Primer composition for detachment and laminate

Abstract

To surely bond a lower layer (base material layer) and an upper layer such as a printing layer or a resin layer at a time of use, to simply separate the upper layer from the lower layer (base material layer) under a milder condition after use and to easily separate the upper layer from a release soln. and to improve moisture resistance.SOLUTION: A primer composition for detachment comprising a titanium-modified polyethyleneimine-based compound having an amine value of 5.0 to 25. 0mmol / g for forming a primer layer for detachment of a laminate in which a lower layer (substrate layer), the primer layer for detachment, and an upper layer are formed in this order.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a release primer composition and 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, the use of hot water as a release liquid is not sufficient for desorption, and when used in a laminate printing ink composition, there is a problem that moisture resistance is insufficient and laminate strength is reduced. There is also a laminated paper in which an adhesive is applied to a base layer film and a paper base layer is bonded to the laminated paper, and printing is then performed on the paper base layer side of the laminated paper. However, this has the problem that the adhesive remains on the base layer film even after the paper base layer is removed. [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 aims to provide a method for bonding a lower layer (substrate layer) to an upper layer such as a printed layer or a resin layer reliably during use, and to easily separate the upper layer from the lower layer (substrate layer) under milder conditions after use, and to easily separate and release the upper layer from the release liquid thereafter, while also providing good moisture resistance. [Means for solving the problem]

[0007] The present inventors have found that the above problems can be solved by using the following release primer composition and laminate, and have arrived at the present invention. 1. A detachable primer composition, which is a titanium-modified polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g, for forming a detachable primer layer of a laminate in which a lower layer, a detachable primer layer, and an upper layer are formed in this order. 2. The release primer composition according to 1, wherein the titanium-modified polyethyleneimine compound has a number average molecular weight of 1,000 to 200,000. 3. The release primer composition according to 1 or 2, wherein the titanium-modified polyethyleneimine compound has a mass average molecular weight of 4,000 to 800,000. 4. A laminate comprising a lower layer on which a removable primer layer formed from the removable primer composition according to any one of 1 to 3 is formed, and an upper layer on the removable primer layer. 5. A laminate comprising a lower layer on which a detachable primer layer formed from the detachable primer composition described in any one of 1 to 3 is formed, a paper layer on which an adhesive layer is interposed, and a printed layer on which a printed layer is formed. 6. A separation and recovery method for treating the laminate according to 4 or 5 by a method comprising the following steps (1) to (3): (1) A shredding step in which the laminate is shredded to obtain shredded material. (2) A separation step in which the shredded material is immersed in a desorption liquid to separate the lower layer. (3) A recovery step for recovering the separated lower layer. 7. The separation and recovery method according to 6, wherein the eluent is hot water. [Effects of the Invention]

[0008] According to the present invention, the laminate obtained can reliably bond the lower layer (substrate layer) to the upper layer, which is the printed layer, resin layer, or other layer, when used. Furthermore, the laminate has excellent moisture resistance, adhesiveness, lamination strength, and blocking resistance. Furthermore, when the material is recycled after use, the upper layer can be easily separated from the lower layer (substrate layer) under mild conditions, i.e., with water or hot water at 20°C, and the upper layer can then be easily separated from the release solution. [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; [Figure 3] 1 is a diagram showing an example of a laminate of the present invention; [Figure 4] 1 is a diagram showing an example of a laminate of the present invention; [Figure 5] 1 is a diagram showing an example of a laminate of the present invention; [Figure 6] 1 is a diagram showing an example of a laminate of the present invention; DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention is based on the following points and can be used for laminates and laminated laminates of printed materials for various printing methods and various applications. In this specification, the detachment primer composition of the present invention is sometimes simply referred to as a "primer composition or primer," and a layer consisting of one or more layers having a target surface on which a layer consisting of the detachment primer composition of the present invention is directly formed is simply referred to as a "lower layer (substrate layer)." When there are multiple layers consisting of the detachment primer composition of the present invention, any one of the one or more layers having a target surface is referred to as a "lower layer (substrate layer) or simply a lower layer." A layer consisting of one or more layers having a surface directly disposed on the layer consisting of the removal primer composition on the side opposite the lower layer (substrate layer) of the layer consisting of the removal primer composition is simply referred to as an "upper layer." The layer made of the removable primer composition is sometimes simply referred to as a "removable primer layer." The present invention is significant in that it employs a specific composition as the release primer layer. 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. The structure of the laminate obtained by using the release primer composition of the present invention is not particularly limited, and examples of such a structure include the following two structures. As shown in Figure 1, the structure comprises a lower layer (substrate layer) such as a resin, paper, metal layer, or printed layer, on which a detachable primer layer of the present invention is formed, either directly or via an adhesive, and an upper layer such as a resin, paper, metal layer, or printed layer is then formed, either directly or via an adhesive. As shown in Figure 2, the structure is such that a detachable primer layer of the present invention is formed on a lower layer (substrate layer) such as a resin, paper, metal layer, printed layer, etc., directly or via an adhesive, and an upper layer (1) of a resin, paper, metal layer, printed layer, etc. is formed on top of that, directly or via an adhesive, and a detachable primer layer of the present invention is further formed on top of that, directly or via an adhesive, and an upper layer (2) of a resin, paper, metal layer, printed layer, etc. is formed on top of that, directly or via an adhesive.

[0011] [Removal primer composition] The detachment primer composition of the present invention is a detachment primer composition containing a titanium-modified polyethyleneimine compound having an amine value of 5.0 to 25.0 mmol / g. A detachable primer layer may be provided directly between the lower layer (substrate layer) and the upper layer (1) or between the upper layers to integrate the lower layer (substrate layer) and the upper layer (1) or between the upper layers, and the detachable primer composition of the present invention may also be provided between multiple layers constituting the lower layer (substrate layer) and / or the upper layer. The primer composition for detachment of the present invention is a primer composition for separating the lower layer (substrate layer) of a laminate after use, the upper layer, etc. from the lower layer (substrate layer) such as a resin film which is the lower layer (substrate layer) for the laminate and the upper layer such as a printed layer formed thereon, and detaching the upper layer such as the printed layer from the lower layer (substrate layer). It is also a primer composition for detaching the upper layer (1) and the upper layer (2) from each other. This primer composition for detachment may be either an aqueous or an oily composition. The primer composition for detachment of the present invention exhibits the properties of a primer. For example, when forming an anchor coat layer for surface treatment on the printed surface which is the upper layer formed on the lower layer (substrate layer) and laminating a resin film or the like thereon, it is different from the anchor coat agent in terms of its use and required properties. The present invention is a composition for previously forming a primer layer in order to improve the adhesiveness between the lower layer (substrate layer) and these upper layers before providing the upper printed layer with a printing ink composition or before providing the upper film layer or the like on the lower layer (substrate layer). As the primer composition for detachment, a titanium-modified polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g can be used.

[0012] <A titanium-modified polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g> The primer composition for detachment containing a titanium-modified polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g is not particularly limited. Also, the compound included in the "polyethyleneimine-based compound" was taken as the "polyethyleneimine compound" for example. As the titanium-modified polyethyleneimine compound contained in the primer composition in the present invention, when a laminate is provided as the upper layer, from the viewpoint of its strength, those having a number average molecular weight of 1,000 to 200,000 are preferable. Among them, those of 2,000 or more are preferable, and those of 5,000 or more are more preferable. Also, those of 200,000 or less are preferable. In addition, the mass average molecular weight of the titanium-modified polyethyleneimine-based compound is preferably 4,000 to 800,000. As such a titanium-modified polyethyleneimine compound, Orgatix WS-700 and Titabond T-100 can be used.

[0013] <B. Compounds that can be used in combination with the above titanium-modified polyethyleneimine-based compound without impairing the effect> The primer composition for desorption in the present invention contains a titanium-modified polyethyleneimine-based compound, and within a range that does not impair the effects of the present invention, if necessary, polyethyleneimine, polybutadiene, siloxane-modified polyethyleneimine compound, epoxy group-containing silane coupling agent, isocyanate group-containing silane coupling agent, polyvinyl alcohol, ethylene vinyl alcohol copolymer resin (EVOH), and the like can be contained. One or more selected from other compounds. Also, these compounds may not be contained. In addition, the above non-impairing range means that with respect to 100 parts by mass of the solid content of the titanium-modified polyethyleneimine-based compound in the primer composition for desorption, the content of the above compounds such as polyethyleneimine and various silane coupling agents is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 50 parts by mass or less, and most preferably 25 parts by mass or less. The less the content of these compounds, the more the effect of using the titanium-modified polyethyleneimine-based compound can be exerted. As these compounds, for example, the compounds shown below can be adopted. (Polyethyleneimine) As the polyethyleneimine-based compound, when laminating, from the viewpoint of its strength, those having a number average molecular weight of 1,000 to 200,000 are preferable. Among them, 2,000 or more is preferable, and 5,000 or more is more preferable. Also, those of 200,000 or less are preferable. In addition, the mass average molecular weight of the modified polyethyleneimine-based compound is preferably 4,000 to 800,000. Furthermore, polyethyleneimine compounds having all of the amino groups in the molecule, from primary amino groups to tertiary amino groups, are preferred, and among these, in terms of the content based on the number of each amino group, it is preferred that the secondary amino groups are contained in greater numbers than the primary and tertiary amino groups, and it is even more preferred that the content of secondary amino groups among all the amino groups from primary to tertiary is 40% or more in terms of the number of groups.

[0014] (Polybutadiene compounds) The polybutadiene compound is preferably an aqueous composition. In order 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 the polybutadiene compound, is preferred. Note that it is preferable that the polybutadiene compound is not crosslinked in order to exhibit releasability. Specific examples include EL-451 (Toyo-Morton Co., Ltd.) and T-180E (Nippon Soda Co., Ltd.).

[0015] (Siloxane-modified polyethyleneimine compound) The siloxane-modified polyethyleneimine compound includes 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 a carbon atom; and each Y independently represents a hydrolyzable group]; and a silane coupling agent-modified polyethyleneimine compound, i.e., a siloxane-modified polyethyleneimine compound, which is obtained by reacting a component comprising: This siloxane-modified polyethyleneimine compound has a structure in which the group R of the silane coupling agent reacts with the amino group of the polyethyleneimine, and the silane coupling agent is bonded to the polyethyleneimine. The amine value of the siloxane-modified polyethyleneimine compound is preferably 5.0 mmol / g or more and 15.0 mmol / g or less. It should be noted that C. siloxane-modified polyethyleneimine compound is not included in the above A. titanium-modified polyethyleneimine compound and B. polyethyleneimine compound, and is a compound different from the titanium-modified polyethyleneimine compound.

[0016] (epoxy group-containing silane coupling agent) Examples of epoxy group-containing silane coupling agents include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethoxydimethoxysilane, 3-glycidyloxypropylmethoxydiethoxysilane, and 3-glycidyloxypropyltriethoxysilane.

[0017] (Isocyanate group-containing silane coupling agent) Examples of silane coupling agents containing an isocyanate group include 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 2-isocyanateethyltriethoxysilane, and 2-isocyanateethyltrimethoxysilane.

[0018] (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 substituted with hydroxyl groups, and a degree of saponification of 90% or more is preferred. 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.

[0019] (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. 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.

[0020] [Removable primer layer] The detachable primer layer of the present invention can be obtained by applying or printing the above-mentioned detachable primer composition directly onto the surface of the lower layer (substrate layer) or the like. The release primer layer on the lower layer (substrate layer) obtained from the release primer composition containing the titanium-modified polyethyleneimine compound of the present invention having an amine value of 5.0 to 25.0 mmol / g has a solid density of 0.010 g / m 2 More than 0.015 g / m is preferable. 2 More preferably, 0.020 g / m or more 2 More preferably, the content is 0.400 g / m or more. 2 Preferably less than 0.300 g / m 2 Less than 0.200 g / m is more preferable. 2 More preferably, 0.100 g / m or less 2 The following are most preferred:

[0021] <Method for producing a release primer composition> The release primer composition can be obtained by adding a solvent or the like to a 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. If necessary, additives can be added. However, the additives can be used within a range that does not impair the effects of the present invention. When the detachment primer composition of the present invention contains a titanium-modified polyethyleneimine compound and a silane coupling agent containing a glycidyl group and / or a silane coupling agent containing an isocyanate group, 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 a glycidyl group and / or a silane coupling agent containing an isocyanate group and stirring the mixture.

[0022] [Lower layer (base material layer)] The lower layer (substrate layer) in the present invention is a layer on whose surface a detachable primer layer containing the titanium-modified polyethyleneimine compound of the present invention is formed directly. When the laminate has multiple detachable primer layers, any one of the multiple detachable primer layers, either the outermost layer or the innermost layer, is designated as the lower layer (substrate layer). The lower layer (substrate layer) in the present invention is not particularly limited, and may be a lower layer (substrate layer) made of a known resin that can be printed on its surface, or a lower layer (substrate layer) having a layer on which a sheet is laminated or a coating liquid is applied. Examples of such lower layers (substrate layers) include resin films such as polyesters such as polyethylene terephthalate (PET), polyolefins such as polyethylene (PE) and polypropylene (PP), and polyamides such as nylon; the above-mentioned resin films having metal layers such as aluminum; the above-mentioned resin films having transparent vapor deposition layers; shrinkable polypropylene films (particularly shrinkable untreated polypropylene films), shrinkable polyvinyl chloride films, shrinkable polyethylene phthalate films, and other shrinkable plastic films; metal sheets; metal foils; coated paper; uncoated paper; and the like; or a lower layer (substrate layer) made by laminating two or more of these lower layers (substrate layers), or a lower layer (substrate layer) having a decorative layer such as a printing layer.

