten resin using an extrusion laminator to provide an upper sealant layer.

[0057] [Layer Separation Method of Laminate of the Present Invention] ·First step (optional) In order to separate the laminate of the present invention into, for example, a lower layer (base layer), an intermediate layer, and an upper layer, the laminate is first cut into thin strips or the like by any means.

[0058] ·Second process The divided laminate is immersed in a sufficiently large amount of water (not basic) at a temperature of 20°C to 90°C, preferably about 40°C to 80°C, to dissolve and remove only the removable primer layer that constitutes the laminate. This water may contain a surfactant or the like. As a result, the two layers adjacent to both sides of the removable primer layer and bound by the removable primer layer are separated from each other.

[0059] ·3rd step (optional) The monolayer film or film-like material having no detachable layer separated from the laminate in the second step is separated from the film-like material having a detachable layer. When the monolayer film or film-like material having no detachable layer is made of, for example, a polyester resin, the separated polyester resin can be washed, dried, etc., and then pelletized by known means for reuse.

[0060] ·4th process The laminate obtained in the second or third step is immersed in a sufficiently large amount of basic water to dissolve the release layer. The basic water may be a known water-soluble basic compound such as an alkali metal hydroxide, ammonia, or an amine compound. The concentration of this basic compound is preferably 0.5 to 15% by mass, more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more. Furthermore, when treating waste liquid after use, a concentration of 5.0% by mass or less is preferred, and 3.0% by mass or less is even more preferred. The water may further contain a surfactant or the like. The release liquid used for release may be at room temperature, around 25°C, or heated to 25 to 90°C. The immersion time is preferably 1 minute to 12 hours, more preferably 1 hour or less, even more preferably 30 minutes or less, and most preferably 10 minutes or less. In this step, the detachment layer that constituted the laminate is dissolved and removed, and the insoluble layer in the laminate is dispersed in basic water. In this way, the order of layers to be recovered can be determined by substantially specifying the dissolution order of the release primer layers. In particular, when a part of the initial laminate before treatment includes a layer that particularly needs to be recovered selectively, it is useful to prepare the structure of that layer in advance as the laminate of the present invention. [Example]

[0061] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass."

[0062] <Lower layer (base material layer)> OPP: Biaxially oriented polypropylene film P-2161#25 (manufactured by Toyobo Co., Ltd.) PET: Polyethylene terephthalate film E-5102#12 (manufactured by Toyobo Co., Ltd.) NY: Nylon film ONY-15#12 (manufactured by Unitika Ltd.) PE: 0.25 μm thick corona-treated L-LDPE film (linear low-density polyethylene, manufactured by Mitsui Chemicals Tocello)

[0063] <Anchor coating agent> Takelac A-3210 / Takelac A-3072 (Mitsui Chemicals) diluted with ethyl acetate to a solid content of 7%

[0064] <Removable primer layer> (Layer obtained from a release primer composition containing a titanium-modified polyethyleneimine compound) A titanium-modified polyethyleneimine compound-containing detachment primer composition was obtained by mixing 21.1 parts by mass of WS-700 (solid content 9.5%) and 88.9 parts by mass of ethanol to give a solid content concentration of 2% by mass. In the examples in the following tables, the value of the release solution application amount (dry) is the application amount (g / m) after applying and drying this release primer composition. 2 ) (Application conditions for detachment primer composition 1 containing titanium-modified polyethyleneimine compound) Coating conditions Coating machine: Gravure printing machine Coating speed: 100m / min Plate: Helio 175 line / inch (130°) solid plate (wet coating amount 6 g / m 2 degree) Drying temperature: 70℃ When printing with a gravure printer, for example, after adjusting the solid content mass of the release primer as shown in Table 1 below, printing with the gravure printer under the above conditions will result in the following coating amount (g / m 2 ) The coating amount of the release primer composition per unit area in the following examples and comparative examples is the solid content of each component. This coating amount was adjusted by diluting each release primer composition with ethanol to the desired concentration.

[0065] [Table 1]

[0066] <Detachment layer> (A composition for desorption that does not contain a titanium-modified polyethyleneimine-based compound (a composition corresponding to the comparative example), the layer obtained therefrom) In the comparative examples in the following table, the value of the desorption liquid coating amount (dry) is the coating amount (g / m 2 ) after applying and drying these desorption primer compositions containing a silane coupling agent.

