Printed materials and packaging

Abstract

To provide printed materials with reduced appearance defects. [Solution] A printed material 101 that has been offset printed using an active energy ray curable ink containing an active energy ray curable resin, comprising: an ink layer 2 containing an active energy ray curable ink; a substrate layer 1 having affinity for the active energy ray curable resin; and an extruded resin layer 3 laminated on the ink layer 2 and / or the substrate layer 1.

Description

[Technical Field]

[0001] The present invention relates to a printed material that has been offset printed using an active energy ray curable ink, and a package formed from said printed material. [Background technology]

[0002] In packaging bags for food and other products, printing (ink layer) or the like may be applied to the inner or outer surface of the outermost base layer for decorative purposes. Conventionally, this type of printing has mainly been done using gravure printing (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2022-9134 [Overview of the project] [Problems that the invention aims to solve]

[0004] The packaging bag described in Patent Document 1 is manufactured from a laminate having a film substrate layer, a printed layer, and a laminate layer. The printed layer is formed by gravure printing, and the ink composition used in this process contains an organic solvent such as esters and a polyurethane urea resin.

[0005] As described above, conventional packaging bags, including those described in Patent Document 1, have used organic solvents for gravure printing. However, in recent years, due to environmental concerns, there has been a demand for printing methods that do not use organic solvents. However, when organic solvents are replaced with, for example, water-based solvents in gravure printing, problems arise such as a decrease in print quality, which limits design options; a decrease in the physical properties of the printed layer; and a decrease in productivity due to longer drying times.

[0006] To solve these problems, it is conceivable to replace gravure printing with offset printing using active energy ray-curable inks, for example, which do not use organic solvents, to form printed materials. When active energy ray-curable inks are used, organic solvents are not used, so VOCs (volatile organic compounds) during manufacturing can be eliminated, and the environmental impact can be reduced.

[0007] However, when a dry laminate layer is laminated onto an ink layer containing an active energy ray curing ink to form a printed material, lifting may occur between the printed layer and the dry laminate layer when the printed material is subjected to bending or other loads, potentially resulting in a defective appearance. Similarly, when a dry laminate layer is laminated onto a substrate layer to form a printed material, lifting may occur between the substrate layer and the dry laminate layer when the printed material is subjected to the same loads, potentially resulting in a defective appearance.

[0008] This invention has been made in view of the above circumstances, and aims to provide printed materials with suppressed appearance defects, and packaging materials using said printed materials. [Means for solving the problem]

[0009] The characteristic configuration of the printed material according to the present invention, which solves the above problems, is A printed material that has been offset printed using an active energy ray curable ink containing an active energy ray curable resin, An ink layer containing the aforementioned active energy ray curable ink, A substrate layer having affinity for the active energy ray curable resin, The ink layer and / or the extruded resin layer laminated on the substrate layer The goal is to provide for it.

[0010] Here, the extruded resin layer is formed by laminating a molten resin onto an ink layer containing an active energy ray-curable ink (hereinafter also simply referred to as the "ink layer") and / or a substrate layer, and then cooling and solidifying it. Conventionally, a dry laminate layer was laminated onto the ink layer. In printed materials with this configuration, when an extruded resin layer is laminated (formed) onto an ink layer, the adhesive strength between the ink layer and the extruded resin layer is greater than that between the ink layer and the dry laminate layer. In addition, the ink layer is harder (more rigid) than an ink layer formed by gravure printing as described in Patent Document 1 (referred to as a "gravure ink layer" to distinguish it from the ink layer in this invention). Therefore, when a load (stress) such as bending is applied to the printed material, the deformation of the ink layer does not easily follow the deformation of the substrate layer. In this case, the laminate of the ink layer and the dry laminate layer has low rigidity, making it easy for lifting to occur between the ink layer and the dry laminate layer. In contrast, the laminate of the ink layer and the extruded resin layer has higher rigidity compared to the laminate of the ink layer and the dry laminate layer, making it less likely for lifting to occur between the ink layer and the extruded resin layer. These increases in adhesive strength and rigidity suppress lifting between the ink layer and the extruded resin layer. Even when an extruded resin layer is laminated onto a base layer, the laminate of the base layer and the extruded resin layer has higher rigidity compared to the laminate of the base layer and the dry laminate layer, and therefore, as described above, lifting between the base layer and the extruded resin layer is suppressed. In this way, by laminating an extruded resin layer on the ink layer and / or substrate layer, lifting between the ink layer and / or substrate layer and the extruded resin layer can be suppressed, resulting in a printed material with reduced appearance defects. Furthermore, when the extruded resin layer is located in the innermost layer (contents side), the extruded resin layer can also function as a sealant layer.

[0011] In the printed material according to the present invention, The active energy beam is preferably an electron beam.

[0012] According to the printed matter of this configuration, by using an active energy ray as an electron beam, redissolution of the ink in the ink layer can be suppressed. Here, "redissolution" means that when solvent-based coating such as the dry lamination method is applied to the surface (printing surface) of the ink layer, the ink in the ink layer is dissolved by the solvent. When redissolution occurs, the shape of the halftone dots in the ink layer is distorted, which may lead to a deterioration in appearance. Also, since the surface of the ink layer becomes rough, the adhesive strength (adhesive force) may decrease. However, by suppressing the redissolution of the ink as described above, it is possible to suppress a deterioration in the appearance of the ink layer, suppress a decrease in the adhesive force between the base material layer and the ink layer, and suppress the peeling of the ink from the ink layer. Also, discoloration of the ink layer can be suppressed.

[0013] In the printed matter according to the present invention, It is preferable that the ink layer substantially does not contain a polymerization initiator.

[0014] When a polymerization initiator is contained, the polymerization initiator that has not been used in the curing reaction may remain in the cured product and may have an adverse effect on the environment and health. However, according to the printed matter of this configuration, as described above, by using an active energy ray as an electron beam, an active energy ray-curable ink can be cured. Therefore, even if a polymerization initiator is not substantially blended, an ink layer excellent in characteristics such as design and durability can be formed while avoiding the above adverse effects.

[0015] In the printed matter according to the present invention, The thickness of the extruded resin layer is preferably 3 to 100 μm.

[0016] According to the printed matter of this configuration, by setting the thickness of the extruded resin layer within the above range, floating between the ink layer and / or the base material layer and the extruded resin layer can be further suppressed.

[0017] In the printed matter according to the present invention, It is preferable to further provide an anchor coat layer between the ink layer and / or the base material layer and the extruded resin layer.

[0018] According to the printed matter of this configuration, by further providing an anchor coat layer, when the main material of the ink layer and / or the base material layer and the main material of the extrusion resin layer are different resins, it enables the adhesion between the ink layer and / or the base material layer and the extrusion resin layer itself, and can effectively exert the function of suppressing the lifting of the extrusion resin layer. When the main material of the ink layer and / or the base material layer and the main material of the extrusion resin layer are the same resin, the adhesiveness between the ink layer and / or the base material layer and the extrusion resin layer can be further enhanced.

[0019] In the printed matter according to the present invention, The offset printing is waterless offset printing without using dampening water, The active energy ray-curable ink is an ink for the waterless offset printing, It is preferable to provide the anchor coat layer between the ink layer and the extrusion resin layer.

[0020] According to the printed matter of this configuration, when the printed matter is a printed matter subjected to waterless offset printing using an ink for waterless offset printing, by providing an anchor coat layer between the ink layer and the extrusion resin layer, regardless of the type of the resin composition for forming the anchor coat layer (that is, whether the resin composition for forming the anchor coat layer is an aqueous resin composition compatible with water or a non-aqueous resin composition incompatible with water), the adhesive strength between the ink layer and the extrusion resin layer can be increased. As a result, the printed matter can more surely exert the effect of suppressing the appearance defect caused by the rigidity of the extrusion resin layer.

[0021] In the printed matter according to the present invention, An anchor coat layer is provided between the ink layer and the extrusion resin layer, It is preferable that the anchor coat layer is formed of a non-aqueous resin composition incompatible with water.