[0023] Furthermore, the lower layer (substrate layer) of the present invention also includes a layer on the surface of which a pretreatment layer has been formed in advance in order to form a detachment primer layer containing a titanium-modified polyethyleneimine compound. In this case, the entire layer including the pretreatment layer is referred to as the lower layer (substrate layer). Furthermore, a laminate having a thermoplastic resin layer and an ethylene-based resin layer may or may not be used as the lower layer (base layer). Furthermore, as such a lower layer (substrate layer), a resin film that serves as a lower layer (substrate layer) for a known laminate, a resin film for surface printing or shrink printing, a resin film laminated to a paper substrate layer, etc. can be used. Furthermore, after forming a printed layer as an upper layer on a lower layer (substrate layer) via a removable primer layer, the removable primer composition of the present invention may be applied onto the upper printed layer to form a sealant layer by dry lamination or extrusion lamination.

[0024] [Upper layer] The layer that can be used as the upper layer in the present invention can be selected as needed from the various materials that can be used for the lower layer (substrate layer) described above and the various printed layers described below. The upper layer may consist of one layer, but as described above in connection with FIGS. 3 to 5, it may also be formed of any number of layers. At least one of the upper layers, which consists of three or more layers, and / or at least one of the lower layers (substrate layers) when the upper layer consists of three or more layers, may have a release layer that is a release primer composition containing the titanium-modified polyethyleneimine compound of the present invention. This release layer that is a release primer composition containing the titanium-modified polyethyleneimine compound can also be released under mild conditions.

[0025] [Laminate of the present invention] The entire laminate having a removable primer layer according to the present invention can be roughly divided into those shown in FIG. 1 and FIG. FIG. 1 is a diagram showing a laminate having a lower layer (substrate layer), a detachable primer layer formed from the detachable primer composition of the present invention, and an upper layer, with an adhesive layer formed between these layers as needed. Fig. 2 is a diagram showing a laminate having a lower layer (substrate layer), a detachable primer layer formed from the detachable primer composition of the present invention, and an upper layer (1), and further having a detachable primer layer and an upper layer (2) on the upper layer (1), with an adhesive layer formed between these layers as needed. In the structure shown in Fig. 2, the layers from the upper layer (1) to the upper layer (2) are collectively referred to as the upper layer. In the laminate of FIG. 2, when more layers are laminated, any one or more layers may be laminated on the upper layer (2) as long as the effects of the present invention are not impaired.

[0026] Examples of the structure shown in Figure 1, focusing on the upper layer, are shown in three structures in Figures 3 to 5. The detachment primer layer in Figures 3 to 5 is a layer made of the detachment primer composition of the present invention. The lower layer (substrate layer) and / or upper layer of the laminate may be made of multiple layers, and a detachment primer layer containing a titanium-modified polyethyleneimine compound may be provided among them. The structures of the laminates shown in these figures are merely examples, and the present invention is not limited to these structures. The first laminate is a laminate, as shown in Figure 3, which is composed of a lower layer (substrate layer), a detachment primer layer containing a titanium-modified polyethyleneimine compound, and a printed layer as an upper layer directly in contact with the detachment primer layer. The second laminate, as shown in Figure 4, is a laminate consisting of a lower layer (substrate layer), a detachment primer layer containing a titanium-modified polyethyleneimine compound, and a printed layer and a film layer laminated in that order as upper layers in direct contact with the detachment primer layer. The third laminate may have a lower layer (substrate layer), a detachable primer layer containing a titanium-modified polyethyleneimine compound, and a film layer provided as an upper layer (1) in direct contact with the detachable primer layer, as shown in Figure 5. Furthermore, one or more two-layer sets may be provided on the film layer of the upper layer (1), each set comprising another detachable primer layer of the present invention and another film layer provided thereon as an upper layer (2). The laminate shown in Figure 2 is a laminate, as shown in Figure 6, for example, which is composed of a lower layer (substrate layer), a detachment primer layer containing a titanium-modified polyethyleneimine compound, and, directly in contact with the detachment primer layer, a printed layer as an upper layer (1), a detachment primer layer containing a titanium-modified polyethyleneimine compound, and a film layer as an upper layer (2) laminated in this order. In these cases, the upper layers, ie, the print layer and the film layer, may each independently be made up of a plurality of layers. Furthermore, for example, a structure consisting of a printed layer as an upper layer (2) as shown in FIG. 2 may be provided on the film layer that is the upper layer (1) of the laminate shown in FIG. 4, in direct contact with the detachable primer layer according to the present invention as shown in FIG. 3.

[0027] The laminate of the present invention is not limited to these examples, and may have other layer structures. The layer that forms the upper film layer may be any layer that is made of a material that can be used for the lower layer (base layer) and can be selected arbitrarily depending on the application of the laminate. Furthermore, the lower layer (substrate layer) and upper layer of any of the laminates may or may not have a printed layer for various purposes such as reverse printing, front printing, shrink printing, etc., as a layer that is not in direct contact with the detachment primer layer of the present invention. Any of the laminates may have the layer structure shown in FIGS. 3 to 6 in the lower layer (base layer) and / or in the upper layer. Furthermore, the positions of the lower layer (substrate layer) and the upper layer may be interchanged with respect to the detachment primer layer.

[0028] [The first laminate shown in Figure 3, having a lower layer (substrate layer), a detachment primer layer containing a titanium-modified polyethyleneimine compound, and an upper layer in direct contact with the detachment primer layer, which is a printed layer] In this case, the detachment primer composition of the present invention is used to detach the lower layer (substrate layer) and the printed layer in the upper layer. In this case, the layer in direct contact with the detachment primer layer containing the titanium-modified polyethyleneimine compound is the upper printed layer. In this case, the upper printed layer consists of one or more layers. This upper printed layer may be used in surface printing, shrink printing, etc.

[0029] The second laminate shown in Figure 4 has a lower layer (substrate layer), a detachment primer layer containing a titanium-modified polyethyleneimine compound, a printed layer (upper layer 1) that is in direct contact with the detachment primer layer, and a film layer (upper layer 2) that is in contact with the printed layer (upper layer 1), resulting in a laminate having a printed layer (upper layer 1) and a film layer (upper layer 2) as upper layers. In addition, in a printed matter in which a lower layer (substrate layer), a removable primer layer, a printed layer (upper layer 1), and an upper layer including a film layer (upper layer 2) are formed in this order, the lower layer (substrate layer) and the upper layer can be any of the above. Such a film layer (upper layer 2) can be formed by any known method that results in the formation of a layer other than a printed layer (upper layer 1), such as laminating a film (upper layer 2) onto the printed layer (upper layer 1) with or without an adhesive layer, applying and drying a paint to form a film layer (upper layer 2) that is a coating layer, or melting an anchor coating agent layer onto the printed layer (upper layer 1) to form a resin layer (upper layer 2). The printed layer (upper layer 1) may also be a printed layer for various purposes, such as reverse printing. In this case, the print layer (upper layer 1) and the film layer (upper layer 2) among the upper layers may each independently consist of one layer or multiple layers.

[0030] [A laminate comprising a lower layer (substrate layer), a detachable primer layer containing a titanium-modified polyethyleneimine compound, and, directly in contact with the detachable primer layer, a printed layer (upper layer 1) as upper layers, a detachable primer layer containing a titanium-modified polyethyleneimine compound, and a film layer (upper layer 2) laminated in this order] In the third printed matter shown in Figure 5, which is formed in the order of a lower layer (substrate layer), a removable primer layer, a printed layer (upper layer 1), and an upper layer including a removable primer layer and a film layer (upper layer 2), the lower layer (substrate layer) and the upper layer can be any of the above. As a means for forming such a film layer (upper layer 2), known means that can ultimately form a layer other than a printed layer (upper layer 1) can be used, such as laminating a film (upper layer 2) onto the upper layer, which is a detachable primer layer, with or without an adhesive layer therebetween, applying and drying a paint to form a film layer (upper layer 2) that is a coating layer, or melting an anchor coating agent layer onto the upper layer, which is a detachable primer layer, to form a resin layer (upper layer 2).The printed layer (upper layer 1) may also be a printed layer (upper layer 1) for various purposes, such as reverse printing. In this case, the print layer (upper layer 1) and the film layer (upper layer 2) among the upper layers may each independently consist of one layer or multiple layers.

[0031] [Laminate having a lower layer (substrate layer), a detachable primer layer containing a titanium-modified polyethyleneimine compound, and an upper layer in direct contact with the detachable primer layer which is a film layer that is not a printed layer] The fourth laminate shown in Figure 6 is one in which a detachment primer layer containing a titanium-modified polyethyleneimine compound is formed on a lower layer (substrate layer), and an upper layer that is in direct contact with the detachment primer layer is a film layer that is not a printed layer. As a means for forming such an upper film layer, any known means that can ultimately form a layer that is not a printed layer as an upper layer can be used, such as laminating an upper film layer onto a detachment primer layer containing a titanium-modified polyethyleneimine compound, with or without an adhesive layer therebetween, or applying and drying a paint to form an upper film layer. In this case, the upper layer is composed of one or more layers, and the layer in direct contact with the detachment primer layer containing the titanium-modified polyethyleneimine compound in Fig. 3 is a film layer, not a printed layer. The layer in direct contact with the detachment primer layer may be a layer made of a material listed for the lower layer (substrate layer) above, an optional adhesive layer, an optional primer layer, or the like. The upper film layer may be composed of one or more layers. When the upper film layer is composed of two or more layers, a layer similar to the detachable primer layer in Fig. 3 may be formed between the layers to bond them together.

[0032] The uses of the four types of laminates, the first to fourth types, are not particularly limited. Furthermore, for each laminate, only a detachment primer composition containing the titanium-modified polyethyleneimine compound of the present invention is used as the detachment primer composition. Furthermore, a separate primer layer other than the detachment layer may be included.

[0033] (Components that can be contained in reverse printing ink compositions, front printing ink compositions, and shrink printing ink compositions) (pigment) In printing using the primer composition of the present invention, the pigment contained in the printing ink composition can be one or more of conventionally used inorganic and organic pigments. The content in each printing ink composition is usually about 1 to 50% by mass.

[0034] <<Reverse printing>> For example, the reverse printing ink composition for forming the printing layer of the present invention shown in Figs. 4 and 5 contains a binder resin and various additives in addition to the above pigment. Examples of usable reverse printing ink compositions include (1) gravure printing ink compositions for reverse printing, (2) active energy ray-curable inkjet printing ink compositions for reverse printing, and (3) active energy ray-curable offset printing ink compositions for reverse printing.

[0035] <(1) Gravure printing ink composition for reverse printing> The gravure printing ink composition for reverse printing contains, in addition to the above pigment, a known binder resin and various additives. The binder resin includes a polyurethane resin, preferably a polyurethane resin having an amine value from the viewpoints of the stability, adhesiveness and lamination suitability of the printing ink composition.

[0036] (Printing method using reverse printing ink composition and laminate obtained thereby) Next, a method for obtaining a laminate print using the reverse printing ink composition will be described. Methods for obtaining laminated prints include at least the following printing methods. For example, in the configuration of Fig. 4, the release primer composition of the present invention is applied to a resin film that will serve as a known lower layer (substrate layer) for lamination. Thereafter, an upper layer is formed inline or off-line using one selected from (1) a gravure printing ink composition for reverse printing, (2) an actinic ray-curable inkjet printing ink composition for reverse printing, and (3) an actinic ray-curable offset printing ink composition for reverse printing, and the resulting ink is printed by various printing methods and dried or cured. In the configuration of Figure 6, the release primer composition of the present invention is applied to a resin film that will serve as a known lower layer (substrate layer) for lamination. Thereafter, the upper layer (1) is formed inline or offline using one of the following: (1) a gravure printing ink composition for reverse printing, (2) an active energy ray-curable inkjet printing ink composition for reverse printing, or (3) an active energy ray-curable offset printing ink composition for reverse printing, and then printed by various printing methods, followed by drying or curing. Next, the release primer composition that will form the upper layer of the present invention is applied to any location on the surface side of the reverse printing ink layer (the lower layer side from the surface layer after final lamination) and dried using a dryer. A resin film or the like that will become the upper layer (2) can be laminated by various methods on the side of the upper layer (1) made from the gravure laminate printing ink composition obtained by the above method, or on the side of the upper layer made from the detachment primer composition of the present invention obtained by the above method, to form a sealant layer for the upper layer (2), thereby obtaining a laminated printed product for packaging bags, etc. Examples of this lamination method include an extrusion lamination method in which a molten polymer that will become the upper layer (2) is laminated on the surface of the printed layer of the upper layer (1) and the surface of the detachment primer layer of the upper layer, with or without coating an anchor coating agent, and a dry lamination method in which an adhesive is applied to the surface of the printed product of the upper layer (1) and the surface of the detachment primer layer of the upper layer, and then a film-like polymer that will become the upper layer (2) is laminated thereon. The resin layer or film-like polymer that forms the upper layer (2) formed by extrusion lamination can be made of resin such as unstretched polypropylene or VMCPP (aluminum-deposited unstretched polypropylene).