[0067] In the following table, the lower layer and the upper layer are described. This is when the substrate or the layer closer to the substrate layer is desorbed by the desorption layer of the example or the desorption layer of the comparative example, and the case is defined as the lower layer, and other cases are defined as the upper layer.

[0068] <Desorption composition containing a polyethyleneimine compound> Desorption composition containing a polyethyleneimine compound Epomin P-1000 (trade name Epomin P-1000, manufactured by Nippon Shokubai Co., Ltd., number average molecular weight 70,000, mass average molecular weight 350,000, amine value 18 mmol / g, amine ratio (primary: secondary: tertiary (%)) = 25 / 50 / 25) was diluted with a mixed solvent containing 50% by mass of purified water and 50% by mass of isopropyl alcohol so that the solid content concentration was 2% by mass to obtain a desorption composition 1 containing a polyethyleneimine compound. This polyethyleneimine compound dissolves in hot water. The above number average molecular weight (Mn) was measured by the viscosity method, and the mass average molecular weight (Mw) was measured by the GPC method. Amine value: Measured by acid titration in a non-aqueous system. Amine ratio: Measured by NMR (13C). In the comparative examples in the following table, the value of the desorption liquid coating amount (dry) is the coating amount (g / m 2 ) after applying and drying this desorption composition containing a polyethyleneimine-based compound.

[0069] <A-1. Desorption primer composition containing a polyethyleneimine compound and a glycidyl group-containing silane coupling agent> A mixture of a polyethyleneimine-based compound (trade name: Epomin P-1000, manufactured by Nippon Shokubai Co., Ltd.) and 3-glycidyloxypropyltrimethoxysilane (amino group / glycidyl group = 1.5) was diluted with a mixed solvent containing 50% by mass of purified water and 50% by mass of isopropyl alcohol so that the solid content concentration became 2% by mass to obtain a primer composition for detachment containing a polyethyleneimine-based compound. <A-2. Primer composition for detachment containing a polyethyleneimine compound and an isocyanate group-containing silane coupling agent> A mixture of a polyethyleneimine-based compound (trade name: Epomin P-1000, manufactured by Nippon Shokubai Co., Ltd.) and triethoxy(3-isocyanatopropyl)silane (amino group / isocyanate group = 1.5) was diluted with a mixed solvent containing 50% by mass of purified water and 50% by mass of isopropyl alcohol so that the solid content concentration became 2% by mass to obtain a primer composition for detachment containing a polyethyleneimine-based compound. <A-3. Primer composition for detachment containing a siloxane-modified polyethyleneimine compound> Trimethoxysilylpropyl-modified polyethyleneimine (trade name: SSP-060, manufactured by Gelest), molecular weight 1,500 to 1,800, amine value 10 mmol / g, the amine value was measured by acid titration in a non-aqueous system, and the amine ratio was measured by NMR (13C).) was diluted with a mixed solvent containing 50% by mass of purified water and 50% by mass of isopropyl alcohol so that the solid content concentration became 2% by mass to obtain a primer composition for detachment containing a polyethyleneimine-based compound.

[0070] <B. Primer composition for detachment containing a polybutadiene-based compound> A polybutadiene-based compound (trade name: Titabond T-180E, (solid content concentration 10% by mass), manufactured by Nippon Soda Co., Ltd.) was diluted with a mixed solvent containing 50% by mass of purified water and 50% by mass of isopropyl alcohol so that the solid content concentration became 2% by mass to obtain a primer composition for detachment containing a polybutadiene-based compound. <C. Primer composition for detachment containing polyvinyl alcohol> To 95 parts by mass of a mixed solvent containing 50% by mass of purified water and 50% by mass of isopropyl alcohol, 5 parts by mass of Kuraray Poval 5-98 (polyvinyl alcohol with a saponification degree of 90% or more) was added and stirred to obtain a polyvinyl alcohol-containing primer composition for release with a solid content concentration of 5% by mass. <Primer composition for release containing an ethylene vinyl alcohol-based resin> To 95 parts by mass of a mixed solvent containing 50% by mass of purified water and 50% by mass of isopropyl alcohol, 5 parts by mass of an ethylene vinyl alcohol copolymer (trade name: Soanol V2504NB (ethylene content 25 mol%)) was added and stirred and dissolved at 80 °C to obtain Primer Composition 1 for release with a solid content of 5% by mass. <Primer composition for release containing an ethylene vinyl alcohol-based resin and an inorganic layered compound> 5 parts by mass of montmorillonite (trade name: Kunipia F, Kunimine Industries Co., Ltd.), which is an inorganic layered compound, was added while stirring into 95 parts by mass of purified water and sufficiently dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain an inorganic layered compound dispersion with a solid content of 5% by mass. Next, while stirring 85 parts by mass of the primer composition for release D at high speed, 15 parts by mass of the inorganic layered compound dispersion was added, and then further dispersed at a pressure of 50 MPa using a high-pressure dispersion device and filtered through a 255-mesh filter to obtain Primer Composition 5 for release with a solid content of 5% by mass (ethylene vinyl alcohol copolymer resin / inorganic layered compound = 85 / 15 (solid content mass ratio)).