[0022] According to this configuration, by providing an anchor coat layer formed from a water-incompatible non-aqueous resin composition between the ink layer and the extruded resin layer, the adhesive strength between the ink layer and the extruded resin layer can be increased regardless of the type of ink used (i.e., whether the ink is for water-based offset printing or waterless offset printing). As a result, the printed material can more reliably exhibit the effect of suppressing appearance defects caused by the rigidity of the extruded resin layer.

[0023] In the printed material according to the present invention, Preferably, the adhesive strength between the ink layer and / or the substrate layer and the extruded resin layer, as measured in accordance with JIS K 6854-3:1999, is 2 N / 15 cm or more.

[0024] According to the printed material with this configuration, by setting the adhesive strength within the above range, lifting between the ink layer and / or substrate layer and the extruded resin layer can be further suppressed.

[0025] In the printed material according to the present invention, It is preferable to further provide a sealant layer on the back side of the extruded resin layer.

[0026] According to this configuration, by further providing a sealant layer on the back side of the extruded resin layer, it becomes possible to apply heat sealing more reliably.

[0027] Another characteristic configuration of the packaging according to the present invention, which solves the above problem, is: This is because it was formed by the aforementioned printed material.

[0028] According to this packaging configuration, by forming it with the above-mentioned printed material, it is possible to obtain a packaging with excellent appearance and durability, in which lifting between the ink layer and / or base material layer and the extruded resin layer is suppressed. [Brief explanation of the drawing]

[0029] [Figure 1]Figure 1 is a schematic cross-sectional view showing the layer structure of a printed material according to the first embodiment of the present invention. [Figure 2] Figure 2 is a schematic diagram illustrating an example of a printing method used in the present invention. [Figure 3] Figure 3 is a schematic cross-sectional view showing the layer structure of a printed material according to a second embodiment of the present invention. [Figure 4] Figure 4 is a schematic cross-sectional view showing the layer structure of a printed material according to the third embodiment of the present invention. [Figure 5] Figure 5 is a schematic cross-sectional view showing the layer structure of a printed material according to the fourth embodiment of the present invention. [Figure 6] Figure 6 is a schematic cross-sectional view showing the layer structure of a printed material according to the fifth embodiment of the present invention. [Figure 7] Figure 7 is a schematic cross-sectional view showing the layer structure of a printed material according to the sixth embodiment of the present invention. [Figure 8] Figure 8 is a schematic cross-sectional view showing the layer structure of a printed material according to the seventh embodiment of the present invention. [Figure 9] Figure 9 is a schematic cross-sectional view showing the layer structure of a printed material according to the eighth embodiment of the present invention. [Figure 10] Figure 10 is a schematic diagram showing an example of a packaged product equipped with a packaging body according to the ninth embodiment of the present invention. [Figure 11] Figure 11 is a graph showing the measurement results of loop stiffness. [Figure 12] Figure 12 is a graph showing the results of the color difference measurement. [Modes for carrying out the invention]

[0030] The following describes embodiments of the printed material and packaging according to the present invention. However, the present invention is not intended to be limited to the embodiments, examples, and drawings described below. Note that the layer configurations shown in each figure do not strictly represent the actual structure, shape, dimensions, thickness ratios, and relative sizes of each layer.

[0031] [Printed material] The first to tenth embodiments of the printed material of the present invention will now be described. It should be noted that the printed material of the present invention is obtained by irradiation with active energy rays, but it may be considered impractical to specify the structure of the ink layer formed by irradiation with active energy rays as a physical object.

[0032] [First Embodiment] Figure 1 is a schematic cross-sectional view showing the layer structure of a printed material according to the first embodiment of the present invention.

[0033] The printed material 101 shown in Figure 1 is a laminate formed by reverse offset printing. The printed material 101 comprises, from the top (surface side), a base layer 1 having affinity for an active energy ray curable resin, an ink layer 2 containing an active energy ray curable resin, and an extruded resin layer 3 laminated on the ink layer 2.

[0034] Active energy rays are energy rays capable of generating radical-like active species, and examples include electromagnetic waves such as X-rays and gamma rays, particle beams such as electron beams (EB), proton beams, and alpha rays, and non-ionizing radiation such as microwaves and ultraviolet rays. Of these, electron beams (EB) are preferred for offset printing with active energy ray-curable inks because they have a higher active energy (energy that generates radical-like active species) than ultraviolet rays (UV) but are less likely to be absorbed by pigments contained in inks. Generally, when curing resins (monomers) by irradiation with ultraviolet rays (UV), a polymerization initiator is required. However, when a polymerization initiator is included, there is a risk that the polymerization initiator that was not used in the curing reaction may remain in the cured product. Also, even if a polymerization initiator is included, the resin may not be sufficiently cured, and unreacted residual monomers may remain. Considering these factors, it is preferable that the active energy ray is one that does not contain ultraviolet rays (i.e., something other than ultraviolet rays). Furthermore, it is even more preferable that the active energy ray is one with higher active energy than ultraviolet rays, as this eliminates the need for a polymerization initiator. Furthermore, by not incorporating polymerization initiators, adverse environmental and health effects from residual polymerization initiators and monomers can be avoided. In addition, an ink layer 2 with excellent properties such as design and durability can be formed.

[0035] <Ink layer> The ink layer (printing layer) 2 contains an active energy ray-curable ink (hereinafter also referred to as "ink") containing an active energy ray-curable resin. The content of the active energy ray-curable resin in the ink layer 2 is preferably 30% by weight or more, more preferably 50% by weight or more, and even more preferably 60% by weight or more. The active energy ray-curable resin has the property of crosslinking (curing) between molecules of the active energy ray-curable resin (crosslinking property) or the property of chemically bonding (curing) the active energy ray-curable resin with other resins, etc. (curing property) by generating radical active species in the molecule upon irradiation with active energy rays, and by the formation of new bonds between the active species.

[0036] As mentioned above, it is preferable that the active energy ray curable resin is a resin that hardens with active energy rays that do not contain ultraviolet light, and more preferably a resin that hardens with active energy rays higher than ultraviolet light. By selecting these resins as active energy ray curable resins, polymerization initiators are not required in the reaction of the active energy ray curable resin, and the residue of polymerization initiators and residual monomers after hardening can be reduced, which is advantageous not only from a hygiene perspective but also from an environmental and health perspective. In addition, when curing the resin by irradiation with active energy rays, if ultraviolet light is used, the pot life (the time it takes for the active energy ray curable resin to harden during storage (i.e., the time it exists without hardening)) is shortened, and the concentration and viscosity of the active energy ray curable resin may change as it hardens over time. Furthermore, because ultraviolet light has low transmittance to active energy ray curable resins, hardening progresses on the surface (irradiated surface) side where ultraviolet light is irradiated in the thickness direction, but hardening does not progress as you move away from the irradiated surface, creating a gradient in the degree of hardening, making it difficult to harden the active energy ray curable resin uniformly. However, as described above, by using active energy rays that do not contain ultraviolet light, or active energy rays with higher activity energy than ultraviolet light (for example, electron beams), it is possible to cure active energy ray-curable resins instantaneously (more quickly than when using ultraviolet light) without the need to incorporate polymerization initiators. As a result, the pot life is significantly extended, and the active energy rays can penetrate deeper into the active energy ray-curable resin than ultraviolet light can. Consequently, even when the active energy ray-curable resin is relatively thick, it can be cured more uniformly (with a smaller gradient) than when using ultraviolet light. Furthermore, because the active energy rays can reach the entire resin in the thickness direction, curing defects can be reduced even when the active energy ray-curable resin is relatively thick.

[0037] Furthermore, when an electron beam is used as the active energy beam, the redissolution of the ink in the ink layer 2 can be suppressed. This suppresses a decrease in the adhesive strength between the substrate layer 1 and the ink layer 2, and prevents the ink from falling off the ink layer 2. In addition, discoloration of the ink layer 2 can be suppressed.

[0038] The ink, which is the raw material for ink layer 2, contains the above-mentioned active energy ray-curable resin that hardens upon irradiation with active energy rays, and may further contain a pigment.