[0037] The extrusion lamination method involves coating the surface of the upper layer (1) made of a printing ink composition and the surface of the upper layer made of a release primer composition with an anchor coating agent such as a titanium-based, urethane-based, imine-based, or polybutadiene-based agent as needed, and then laminating a molten polymer that will become the upper layer (2) using a known extrusion laminator, with or without coating.The molten resin can also be sandwiched between other materials to form an intermediate layer.In this case, it is not necessary to use a polyethyleneimine-based anchor coating agent. The molten polymer used in the extrusion lamination method to form the upper layer (2) may be any of the conventionally used resins such as low-density polyethylene, ethylene-vinyl acetate copolymer, polypropylene, etc. Among these, the effect of the present invention is enhanced when it is composed of low-density polyethylene, which is prone to generate carbonyl groups due to oxidation during melting.

[0038] The dry lamination method involves applying an adhesive such as a urethane or isocyanate adhesive to the surface of the printed layer (upper layer 1) made from the reverse printing ink composition and the surface of the detachable primer layer (upper layer) made from the detachable primer composition, and then laminating a resin film that will become the upper layer (2) using a known dry laminating machine. In the present invention, in consideration of retort resistance, it is not necessary to use a laminated product for retort applications. Examples of the resin film used in this case include oriented and unoriented polyolefins such as polyethylene and polypropylene, polyester, nylon, cellophane, vinylon, etc. Furthermore, with regard to these resin films, films obtained by processing in advance such as coating or kneading in an anti-fogging 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.

[0039] <<Surface printing>> Examples of surface printing ink compositions that can be used for the laminate having the structure shown in FIG. 3 include (1) a gravure printing ink composition for surface printing, (2) an active energy ray-curable inkjet printing ink composition for surface printing, and (3) an active energy ray-curable offset printing ink composition for surface printing. (1) Gravure printing ink composition for surface printing The gravure printing ink composition for surface printing contains a known pigment, a binder resin and various additives. The binder resin contained in the gravure printing ink composition for surface printing can be selected from the following resins, for example, a combination of cellulose resin and polyamide resin, a combination of cellulose resin and polyurethane resin, a combination of polyurethane resin and the above-mentioned vinyl chloride-vinyl acetate copolymer, a combination of acrylic resin and polyurethane resin, a combination of cellulose resin and acrylic resin, cellulose resin alone, or the above-mentioned vinyl chloride-vinyl acetate copolymer alone.

[0040] <Energy beam curable printing ink composition for surface printing> As the energy beam curable printing ink composition for surface printing, known UV curable inkjet printing ink compositions, energy beam EB (electron beam) curable offset printing ink compositions for surface printing, etc. can be used.

[0041] (Printing method using surface printing ink composition and laminate obtained thereby) Next, a method for obtaining a surface-printed matter using the surface-printing ink composition will be described. A removable primer layer is formed on a surface printing lower layer (substrate layer) using the removable primer composition of the present invention. Then, the surface printing ink composition that will become the upper layer is printed inline or offline using a conventional printing method. The printing, printing speed, drying temperature, and curing conditions can be appropriately selected from known speeds, temperatures, and curing conditions. The lower layer (substrate layer) can be the same as that used for reverse printing.

[0042] <<Printing for shrink packaging>> As the ink composition for shrink packaging that can be used for the laminate having the structure shown in FIG. 3, known ink compositions for shrink packaging can be used.

[0043] (Printing method using shrink printing ink composition and laminate obtained thereby) Next, a method for obtaining a shrink-printed matter using the shrink printing ink composition will be described. A removable primer composition is applied to a shrink-printing lower layer (substrate layer) to form a removable primer layer. Then, shrink printing is performed inline or offline using a conventional printing method with the shrink-printing ink composition that will become the upper layer. The printing speed and drying temperature can be appropriately selected from known speeds and temperatures. The lower layer (substrate layer) can be the same as that used for reverse printing.

[0044] <<Printing on the paper base layer side of laminated paper>> As the printing ink composition for the upper layer used for printing on the paper base layer side of the laminated paper that is the lower layer, which can be used for a laminate having the structure shown in Figure 4, a known aqueous flexographic printing ink composition can be used.

[0045] <Laminate having a lower layer (substrate layer), a detachable primer layer containing a titanium-modified polyethyleneimine compound, and a film layer as an upper layer in direct contact with the detachable primer layer> The film layers used as the lower layer (base layer) and upper layer in FIG. 5 and the like can be the film layers described above. The titanium-modified polyethyleneimine compounds that can be used are those described above. <Method of manufacturing laminate> After forming an adhesive layer on the lower layer (substrate layer) without adhesive or with adhesive applied, the detachable primer composition of the present invention is applied to form a detachable primer layer, and then, after forming an adhesive layer without adhesive or with adhesive applied inline or offline, a film layer can be laminated as an upper layer to obtain a laminate. Furthermore, after forming an adhesive layer on the above film layer (upper layer 1) without adhesive or with adhesive applied, the detachable primer composition of the present invention is applied to form a detachable primer layer, and then, after forming an adhesive layer without adhesive or with adhesive applied inline or offline, a second film layer (upper layer 2) is laminated to obtain a laminate.

[0046] (Desorption method) A laminate having one or more release layers made of the release primer composition of the present invention can be immersed in a release solution to dissolve the release layer, thereby separating the layers of the laminate at the release layer. By separating the layers in this manner, the layers other than the release layer can be separated and recovered in a solid state. For rapid separation, it is preferable to cut the laminate into small pieces. By immersing the laminate in a release liquid, the release layer exposed at the end surface of the laminate comes into contact with the release liquid and dissolves. As the release liquid penetrates into the release layer, the release layer dissolves toward the inside. As a result, the release layer dissolves in the release liquid, and the two layers fixed by the release layer separate from each other and disperse in the release liquid. The release layer made of the release primer composition of the present invention can be prepared by using, as the release liquid in the above-mentioned release method, water at room temperature such as 20° C., hot water at 20 to 90° C., or an alkaline aqueous solution. It is not particularly necessary to contain a surfactant such as a nonionic surfactant or an alcohol-based solvent, but they may be contained. As the desorption liquid in the present invention, hot water at 40 to 80°C is preferably used. [Example]

[0047] 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." The numerical values ​​for the amounts of each material in the tables are also in "parts by mass." The desorption primer composition used in the examples and comparative examples is a mixture of solvents with a mass composition of 8 parts ethanol and 2 parts water. However, the present invention is not limited to this mixture. In the examples in the following table, the value of the coating amount (dry) of each coating solution is the coating amount (g / m) after coating and drying. 2 )

[0048] (Application conditions for the detachment primer composition common to each example and comparative example) 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℃

[0049] For example, when the solid mass % in the release primer is set as shown in Table 1 below and then printed under the above gravure printing conditions, the following coating amount (g / m 2 ) The coating amount per unit area of ​​the detachment primer composition in the following examples and comparative examples is the coating amount of the detachment primer composition after coating and drying (the total solid content of each component contained in the detachment primer composition). This coating amount was adjusted by diluting with water depending on the concentration of each detachment primer composition. For examples and comparative examples in which the coating amount was not listed in Tables 1 and 2 below, the coating amount was determined based on the coating amount in Table 1 below and the concentration of the solid content by mass in the detachment primer.

[0050] <<Removal primer composition>> <Titanium-modified polyethyleneimine compound> <Removable primer layer (sometimes called "Removable layer of the example")> (Removal primer composition containing titanium-modified polyethyleneimine compound (composition corresponding to the examples)) A titanium-modified polyethyleneimine compound-containing detachment primer composition was obtained by mixing 21.1 parts by mass of a titanium-modified polyethyleneimine compound (Orgatix WS-700 (manufactured by Matsumoto Fine Chemical Co., Ltd., solid content 9.5% by mass)) and 88.9 parts by mass of ethanol to a solid content concentration of 2% by mass.

[0051] <Polyethyleneimine> (Layer obtained from a polyethyleneimine-containing release primer composition (composition corresponding to a comparative example)) Polyethyleneimine: Trade name Epomin P-1000 (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, Solid content: 30%

[0052] [Table 1]

[0053] (Printing conditions of the printing ink composition for reverse printing common to each example and comparative example of reverse printing) Coating machine: Gravure printing machine Coating speed: 100 m / min Printing plate: Solid plate of Helio 175 line / inch (130°) Drying temperature: 55 °C (Printing conditions of the printing ink composition for active energy ray-curable inkjet for each example of reverse printing) 0.1 cc of each was transferred using a simple color development machine (RI tester, manufactured by Toyoei Seiko Co., Ltd.), and irradiated with an electron beam at a conveyor speed of 10 m / min using an electron beam curing device (EC90, manufactured by Iwasaki Electric Co., Ltd.) (acceleration voltage 90 kV, irradiation dose 30 kGy) to completely cure and form each printing layer. (Printing conditions of the printing ink composition for active energy ray-curable offset printing for each example of reverse printing) 0.1 cc of each was transferred using a simple color development machine (RI tester, manufactured by Toyoei Seiko Co., Ltd.), and with a UV-LED light lamp manufactured by Foseon Technology Co., Ltd., at a distance of 2 cm between the lamp and the coating surface of the ink, and completely cured with a UV integrated light amount of 180 mJ / cm 2 to form a printing layer.

[0054] <Examples and comparative examples of reverse printing using a titanium-modified polyethyleneimine compound> · Gravure printing ink composition for reverse printing <Production example of polyurethane resin varnish 1> To obtain a printing ink composition that can be used for the laminate shown in FIG. 4, a four-neck flask equipped with a stirrer, a condenser, and a nitrogen gas inlet tube was charged with 200 parts by mass of a polyester diol having a mass average molecular weight of 2,000 obtained from sebacic acid (derived from castor oil) / succinic acid (derived from plant) in a mass ratio of 30 / 70 and 1,3-propanediol (derived from plant), 17.6 parts by mass of isophorone diisocyanate, and 21.0 parts by mass of hydrogenated MDI, and the mixture was reacted at 100 to 105°C for 6 hours while introducing nitrogen gas. The mixture was allowed to cool to near room temperature, and 400 parts by mass of ethyl acetate and 171 parts by mass of isopropyl alcohol were added, followed by the addition of 8.2 parts by mass of isophoronediamine to extend the chain, and then 0.35 parts by mass of monoethanolamine was added to cause a reaction.The reaction was then stopped by the addition of 1.3 parts by mass of isophoronediamine and 0.6 parts by mass of diethylenetriamine, yielding polyurethane resin varnish 1 (solid content 30% by mass, amine value 6.4 mgKOH / g).

[0055] <Production example of polyurethane resin varnish 2> A four-neck flask equipped with a stirrer, a condenser, and a nitrogen gas inlet tube was charged with 100 parts by weight of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 2,000, 100 parts by weight of polypropylene glycol having a mass average molecular weight of 2,000, 17.6 parts by weight of isophorone diisocyanate, and 21.0 parts by weight of hydrogenated MDI. The mixture was allowed to react for 6 hours at 100 to 105 ° C. while introducing nitrogen gas. After cooling to near room temperature, 400 parts by weight of ethyl acetate and 171 parts by weight of isopropyl alcohol were added, and then 8.2 parts by weight of isophorone diamine was added to extend the chain. 0.35 parts by weight of monoethanolamine was added to react, and then 1.3 parts by weight of isophorone diamine and 0.6 parts by weight of diethylenetriamine were added to terminate the reaction. Polyurethane resin varnish 2 (solids content 30% by weight, amine value 6.4 mg KOH / g) was obtained.