[0071] <Ink composition used in the example where Intermediate Layers 1 to Intermediate Layers 4 are formed of the ink composition for reverse printing> (Intermediate Layer 1: Gravure printing ink composition for reverse printing) A mixed solvent (ethyl acetate / propyl acetate / IPA (isopropyl alcohol) = 50 / 25 / 25) was added to the gravure printing ink composition for reverse printing (Bellflowra R Blue 800MK (for lamination) (Sakata Inx)) and diluted to 16 seconds using a Rheometric Scientific Zahn Cup No. 3. The diluted ink composition for reverse printing was printed and dried using a bar coater.

[0072] (Intermediate layer 2: UV-curable inkjet printing ink composition) A UV-curable inkjet printing ink composition (BSR06) (Sakata Inx Corporation) was printed using a bar coater. This was then exposed to a UV-LED lamp (Phoseon Technology Corporation) at a distance of 2 cm from the ink coating surface, with a UV cumulative light intensity of 180 mJ / cm. 2 It was completely hardened.

[0073] (Intermediate layer 3: UV-curable offset printing ink composition) A UV-curable offset printing ink composition was prepared by mixing and stirring 50.0 parts by weight of rosin-modified maleic acid resin (Harima M-453, Harima Chemicals), 41.0 parts by weight of trimethylolpropane (6EO) triacrylate, 2.0 parts by weight of dimethyl silicone oil (KF-96H-100,000cs), 5.0 parts by weight of 2-methyl-1(4-methylthiophenyl)-2-morpholinopropan-1-one, and 4,4'-bis(diethylamino)benzophenone. The ink was printed using a bar coater with a UV-LED lamp manufactured by Phoseon Technologies, Inc., at a distance of 2 cm from the ink surface, with a UV cumulative light intensity of 180 mJ / cm. 2 It was completely hardened.

[0074] (Intermediate layer 4: Electron beam (EB) curable offset printing ink composition) An electron beam (EB)-curable printing ink composition (22.7 parts by weight of PB15:3, 40.0 parts by weight of polyester acrylate oligomer CN704 (Sartomer), 36.2 parts by weight of 6EO-modified TMPTA (6EO-modified trimethylolpropane triacrylate), 0.1 parts by weight of methyl hydroquinone, and 1.0 part by weight of dimethyl silicone oil TSF-451-5M (Momentive)) was mixed and stirred, and 0.1 cc of each was transferred and applied using a simple color developer (RI Tester, Toyoe Seiko Co., Ltd.). This was then irradiated with electron beams using an electron beam (EB) curing device (EC90, Iwasaki Electric Co., Ltd.) (accelerating voltage 90 kV, exposure dose 30 kGy) at a conveyor speed of 10 m / min, allowing it to be completely cured.

[0075] <Upper layer (sealant layer)> (For dry lamination) Top layer (sealant layer) RXC-22#60: Unstretched propylene film (Mitsui Chemicals Tocello Co., Ltd.) :TUX™: Linear low-density polyethylene (Mitsui Chemicals Tocello Co., Ltd.) <Adhesive> When the resin layer to be coated was P-2161#25 (biaxially oriented polypropylene film (OPP)), the adhesive used was Takelac A-969V / Takelac A-5 (solid content 30% by mass, manufactured by Mitsui Chemicals). When the resin layer to be coated was PET, NY, or PE, the adhesive was Takelac A-515 / Takelac A-50 (solid content 30% by mass, manufactured by Mitsui Chemicals, Inc.).