[0039] Examples of active energy ray curable resins, which are one of the raw materials for ink layer 2, include resin compositions having (a) a resin having hydrophilic groups and ethylene unsaturated groups (referred to as "resin (a)"), (b) a polyfunctional (meth)acrylate having hydrophilic groups (referred to as "polyfunctional (meth)acrylate (b)"), and (c) a hydrophobic difunctional (meth)acrylate (referred to as "difunctional (meth)acrylate (c)"). Note that "(meth)acrylate" means "acrylate and / or methacrylate".

[0040] (Resin (a)) Resin (a) has hydrophilic groups. Examples of hydrophilic groups include hydroxyl groups, amino groups, mercapto groups, carboxyl groups, sulfo groups, and phosphate groups. Among these, carboxyl groups and hydroxyl groups are preferred because they provide good dispersibility of pigments in the ink.

[0041] Resin (a) has ethylenically unsaturated groups. The iodine value of the ethylenically unsaturated groups is preferably 0.5 mol / kg or more, more preferably 1.0 mol / kg or more, and even more preferably 1.5 mol / kg or more. By setting the iodine value of the ethylenically unsaturated groups to be above the lower limit, good curing sensitivity by irradiation with active energy rays can be obtained. The iodine value of the ethylenically unsaturated groups is preferably 3.0 mol / kg or less, more preferably 2.5 mol / kg or less, and even more preferably 2.2 mol / kg or less. By setting the iodine value of the ethylenically unsaturated groups to be below the upper limit, the storage stability of the ink is improved. The iodine value is measured in accordance with the method described in section 6.0 of the test method of JIS K 0070:1992.

[0042] A resin (a) having hydrophilic groups and ethylenically unsaturated groups can be obtained, for example, by the following method. Specifically, a resin (a) having hydrophilic groups and ethylenically unsaturated groups can be obtained by adding ethylenically unsaturated compounds having glycidyl groups or isocyanate groups, acrylic acid chloride, methacrylate chloride, allyl chloride, etc., to active hydrogen-containing groups such as mercapto groups, amino groups, hydroxyl groups, carboxyl groups, etc., in a resin having hydrophilic groups. However, the method for producing resin (a) is not limited to this.

[0043] Examples of ethylenically unsaturated compounds having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl crotonic acid, and glycidyl isocrotonic acid.

[0044] Examples of ethylenically unsaturated compounds having an isocyanate group include acryloyl isocyanate, methacryloyl isocyanate, acryloylethyl isocyanate, and methacryloylethyl isocyanate.

[0045] The acid value of resin (a) is preferably 30 mg KOH / g or higher, more preferably 60 mg KOH / g or higher, and even more preferably 75 mg KOH / g or higher. Setting the acid value above the lower limit improves the pigment dispersibility of the ink. The acid value of resin (a) is preferably 250 mg KOH / g or lower, more preferably 200 mg KOH / g or lower, and even more preferably 150 mg KOH / g or lower. Setting the acid value below the upper limit maintains appropriate fluidity of the ink. The acid value of resin (a) is measured in accordance with the neutralization titration method described in section 3.1 of JIS K 0070:1992.

[0046] The hydroxyl value of resin (a) is preferably 30 mg KOH / g or higher, more preferably 75 mg KOH / g or higher, and even more preferably 100 mg KOH / g or higher. Setting the hydroxyl value of resin (a) above the lower limit improves the pigment dispersibility of the ink. The hydroxyl value of resin (a) is preferably 350 mg KOH / g or lower, more preferably 275 mg KOH / g or lower, and even more preferably 250 mg KOH / g or lower. Setting the hydroxyl value of resin (a) below the upper limit ensures proper ink fluidity. The hydroxyl value of resin (a) is measured in accordance with the neutralization titration method described in section 7.1 of JIS K 0070:1992.

[0047] The weight-average molecular weight (Mw) of resin (a) is preferably 5,000 or more, more preferably 15,000 or more, and even more preferably 20,000 or more. Setting the weight-average molecular weight (Mw) of resin (a) above the lower limit increases the viscosity of the ink under high shear. The weight-average molecular weight (Mw) of resin (a) is preferably 100,000 or less, more preferably 75,000 or less, and even more preferably 50,000 or less. Setting the weight-average molecular weight (Mw) of resin (a) below the upper limit increases the fluidity of the ink. The weight-average molecular weight (Mw) of resin (a) is measured in polystyrene equivalent using gel permeation chromatography (GPC).

[0048] The content of resin (a) in the ink is preferably 3 to 50% by mass, more preferably 4 to 35% by mass, even more preferably 5 to 20% by mass, and particularly preferably 10 to 15% by mass. By setting the content within the above range, the pigment dispersibility of the ink can be made appropriate.

[0049] Examples of resin (a) include acrylic resins, styrene-acrylic resins, styrene-maleic acid resins, rosin-modified maleic acid resins, rosin-modified acrylic resins, epoxy resins, polyester resins, polyurethane resins, and phenolic resins. Of these, acrylic resins, styrene-acrylic resins, and styrene-maleic acid resins are preferred in terms of ease of monomer acquisition, low cost, ease of synthesis, compatibility with other components in the ink, and pigment dispersibility. Resin (a) may be used alone or as a mixture of two or more types.

[0050] More preferred specific examples of resin (a) include (meth)acrylic acid copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-(meth)acrylic acid copolymer, styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid-(meth)acrylic acid copolymer, styrene-maleic acid-(meth)acrylic acid ester copolymer, and the like.

[0051] (Polyfunctional (meth)acrylate(b)) The hydrophilic groups contained in the polyfunctional (meth)acrylate (b) help to disperse and stabilize the pigment in the ink, thereby suppressing an excessive decrease in ink viscosity even under high shear conditions. Examples of hydrophilic groups include ethylene oxide skeletons, carboxyl groups, hydroxyl groups, amino groups, and sulfonic acid groups. Of these, hydroxyl groups, which have particularly high hydrophilicity, are preferred.

[0052] The polyfunctional (meth)acrylate (b) is preferably a urethane acrylate containing urethane groups. When the content of polyfunctional (meth)acrylate (b) in the ink increases, or when its molecular weight increases, the viscosity of the ink increases and its fluidity decreases. Therefore, by appropriately setting the content of urethane groups in the urethane acrylate, the cohesive force of the ink can be increased, and as a result, the adhesion of the ink layer 2 is improved. By appropriately setting the content of urethane groups in the urethane acrylate, peeling of the ink layer 2 is suppressed, especially during hot water treatment, and the durability of the ink layer 2 is increased. The urethane bonding group can suppress entanglement of molecular chains due to its relatively high rigidity structure (hard segment). As a result, the increase in ink viscosity can be suppressed, and the cohesive force of the ink printed (coated) on the substrate layer 1 can be increased. In this way, it is presumed that the adhesion between the ink layer 2 and the substrate layer 1 is improved. Furthermore, it is presumed that the polyfunctional (meth)acrylate (b) contains urethane acrylate, which crosslinks with radical species generated from the unsaturated groups of resin (a) upon irradiation with active energy rays, and that this strong covalent bond can cure the ink particles. It is preferable to set the proportion of urethane bonds in the polyfunctional (meth)acrylate (b) to 0.05% by mass or less in the ink. The proportion of urethane bonds is measured by nuclear magnetic resonance (NMR).

[0053] The content of polyfunctional (meth)acrylate (b) in the ink is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. By setting the content of polyfunctional (meth)acrylate (b) above the lower limit above, the adhesion of the ink layer 2 and the fluidity of the ink are improved. The content of polyfunctional (meth)acrylate (b) in the ink is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less. By setting the content of polyfunctional (meth)acrylate (b) below the upper limit above, the increase in viscosity of the ink due to intermolecular forces between polar groups is suppressed, and the fluidity is improved.

[0054] The hydroxyl value of polyfunctional (meth)acrylate (b) is preferably 30 mg KOH / g or higher, more preferably 75 mg KOH / g or higher, and even more preferably 100 mg KOH / g or higher. Setting the hydroxyl value of polyfunctional (meth)acrylate (b) above the lower limit above improves the fluidity of the ink. The hydroxyl value of polyfunctional (meth)acrylate (b) is preferably 200 mg KOH / g or less, more preferably 180 mg KOH / g or less, and even more preferably 160 mg KOH / g or less. Setting the hydroxyl value of polyfunctional (meth)acrylate (b) below the upper limit above suppresses the increase in ink viscosity due to intermolecular forces between polar groups, and improves the fluidity of the ink.