[0056] <Production Example of Polyurethane Resin Varnish 3 Obtained by Using a Compound in Which the Amino Group of a Polyamine Compound is Ketiminated with a Ketone Compound> (Method of producing ketimine solution 1) 51 parts of isophoronediamine, 31.2 parts of N-(2-hydroxyethyl)ethylenediamine, and 174 parts of acetone were mixed and stirred at room temperature for 1 hour, to obtain Ketimine Solution 1. (Method of manufacturing polyurethane resin) A four-neck flask equipped with a stirrer, a condenser, and a nitrogen gas inlet tube was charged with 400 parts of 3-methyl-1,5-pentyleneadipate diol having a number average molecular weight of 4,000, 33.3 parts of isophorone diisocyanate, and 0.04 parts of tetrabutyl titanate, and the mixture was reacted at 90 to 100°C for 6 hours while introducing nitrogen gas. Next, 812 parts of propyl acetate and 203 parts of isopropyl alcohol were added, and the mixture was cooled to near room temperature. 32.29 parts of the above ketimine solution 1 was added and stirred for 20 minutes, and then 3 parts of water was added and stirred for 15 minutes to obtain polyurethane resin varnish 3 (solid content 30%) with a mass average molecular weight of 35,000 and an amine value of 6.5 mgKOH / g. <Vinyl chloride / vinyl acetate copolymer> Solvine TA-3, Nissin Chemical Industry Co., Ltd. <Rosin and its derivatives> Polymerized rosin: Acid value 160mgKOH / g

[0057] <Chlorinated polypropylene varnish> 40 parts by mass of chlorinated polypropylene (solid content 50%) with a chlorination degree of 40% and a mass average molecular weight of 100,000 and 60 parts by mass of methylcyclohexane were mixed and stirred to obtain a chlorinated polypropylene varnish with a solid content of 20%. <Silica particles> Average particle size: 4.5μm <Polyethylene wax> Average particle size: 2.11μm <Fatty acid amide> Ethylenebisstearamide

[0058] <Production example of gravure printing ink composition for reverse printing> Ten parts by mass of pigment (CIPB15:4), 30 parts by mass of each of polyurethane resin varnishes 1 to 3, and 3 parts by mass of vinyl chloride-vinyl acetate copolymer (Solvine TA-3) were kneaded using a paint conditioner from Red Devil, and then 2 parts by mass of chlorinated propylene varnish (solid content 20%), 0.5 parts by mass of polymerized rosin, 0.5 parts by mass of silica particles, 0.2 parts by mass of polyethylene wax, 0.2 parts by mass of ethylene bisstearamide, 51 parts by mass of solvent, and 2 parts by mass of water were added to obtain a printing ink composition for reverse printing. UV-curable inkjet printing ink composition for reverse printing BSR06 (Sakata Inx Corporation) was used as the UV-curable inkjet printing ink composition for reverse printing. UV-curable offset printing ink composition for reverse printing A UV-curable printing ink composition was prepared by blending 50.0 parts by mass of rosin-modified maleic acid resin (Halima M-453, Harima Chemicals), 41.0 parts by mass of trimethylolpropane (6EO) triacrylate, 2.0 parts by mass of dimethyl silicone oil (KF-96H-100,000cs), 5.0 parts by mass of 2-methyl-1(4-methylthiophenyl)-2-morpholinopropan-1-one, and 4.4-bis(diethylamino)benzophenone.

[0059] (Printing base material layer) P-2161#25: Biaxially oriented polypropylene film (thickness 25 μm) (Toyobo Co., Ltd.) (Removal primer) Titanium-modified polyethyleneimine (each of the release primer compositions of the examples) Polyethyleneimine (trade name Epomin-1000 (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 (each release primer composition for comparative examples)

[0060] Number average molecular weight: Number average molecular weight (Mn) measured by P-1000 viscosimetry Mass average molecular weight: Mass average molecular weight (Mw) by GPC method Amine value: Measured by acid titration using a non-aqueous system Amine ratio: measured by NMR (13C)

[0061] (Reverse printing, lamination, and test results) <Dry Laminate 1 (Lower layer (base layer) film: normal film)> A detachable primer composition containing each detachable primer composition containing titanium-modified polyethyleneimine was applied to the treated surface of the lower layer, P-2161#25, and dried under the above-mentioned conditions to obtain each detachable primer layer, so as to form the following laminate structure 1. On the surface of each detachable primer layer, each reverse-printing printing ink composition (in the case of each reverse-printing gravure printing ink, each diluted ink composition was further added with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent and diluted to 16 seconds in a Zahn Cup No. 3 manufactured by Rigo Co., Ltd., and then printed using a gravure printing machine) was printed under the above-mentioned conditions and dried or cured to obtain a printed layer (upper layer 1). An adhesive (Takelac A-969V / Takelac A-5, solid content 30% by mass) was applied on top of it, and then VMCPP, which would become the upper layer 2, was adhered using a dry laminating machine to create a laminated printed matter with the laminate structure 1 shown below. The results are shown in Table 2.

[0062] <Dry Laminate 2 (Lower layer (base layer) film: transparent vapor deposition film)> Titanium-modified polyethyleneimine was applied and dried under the above conditions to the treated surface of various transparent vapor-deposited PET or NY films as the lower layer to obtain each detachable primer layer, so as to form the following laminate structure 2. On the surface of each detachable primer layer, each reverse-printing printing ink composition (in the case of each reverse-printing gravure printing ink, each diluted ink composition was further added with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent and diluted to 16 seconds in a Zahn Cup No. 3 manufactured by Rigo Co., Ltd., and then printed using a gravure printing machine) was printed under the above conditions and dried or cured to obtain a printed layer (upper layer 1). An adhesive (Takelac A-515 / Takelac A-50, solid content 30% by mass) was applied on top of it, and then RXC-22#60, which would become the upper layer 2, was adhered using a dry laminating machine to create a laminated printed matter with the laminate structure 2 shown below. The results are shown in Table 3.

[0063] <Extrusion Lamination 1> To obtain the following laminate structure 3, a release primer composition containing titanium-modified polyethyleneimine was applied to the treated surface of the lower layer of various films, PET, NY, or transparent vapor-deposited PET or transparent vapor-deposited NY, using a gravure printing machine under the following conditions, followed by drying, to obtain each release primer layer. On the surface of each of these detachable primer layers, each of the reverse printing ink compositions (in the case of each of the reverse printing gravure printing inks, each diluted ink composition was further diluted with a mixed solvent of normal propyl acetate / isopropyl alcohol = 80 / 20 and diluted to 16 seconds in a Zahn Cup No. 3 manufactured by Rigo Co., Ltd., using a gravure printing machine) was printed or printed under the above conditions, dried or cured to obtain a printed layer (upper layer 1). An AC agent (Takelac A-3210 / Takelac A-3072, solid content 7% by mass) was applied on top of it, and then molten polyethylene, which would become the upper layer, was laminated using an extrusion laminator to create a laminated print with laminate structure 3 shown below. The results are shown in Table 4.

[0064] <Extrusion Lamination 2> A detachable primer composition containing titanium-modified polyethyleneimine was applied to the treated surface of the lower layer OPP film and dried under the above conditions to obtain each detachable primer layer, so as to form the following laminate structure 4. On the surface of each detachable primer layer, each reverse-printing printing ink composition (in the case of each reverse-printing gravure printing ink, each diluted ink composition was further added with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent and diluted to 16 seconds in a Zahn Cup No. 3 manufactured by Rigo Co., Ltd., and then printed using a gravure printing machine) was printed under the above conditions and dried or cured to obtain a printed layer (upper layer 1). An AC agent (Epomin P-1000, solid content 0.7% by mass) was applied on top of it, and then molten polyethylene, which would become the upper layer, was laminated on top of it using an extrusion laminator to create a laminated print with the following laminate structure 4. The results are shown in Table 5.

[0065] In the following examples, the results for laminate structure 1 are shown in Table 2, the results for laminate structure 2 are shown in Table 3, the results for laminate structure 3 are shown in Table 4, and the results for laminate structure 4 are shown in Table 5, respectively.

[0066] Laminate structure 1 : P-2161#25 (lower layer) / each titanium-modified polyethyleneimine / each reverse printing ink composition (upper layer 1) / adhesive (Takelac A-969V / Takelac A-5 solids 30%) / VMCPP (upper layer 2) P-2161#25: Biaxially oriented polypropylene film (thickness 25 μm) (Toyobo Co., Ltd.) Adhesive (Takelac A-969V / Takelac A-5): Two-component adhesive, solid content 30% by mass (Mitsui Chemicals) VMCPP: Aluminum-coated non-oriented polypropylene (Toray)

[0067] Laminate structure 2 : Transparent vapor-deposited PET or transparent vapor-deposited NY (lower layer) / each titanium-modified polyethyleneimine / each reverse printing ink composition (upper layer 1) / adhesive (Takelac A-515 / Takelac A-50, solid content 30% by mass, solid content 30%) / RXC-22#60 (upper layer 2) Vapor-deposited PET: GL-ARH-F (Toppan Printing Co., Ltd.) Transparent vapor deposition NY: GL-ARH-W (Toppan Printing Co., Ltd.) Adhesive (Takelac A-515 / Takelac A-50): Two-component adhesive, solid content 30% by mass (Mitsui Chemicals) RXC-22#60: Unstretched propylene film (Mitsui Chemicals Tocello Co., Ltd.)

[0068] Laminate structure 3 PET or NY or transparent vapor-deposited PET or transparent vapor-deposited NY (lower layer) / each titanium-modified polyethyleneimine / each reverse printing ink composition (upper layer 1) / AC agent (Takelac A-3210 / Takelac A-3072, solid content 7% by mass) / melt-molten polyethylene (upper layer 2) PET: Polyethylene terephthalate film E-5102#12 (Toyobo Co., Ltd.) NY: Nylon film ON-15#12 (Unitika) Vapor-deposited PET: GL-ARH-F (Toppan Printing Co., Ltd.) Transparent vapor deposition NY: GL-ARH-W (Toppan Printing Co., Ltd.) AC agent (Takelac A-3210 / Takelac A-3072): solid content 7% by mass (Mitsui Chemicals) Melting polyethylene: Sumikathene L705, melting temperature 106°C (Sumitomo Chemical Co., Ltd.)

[0069] Laminate structure 4 OPP / each titanium-modified polyethyleneimine (lower layer) / each reverse printing ink composition (upper layer 1) / AC agent (Epomin P-1000, solid content 0.7% by mass) / molten polyethylene (upper layer 2) OPP film: Corona-discharged biaxially oriented polypropylene film P-2161#25 (Toyobo Co., Ltd.) NY: Nylon film ON-15#12 (Toyobo Co., Ltd.) AC agent (Epomin P-1000): Polyethyleneimine, solid content 0.7% by mass (Sannihon Shokubai Co., Ltd.) Melting polyethylene: Sumikathene L705, melting temperature 106°C (Sumitomo Chemical Co., Ltd.)

[0070] <<Evaluation Results>> <Evaluation of film detachment> After printing, 1.5 g of each of the above printed materials (laminates) was thoroughly dried and then shredded into small pieces of approximately 15 mm MD×25 mm TD to obtain samples for film detachment tests.

[0071] <Film removal test (hot water)> (detachment) Desorption (hot water) conditions: 100 g of desorption solution consisting of water was placed in a 200 cc HDPE (high density polyethylene) container, and heated to 70°C using a water bath. (Mixed with hot water as the supernatant) Each of the film detachment 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 detachment liquid and the various film pieces were separated using a stainless steel mesh with openings of approximately 2 mm.

[0072] (rinse) After the removal, each film was transferred to a 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 peelability of the upper ink layer from the lower ink layer was visually evaluated.

[0073] <Film removal test (alkaline aqueous solution)> (detachment) Desorption (hot water) conditions: 2.0 parts by mass of sodium hydroxide was added to 98.0 parts by mass of water in a 200 cc HDPE (high density polyethylene) container, and the mixture was stirred and dissolved to obtain a desorption liquid consisting of an alkaline aqueous solution. The alkaline aqueous solution was heated to 70°C using a hot water bath. (Mixed with a release solution consisting of an alkaline aqueous solution) After the release solution, consisting of the alkaline aqueous solution, was heated to 70°C, each of the film release test samples was separately placed into the 70°C 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 the various film pieces were separated using a stainless steel mesh with openings of approximately 2 mm.

[0074] (rinse) After the film was removed, it was transferred to a 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 it to stand for 5 minutes, the film pieces were separated from the water using a stainless steel mesh. After drying the various film pieces, the peelability of the upper ink layer from the lower layer (base layer) was visually evaluated.

[0075] (Evaluation criteria) ○: The upper layer was completely peeled off from the lower layer (base layer). ×: Not peeled

[0076] <Moisture resistance test of laminate layer> ◯: The peel strength of the laminate layer does not decrease even when the laminate sample is left standing in an environment of 40°C and 90% RH for one month. △: The peel strength of the laminate layer does not decrease even when the laminate sample is left standing in an environment of 40°C and 70% RH for one month. ×: When a laminate sample is left standing in an environment of 40°C and 70% RH for one month, the peel strength decreases.

[0077] <Evaluation of adhesion to the lower layer (base layer)> Tape adhesive strength (for each printed item 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.

[0078] <Blocking resistance> Using the gravure printing machine described above, each release primer composition was applied to the treated surface of the lower layer (various films) in a predetermined coating amount and dried under the above conditions. On the surface of each release primer layer, each reverse printing ink composition (in the case of each reverse printing gravure printing ink, each diluted ink composition was further diluted with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent and diluted to 16 seconds in a Zahn Cup No. 3 manufactured by Rigo Co., Ltd., using a gravure printing machine) was printed or printed under the above conditions, dried or cured to obtain each printed layer (upper layer 1). Next, the printed surface of each printed layer (upper layer 1) and the untreated surface of each film were combined, and 400 g / cm 2 After leaving the film at 40°C for 12 hours under a load of 1.0 g, the blocking resistance was evaluated based on the state of each film when peeled off. (Evaluation criteria) ○: Peels off without resistance, and there is absolutely no transfer of the printed layer (upper layer 1) or the removable primer layer △: There is resistance, but the printed layer (upper layer 1) and the removable primer layer do not transfer at all ×: Migration of the printed layer (upper layer 1) or the removal primer was observed

[0079] The following evaluations were the same regardless of whether the reverse gravure printing ink composition, the actinic energy ray-curable inkjet printing ink composition, or the actinic energy ray-curable offset printing ink composition was used with the three types of polyurethane resin varnish. The results are shown below. The reverse-printing ink compositions listed in Tables 2 to 15 are the reverse-printing gravure printing ink composition, the reverse-printing actinic energy ray-curable inkjet printing ink composition, and the actinic energy ray-curable offset printing ink composition. The results for these three ink compositions are the same and are shown in Tables 2 to 5 below.