[0076] (For extrusion lamination) Upper layer (sealant layer): Melting polyethylene "Sumikasen L705" (Sumitomo Chemical Co., Ltd.) Melting temperature 106°C Anchor coating agent used: Takelac A-3210 / Takelac A-3072, solid content 7% by mass

[0077] <Method of manufacturing laminate> If necessary, an anchor coating agent is applied to each of the resin substrate layers as the lower layer in a dry coating amount of 0.1 g / m 2The resulting coating was applied and dried to a thickness of 100 μm to obtain an anchor coating layer. Next, the resin substrate layer or the coated surface coated with the anchor coating agent was coated with a predetermined coating amount of each of the detachable primer compositions forming the detachable primer layer or the detachable primer composition composition forming the detachable layer as the above-mentioned detachable primer layer (A), and then dried to obtain a sample on which each of the detachable primer layers or the detachable layer was formed. Thereafter, various printing ink compositions serving as intermediate layers (in the case of reverse printing ink compositions, diluted reverse printing ink compositions prepared by adding a mixed solvent (ethyl acetate / propyl acetate / IPA (isopropyl alcohol) = 50 / 25 / 25) and diluting to 16 seconds in a Rigosha Zahn Cup No. 3) were printed on top of each of the detachable primer layers or the detachable layer, followed by drying and curing in the manner described above to form intermediate printing layers. Next, when each release primer composition (A) is used as a release primer layer, a release primer composition that forms a release layer was applied as a release primer composition (B), and when each release primer composition (A) is used as a release layer, a release primer composition that forms a release primer layer was applied to a predetermined coating amount and dried to obtain a sample on which each release primer composition layer (B) was formed. Thereafter, an adhesive was applied and the dry lamination method was used, or an anchor coating agent was applied and the upper sealant layer was laminated by the extrusion lamination method to obtain each laminate. In the case of the dry lamination method, each removable primer layer (B) is applied to the upper sealant layer in a predetermined amount and dried to obtain each laminate in which each removable primer layer (B) is laminated on the upper sealant layer, and each printed layer is also obtained by applying an adhesive to the dry lamination method. [Without a release layer] Various printing ink compositions (in the case of reverse printing ink compositions, diluted reverse printing ink compositions prepared by adding a mixed solvent (ethyl acetate / propyl acetate / IPA (isopropyl alcohol) = 50 / 25 / 25) and diluting to 16 seconds in a Rigosha Zahn Cup No. 3) were printed onto each of the above upper resin substrate layers, followed by drying and curing in the manner described above to form intermediate printed layers. Next, an adhesive was applied to the intermediate printed layer and the upper sealant layer was laminated thereon by dry lamination, or an anchor coating agent was applied and the sealant layer was laminated thereon by extrusion lamination, to obtain each laminate.

[0078] <Releasability test> (Separation process 1: Ink release test (hot water)) The sample laminate was cut into small pieces of approximately 15 mm MD x 25 mm TD to obtain samples for ink release test. 100 g of the release solution consisting of water was placed in a 200 cc HDPE (high density polyethylene) container and heated to 70°C in a hot water bath. (Mixed with hot water as the supernatant) Each of the ink release test samples was placed separately in hot water at 70°C in an HDPE container and stirred for 30 minutes using a stainless steel stirring blade with a blade diameter of 25 mm. After stirring, the HDPE container was removed from the water bath and allowed to stand at room temperature for 5 minutes. The release solution and each film piece, including the resin substrate layer, were separated using a stainless steel mesh with a mesh opening of approximately 2 mm. (rinse) After removal, each film piece was transferred to another 200cc HDPE container and 100g of water was added. The mixture was stirred for 5 minutes using a stainless steel stirring blade with a blade diameter of 25mm. After leaving the mixture to stand for 5 minutes, the film pieces were separated from the water using a stainless steel mesh. After drying the film pieces, the ink separation (peelability) from the films was visually evaluated.