[0055] The weight-average molecular weight (Mw) of the polyfunctional (meth)acrylate (b) is preferably 100 or more, more preferably 150 or more, and even more preferably 200 or more. Setting the weight-average molecular weight (Mw) above the lower limit above makes the ink coating more flexible and improves the adhesion of the ink layer 2. The weight-average molecular weight (Mw) of the polyfunctional (meth)acrylate (b) is preferably 1,000 or less, more preferably 700 or less, and even more preferably 500 or less. Setting the weight-average molecular weight (Mw) below the upper limit above suppresses the increase in ink viscosity and improves the ink's fluidity. The weight-average molecular weight (Mw) can be measured in polystyrene equivalent using gel permeation chromatography (GPC). Furthermore, if the ink contains multiple types of polyfunctional (meth)acrylate (b), the sum of their average values ​​is used as the weight-average molecular weight (Mw) of the polyfunctional (meth)acrylate (b) in this invention.

[0056] The polyfunctional (meth)acrylate (b) preferably has a hydroxyl group. Examples of polyfunctional (meth)acrylates (b) having a hydroxyl group include poly(meth)acrylates of polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, diglycerin, ditrimethylolpropane, isocyanuric acid, and dipentaerythritol, and alkylene oxide adducts thereof. Specifically, examples include trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. Furthermore, examples include ethylene oxide adducts, propylene oxide adducts, butylene oxide adducts, tetramethylene oxide adducts, etc. of these compounds. Of these, pentaerythritol tri(meth)acrylate, diglycerin tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate are preferred because they can improve the pigment dispersibility and fluidity of the ink. The polyfunctional (meth)acrylate (b) may be used alone or as a mixture of two or more.

[0057] (2-functional (meth)acrylate(c)) The difunctional (meth)acrylate (c) has a hydroxyl value of 5 mgKOH / g or less and exhibits hydrophobicity. The difunctional (meth)acrylate (c) preferably has a chain-like aliphatic skeleton with 8 to 18 carbon atoms. The chain-like aliphatic skeleton may be a linear skeleton or a branched skeleton, and may consist of saturated or unsaturated bonds. Since the difunctional (meth)acrylate (c) is moderately compatible with resin (a) and polyfunctional (meth)acrylate (b), entanglement of molecular chains in the ink is suppressed. As a result, stringiness (tendency to pull) when the ink is transferred is suppressed, and consequently, ink transferability is improved. In addition, the inclusion of the difunctional (meth)acrylate (c) in the ink reduces the surface tension of the ink and improves wettability to the substrate layer 1, thus improving ink transferability. Here, ink transferability refers to the property of how easily ink is transferred from rubber (metal) roller to rubber (metal) roller, from rubber (metal) roller to printing plate, from printing plate to blanket, and from blanket to substrate layer. Ink transferability is evaluated by the ink transfer rate.

[0058] The carbon number of the bifunctional (meth)acrylate (c) is preferably 8 or more, more preferably 9 or more, and even more preferably 10 or more. By setting the carbon number of the bifunctional (meth)acrylate (c) to be above the lower limit above, the compatibility with resin (a) and polyfunctional (meth)acrylate (b) is appropriately maintained, and as a result, the ink transferability is improved. The carbon number of the bifunctional (meth)acrylate (c) is preferably 18 or less, more preferably 16 or less, and even more preferably 14 or less. By setting the carbon number of the bifunctional (meth)acrylate (c) to be below the upper limit above, deterioration of compatibility with resin (a) and polyfunctional (meth)acrylate (b), increase in ink viscosity, and deterioration of ink transferability are suppressed.

[0059] The content of the difunctional (meth)acrylate (c) in the ink is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. On the other hand, the content of the difunctional (meth)acrylate (c) in the ink is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less. By setting the content of the difunctional (meth)acrylate (c) within the above ranges, the compatibility with the resin (a) and the polyfunctional (meth)acrylate (b) is appropriately maintained, and as a result, the ink transferability is improved.

[0060] Examples of difunctional (meth)acrylates (c) include 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,11-undecanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, and 1,14-tetradecanediol Examples include 1,10-decanediol di(meth)acrylate, 1,15-pentadecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,17-heptadecanediol di(meth)acrylate, 1,18-octadecanediol di(meth)acrylate, 4-methyl-1,10-decanediol di(meth)acrylate, and 4-ethyl-1,10-decanediol di(meth)acrylate. Also, polyester di(meth)acrylates having an aliphatic skeleton with 8 to 18 carbon atoms as repeating units are also examples. Of these, 1,10-decanediol di(meth)acrylate is more preferred because it maintains appropriate compatibility with resin (a) and polyfunctional (meth)acrylate (b), and can improve ink transferability. The number of functions refers to the number of structures derived from (meth)acrylate. The bifunctional (meth)acrylate (c) may be used alone or in combination of two or more types.

[0061] The weight-average molecular weight (Mw) of the difunctional (meth)acrylate (c) is preferably 100 or higher, more preferably 150 or higher, and even more preferably 200 or higher. By setting the weight-average molecular weight (Mw) of the difunctional (meth)acrylate (c) to be above the lower limit, the ink coating film becomes more flexible, and as a result, the adhesion to the substrate layer 1 is improved. The weight-average molecular weight (Mw) of the difunctional (meth)acrylate (c) is preferably 1,000 or lower, more preferably 700 or lower, and even more preferably 500 or lower. By setting the weight-average molecular weight (Mw) of the difunctional (meth)acrylate (c) to be below the upper limit, the viscosity of the ink is well maintained, and as a result, the fluidity of the ink is good. The weight-average molecular weight (Mw) of the difunctional (meth)acrylate (c) is measured in polystyrene equivalent using gel permeation chromatography (GPC).

[0062] When the total amount of polyfunctional (meth)acrylate (b) is used as a reference (1.00 parts by mass), the content ratio of difunctional (meth)acrylate (c) is preferably 0.02 parts by mass or more, more preferably 0.04 parts by mass or more, and even more preferably 0.06 parts by mass or more, in order to maintain appropriate compatibility with polyfunctional (meth)acrylate (b) and improve ink transferability. On the other hand, the content ratio of difunctional (meth)acrylate (c) is preferably 0.30 parts by mass or less, more preferably 0.20 parts by mass or less, even more preferably 0.15 parts by mass or less, and particularly preferably 0.10 parts by mass or less.

[0063] When the total amount of resin (a) is used as a reference (1.00 parts by mass), the content ratio of the difunctional (meth)acrylate (c) is preferably 0.10 parts by mass or more, more preferably 0.15 parts by mass or more, and even more preferably 0.20 parts by mass or more, in order to maintain appropriate compatibility with resin (a) and improve ink transferability. On the other hand, the content ratio of the difunctional (meth)acrylate (c) is preferably 0.60 parts by mass or less, more preferably 0.45 parts by mass or less, and even more preferably 0.30 parts by mass or less.

[0064] When the active energy ray-curable resin contained in the ink has urethane bonds, the content of urethane bonds in the ink is preferably 0.05% by mass or less. The content of urethane bonds is measured by nuclear magnetic resonance (NMR).

[0065] <Pigments> The ink preferably contains organic pigments and / or inorganic pigments in addition to an active energy ray curable resin. Examples of organic pigments include phthalocyanine pigments, soluble azo pigments, insoluble azo pigments, lake pigments, quinacridone pigments, isoindoline pigments, slene pigments, and metal complex pigments. Specifically, examples include phthalocyanine blue, phthalocyanine green, azo red, monoazo red, monoazo yellow, disazo red, disazo yellow, quinacridone red, quinacridone magenta, and isoindoline yellow.

[0066] Examples of inorganic pigments include titanium dioxide, zinc oxide, alumina white, calcium carbonate, barium sulfate, red iron oxide, cadmium red, lead yellow, zinc yellow, Prussian blue, ultramarine blue, oxide-coated glass powder, silicate minerals (mica), oxide-coated mica, oxide-coated metal particles, aluminum powder, gold powder, silver powder, copper powder, zinc powder, stainless steel powder, nickel powder, bentonite, iron oxide, carbon black, and graphite.