[0080] [Table 2]

[0081] [Table 3]

[0082] [Table 4]

[0083] [Table 5]

[0084] <Comparative Example Dry Laminate 1 (Base Film: Regular Film)> (Comparative example with removable primer layer) To obtain the laminate structure 1 of the comparative example described below, each comparative release primer composition (a release primer composition containing a polyethyleneimine composition) diluted to a predetermined coating amount was applied to the treated surface of each film (lower layer) under the above-mentioned conditions and dried. On the surface of this release primer layer, each reverse printing ink composition (in the case of each reverse printing gravure printing ink, each diluted ink composition was further added with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent and diluted to 16 seconds in a Rigo Zahn Cup No. 3, and the diluted ink composition was printed using a gravure printing machine) was printed or printed under the above-mentioned conditions, and dried or cured to obtain a printed layer (upper layer 1). An adhesive (Takelac A-969V / Takelac A-5, solids content 3%) was applied thereon, and VMCPP, which would become upper layer 2, was further adhered using a dry laminator to prepare a laminate print of the comparative example laminate structure 1 described below. The results are shown in Table 6.

[0085] (When there is no removable primer layer) To obtain the laminate structure 1 of the comparative example below, the treated surface of each film (lower layer) was printed or printed with each reverse printing ink composition (in the case of each reverse printing gravure printing ink, the diluted ink composition was further diluted with an 80 / 20 mixture of normal propyl acetate and isopropyl alcohol to a 16-second print time using a Rigo Zahn Cup No. 3, and the diluted ink composition was printed using a gravure printing press) under the above conditions, followed by drying or curing to obtain a printed layer (upper layer 1). An adhesive (Takelac A-969V / Takelac A-5, 30% solids) was applied thereon, and VMCPP, which would become upper layer 2, was then adhered using a dry laminator to produce a laminate print without a removable primer layer of the laminate structure 1 of the comparative example below. The results are shown in Table 6.

[0086] <Comparative Example Dry Laminate 2 (Base Layer Film: Transparent Vapor Deposited Film)> (Comparative example with removable primer layer) A comparative example of a detachment primer composition (a detachment primer composition containing a polyethyleneimine composition) diluted to a predetermined coating amount was applied to the treated surface of various transparent vapor-deposited PET or transparent vapor-deposited NY films (lower layer) and dried under the above-mentioned conditions to form the following laminate structure 2. Each reverse-printing printing ink composition (in the case of each reverse-printing gravure printing ink, each diluted ink composition was further diluted with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent to a 16-second viscosity using a Zahn Cup No. 3 manufactured by Rigo Co., Ltd., and printed using a gravure printing machine) was printed or printed under the above-mentioned conditions, followed by drying or curing, to obtain a printed layer (upper layer 1). An adhesive (Takelac A-515 / Takelac A-50, solid content 30% by mass) was applied on top of it, and then RXC-22#60, which would become the upper layer 2, was adhered using a dry laminating machine to create a laminated printed matter with laminate structure 2 of the comparative example below. The results are shown in Table 7.

[0087] (Comparative example without removable primer layer) To obtain the laminate structure 2 below, each reverse printing ink composition (in the case of each reverse printing gravure printing ink, each diluted ink composition was further diluted with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent and diluted to 16 seconds in a Zahn Cup No. 3 manufactured by Rigo Co., Ltd. using a gravure printing machine) was printed or printed on the treated surface of various transparent vapor-deposited PET or transparent vapor-deposited NY films (lower layer) under the above conditions, and dried or cured to obtain a printed layer (upper layer 1). An adhesive (Takelac A-515 / Takelac A-50, solid content 30% by mass) was applied on top of the laminate, and then RXC-22#60, which would become the upper layer 2, was adhered using a dry laminating machine to create a laminate printout without a removable primer layer, as in the laminate structure 2 of the comparative example below. The results are shown in Table 7.

[0088] <Extrusion Laminate 1 of Comparative Example> (Comparative example with removable primer layer) A comparative example of a detachment primer composition (a detachment primer composition containing a polyethyleneimine composition) diluted to a predetermined coating amount was applied and dried under the above-mentioned conditions to the treated surface of various films (lower layer) of PET, NY, or transparent vapor-deposited PET or transparent vapor-deposited NY, so as to form the following laminate structure 3. Furthermore, each reverse-printing printing ink composition (in the case of each reverse-printing gravure printing ink, each diluted ink composition was further added with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent and diluted to 16 seconds in a Zahn Cup No. 3 manufactured by Rigo Co., Ltd., using a gravure printing machine) was printed or printed under the above-mentioned conditions, and dried or cured to obtain a printed layer (upper layer 1). An AC agent (Takelac A-3210 / Takelac A-3072, solid content 7% by mass) was applied on top of the laminate, and then molten polyethylene, which would become the upper layer 2, was laminated on top of it using an extrusion laminator to create a laminated printed matter with laminate structure 3 of the comparative example below. The results are shown in Table 8.

[0089] (Comparative example without removable primer layer) To obtain the laminate structure 3 below, each reverse printing ink composition (in the case of each reverse printing gravure printing ink, each diluted ink composition was further diluted with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent and diluted to 16 seconds in a Zahn Cup No. 3 manufactured by Rigo Co., Ltd. using a gravure printing machine) was printed or printed under the above conditions, dried or cured to obtain a printed layer (upper layer 1) on the treated surface of various films (lower layer) of PET, NY, or transparent vapor-deposited PET or transparent vapor-deposited NY. An AC agent (Takelac A-3210 / Takelac A-3072, solid content 7% by mass) was applied on top of the laminate, and then molten polyethylene, which would become the upper layer 2, was laminated using an extrusion laminator to create a laminate print that does not have a removable primer layer, similar to the laminate structure 3 of the comparative example below. The results are shown in Table 8.

[0090] <Extrusion Laminate 2 of Comparative Example> (Comparative example with removable primer layer) A comparative example of a detachment primer composition (a detachment primer composition containing a polyethyleneimine composition) diluted to a predetermined coating amount was applied and dried under the above-mentioned conditions to the treated surface of an OPP film (lower layer) to form the following laminate structure 4. Onto the surface of each detachment primer composition, each reverse-printing printing ink composition (in the case of each reverse-printing gravure printing ink, each diluted ink composition was further added with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent and diluted to 16 seconds in a Zahn Cup No. 3 manufactured by Rigo Co., Ltd., using a gravure printing machine) was printed or printed under the above-mentioned conditions, and dried or cured to obtain a printed layer (upper layer 1). An AC agent (Takelac A-3210 / Takelac A-3072, solid content 7% by mass) was applied on top of the laminate, and then molten polyethylene, which would become the upper layer 2, was laminated on top of it using an extrusion laminator to create a laminated printed matter with laminate structure 4 of the comparative example below. The results are shown in Table 9.

[0091] (Comparative example without removable primer layer) Each reverse printing ink composition (in the case of each reverse printing gravure printing ink, each diluted ink composition was further diluted with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent and diluted to 16 seconds in a Zahn Cup No. 3 manufactured by Rigo Co., Ltd., using a gravure printing machine) was printed or printed under the above conditions, dried or cured, and (upper layer 1) was obtained, so as to obtain laminate structure 4 below. An AC agent (Takelac A-3210 / Takelac A-3072, solid content 7% by mass) was applied on top of the laminate, and then molten polyethylene, which would become the upper layer 2, was laminated using an extrusion laminator to create a laminate print that does not have a removable primer layer, similar to the laminate structure 4 of the comparative example below. The results are shown in Table 9.

[0092] Comparative example laminate structure 1: (Comparative example with removable primer layer) P-2161#25 (lower layer) / each comparative release primer composition (release primer composition containing a polyethyleneimine composition) / each reverse printing ink composition (upper layer 1) / adhesive (Takelac A-969V / Takelac A-5 solids content 30%) / VMCPP (upper layer 2) (Comparative example: Laminate structure 1 without detachable primer layer) P-2161#25 (bottom layer) / each reverse printing ink composition (top layer 1) / adhesive (Takelac A-969V / Takelac A-5 solids 30%) / VMCPP (top layer 2) P-2161#25: Biaxially oriented polypropylene film (thickness 25 μm) (Toyobo Co., Ltd.) Adhesive (Takelac A-969V / Takelac A-5): Aromatic ether-based two-component adhesive, solid content 30% by mass (Mitsui Chemicals) VMCPP: Aluminum-coated non-oriented polypropylene (Toray)

[0093] Comparative example laminate structure 2: (Comparative example with removable primer layer) Transparent vapor-deposited PET or transparent vapor-deposited NY (lower layer) / each comparative release primer composition (release primer composition containing a polyethyleneimine composition) / each reverse-printing printing ink composition (upper layer 1) / adhesive (Takelac A-515 / Takelac A-50, solids content 30% by mass, solids content 30%) / RXC-22#60 (upper layer 2) (Comparative example: Laminate structure 2 without detachable primer layer) Transparent vapor-deposited PET or transparent vapor-deposited NY (bottom layer) / each reverse printing ink composition (top layer 1) / adhesive (Takelac A-515 / Takelac A-50, solid content 30% by mass, solid content 30%) / RXC-22#60 (top layer 2) Vapor-deposited PET: GL-ARH-F (Toppan Printing Co., Ltd.) Transparent vapor deposition NY: GL-ARH-W (Toppan Printing Co., Ltd.) Adhesive (Takelac A-515 / Takelac A-50): Two-component adhesive, solid content 30% by mass (Mitsui Chemicals) RXC-22#60: Unstretched propylene film (Mitsui Chemicals Tocello Co., Ltd.)

[0094] Comparative example laminate structure 3: (Comparative example with removable primer layer) PET or NY or transparent vapor-deposited PET or transparent vapor-deposited NY (lower layer) / release primer composition containing a polyethyleneimine composition / each reverse printing ink composition (upper layer 1) / AC agent (Takelac A-3210 / Takelac A-3072, solids content 7% by mass) / molten polyethylene (upper layer 2) (Comparative example: Laminate structure 3 without removable primer layer) PET or NY or transparent vapor-deposited PET or transparent vapor-deposited NY (lower layer) / each reverse printing ink composition (upper layer 1) / AC agent (Takelac A-3210 / Takelac A-3072, solid content 7% by mass) / melt polyethylene (upper layer 2) PET: Polyethylene terephthalate film E-5102#12 (Toyobo Co., Ltd.) NY: Nylon film ON-15#12 (Unitika) Vapor-deposited PET: GL-ARH-F (Toppan Printing Co., Ltd.) Transparent vapor deposition NY: GL-ARH-W (Toppan Printing Co., Ltd.) AC agent (Takelac A-3210 / Takelac A-3072): solid content 7% by mass (Mitsui Chemicals) Melting polyethylene: Sumikathene L705, melting temperature 106°C (Sumitomo Chemical Co., Ltd.)

[0095] Comparative example laminate structure 4: (Comparative example with removable primer layer) OPP (lower layer) / comparative detachment primer composition (detachment primer composition containing a polyethyleneimine composition) / each reverse printing ink composition (upper layer 1) / AC agent (Epomin P-1000, solids content 0.7% by mass) / molten polyethylene (upper layer 2) (Comparative example: Laminate structure 4 without detachable primer layer) OPP (lower layer) / each reverse printing ink composition (upper layer 1) / AC agent (Epomin P-1000, solid content 0.7% by mass) / melt polyethylene (upper layer 2) OPP film: Corona-discharged biaxially oriented polypropylene film P-2161#25 (Toyobo Co., Ltd.) AC agent (Epomin P-1000): Polyethyleneimine, solid content 0.7% by mass (Sannihon Shokubai Co., Ltd.) Molten polyethylene: Sumikasen L705, resin temperature 355°C (Sumitomo Chemical Co., Ltd.)

[0096] <<Evaluation Results>> The evaluation results were obtained using the same evaluation methods as those for the laminate structures 1 to 5 above.

[0097] [Table 6]

[0098] [Table 7]

[0099] [Table 8]

[0100] [Table 9]

[0101] When the detachment primer composition of the present invention was applied, it was possible to smoothly detach it with both water and an alkaline aqueous solution, and the moisture resistance, adhesion, and blocking resistance immediately after printing were also excellent. However, in the comparative examples, when polyethyleneimine was applied, moisture resistance was poor, and when the detachment primer composition was not applied, both moisture resistance and detachment properties in hot water could not be achieved.

[0102] An example of the configuration of Figure 5 will be described, in which a release primer layer formed from the titanium-modified polyethyleneimine composition of the present invention is provided on the printed layer of the upper layer 1 and the film layer of the upper layer 2 in the configuration of Figure 4. The constituent materials are the same as those explained in the configuration of the above embodiment shown in FIG. 4, and therefore will not be described here. (Reverse printing, lamination, and test results) <Dry Laminate 3 (Base film (lower layer): Regular film)> Each release primer composition containing titanium-modified polyethyleneimine was applied to the treated surface of P-2161#25 (lower layer) under the above-mentioned conditions and dried to obtain each release primer layer, so as to form the following laminate structure 5. Each reverse-printing printing ink composition (in the case of each reverse-printing gravure printing ink, the diluted ink composition was further diluted with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent to a 16-second print time using a Rigo Zahn Cup No. 3, using a gravure printing machine) was printed and dried under the above-mentioned conditions to obtain a printed layer (upper layer 1). Next, each release primer composition containing titanium-modified polyethyleneimine was applied to the surface of the printed layer under the above-mentioned conditions and dried to obtain each release primer layer. An adhesive (Takelac A-969V / Takelac A-5, solid content 30% by mass) was applied to each of the removable primer layers, and VMCPP (upper layer 2) was then adhered using a dry laminating machine to create a laminated print with the following laminate structure 5. The results are shown in Table 10.