[0079] <Separation process 2: Ink release test (NaOH)> After the ink release property test (hot water), the sample laminate was cut into small pieces of about MD 15 mm x TD 25 mm to obtain samples for the ink release property test. 2.0 parts by mass of sodium hydroxide was added to 98.0 parts by mass of water, and the mixture was stirred and dissolved to obtain a release liquid consisting of an alkaline aqueous solution. (Mixed with a release solution consisting of an alkaline aqueous solution) After the release solution comprising the alkaline aqueous solution was heated to 70°C, the laminated portion integrated with the release layer separated (peeled) in the separation (peeling) step was placed in the release solution comprising the alkaline aqueous solution and stirred for 30 minutes using a stainless steel stirring blade with a blade diameter of 25 mm. After stirring, the HDPE container was removed from the hot water bath and allowed to stand at room temperature for 5 minutes. The release solution and each film piece, including the resin substrate layer, were separated (peeled) using a stainless steel mesh with a mesh opening of approximately 2 mm. (rinse) After removal, each film piece was transferred to another HDPE container with a volume of 200 cc, and 100 g of water was added. The mixture was stirred for 5 minutes using a stainless steel impeller with a blade diameter of 25 mm. After leaving it to stand for 1 minute, the various film pieces were separated (peeled) from the water using a stainless steel mesh. After drying the various film pieces, the separation (peelability) of the ink from the various films was visually evaluated.

[0080] (Separation (peeling) process 1 of film separated (peeled) between layers) In the case of the laminates (A), (B), (C), and (I) below, The release solution and various film pieces were separated (peeled) using a stainless steel mesh with a mesh size of approximately 2 mm to separate (peel) the middle layer (printed layer) that had a release primer layer between it and the lower layer (base material layer). In the case of the laminates (D), (E), (F), and (J) below, The release liquid and various film pieces were separated (peeled) using a stainless steel mesh with mesh openings of approximately 2 mm to separate (peel) the top layer (sealant layer) (which may have an adhesive layer) and the intermediate layer (printed layer) or intermediate layer (resin film layer) (which may have an adhesive layer), which had a release primer layer in between. In the case of the laminates (G) and (H) below, An attempt was made to separate the phase-separated laminate using a stainless steel mesh with a mesh size of approximately 2 mm, but separation (peeling) did not occur.

[0081] (Separation (peeling) process 2 of film separated (peeled) between layers) In the case of the laminates (A), (B), (C), and (I) below, The release liquid and various film pieces were separated (peeled) using a stainless steel mesh with a mesh size of approximately 2 mm to separate (peel) the upper layer (sealant layer) (which may have an adhesive layer) and the intermediate layer (printed layer or resin film layer) (which may have an adhesive layer), which had a release layer in between. In the case of the laminates (D), (E), (F), and (J) below, The release liquid and various film pieces were separated (peeled) using a stainless steel mesh with a mesh size of approximately 2 mm to separate (peel) the middle layer (printed layer) that had a release layer between them (and sometimes an anchor coat) and the lower layer (base layer). In the case of the laminates (G) and (H) below, An attempt was made to separate the phase-separated laminate using a stainless steel mesh with a mesh size of approximately 2 mm, but separation (peeling) did not occur.

[0082] In the laminates (A), (B), (C), and (I) below, when both the detachment primer layer A and the detachment primer layer B are detachment layers that do not contain the titanium-modified polyethyleneimine compound described above (excluding polyethyleneimine compounds), separation (peeling) did not occur in the process using hot water as the release liquid, but separation (peeling) occurred in the process using an alkaline aqueous solution as the release liquid.

[0083] (Evaluation criteria) <First step: Step using hot water as the desorption liquid> ○: Separation (peeling) occurred. ×: No separation (peeling) occurred. <Second step: Step using an alkaline aqueous solution as the release liquid> ○: Separation (peeling) occurred. ×: No separation (peeling) occurred.

[0084] <Tape adhesion (printed items immediately after printing and drying)> Adhesion was evaluated according to the following criteria based on the degree of peeling of the printed film when cellophane tape was applied to the printed surface of each of the obtained prints and then quickly peeled off. (Evaluation Criteria) ◯: Peeling from the film was less than 5% of the area of ​​the printed coating. △: 5% or more but less than 30% of the area of ​​the printed coating peeled off from the film. ×: 30% or more of the area of ​​the printed coating peeled off from the film.