[0067] For inks printed as a base color for a transparent substrate layer 1, white pigments such as titanium dioxide, zinc oxide, and alumina white are preferred to provide opacity. A particle size of 200-300 nm is preferred for the white pigment, from the viewpoint that scattering can most effectively reduce the transmittance of visible light. The pigment may be used individually or in a mixture of two or more types.

[0068] For organic pigments or carbon black with a specific gravity of 2 or less, the pigment content in the ink is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of improving print density. Furthermore, from the viewpoint of improving ink fluidity and obtaining good transferability, the content is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. For inorganic pigments with a specific gravity greater than 2, from the viewpoint of improving print density, the content is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. Furthermore, from the viewpoint of improving ink fluidity and obtaining good transferability, the content is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0069] The ink may contain other components such as sensitizers. Furthermore, it is preferable that the ink contains a surfactant. The inclusion of a surfactant in the ink allows it to absorb dampening solution and stabilize the emulsified state during wet printing. The surfactant content in the ink is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the standpoint of stabilizing the emulsified state. Additionally, from the standpoint of suppressing mismatch with dampening solution due to excessive absorption of dampening solution during printing, the surfactant content is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0070] On the other hand, it is preferable that the ink substantially does not contain polymerization initiators. This is because the ink can be cured by irradiation with active energy rays even without the inclusion of polymerization initiators. Here, "substantially contained" does not mean that the presence of polymerization initiators is completely excluded, but rather that the ink may contain polymerization initiators in a type and amount that does not adversely affect the adhesion and reproducibility of the ink layer 2 to the substrate layer 1. In other words, it is not intended that the polymerization initiator content be strictly 0% in all cases. For example, if a trace amount of polymerization initiator is unintentionally included, or if a trace amount of polymerization initiator is intentionally included but does not produce any effect due to that polymerization initiator, the ink will be considered to not contain polymerization initiators. Examples of cases where trace amounts of polymerization initiator may be unintentionally included include, in the case of ink or printed material 101 manufacturing equipment, cases where trace amounts of polymerization initiator adhering to containers or pipes contaminate the ink if another product containing polymerization initiator has been manufactured previously, or cases where fine particles of polymerization initiator suspended or volatilized in the air of the manufacturing room adhere to the ink during manufacturing. In such cases, even if the product contains trace amounts of polymerization initiator, it shall be treated as if it substantially does not contain polymerization initiator.

[0071] The viscosity of the ink is measured using a cone-plate rotary viscometer at 25°C and a rotation speed of 0.5 rpm. The viscosity (A) is preferably 5 to 100 Pa·s, more preferably 10 to 80 Pa·s, and even more preferably 20 to 60 Pa·s. Setting the viscosity (A) above the lower limit of each of the above ranges improves the transferability of the ink. Setting the viscosity (A) below the upper limit of each of the above ranges improves the fluidity of the ink, and in the case of white ink in particular, the opacity may be improved.

[0072] At a rotational speed of 50 rpm, the viscosity (B) is preferably 10 to 40 Pa·s, more preferably 15 to 35 Pa·s, and even more preferably 20 to 30 Pa·s. Setting the viscosity (B) above the lower limit of each of the above ranges improves the ink transferability. Setting the viscosity (B) below the upper limit of each of the above ranges can improve the ink transferability.

[0073] The viscosity ratio (B) / (A), which is the ratio of viscosity (A) to viscosity (B), is preferably 0.25 to 0.4, more preferably 0.30 to 0.4, and even more preferably 0.35 to 0.4. By setting the viscosity ratio (B) / (A) within the above range, high-quality printed materials with smooth image areas can be obtained.

[0074] By using an ink containing the above components, setting the ink's physical properties as described above, performing offset printing, and irradiating it with active energy rays (i.e., performing EB offset printing), it becomes possible to achieve high-precision reproducibility comparable to, or even exceeding, that of gravure printing.

[0075] <Base material layer> The base layer 1 is a layer that has affinity for the active energy ray-curable resin. "Having affinity for the active energy ray-curable resin" means that the surface of the base layer 1 has properties that increase adhesion to the active energy ray-curable resin in the ink layer 2 upon irradiation with active energy rays. The reason why the adhesion of the surface of the base layer 1 increases upon irradiation with active energy rays is not entirely clear, but it is presumed that the active energy rays generate radical active species in the resin molecules present on the surface of the base layer 1, and that these active species interact with the radical active species generated in the molecules of the active energy ray-curable resin in the ink layer 2 through some kind of interaction, such as crosslinking (covalent bonding), weaker electrostatic interactions (dipole interactions, van der Waals forces, etc.), or other interactions. The property of the base layer 1 to "have affinity for the active energy ray-curable resin" is preferably achieved by the base layer 1 containing a resin that has affinity for the active energy ray-curable resin.

[0076] In the reverse printing of this embodiment, it is desirable that the base layer 1 be transparent, or at least semi-transparent, so that the ink layer 2 can be seen. Therefore, a transparent thermoplastic resin is preferably used as the base layer 1. Specifically, examples include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene; alicyclic polyolefin resins; polyamide resins such as nylon 6 and nylon 66; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polypropylene terephthalate, polybutyl succinate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, and polyethylene diphenylate; polycarbonate resins; polyarylate resins; polyacetal resins; polyphenylene sulfide resins; fluorine resins such as trifluoroethylene resins, tetrafluoroethylene-hexafluoropropylene copolymers, and vinylidene fluoride resins; acrylic resins; methacrylic resins; polyacetal resins; polyglycolic acid resins; and polylactic acid resins. Of these, polyester resins are preferred because they can enhance strength, heat resistance, and transparency. Polyolefin resins are also preferred because they can enhance transparency, and polyethylene is more preferred. Thermoplastic resins may be used individually or in mixtures of two or more types.

[0077] The base layer 1 may be a single layer or multiple layers. If the base layer 1 is a single layer, it may only have a resin film formed from the thermoplastic resin. If the base layer 1 has multiple layers, examples of the base layer 1 include the following laminates. If the base layer 1 has two layers, examples of the base layer 1 include a laminate having the resin film as the base and an easy-adhesion layer described later (resin film / easy-adhesion layer), a laminate having the resin film layer and a barrier layer described later (resin film / barrier layer), etc. If the base layer 1 has three layers, examples of the base layer 1 include a laminate having the resin film layer, an easy-adhesion layer and a barrier layer in that order (resin film layer / easy-adhesion layer / barrier layer), a laminate having the resin film and two types of barrier layers (resin film / barrier layer / barrier layer), etc. The barrier layer included in the base layer 1 may be a single layer or multiple layers. Examples of barrier layers include a transparent vapor-deposited layer formed by vapor-depositing an inorganic compound or the like onto the resin film, a barrier coating layer such as polyvinylidene chloride (PVDC), and a stretched film layer such as a stretched (e.g., biaxially oriented) polypropylene (OPP) film. Specific examples of substrate layers 1 having such barrier layers include a transparent vapor-deposited film formed by vapor-depositing an inorganic compound or the like onto the resin film, a PVDC-coated film formed by coating the resin film with polyvinylidene chloride (PVDC), and an OPP barrier film formed by laminating an OPP film onto the resin film.

[0078] The resin film may have multiple layers laminated on it as barrier layers, such as the transparent vapor-deposited layer, the barrier coat layer, and the stretched film layer. For example, the base layer 1 may be a laminate (resin film / transparent vapor-deposited layer / barrier coat layer) in which the resin film, the transparent vapor-deposited layer, and the barrier coat layer are laminated in that order. For example, the base layer 1 may be a laminate (resin film / barrier coat layer) in which the resin film and the barrier coat layer are laminated in that order. In this case, where the base layer 1 has the resin film layer and one or more barrier layers, the ink layer 2 may be laminated on one surface of the base layer 1 (for example, the resin film side surface), or on the other surface (for example, the barrier layer side surface). It is preferable that at least the outermost layer on the ink layer 2 side of the base layer 1 is a resin layer.