[0103] <Dry Laminate 4 (Base film (lower layer): transparent vapor deposition film)> Titanium-modified polyethyleneimine was applied to the treated surface of various transparent vapor-deposited PET or transparent vapor-deposited NY films (lower layer) under the above-mentioned conditions and dried to obtain each detachable primer layer, so as to obtain the following laminate structure 6. Each reverse-printing printing ink composition (in the case of each reverse-printing gravure printing ink, the diluted ink composition was further diluted with an 80 / 20 mixed solvent of normal propyl acetate and isopropyl alcohol to a 16-second print time using a Rigo Zahn Cup No. 3, using a gravure printing machine) was printed and dried under the above-mentioned conditions to obtain a printed layer (upper layer 1). Next, each titanium-modified polyethyleneimine-containing detachable primer composition was applied to the surface of the printed layer under the above-mentioned conditions and dried to obtain each detachable primer layer. An adhesive (Takelac A-515 / Takelac A-50, solid content 30% by mass) was applied to each of the removable primer layers, and then RXC-22#60 (upper layer 2) was adhered using a dry laminating machine to create a laminated printed material with the following laminate structure 6. The results are shown in Table 11.

[0104] <Extrusion Lamination 3> To obtain the following laminate structure 7, a detachable primer composition containing titanium-modified polyethyleneimine was applied to the treated surface of various films (lower layer) made of PET, NY, or transparent vapor-deposited PET or transparent vapor-deposited NY, and dried using a gravure printing machine under the conditions described below to obtain each detachable primer layer. On the surface of each detachable primer layer, each reverse-printing printing ink composition (in the case of each reverse-printing gravure printing ink, each diluted ink composition was further added with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent and diluted to 16 seconds using a Zahn Cup No. 3 manufactured by Rigo Co., Ltd., and printed using a gravure printing machine) was printed or printed under the conditions described above, and dried or cured to obtain a printed layer (upper layer 1). Next, each detachable primer composition containing titanium-modified polyethyleneimine was applied to the surface of the printed layer and dried under the conditions described above to obtain each detachable primer layer. An AC agent (Takelac A-3210 / Takelac A-3072, solid content 7% by mass) was applied to each of the release primer layers, and then molten polyethylene (upper layer 2) was laminated using an extrusion laminator to create a laminate print with the following laminate structure 7. The results are shown in Table 12.

[0105] <Extrusion Lamination 4> A detachable primer composition containing titanium-modified polyethyleneimine was applied to the treated surface of the OPP film (lower layer) under the above-mentioned conditions and dried to obtain each detachable primer layer, so as to obtain the following laminate structure 8. On the surface of each detachable primer layer, each reverse-printing printing ink composition (in the case of each reverse-printing gravure printing ink, each diluted ink composition was further added with a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent and diluted to 16 seconds in a Zahn Cup No. 3 manufactured by Rigo Co., Ltd., using a gravure printing machine) was printed or printed under the above-mentioned conditions, and dried or cured to obtain a printed layer (upper layer 1). Next, each detachable primer composition containing titanium-modified polyethyleneimine was applied to the surface of the printed layer under the above-mentioned conditions and dried to obtain each detachable primer layer. An AC agent (Epomin P-1000, solid content 0.7% by mass) was applied onto each of the release primer layers, and then molten polyethylene (upper layer 2) was laminated using an extrusion laminator to create a laminate print with the following laminate structure 8. The results are shown in Table 13.

[0106] Laminate structure 5 : P-2161#25 (lower layer) / each titanium-modified polyethyleneimine / each reverse printing ink composition (upper layer 1) / each titanium-modified polyethyleneimine / adhesive (Takelac A-969V / Takelac A-5 solids 30%) / VMCPP (upper layer 2) P-2161#25: Biaxially oriented polypropylene film (thickness 25 μm) (Toyobo Co., Ltd.) Adhesive (Takelac A-969V / Takelac A-5): Two-component adhesive, solid content 30% by mass (Mitsui Chemicals) VMCPP: Aluminum-coated non-oriented polypropylene (Toray)

[0107] Laminate structure 6 : Transparent vapor-deposited PET or transparent vapor-deposited NY (lower layer) / each titanium-modified polyethyleneimine / each reverse printing ink composition (upper layer 1) / each titanium-modified polyethyleneimine / adhesive (Takelac A-515 / Takelac A-50, solids 30% by mass, solids 30%) / RXC-22#60 (upper layer 2) Vapor-deposited PET: GL-ARH-F (Toppan Printing Co., Ltd.) Transparent vapor deposition NY: GL-ARH-W (Toppan Printing Co., Ltd.) Adhesive (Takelac A-515 / Takelac A-50): Two-component adhesive, solid content 30% by mass (Mitsui Chemicals) RXC-22#60: Unstretched propylene film (Mitsui Chemicals Tocello Co., Ltd.)

[0108] Laminate structure 7 PET or NY or transparent vapor-deposited PET or transparent vapor-deposited NY (lower layer) / each titanium-modified polyethyleneimine / each reverse printing ink composition (upper layer 1) / each titanium-modified polyethyleneimine / AC agent (Takelac A-3210 / Takelac A-3072, solid content 7% by mass) / melt-molten polyethylene (upper layer 2) PET: Polyethylene terephthalate film E-5102#12 (Toyobo Co., Ltd.) NY: Nylon film ON-15#12 (Unitika) Vapor-deposited PET: GL-ARH-F (Toppan Printing Co., Ltd.) Transparent vapor deposition NY: GL-ARH-W (Toppan Printing Co., Ltd.) AC agent (Takelac A-3210 / Takelac A-3072): solid content 7% by mass (Mitsui Chemicals) Melting polyethylene: Sumikathene L705, melting temperature 106°C (Sumitomo Chemical Co., Ltd.)

[0109] Laminate structure 8 OPP (lower layer) / each titanium-modified polyethyleneimine / each reverse printing ink composition (upper layer 1) / each titanium-modified polyethyleneimine / AC agent (Epomin P-1000, solid content 0.7% by mass) / molten polyethylene (upper layer 2) OPP film: Corona-treated biaxially oriented polypropylene film P-2161#25 (Toyobo Co., Ltd.) NY: Nylon film ON-15#12 (Toyobo Co., Ltd.) AC agent (Epomin P-1000): Polyethyleneimine, solid content 0.7% by mass (Sannihon Shokubai Co., Ltd.) Melting polyethylene: Sumikathene L705, melting temperature 106°C (Sumitomo Chemical Co., Ltd.)

[0110] <<Evaluation Results>> The film releasability was measured by the following method. Other evaluation results were obtained using the same evaluation methods as those for the laminate structures 1 to 5 above. <Evaluation of film detachment> After printing, 1.5 g of each of the above printed materials (laminates) was thoroughly dried and then shredded into small pieces of approximately 15 mm MD×25 mm TD to obtain samples for film detachment tests.

[0111] <Film removal test (hot water)> (detachment) Desorption (hot water) conditions: 100 g of desorption solution consisting of water was placed in a 200 cc HDPE (high density polyethylene) container, and heated to 70°C using a water bath. (Mixed with hot water as the supernatant) Each of the film detachment 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 detachment liquid and the various film pieces were separated using a stainless steel mesh with openings of approximately 2 mm.

[0112] (rinse) After removal, the various films were transferred to a 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 various film pieces, the peelability between the lower layer (base layer) and upper layer 1 (printed layer), and between upper layer 1 (printed layer) and upper layer 2 (sealant layer) was visually evaluated.

[0113] <Film removal test (alkaline aqueous solution)> (detachment) Desorption (hot water) conditions: 2.0 parts by mass of sodium hydroxide was added to 98.0 parts by mass of water in a 200 cc HDPE (high density polyethylene) container, and the mixture was stirred and dissolved to obtain a desorption liquid consisting of an alkaline aqueous solution. The alkaline aqueous solution was heated to 70°C using a hot water bath. (Mixed with a release solution consisting of an alkaline aqueous solution) After the release solution, consisting of the alkaline aqueous solution, was heated to 70°C, each of the film release test samples was separately placed into the 70°C 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 the various film pieces were separated using a stainless steel mesh with openings of approximately 2 mm.

[0114] (rinse) After the detachment, the film was transferred to a 200 cc HDPE container and 100 g of water was added. The mixture was stirred for 5 minutes using a 25 mm diameter stainless steel stirring blade. 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 various film pieces, the peelability between the lower layer (lower layer) and upper layer 1 (printed layer), and between upper layer 1 (printed layer) and upper layer 2 (sealant layer) was visually evaluated.

[0115] (Evaluation criteria) ◯: Upper layer 1 (printed layer) completely peeled off from lower layer (base layer), upper layer 1 (printed layer) completely peeled off from upper layer 2 (sealant layer). ×: Not peeled

[0116] [Table 10]

[0117] [Table 11]

[0118] [Table 12]

[0119] [Table 13]

[0120] When the detachment primer composition of the present invention was applied, it was possible to smoothly detach it with both water and an alkaline aqueous solution, and the moisture resistance, adhesion, and blocking resistance immediately after printing were also excellent.

[0121] <<Laminate formed of substrate layer (lower layer) / detachable primer layer / film layer 2 (upper layer 1) / detachable primer layer / film layer 3 (upper layer 2)>>

[0122] <Laminate structure of the example> Each titanium-modified polyethyleneimine composition of the present invention was applied to a PET film substrate layer (lower layer) and dried under the conditions described above to obtain a detachable primer layer. An adhesive (Takelac A-515 / Takelac A-50, solids content 30% by mass (Mitsui Chemicals Inc.)) was applied to each detachable primer layer, followed by dry lamination with film 1 (nylon film, upper layer 1) using a dry laminator. Each titanium-modified polyethyleneimine composition of the present invention was then applied and dried under the conditions described above to obtain a detachable primer layer. An adhesive (Takelac A-515 / Takelac A-50, solid content 30% by mass (Mitsui Chemicals)) was applied onto each of these detachable primer layers, and then film 2 (unstretched propylene film, upper layer 2) was dry laminated using a dry laminator to obtain the laminate of the example. The results are shown in Table 14.

[0123] <Laminate structure of comparative example> The comparative example of a detachable primer composition (a detachable primer composition containing a polyethyleneimine composition) was applied to a PET film (upper layer 1) as a base layer under the above-mentioned conditions and dried to obtain a detachable primer layer. An adhesive (Takelac A-515 / Takelac A-50, solids content 30 mass% (Mitsui Chemicals, Inc.)) was applied to the detachable primer layer, and then film 1 (nylon film, upper layer 1) was dry laminated using a dry laminator. Furthermore, the comparative example of a detachable primer composition (a detachable primer composition containing a polyethyleneimine composition) was applied to the surface of film 1 (nylon film) under the above-mentioned conditions and dried to obtain a detachable primer layer. An adhesive (Takelac A-515 / Takelac A-50, solid content 30% by mass (Mitsui Chemicals)) was applied onto each of these detachable primer layers, and then film 2 (unstretched propylene film, upper layer 2) was dry laminated using a dry laminator to obtain the laminate of the example. The results are shown in Table 15.

[0124] Base layer (lower layer): PET film (polyethylene terephthalate film, E5102 (Toyobo Co., Ltd.)) Film 1 (top layer 1): Nylon film (NY Film ON-15#12 (Toyobo Co., Ltd.)) Film 2 (upper layer 2): Sealant film (L-LDPE: unstretched linear low-density polyethylene film) TUX-HC, manufactured by RM Tocello Co., Ltd. Adhesive: Takelac A-515 / Takelac A-50, solid content 30% by mass (Mitsui Chemicals) Film 2: RXC-22#60: Unstretched propylene film (Mitsui Chemicals Tocello Co., Ltd.)

[0125] <<Evaluation Results>> The evaluation was carried out by the following method. <Evaluation of film detachment> After printing, 1.5 g of each of the above printed materials (laminates) was thoroughly dried and then shredded into small pieces of approximately 15 mm MD×25 mm TD to obtain samples for film detachment tests.

[0126] <Film removal test (hot water)> (detachment) Desorption (hot water) conditions: 100 g of desorption solution consisting of water was placed in a 200 cc HDPE (high density polyethylene) container, and heated to 70°C using a water bath. (Mixed with hot water as the supernatant) Each of the film detachment 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 detachment liquid and the various film pieces were separated using a stainless steel mesh with openings of approximately 2 mm.

[0127] (rinse) After the detachment, the various films were transferred to a 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 various film pieces, the peelability between the lower layer (substrate layer) and upper layer 1 (Film 1), and between upper layer 1 (Film 1) and upper layer 2 (Film 2) was visually evaluated.