[0085] <Peel strength> After each laminate was obtained, it was cut into a width of 15 mm, and the T-peel strength was measured using a peel tester manufactured by Yasuda Seiki Seisakusho. (Evaluation criteria) When the base layer is OPP ○: Peel strength is 1.2N / 15mm or more △: Peel strength is 0.7N / 15mm or more and less than 1.2N / 15mm ×: Peel strength is less than 0.7N / 15mm When the base layer is PET, NY, or PE ○: Peel strength is 5N / 15mm or more △: Peel strength is 3N / 15mm or more and less than 5N / 15mm ×: Peel strength is less than 3N / 15mm

[0086] Examples of laminates (A) to (J) having a detachable primer layer and a detachable layer are shown below. The present invention may also be a laminate consisting of a lower layer (substrate layer), a detachable primer layer, and an intermediate layer (printed layer or resin film layer). The laminate of the present invention is not limited to these laminates. (A) Lower layer (substrate layer (OPP, PET, NY, PE)) / Removable primer layer formed from a removable primer composition / Middle layer (printed layer) / Removable layer formed from a removable composition / Adhesive layer / Upper layer, sealant layer (dry laminate) (B) Lower layer (substrate layer (OPP, PET, NY, PE)) / detachable primer layer formed from detachable primer composition / middle layer (printed layer) / adhesive layer / detachable layer formed from detachable composition / upper layer sealant layer (dry laminate) (C) Lower layer (substrate layer (OPP, PET, NY, PE)) / Removable primer layer formed from a removable primer composition / Middle layer (printed layer) / Removable layer formed from a removable composition / Anchor coat layer / Upper layer, sealant layer (extrusion laminate) (D) Lower layer (substrate layer (OPP, PET, NY, PE)) / anchor coat layer if necessary / release layer formed from release composition / middle layer (printed layer) / release primer layer formed from release primer composition / adhesive layer / upper layer sealant layer (dry laminate) (E) Lower layer (substrate layer (OPP, PET, NY, PE)) / anchor coat layer if necessary / release layer formed from release composition / middle layer (printed layer) / adhesive layer / release primer layer formed from release primer composition / upper layer sealant layer (dry laminate) (F) Lower layer (substrate layer (OPP, PET, NY, PE)) / anchor coat layer if necessary / release layer formed from release composition / middle layer (printed layer) / adhesive layer / release primer layer formed from release primer composition / anchor coat layer / upper layer sealant layer (extrusion laminate) (G) Lower layer (base material layer (OPP, PET, NY, PE)) / middle layer (printing layer) / adhesive layer / upper layer sealant layer (dry laminate) (H) Base layer (OPP, PET, NY, PE) / Middle layer (printed layer) / Anchor coat layer / Upper layer sealant layer (extrusion laminate) (I) Lower layer (substrate layer (OPP, PET, NY, PE)) / detachable primer layer formed from detachable primer composition / middle layer (resin film layer) / detachable layer formed from detachable composition / adhesive layer / upper layer, resin film layer (J) Lower layer (substrate layer (OPP, PET, NY, PE)) / anchor coat layer / detachable layer formed from detachable composition / middle layer (resin film layer) / detachable primer layer formed from detachable primer composition / adhesive layer / upper layer (resin film layer)

[0087] In obtaining the laminates (A) to (J) above, the detachable primer layer, detachable layer, and adhesive layer were all applied to a predetermined thickness using a bar coater and dried. The adhesive layer that contacts the upper layer (sealant layer) was applied to the resin layer that would become the upper layer (sealant layer), and then laminated. The printing layer was applied by any means.

[0088] When an intermediate layer (printing layer) is provided using various reverse printing ink compositions (A) Laminate Lower layer (substrate layer (OPP, PET, NY, PE)) / detachable primer layer (layer of detachable primer composition containing titanium-modified polyethyleneimine compound) / middle layer (printed layer) / detachable layer (layer of detachable primer composition that is not titanium-modified polyethyleneimine compound) / adhesive layer / upper layer, which is a sealant layer (dry laminate) Laminates were obtained having the structures shown in Table 2 below. For each of Laminates 1 to 5 (A), a laminate was obtained consisting of a base material layer as the lower layer, a printed layer as the intermediate layer, and a sealant layer as the upper layer. As shown in Tables 3 and 4, these laminates were further evaluated for releasability, adhesion, and peel strength by varying the amount of the detachable primer layer applied and the type of detachable layer. Regarding detachability, for all laminates, the layer having the detachable primer layer was evaluated as ◯ for separability (peelability) in hot water, and the layer having the detachable layer was evaluated as × for separability (peelability) in hot water, but the separability (peelability) in an alkaline aqueous solution was evaluated as ◯, demonstrating the effectiveness of the present invention. The evaluation results for each of the other evaluation items were ◯.