[0079] The thickness of the base layer 1 is preferably 9 to 200 μm, more preferably 9 to 100 μm, even more preferably 9 to 50 μm, and particularly preferably 9 to 35 μm. By setting the thickness of the base layer 1 to be above the lower limit of each of the above ranges, it is not made too thin, and the strength of the printed material 101 is increased. Furthermore, by setting the thickness of the base layer 1 to be below the upper limit of each of the above ranges, the processability of the printed material 101 is increased.

[0080] The base layer 1 is preferably surface-treated. Specifically, for example, the base layer 1 is preferably a resin film formed from the thermoplastic resin, on which the surface has been surface-treated. This improves the adhesion between the base layer 1 and the layer adjacent to it.

[0081] The surface treatment method is not particularly limited, but examples include physical treatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and / or nitrogen gas, glow discharge treatment, and chemical treatments such as oxidation treatment using chemicals.

[0082] The base layer 1 may further contain additives. Examples of additives include crosslinking agents, antioxidants, antiblocking agents, lubricants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins.

[0083] For example, when the substrate layer 1 contains an antistatic agent, and the antistatic function is activated when the antistatic agent is exposed on the surface, it has conventionally been difficult to control the amount of exposure of the antistatic agent. However, in this embodiment, the degree of crystallinity of the substrate layer 1 can be increased by irradiation with active energy rays, thereby suppressing excessive exposure of the antistatic agent. By limiting the amount of exposure of the antistatic agent in this way, excessive slipperiness of the surface of the substrate layer 1 can be suppressed.

[0084] <Easy adhesion layer> The substrate layer 1 preferably has an easy-adhesion layer to enhance adhesion to the ink layer 2. The easy-adhesion layer is realized by providing a layer (not shown) containing at least one compound selected from, for example, amines, amides, isocyanates, and urethanes on the surface of the resin film formed by the thermoplastic resin on the ink layer 2 side of the substrate layer 1. Functional groups derived from the easy-adhesion layer receive intermolecular forces such as hydrogen bonding with the hydrophilic resin (a) and the polyfunctional (meth)acrylate (b) in the ink, thereby enhancing the transferability of the ink and the adhesion between the ink layer 2 and the substrate layer 1.

[0085] Examples of amines include ethylenediamine, propylenediamine, hexamethylenediamine, phenylenediamine, tolylenediamine, diphenyldiamine, diaminodiphenylmethane, diaminocyclohexylmethane, ethylenediaminetetraacetic acid, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and other N,N-dialkylaminoalkyl (meth)acrylates, 2-(methacryloyloxy)ethyltrimethylammonium chloride, and 2-(methacryloyloxy)ethyltrimethylammonium Examples include nium bromide, (meth)acryloyloxyalkyltrialkylammonium salts such as 2-(methacryloyloxy)ethyltrimethylammonium dimethyl phosphate, (meth)acryloylaminoalkyltrialkylammonium salts such as methacryloylaminopropyltrimethylammonium chloride and methacryloylaminopropyltrimethylammonium bromide, tetraalkyl (meth)acrylates such as tetrabutylammonium (meth)acrylate, and trialkylbenzylammonium (meth)acrylates such as trimethylbenzylammonium (meth)acrylate. Amines may be used individually or in combination of two or more.

[0086] Examples of amides include aliphatic amides such as ethylenebisstearamide and hexamethylenebisstearamide, and N,N-dialkylaminoalkyl(meth)acrylamides such as N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, and N,N-dimethylaminopropyl(meth)acrylamide. Amides may be used individually or in combination of two or more.

[0087] Examples of isocyanates include aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane-4,4-diisocyanate, aromatic aliphatic diisocyanates such as xylylene diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate and 1,3-bis(isocyanatemethyl)cyclohexane, aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate, and polyisocyanates obtained by pre-adding these compounds, either individually or in combination, with trimethylolpropane, etc. For example, including amine compounds and isocyanate compounds in the easy-adhesion layer also includes having an amino group and an isocyanate group in a single compound. Isocyanates may be used individually or in combination of two or more types.

[0088] Urethanes contain at least a polyol and an isocyanate compound, and optionally a chain extender. Urethanes can be obtained, for example, by polymerizing a polyol and an isocyanate compound by a known polymerization method. Examples of polyols include polyester polyols obtained by the reaction of polycarboxylic acids (e.g., malonic acid, succinic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.) or their acid anhydrides with polyhydric alcohols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, neopentyl glycol, 1,6-hexanediol, etc.), polyether polyols such as polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, and polyhexamethylene ether glycol, polycarbonate polyols, polyolefin polyols, and acrylic polyols. Polyurethanes may be used individually or in mixtures of two or more types.

[0089] The content of amines, amides, isocyanates, and urethanes in the easy-adhesion layer is not particularly limited, but is preferably 0.1 to 80% by mass, more preferably 1 to 50% by mass, and even more preferably 5 to 20% by mass.

[0090] The easy-adhesion layer may further contain a resin component. The resin component is not particularly limited as long as it has adhesion to the resin film of the base layer 1 and / or the ink layer 2, but for example, polyester resins, polycarbonate resins, epoxy resins, alkyd resins, acrylic resins, urea resins, urethane resins, etc. can be suitably used. Of these, polyester resins, acrylic resins, and urethane resins are preferred, and polyester resins having a phthalate skeleton are more preferred.

[0091] The easy-adhesion layer may appropriately contain various additives such as crosslinking agents, plasticizers, heat stabilizers, weather stabilizers, organic and / or inorganic fine particles, waxes, antioxidants, weathering agents, antistatic agents, and pigments, to the extent that they do not impair the properties of the film. As crosslinking agents, for example, melamine-based crosslinking agents, aziridine-based crosslinking agents, epoxy-based crosslinking agents, methylolated or alkylolated urea-based crosslinking agents, acrylamide-based crosslinking agents, polyamide-based crosslinking agents, oxazoline-based crosslinking agents, carbodiimide-based crosslinking agents, isocyanate-based crosslinking agents, various silane coupling agents, and various titanate-based coupling agents can be used.

[0092] The thickness of the easy-adhesion layer can be adjusted as appropriate depending on optical properties and productivity, but is preferably 10 to 5,000 nm, more preferably 50 to 3,000 nm, and even more preferably 100 to 1,000 nm. Setting the thickness of the easy-adhesion layer above the lower limit makes it easier to uniformly apply the raw material liquid of the easy-adhesion layer onto the substrate layer 1 without defects, and as a result, variations in the adhesion of the easy-adhesion layer are reduced. Setting the thickness of the easy-adhesion layer below the upper limit suppresses the easy-adhesion layer from adversely affecting the optical properties.

[0093] <Offset Printing> Figure 2 is a schematic diagram illustrating an example of a printing method used in the present invention. The printing method employed is offset printing.

[0094] Offset printing is a printing method that utilizes the property of oil-based offset printing inks to repel water. Unlike relief printing, which uses printing plates with raised and recessed surfaces, offset printing uses a printing plate 51 without raised and recessed surfaces. Instead of raised and recessed surfaces, the printing plate 51 has an oil-lipophilic image area and a hydrophilic non-image area. Offset printing may be a water-based printing method using dampening solution W (water-based offset printing), or it may be a waterless printing method using a dedicated printing plate 51 to print without using dampening solution (waterless offset printing). In the case of water-based offset printing, during offset printing, first, the non-image area is moistened by dampening solution W supplied to the printing plate 51 from the dampening solution supply roller 52. Next, oil-based ink I is supplied to the printing plate 51 from the ink supply roller 53. At this time, the ink I repels and does not adhere to the non-image area which has been moistened with dampening solution W and is saturated with water, but adheres only to the oil-lipophilic image area. In this way, an image is formed on the surface of the printing plate 51 using ink I, the image using ink I is transferred to the blanket 54, and the image is transferred (printed) from the blanket 54 to the substrate layer 1 which is conveyed by the blanket 54 and roller 55. When the ink I transferred to the substrate layer 1 hardens, an ink layer 2 is formed, which becomes the printed material 101.

[0095] In waterless offset printing, for example, a printing plate with non-image areas formed by silicone resin can be used. In the waterless offset printing method, the silicone resin repels the ink instead of dampening solution, creating non-image areas. Aside from this point, waterless offset printing is also a printing method common to watered offset printing, which uses dampening solution. Therefore, in this specification, the term "offset printing" is used to include not only watered offset printing, which uses dampening solution, but also waterless offset printing. When adopting waterless offset printing, there is no need to emulsify the dampening solution and ink, so the range of ink choices can be broadened.