[0128] <Film removal test (alkaline aqueous solution)> (detachment) Desorption (hot water) conditions: 2.0 parts by mass of sodium hydroxide was added to 98.0 parts by mass of water in a 200 cc HDPE (high density polyethylene) container, and the mixture was stirred and dissolved to obtain a desorption liquid consisting of an alkaline aqueous solution. The alkaline aqueous solution was heated to 70°C using a hot water bath. (Mixed with a release solution consisting of an alkaline aqueous solution) After the release solution, consisting of the alkaline aqueous solution, was heated to 70°C, each of the film release test samples was separately placed into the 70°C 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 the various film pieces were separated using a stainless steel mesh with openings of approximately 2 mm.

[0129] (rinse) After the detachment, the film was transferred to a 200 cc HDPE container and 100 g of water was added. The mixture was stirred for 5 minutes using a 25 mm diameter stainless steel stirring blade. 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 various film pieces, the peelability between the lower layer (lower layer) and upper layer 1 (film 1), and between upper layer 1 (film 1) and upper layer 2 (film 2) was visually evaluated.

[0130] (Evaluation criteria) ◯: Upper layer 1 (film 1) completely peeled off from lower layer (base layer), upper layer 1 (film 1) completely peeled off from upper layer 2 (film 2). ×: Not peeled

[0131] <Moisture resistance test of laminate layer> ◯: The peel strength of the laminate layer does not decrease even when the laminate sample is left standing in an environment of 40°C and 90% RH for one month. △: The peel strength of the laminate layer does not decrease even when the laminate sample is left standing in an environment of 40°C and 70% RH for one month. ×: When a laminate sample is left standing in an environment of 40°C and 70% RH for one month, the peel strength decreases.

[0132] [Table 14]

[0133] [Table 15]

[0134] When the detachment primer composition of the present invention was applied, it was possible to smoothly detach the adhesive with both water and an alkaline aqueous solution, and the adhesiveness and moisture resistance were also excellent. However, when the comparative example detachment primer composition was not applied, both moisture resistance and releasability in hot water could not be achieved, and when polyethyleneimine was applied, moisture resistance was poor.

[0135] <<Example of surface printing>> <Printing ink composition for surface printing> (Polyurethane resin varnish) A four-neck flask equipped with a stirrer, a condenser, and a nitrogen gas inlet tube was charged with 100 parts by weight of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 2,000, 100 parts by weight of polypropylene glycol having a mass average molecular weight of 2,000, 17.6 parts by weight of isophorone diisocyanate, and 21.0 parts by weight of hydrogenated MDI, and the mixture was reacted for 6 hours at 100 to 105 ° C. while introducing nitrogen gas. After cooling to near room temperature, 523.3 parts by weight of ethyl acetate and 223.8 parts by weight of isopropyl alcohol were added, and then 8.2 parts by weight of isophorone diamine was added to extend the chain, and 0.35 parts by weight of monoethanolamine was added to react, and then 1.3 parts by weight of isophorone diamine and 0.6 parts by weight of diethylene triamine were added to terminate the reaction, and a urethane resin (polyurethane resin varnish (solids content 25% by weight)) was obtained.

[0136] (CAB) Cellulose acetate butyrate (Eastman Chemical Company, number average molecular weight 70,000, butyryl content 35-39%)

[0137] (nitrocellulose) 35 parts by mass of nitrocellulose (hydrated with 30% by weight of water) (NOBEL NC CO., Ltd. DLX5-8) was dissolved in a mixed solvent consisting of 58 parts of ethyl acetate and 7 parts of isopropyl alcohol to obtain a nitrocellulose solution with a solid content of 35% by mass.

[0138] (Polyamide resin) Thermoplastic polyamide resin (Mw 8,000, acid value 2, softening point 110°C) made from tall oil fatty acid as a reaction raw material (Polyvinyl chloride) Solvine TA5R (Nissin Chemical Industry Co., Ltd.) (acrylic resin) Hiros-X RL-4032 (solid content 40% by mass) (Seiko PMC Co., Ltd.) (polyethylene wax) PA-60 (solid content 25% by mass) (Polycon Corporation) (Titanium oxide) Typec PFR209 (Ishihara Sangyosha)

[0139] <Preparation of printing ink composition> According to the mass proportions (mass%) in Table 16 below, each material was kneaded with a paint conditioner to prepare a printing ink composition. The obtained printing ink composition was then subjected to gravure printing under the following conditions to obtain a printed matter. Similarly, printing was carried out using a UV-curable inkjet printing ink composition for surface printing, an EB (electron beam)-curable offset printing ink composition for surface printing, and a UV (ultraviolet)-curable offset printing ink composition under the following conditions to obtain a printed matter. The results for the surface printing ink compositions in Table 16 are shown in Table 17.

[0140] <Creating printed materials> -When there is a removable primer layer A detachable primer composition (titanium-modified polyethyleneimine) of an Example or a detachable primer composition (containing a polyethyleneimine composition) of a Comparative Example, diluted to a prescribed coating weight, was applied to a corona-discharge-treated stretched polypropylene film (product name OPP P-2161, 25 μm, manufactured by Toyobo Co., Ltd.) (lower layer) and dried under the conditions described above to obtain a detachable primer layer. A surface-printing ink composition (in the case of a surface-printing gravure printing ink composition, each diluted surface-printing gravure printing ink composition diluted to 16 seconds in a Rigo Zahn Cup No. 3 was used with a gravure printing machine) (upper layer) was printed or printed on the surface of each detachable primer layer under the conditions described below, followed by drying or curing to obtain a surface-printing ink composition print.

[0141] If there is no removable primer layer A surface printing ink composition (in the case of a surface printing gravure printing ink composition, each diluted surface printing gravure printing ink composition was diluted to 16 seconds using a Rigosha Zahn Cup No. 3, and then used with a gravure printing machine) (upper layer) was printed or printed on a corona discharge-treated stretched polypropylene film (trade name OPP P-2161, 25 μm, manufactured by Toyobo Co., Ltd.) (lower layer) and dried or cured under the following conditions to obtain a surface printing ink composition print.

[0142] (Printing method and conditions for gravure printing ink composition for surface printing) Coating machine: Gravure printing machine Coating speed: 100m / min Plate: Helio 175 line / inch (130°) solid plate Drying temperature: 55℃

[0143] [Table 16]

[0144] <UV-curable inkjet printing ink composition for surface printing> As the UV-curable inkjet printing ink composition for surface printing, the UV-curable inkjet printing ink composition prepared below can be used, but is not limited to this composition. Furthermore, the surface printing ink compositions listed in Tables 17 and 18 indicate the following surface printing UV-curable inkjet printing ink compositions, surface printing EB (electron beam)-curable offset printing ink compositions, and UV (ultraviolet)-curable offset printing ink compositions, and the results are common to these ink compositions. (Preparation of UV-curable inkjet printing ink composition for surface printing) 2.6 parts by mass of PB15:4, 1.04% by mass of Solsperse S56000 (manufactured by Lubrizol Japan), 30.00 parts by mass of amine-modified acrylate oligomer (CN371NS, manufactured by Sartomer), 4.50% by mass of 1,6-hexanediol diacrylate, 7.96 parts by mass of neopentyl glycol PO-modified diacrylate, 7.00 parts by mass of dipropylene glycol diacrylate, 5.00 parts by mass of ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 3.00 parts by mass of bis(2,4,6-trimethylbenzoyl)phenoxyphosphine oxide (IGM Resins BV), (2-carboxymethoxythioxanthone)-(polytetramethylene glycol 250) diester (IGM Resins BV), A UV-curable inkjet printing ink composition was prepared containing 2.50 parts by mass of a quinone polymerization inhibitor (UV22, manufactured by BASF), 0.40 parts by mass of a quinone polymerization inhibitor (UV22, manufactured by BASF), and 0.20 parts by mass of a silicone surface conditioner (BYK-377, manufactured by BYK-Chemie).

[0145] (Printing with UV-curable inkjet printing ink composition for surface printing) Each detachable primer composition (titanium-modified polyethyleneimine) of the Examples or the detachable primer composition (a detachable primer composition containing a polyethyleneimine composition) of the Comparative Examples, diluted to a predetermined coating amount, was applied to a corona discharge-treated stretched polypropylene film (trade name OPP P-2161, 25 μm, manufactured by Toyobo Co., Ltd.) (lower layer) and dried under the above-mentioned conditions to obtain each detachable primer layer. The above-mentioned surface-printing UV-curable inkjet printing ink composition, which would become the upper layer, was printed on each detachable primer layer using a bar coater, and the ink was applied using a UV-LED lamp manufactured by Phoseon Technologies, Inc., at a distance of 2 cm from the lamp to the ink-coated surface, with a UV integrated light dose of 180 mJ / cm. 2 The resulting mixture was completely cured to obtain a printed matter (laminate).

[0146] <Electron beam (EB) curable offset printing ink composition for surface printing> As the EB (electron beam) curable offset printing ink composition for sheet printing, the one prepared from the following EB (electron beam) curable offset printing ink composition can be used, but it is not limited to this composition. (Preparation of EB curable offset printing ink composition for sheet printing) 22.7 parts by mass of PB15:3, 40.0 parts by mass of polyester acrylate oligomer: CN704 (manufactured by Sartomer), 36.2 parts by mass of 6EO modified TMPTA (6EO modified trimethylolpropane triacrylate), 0.1 parts by mass of methylhydroquinone, 1.0 parts by mass of dimethyl silicone oil: TSF-451-5M (manufactured by Momentive) were blended and stirred and mixed to obtain an EB curable offset printing ink composition for sheet printing.

[0147] (Printing with EB curable offset printing ink composition for sheet printing) Each primer composition for detachment of the example diluted to a predetermined coating amount or the primer composition for detachment of the comparative example (primer composition for detachment containing a polyethyleneimine composition) was applied and dried under the above conditions on a corona discharge-treated stretched polypropylene film (trade name OPP P-2161, 25 μm, manufactured by Toyobo Co., Ltd.) (lower layer) to obtain each primer layer for detachment. On each primer layer for detachment, 0.1 cc of the above EB curable offset printing ink composition for sheet printing as the upper layer was transferred using a simple color developing machine (RI tester, manufactured by Toyosaki Seiko Co., Ltd.), and irradiated with an electron beam at a conveyor speed of 10 m / min using an electron beam curing device (EC90, manufactured by Iwasaki Electric Co., Ltd.) (acceleration voltage 90 kV, irradiation dose 30 kGy) to be completely cured to obtain a printed matter (laminate).

[0148] <UV (ultraviolet ray) curable offset printing ink composition> As the UV (ultraviolet ray) curable offset printing ink composition, the one prepared from the following UV curable offset printing ink composition can be used, but it is not limited to this composition. (Preparation of UV curable offset printing ink composition) 50.0 parts by mass of rosin-modified maleic acid resin (Harima M-453, manufactured by Harima Chemicals Co., Ltd.), 41.0 parts by mass of trimethylolpropane (6EO) triacrylate, 2.0 parts by mass of dimethyl silicone oil (KF-96H-100,000cs), 5.0 parts by mass of 2-methyl-1(4-methylthiophenyl)-2-morpholinopropan-1-one, and 4.4'-bis(diethylamino)benzophenone were blended and mixed with stirring to obtain a UV-curable offset printing ink composition.

[0149] (Printing with UV-curable offset printing ink composition) Each detachable primer composition (titanium-modified polyethyleneimine) of the Examples or the detachable primer composition (containing a polyethyleneimine composition) of the Comparative Examples, diluted to a predetermined coating amount, was applied to a corona discharge-treated stretched polypropylene film (trade name OPP P-2161, 25 μm, manufactured by Toyobo Co., Ltd.) (lower layer) and dried under the above-mentioned conditions to obtain each detachable primer layer. 0.1 cc of the above-mentioned UV-curable offset printing ink composition, which would serve as the upper layer, was transferred onto each detachable primer composition layer of the sample using a simple color developer (RI Tester, manufactured by Toyoei Seiko Co., Ltd.), and the resulting ink was exposed to a UV-LED lamp manufactured by Phoseon Technologies Co., Ltd. at a distance of 2 cm from the lamp to the ink-coated surface, with a UV integrated light intensity of 180 mJ / cm. 2 The resulting mixture was completely cured to obtain a printed matter (laminate).

[0150] If there is no removable primer layer Each of the above-mentioned surface printing ink compositions (for the surface printing gravure printing ink, the surface printing gravure printing ink was diluted with the respective mixed solvent to a dilution of 16 seconds using a Rigosha Zahn Cup No. 3) (upper layer) was printed onto a crystallizable shrinkable PET (polyethylene terephthalate) film (lower layer) using a gravure printing machine under the following conditions, followed by drying to obtain each printed product. The results are shown in Table 18.

[0151] The resulting printed matter (laminate) was evaluated for releasability, adhesion, blocking resistance, and moisture resistance according to the following evaluation methods. The results are shown in Tables 17 and 18.

[0152] <Evaluation of film detachment> After printing, 1.5 g of each of the above printed materials (laminates) was thoroughly dried and then shredded into small pieces of approximately 15 mm MD×25 mm TD to obtain samples for film detachment tests.