[0089] [Table 2]

[0090] [Table 3]

[0091] [Table 4]

[0092] When a printing layer is formed using various reverse printing ink compositions (B) Laminate Lower layer (substrate layer (OPP, PET, NY, PE)) / detachable primer layer (layer of detachable primer composition containing titanium-modified polyethyleneimine compound) / middle layer (printed layer) / adhesive layer / detachable layer (layer of detachable primer composition that is not titanium-modified polyethyleneimine compound) / upper layer (sealant layer (dry laminate)) Laminates were obtained having the structures shown in Table 5 below. For each of Laminates 6 to 10 in (B), a laminate was obtained with each base material layer as the lower layer, four types of printed layers as the intermediate layer, and each sealant layer as the upper layer. As shown in Tables 6 and 7, for each of these laminates, the amount of the detachable primer layer applied was further changed, and the type of detachable layer was changed, and the detachability, adhesion, and peel strength were evaluated. Regarding detachability, for all laminates, the layer having the detachable primer layer was evaluated as ◯ for separability (peelability) in hot water, and the layer having the detachable layer was evaluated as × for separability (peelability) in hot water, but the separability (peelability) in an alkaline aqueous solution was evaluated as ◯, and the effects of the present invention were obtained. The evaluation results for each of the other evaluation items were ◯. Furthermore, laminates were obtained with different amounts of the removable primer layer applied, and the ink releasability, barrier properties, adhesion, and peel strength were evaluated. The evaluation results for each evaluation item were good for all laminates.

[0093] [Table 5]

[0094] [Table 6]

[0095] [Table 7]

[0096] (C) Laminate Lower layer (resin substrate layer (OPP, PET, NY, PE)) / detachable primer layer (layer of detachable primer composition containing titanium-modified polyethyleneimine compound) / middle layer (printed layer) / detachable layer (layer of detachable primer composition that is not titanium-modified polyethyleneimine compound) / anchor coat layer / upper layer (sealant layer (extrusion laminate)) Each laminate was obtained as shown in the following Table 8. For each of laminates 11 to 15 (C), a laminate was obtained consisting of a base material layer as the lower layer, a printed layer as the intermediate layer, and a sealant layer as the upper layer. As shown in Tables 9 and 10, for each laminate, the amount of the detachable primer layer applied was further changed, and the type of detachable layer was changed, and the detachability, adhesion, and peel strength were evaluated. Regarding detachability, for all laminates, the layer having the detachable primer layer was evaluated as ◯ for separability (peelability) in hot water, and the layer having the detachable layer was evaluated as × for separability (peelability) in hot water, but the separability (peelability) in an alkaline aqueous solution was evaluated as ◯, and the effects of the present invention were obtained. The evaluation results for each of the other evaluation items were ◯. Furthermore, laminates were obtained with different amounts of the removable primer layer applied, and the ink releasability, barrier properties, adhesion, and peel strength were evaluated. The evaluation results for each evaluation item were good for all laminates.

[0097] [Table 8]

[0098] [Table 9]

[0099] [Table 10]

[0100] (D) Laminate Lower layer (resin substrate layer (OPP, PET, NY, PE)) / anchor coat layer as needed / detachment layer (detachment primer composition layer that is not a titanium-modified polyethyleneimine compound) / middle layer (printing layer) / detachment primer layer (detachment primer composition layer containing a titanium-modified polyethyleneimine compound) / adhesive layer / upper layer (sealant layer (dry laminate)) Each laminate was obtained as shown in the following Table 11. For each of laminates 16 to 20 (D), a laminate was obtained consisting of the base material layer as the lower layer, the printed layer as the intermediate layer, and the sealant layer as the upper layer. As shown in Tables 12 and 13, for each laminate, the amount of the detachable primer layer applied was further changed, and the type of detachable layer was changed, and the detachability, adhesion, and peel strength were evaluated. As a result, for all laminates, the layer having the detachable primer layer was evaluated as having an excellent result for separability (peelability) in hot water, and the layer having the detachable layer was evaluated as having an excellent result for separability (peelability) in hot water, but the separability (peelability) in an alkaline aqueous solution was evaluated as having an excellent result, and the effects of the present invention were obtained. The evaluation results for each of the other evaluation items were excellent.