[0096] <Color gamut> Offset printing tends to have lower color density and a narrower color gamut compared to gravure printing. This is presumably because offset printing uses a lower pigment content than gravure printing, and also because different types of pigments are suitable for offset printing.

[0097] <Color density> From the perspective of increasing color density and widening the color gamut, for example, when using seven inks, orange, green, and purple can be selected as complementary colors, and the density of the complementary colors can be appropriately set according to the areas where the color gamut is insufficient. Also, for example, when using six inks, it is preferable to adjust the ink layer 2 with two complementary colors out of the six colors to make the color gamut parameters appropriate.

[0098] <Halftone shape> In offset printing, defects in the shape of halftone dots, such as roughness, may occur at the edges (borders) of the dots in the image. Possible causes include poor ink transfer and poor release from the blanket.

[0099] From the viewpoint of improving the shape of the halftone dots, it is preferable to appropriately set the shape and material of the ink and process materials (rollers, blankets, etc.). Furthermore, in water-based offset printing, the emulsification suitability of the ink can affect the shape, so it is preferable to use an ink with excellent emulsification suitability.

[0100] <Concealing properties> In offset printing, the surface of the ink layer 2 is not always smooth, so when the ink particles harden, tiny gaps exist between the ink particles in the ink layer 2. Therefore, when printing white ink, gaps may form, potentially reducing opacity. To improve opacity, it is preferable to print the white ink twice, or to print the second time in a position shifted from the first time, thereby filling the gaps created by the first print.

[0101] Furthermore, it is preferable to appropriately set the ink's transmittance density and thickness to enhance its opacity. For example, when printing using eight inks, it is effective to use offset printing for seven of the inks and flexographic printing for the white ink.

[0102] Offset printing with active energy irradiation is solvent-free (does not use organic solvents), thus suppressing odors. While water-based gravure printing can also be solvent-free, it is difficult to increase printing speed, resulting in lower productivity. In contrast, this type of offset printing allows for higher printing speeds than water-based gravure printing, and because it is solvent-free, it can increase productivity while suppressing the environmental burden. Furthermore, because offset printing with active energy irradiation does not use organic solvents, it is possible to suppress the generation of VOCs (volatile organic compounds) during the production of printed materials 101, thereby reducing the environmental burden.

[0103] <Irradiation with activated energy rays> After ink is printed onto the substrate layer 1, the active energy ray-curable resin contained in the ink is cured by irradiation with active energy rays, and this is fixed to obtain the ink layer 2. Electron beams (EB) are preferred as the active energy rays. When curing the ink with electron beams, the irradiation dose can be appropriately set according to the thickness of the printed ink, the pigment content in the ink, etc. For electron beams, the irradiation dose is preferably 10-100 kGy, more preferably 20-60 kGy, and even more preferably 25-50 kGy. By setting the irradiation dose above the lower limit, the adhesion between the substrate layer 1 and the ink layer 2 can be further improved. Furthermore, by setting the irradiation dose below the upper limit, the decomposition reaction of the active energy ray-curable resin can be suppressed. Irradiation with active energy rays is preferably carried out in a deoxygenated atmosphere (for example, under a nitrogen-filled environment). Irradiation with active energy rays in the presence of oxygen tends to make it difficult for the active energy ray-curable resin to cure. However, by performing the irradiation with active energy rays in a deoxygenated atmosphere, the active energy ray-curable resin can be made to cure more easily.

[0104] It is preferable to immediately press the laminate with a rubber roll or the like after irradiating it with active energy rays. This increases the adhesive strength between the base material layer 1 and the ink layer 2, thereby improving the tear resistance of the sealed portion when a package is formed using the printed material 101.

[0105] In curing of active energy ray-curable resins by active energy ray irradiation, heating and drying are unnecessary, thus reducing the thermal history of the substrate layer 1 and suppressing pitch fluctuations. This makes it possible to suppress processing defects when forming packaging using printed material 101.

[0106] <Extruded resin layer> In this embodiment, the extruded resin layer 3 is formed by laminating a molten resin onto the ink layer 2 and then cooling and solidifying it. After the base layer 1 and the ink layer 2 are irradiated with active energy rays and the ink layer 2 hardens, the extruded resin layer 3 is provided on the ink layer 2. When the extruded resin layer 3 is placed on the back side of the printed material 101, it can also function as a sealant layer. The resin used for the extruded resin layer 3 (hereinafter referred to as "extruded resin") is a thermoplastic resin. The "back side" refers to the inside (contents side) when the printed material 101 is a package, and corresponds to the bottom side of Figure 1. The same applies to the second to eighth embodiments and Figures 3 to 9.

[0107] Examples of extruded resins include polyolefin resins, polyester resins, copolymer resins, polyamide resins, acrylic resins, synthetic rubber resins, and polyurethane resins. Polyolefin resins may be linear polyolefins, cyclic polyolefins, or carboxylic acid-modified polyolefins, and carboxylic acid-modified polyolefins may be cyclic carboxylic acid-modified polyolefins. Cyclic polyolefins are copolymers of olefins and cyclic monomers, and examples of olefins that are constituent monomers of cyclic polyolefins include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, and isoprene. Examples of cyclic monomers that are constituent monomers of cyclic polyolefins include cyclic alkenes such as norbornene, and specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornadiene. Carboxylic acid-modified polyolefins are polymers modified by block polymerization or graft polymerization of polyolefins with carboxylic acids. Examples of carboxylic acids used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride. Carboxylic acid-modified cyclic polyolefins are polymers obtained by copolymerizing a portion of the monomers constituting a cyclic polyolefin with an α,β-unsaturated carboxylic acid or its anhydride, or by block polymerization or graft polymerization of an α,β-unsaturated carboxylic acid or its anhydride to a cyclic polyolefin. Low-density polyethylene (LDPE), medium-density polyethylene (MDPE), and linear low-density polyethylene (LLDPE) are preferred as polyethylene. Unstretched polypropylene (CPP) is preferred as polypropylene. Unstretched polyethylene terephthalate is preferred as polyester resin. Ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMAA), ethylene-vinyl alcohol copolymer (EVOH), ethylene-acrylic acid copolymer (EAA), and ethylene-acrylic acid ester copolymer (EEA) are preferred as copolymer resins. In addition, various ionomers may be used as extruded resins.In addition to the polyolefin resins and copolymer resins mentioned above, polyamide resins, acrylic resins, synthetic rubber resins, and polyurethane resins can be used, as well as the main components of hot melt. Extruded resins may be used individually or in mixtures of two or more types. For example, a combination of low-density polyethylene (LDPE) and linear low-density polyethylene (LLDPE) may be used.

[0108] Extruded resins exhibit high adhesion to metal layers, paper, and similar resin films, but tend to have low adhesion to different types of resin films. Considering this, in this embodiment, it is preferable that the extruded resin is the same type of resin as the resin contained in the ink layer 2. If the extruded resin is a different type of resin from the resin contained in the ink layer, it is preferable that an anchor coat layer, described later, be provided between the ink layer 2 and the extruded resin layer 3.

[0109] If the extruded resin has high heat resistance, the extrusion temperature must be high, and if the extruded resin temperature is high, there is a risk that the ink, such as gravure ink, will remelt when heat is applied to the ink. However, the ink cured with the active energy rays in this embodiment has suppressed remelting. Therefore, even when a resin with high heat resistance is used as the extruded resin, the design quality of the printed material 101 is maintained well.

[0110] The extruded resin is preferably a biodegradable resin.

[0111] The thickness of the extruded resin layer 3 can be appropriately set considering factors such as the degree to which lifting between it and the ink layer 2 can be suppressed. For example, 3 to 100 μm is preferred, and 10 to 30 μm is more preferred. By setting the thickness of the extruded resin layer 3 within the above range, lifting between the ink layer 2 and the extruded resin layer 3 can be further suppressed.