[0153] <Film removal test (hot water)> (detachment) Desorption (hot water) conditions: 100 g of desorption solution consisting of water was placed in a 200 cc HDPE (high density polyethylene) container, and heated to 70°C using a water bath. (Mixed with hot water as the supernatant) Each of the film detachment 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 detachment liquid and the various film pieces were separated using a stainless steel mesh with openings of approximately 2 mm.

[0154] (rinse) After the removal, each film was transferred to a 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 peelability of the upper ink layer from the lower ink layer was visually evaluated.

[0155] <Film removal test (alkaline aqueous solution)> (detachment) Desorption (hot water) conditions: 2.0 parts by mass of sodium hydroxide was added to 98.0 parts by mass of water in a 200 cc HDPE (high density polyethylene) container, and the mixture was stirred and dissolved to obtain a desorption liquid consisting of an alkaline aqueous solution. The alkaline aqueous solution was heated to 70°C using a hot water bath. (Mixed with a release solution consisting of an alkaline aqueous solution) After the release solution, consisting of the alkaline aqueous solution, was heated to 70°C, each of the film release test samples was separately placed into the 70°C 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 the various film pieces were separated using a stainless steel mesh with openings of approximately 2 mm.

[0156] (rinse) After the detachment, the film was transferred to a 200 cc HDPE container and 100 g of water was added. The film was stirred for 5 minutes using a 25 mm diameter stainless steel stirring blade. After leaving the film to stand for 5 minutes, the film pieces were separated from the water using a stainless steel mesh. After drying, the various film pieces were visually evaluated for peelability of the upper ink layer from the lower layer (base layer).

[0157] (Evaluation criteria) ○: The upper layer was completely peeled off from the lower layer (base layer). ×: Not peeled

[0158] <Moisture resistance test of printed matter (laminate)> Cellophane tape was applied to the printed surface of each of the resulting printed materials (each laminate), and the tape was quickly peeled off. The moisture resistance was evaluated based on the degree of peeling of the printed coating according to the following evaluation criteria. ○: After leaving the laminate sample in a 40℃, 90% RH environment for one month, cellophane tape was applied to each printed surface and then quickly peeled off. When this was done, less than 5% of the printed coating peeled off from the film. △: After leaving the laminate sample in a 40°C, 70% RH environment for one month, cellophane tape was applied to each printed surface and then quickly peeled off. When this was done, less than 5% of the printed coating peeled off from the film. ×: After leaving the laminate samples in a 40°C, 70% RH environment for one month, cellophane tape is applied to each printed surface and then quickly peeled off. When this is done, 5% or more of the printed coating peels off from the film.

[0159] <Evaluation of adhesion to the lower layer (base layer)> Tape adhesive strength (for each printed item 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.

[0160] <Blocking resistance> The printed surface of each printed layer (upper layer) of the obtained printed matter (laminate) and the untreated surface of each film were combined and subjected to a pressure of 400 g / cm 2 After leaving the film at 40°C for 12 hours under a load of 1.0 g, the blocking resistance was evaluated based on the state of each film when peeled off. (Evaluation criteria) ○: Peels off without resistance, and there is absolutely no transfer of the printed layer (upper layer) or the removable primer layer △: There is resistance, but the printed layer (upper layer) and the removable primer layer do not transfer at all ×: Migration of the printed layer (upper layer) or the removal primer was observed

[0161] When titanium-modified polyethyleneimine was applied as a release primer composition, release was possible even when hot water or an alkaline aqueous solution was used as a release liquid for all of the surface printing ink compositions, and the adhesion to a corona-discharge-treated stretched polypropylene film (product name OPP P-2161, 25 μm, manufactured by Toyobo Co., Ltd.) was also good. Furthermore, the moisture resistance and blocking resistance were also good. However, when the detachment primer composition of the comparative example was applied, it was not possible to achieve both moisture resistance and releasability in hot water when the detachment primer composition was not applied.

[0162] [Table 17]

[0163] [Table 18]

[0164] <Example of shrink printing> (acrylic resin synthesis) The monomer composition was n-butyl methacrylate / n-butyl acrylate / 2-hydroxyethyl methacrylate / methyl methacrylate (mass ratio: 35 / 20 / 15 / 30), polymerized by solution polymerization, and the solvent was evaporated. The mass-average molecular weight was 60,000, and the hydroxyl value was 60 mgKOH / g.

[0165] (Production of shrink packaging printing ink composition 1) 10.0 parts by mass of pigment (CIPB15:4), 10.0 parts by mass of the above acrylic resin, 3.5 parts by mass of nitrocellulose (product name: LIG 1 / 8, SNPE Japan), 20.0 parts by mass of methylcyclohexane, 35.5 parts by mass of isopropyl alcohol, and 21.0 parts by mass of ethyl acetate were milled and dispersed in a conventional manner to produce printing ink composition 1 for shrink packaging.

[0166] (Production of shrink packaging printing ink composition 2) 10.0 parts by mass of pigment (CIPB15:4), 9.0 parts by mass of carboxyl group-containing acrylic resin (monomer composition: MAA / MMA / BMA, theoretical acid value 3 mgKOH / g, mass average molecular weight 60,000), 10.0 parts by mass of isopropyl alcohol, and 15.0 parts by mass of ethyl acetate were kneaded using a paint conditioner, and a paint mixture containing 1.2 parts by mass of the carboxyl group-containing acrylic resin, 5.0 parts by mass of cellulose acetate butyrate (CAB-381-0.5, Eastman, number average molecular weight 30,000), 5.0 parts by mass of rosin ester (acid value 7 mgKOH / g), 1.0 part by mass of epoxidized soybean oil, 0.5 parts by mass of stearic acid amide, and Spray 2.2 parts by mass of 30 (Sasol), 0.3 parts by mass of BYK-094 (BYK), 4.5 parts by mass of normal propyl alcohol, 27.4 parts by mass of isopropyl alcohol, and 9.1 parts by mass of ethyl acetate were added and mixed to prepare printing ink composition 2 for shrink packaging.

[0167] (Production of printed matter (laminate)) -When there is a removable primer layer Each detachable primer layer was obtained by applying and drying under the above-mentioned conditions onto a crystallizable shrinkable PET (polyethylene terephthalate) film (lower layer) the detachable primer composition (titanium-modified polyethyleneimine) of each Example or the detachable primer composition (detachable primer composition containing a polyethyleneimine composition) of each Comparative Example shown in Table 21 in the prescribed coating amount shown in Table 20. Each diluted shrinkable printing ink, which was prepared by adding each mixed solvent to each of the shrinkable printing ink compositions described above to form the upper layer and diluting them to 16 seconds using a Rigosha Zahn Cup No. 3, was printed onto the surface of each detachable primer layer using a gravure printing machine under the following conditions, followed by drying, to obtain each printed product. The results are shown in Tables 19 and 20.

[0168] If there is no removable primer layer Each of the above shrink packaging printing ink compositions, which would form the upper layer, was diluted with each of the mixed solvents to a viscosity of 16 seconds using a Rigosha Zahn Cup No. 3. The diluted shrink packaging printing ink was printed on a crystallizable shrinkable PET (polyethylene terephthalate) film (lower layer) using a gravure printing machine under the following conditions, followed by drying to obtain each printed product. The results are shown in Table 19.

[0169] (Printing method and conditions for printing ink composition for shrink packaging) Coating machine: Gravure printing machine Coating speed: 100m / min Plate: Helio 175 line / inch (130°) solid plate Drying temperature: 55℃

[0170] The resulting printed matter (laminate) was evaluated for releasability, adhesion, blocking resistance, and moisture resistance using the same evaluation methods as for surface printing. The results are shown in Tables 19 and 20. Furthermore, the printing ink compositions for surface printing shown in Tables 19 and 20 represent the above-mentioned shrink packaging printing ink compositions 1 and 2, and the results are common to these ink compositions.

[0171] [Table 19]

[0172] [Table 20]

[0173] When titanium-modified polyethyleneimine was applied as a release primer composition, release was possible even when hot water or an alkaline aqueous solution was used as a release liquid for all of the shrink printing ink compositions, and the adhesion to a crystallizable shrinkable PET (polyethylene terephthalate) film was good. Furthermore, the moisture resistance and blocking resistance were also good. However, when the detachment primer composition of the comparative example was applied, it was not possible to achieve both moisture resistance and releasability in hot water when the detachment primer composition was not applied.

[0174] <Example of printing on the paper base layer side of laminated paper> (Production of aqueous flexographic printing ink composition) <Method for manufacturing water-based printing ink> A mixture of 15 parts by mass of a pigment (phthalocyanine blue, CI Pigment Blue 15:3), 15 parts by mass of an alkali-soluble water-soluble resin (Joncryl HPD-671, manufactured by BASF, solids content 25%), 0.5 parts by mass of an (ethylene oxide / propylene oxide) block polymer ((EO / PO) block polymer, HLB value 14, Mw 16000), 0.03 parts by mass of dibutyl glycol, and 22.97 parts by mass of water was kneaded and dispersed using a bead mill, and then 43.25 parts by mass of a styrene-acrylic resin emulsion (acid value 38 mgKOH / g, glass transition temperature 9°C, solids content 38.5%), 2.5 parts by mass of polyethylene wax (Chemipearl W-100, solids content 35% by mass, manufactured by Mitsui Chemicals), and 0.75 parts by mass of an antifoaming agent (SN Defoamer 777#C, manufactured by San Nopco) were added and mixed to obtain an aqueous flexographic printing ink composition.

[0175] (Production of printed matter) If there is a release primer composition Each detachable primer composition (titanium-modified polyethyleneimine) of the Examples or the detachable primer composition (detachable primer composition containing a polyethyleneimine composition) of the Comparative Examples shown in Table 23 was applied to a linear low-density polyethylene film (TUX-HC#50, thickness 25 μm, Mitsui Chemicals Tocello Inc.) (lower layer) in the prescribed application amount shown in Table 22, followed by drying under the above-mentioned conditions to obtain each detachable primer layer. An adhesive (Takelac A-969V / Takelac A-5, solids content 30% by mass) was applied to each detachable primer layer, and then a thick, single-sided glossy bleached kraft paper (OK Blizzard, 770 g / m) was laminated thereon using a dry laminator. 2The laminated paper of the present invention was obtained by adhering a flexographic printing ink composition (upper layer 2) manufactured by Oji Materia Co., Ltd. to the surface of this paper using a 200-line hand proofer, and then drying to obtain a printed matter. The results are shown in Tables 21 and 22.

[0176] If there is no release primer composition An adhesive (Takelac A-969V / Takelac A-5, solid content 30% by mass) was applied to a linear low-density polyethylene film (TUX-HC#50, thickness 25 μm, Mitsui Chemicals Tocello Co., Ltd.) (bottom layer), and then a thick, single-sided glossy bleached kraft paper (OK Blizzard, 770 g / m) was laminated on the film using a dry laminating machine. 2 The laminated paper of the present invention was obtained by adhering a flexographic printing ink composition (upper layer 1) manufactured by Oji Materia Co., Ltd. to the surface of this paper as shown in 25. The flexographic printing ink composition described above, which will become upper layer 2, was applied to the surface of this paper using a 200-line hand proofer and dried to obtain a printed matter. The results are shown in Table 22.

[0177] Laminated paper laminate structure 1: TUX-HC#50 (lower layer) / each titanium-modified polyethyleneimine or (polyethyleneimine composition-containing release primer composition) / adhesive (Takelac A-969V / Takelac A-5 solids 30%) / OK Blizzard (70g / m 2 ) (upper layer 1) / flexographic printing ink composition (upper layer 2) Laminated paper laminate structure 2: TUX-HC#50 (bottom layer) / Adhesive (Takelac A-969V / Takelac A-5 solid content 30%) / OK Blizzard (70g / m 2 ) (upper layer 1) / flexographic printing ink composition (upper layer 2)

[0178] [Table 21]

[0179] [Table 22]

[0180] When titanium-modified polyethyleneimine was applied as the detachment primer composition, detachment was achieved smoothly with both water and an alkaline aqueous solution. However, when the detachment primer composition of the comparative example was applied, and when no detachment primer composition was applied, smooth detachment was not achieved.

Claims

1. A detachable primer composition for forming a detachable primer layer of a laminate in which a lower layer, a detachable primer layer, and an upper layer are formed in this order, the detachable primer composition being a titanium-modified polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g.

2. 2. The release primer composition according to claim 1, wherein the titanium-modified polyethyleneimine compound has a number average molecular weight of 1,000 to 200,000.

3. 3. The detachment primer composition according to claim 1, wherein the titanium-modified polyethyleneimine compound has a mass average molecular weight of 4,000 to 800,000.

4. A laminate comprising a lower layer, a removable primer layer formed from the removable primer composition according to claim 1 or 2, and an upper layer formed on the removable primer layer.

5. A laminate comprising a lower layer on which a detachable primer layer formed from the detachable primer composition according to claim 1 or 2 is formed, a paper layer on which an adhesive layer is interposed, and a printed layer on which a printed layer is formed.

6. A separation and recovery method for treating the laminate according to claim 4 or 5 by a method comprising the following steps (1) to (3): (1) A shredding step of shredding the laminate to obtain shredded material (2) A separation step of immersing the shredded material in a desorption liquid to separate the lower layer. (3) A recovery step of recovering the separated lower layer

7. The separation and recovery method according to claim 6, wherein the eluate is hot water.

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