[0101] [Table 11]

[0102] [Table 12]

[0103] [Table 13]

[0104] (E) Lower layer (substrate layer (OPP, PET, NY, PE)) / anchor coat layer as needed / detachment layer (detachment primer composition layer that is not a titanium-modified polyethyleneimine compound) / middle layer (printing layer) / adhesive layer / detachment primer layer (detachment primer composition layer containing a titanium-modified polyethyleneimine compound) / upper layer (sealant layer (dry laminate)) Laminates were obtained as shown in the following Table 14. For each of laminates 21 to 25 (E), a laminate was obtained consisting of the base material layer as the lower layer, the printed layer as the intermediate layer, and the sealant layer as the upper layer. As shown in Tables 15 and 16, for each laminate, the amount of the detachable primer layer applied was further changed, and the type of detachable layer was changed, and the detachability, adhesion, and peel strength were evaluated. As a result, for all laminates, the layer having the detachable primer layer was evaluated as having an excellent result for separability (peelability) in hot water, and the layer having the detachable layer was evaluated as having an excellent result for separability (peelability) in hot water, but the separability (peelability) in an alkaline aqueous solution was evaluated as having an excellent result, and the effects of the present invention were obtained. The evaluation results for each of the other evaluation items were excellent.

[0105] [Table 14]

[0106] [Table 15]

[0107] [Table 16]

[0108] (F) Lower layer (resin substrate layer (OPP, PET, NY)) / anchor coat layer as needed / detachment layer (detachment primer composition layer that is not a titanium-modified polyethyleneimine compound) / middle layer (printed layer) / detachment primer layer (detachment primer composition layer containing a titanium-modified polyethyleneimine compound) / anchor coat layer / upper layer (sealant layer (extrusion laminate)) Laminates were obtained as shown in Table 17 below. In each of Laminates 26 to 30 (F), the printing layer was a layer made of a reverse printing ink composition, and four types of substrate layers were used for each laminate, so that four types of laminates with different resin substrate layers were obtained in each of Laminates 1 to 5. As shown in Table 18, these laminates were further prepared with different amounts of the detachable primer layer applied, and the ink removability, adhesion, and peel strength were evaluated. The evaluation results for each evaluation item for all laminates were ○. Table 19 shows the results when, in laminate 26 (F) in Table 18, the substrate layer was OPP and the printing layer was a layer made of a reverse-printing printing ink composition, but the detachment primer layer was changed to a mixture of the primer and silane coupling agent in Table 18. Even when a detachment primer composition containing a titanium-modified polyethyleneimine compound was included, if an epoxy silane or isocyanate silane compound was also included, peeling did not occur in hot water.

[0109] [Table 17]

[0110] [Table 18]

[0111] [Table 19]

[0112] (G) Lower layer (resin substrate layer (OPP, PET, NY, PE)) / Middle layer (printing layer) / Adhesive layer / Upper layer (sealant layer (dry laminate)) Laminates were obtained as shown in Table 20 below. For the laminate (G), laminates were obtained of each base material layer as a lower layer, each printed layer and adhesive layer as an intermediate layer, and each sealant layer as an upper layer. The evaluation results for these laminates in terms of adhesion and peel strength were ◯, but as shown in Tables 4, 7, 13, and 16, the releasability was ◯, as no releasability occurred even in separation step 1 (hot water) and separation step 2 (alkaline aqueous solution).

[0113] [Table 20]

[0114] (H) Lower layer (resin substrate layer (OPP, PET, NY, PE)) / Middle layer (printing layer) / Anchor coat layer / Upper layer (sealant layer (extrusion)) Laminates were obtained as shown in the following Table 21. In the laminate (H), a laminate was obtained consisting of each base material layer as a lower layer, each printed layer as an intermediate layer, an adhesive layer, and a sealant layer as an upper layer. The evaluation results for these laminates in terms of adhesion and peel strength were ◯, but as shown in Tables 10 and 19 above, the releasability was ◯, as no releasability occurred even in separation step 1 (hot water) and separation step 2 (alkaline aqueous solution).

[0115] [Table 21]

Claims

[Claim 1] A laminate comprising a substrate layer, a removable primer layer A, an intermediate layer, a removable primer layer B, and an upper layer laminated in this order. Here, one of the detachable primer layer A and the detachable primer layer B is a detachable primer layer formed from a detachable primer composition containing a titanium-modified polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g, and the other is a detachable layer that does not contain a titanium-modified polyethyleneimine-based compound.

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