[0112] In this case, the ink layer 2, when irradiated with active energy rays, tends to have a rougher surface (larger irregularities). Furthermore, when a dry laminate layer is formed on a rough surface, the adhesive in the dry laminate layer penetrates more into the ink layer 2, reducing the amount of adhesive remaining on the surface, and its thickness becomes more susceptible to the effects of the irregularities. As a result, areas with thinner layers may occur, and consequently, the anchoring effect against the irregular structure may not be fully exerted, potentially reducing adhesive strength. On the other hand, the extruded resin layer 3 can form a thicker layer compared to the dry laminate layer, so its thickness is less affected by the irregularities. Therefore, it can fully exert an anchoring effect against the irregular structure, increasing adhesive strength. Thus, when the extruded resin layer 3 is laminated (formed) on the ink layer 2, the adhesive strength between the ink layer 2 and the extruded resin layer 3 is greater than the adhesive strength between the ink layer 2 and the dry laminate layer. In addition, the ink layer 2 is harder (more rigid) than a gravure ink layer formed by gravure printing as described in Patent Document 1. Therefore, when a load (stress) such as bending is applied to the printed material 101, the deformation of the ink layer 2 does not easily follow the deformation of the base material layer 1. In this case, the laminate of the ink layer 2 and the dry laminate layer has low rigidity, so lifting is likely to occur between the ink layer 2 and the dry laminate layer. In contrast, the laminate of the ink layer 2 and the extruded resin layer 3 has higher rigidity compared to the laminate of the ink layer 2 and the dry laminate layer, so lifting is less likely to occur between the ink layer 2 and the extruded resin layer 3. Due to this increase in adhesive strength and rigidity, lifting between the ink layer 2 and the extruded resin layer 3 is suppressed. As a result, the printed material 101 has reduced appearance defects.

[0113] Since no organic solvents are used in forming the extruded resin layer 3, there are no residual solvents, and the adhesion strength can be increased compared to non-solvent adhesives. As a result, the printed material 101 can meet the physical properties required for the strength of the packaging material, and the environmental impact can be reduced. In addition, odors caused by organic solvents can be suppressed.

[0114] The extruded resin layer 3 may further contain additives. Examples of additives include crosslinking agents, antioxidants, antiblocking agents, lubricants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins.

[0115] For example, when the extruded resin layer 3 contains an antistatic agent, and the antistatic function is activated when the antistatic agent is exposed on the surface, it has conventionally been difficult to control the amount of exposure of the antistatic agent. However, in this embodiment, by irradiating the extruded resin layer 3 with active energy rays after lamination, the degree of crystallinity of the extruded resin layer 3 can be increased, thereby suppressing excessive exposure of the antistatic agent. By limiting the amount of exposure of the antistatic agent in this way, excessive slippage of the surface of the extruded resin layer 3 can be suppressed. Furthermore, conventionally, when the extruded resin layer 3 contained an antistatic agent, the antistatic agent sometimes migrated to the ink layer 2 side instead of the sealing surface, resulting in a failure to achieve the desired antistatic performance. However, by increasing the crystallinity of the extruded resin layer 3 as described above, or by irradiating the surface side with active energy rays to increase the crystallinity of the surface side of the resin layer, the migration of the antistatic agent to the ink layer 2 side can be suppressed, thereby enabling the stable expression of the antistatic function (function as an antistatic film).

[0116] <Other layers> The printed material 101 may also be provided with other layers, such as an anchor coat layer, an intermediate layer, a further extruded resin layer (laminate layer and / or sealant layer), a barrier layer, a sealant layer, a dry laminate layer, a coating layer (impact-resistant layer), etc. Embodiments of printed materials having these layers will be described later.

[0117] <Color difference> The printed matter 101 deteriorates due to the heat of heat sealing, and this deterioration can appear as color. It is preferable that the color difference (ΔE) obtained by the following formula (A) is less than 3.0 before and after heating and pressurizing under the heat sealing conditions of a temperature of 220°C, a pressure of 0.2 MPa, and a time of 1.5 seconds. By setting the color difference within the above range, the color difference before and after heat sealing can be reduced. As a result, the heat resistance of the printed matter 101 is enhanced.

[0118] [Number] [In the above formula (A), ΔL * , Δa * , and Δb * represent the differences in lightness (L * a * b * color space) before and after heating and pressurizing under the above heat sealing conditions, respectively, for lightness (L * ), chromaticity (a * ), and (b * ).]

[0119] The upper limit of the above color difference is preferably 1.5 or less, more preferably 1.3 or less, from the viewpoint of sufficiently suppressing discoloration during heat sealing. The lower limit of the above color difference is preferably 0.1 or more, more preferably 0.3 or more, from the viewpoint of ease of manufacture. When the printed matter 101 is viewed in plan from the base material layer 1 side, the coating ratio by the ink layer 2 with respect to the entire area of the region (area) to be measured for the above color difference may be 50 area% or more, may be 70 area% or more, or may be 100 area%. The fact that this coating ratio is 100 area% means that the entire region to be measured for "color difference" is covered by the ink layer 2. The fact that this coating ratio is 50 area% means that half of the region to be measured for "color difference" is covered by the ink layer 2.

[0120] [Adhesive strength (lamination strength)] The printed material 101 preferably has an adhesive strength (peel adhesion strength) of 0.5 N / 15 mm or more, and more preferably 1.0 N / 15 mm or more. The higher the adhesive strength, the better, and there is no particular upper limit to it. It can be set appropriately so that the printed material 101 does not break before peeling (the printed material 101 does not break without peeling). The adhesive strength can be determined, for example, by cutting the printed material 101 to a width of 15 mm to make a measurement sample (see JIS Z 1707:2019), peeling the interlayers at the ends of the measurement sample, and then measuring the interlayer peel strength of the laminate using a tensile testing machine under the conditions of angle: 90° (total 180°), tensile (peel) speed: 300 mm / min, and room temperature, by T-peel (see JIS K 6854-3). This peel strength can be determined as the adhesive strength at room temperature (20°C). By setting the adhesive strength within the above range, the lamination strength of the printed material 101 can be increased.

[0121] In the printed material 101, the content of the same type of resin (for example, polyethylene, etc.) may be 90% by mass or more. In this case, the printed material 101 can be composed as a highly recyclable monomaterial.

[0122] As described above, the printed material 101 of this embodiment includes an extruded resin layer 3, which suppresses lifting between the ink layer 2 and the extruded resin layer 3, thus suppressing defects in appearance of the printed material 101.

[0123] In printed material 101, even if odor components are generated after irradiation with active energy rays, the heat generated by the extruded resin during the formation of the extruded resin layer 3 causes the odor components to volatilize, resulting in printed material 101 having reduced odor.

[0124] <Application> Because the printed material 101 of this embodiment suppresses internal layer separation, it can be suitably used not only for light packaging but also for packaging that is heated or subjected to moist heat, such as boiled or retort foods, resealable pouches, and microwaveable foods. For example, it can be used as a steam-venting packaging material, aerated boiling packaging material, retort packaging material, etc., as described below. It can also be applied to the manufacturing processes of the contents and packaging described below.

[0125] (Steam-venting packaging material) Because the printed material 101 has high rigidity, it can deform as a surface when steam escapes, thus preventing blockage of the steam vent. Consequently, steam is prevented from escaping from sources other than the steam vent. Furthermore, it is preferable that the printed material 101 does not tear at the seal when heated at 600W for 3 minutes. This enhances the heat resistance of the printed material 101, making it particularly suitable for use as packaging material for microwave-heated food. Because the printed material 101 has high ink heat resistance, the heat from the steam vent prevents the ink from remelting. This prevents a decrease in design quality due to remelting. Considering this point, it is particularly effective when the ink layer 2 is provided near the steam vent. Because printed material 101 has high adhesive strength, it can prevent a decrease in seal strength. This prevents steam from escaping from anywhere other than the steam vent. The active energy ray curing ink (especially acrylic resin) of printed material 101 has a higher thermal conductivity compared to gravure ink (especially urethane-based resin), which allows it to dissipate overheating during microwave cooking and prevent heat pinholes. This suppresses bag rupture during microwave cooking.

[0126] (Air-filled boilable packaging) Because the printed material 101 has high adhesive strength, a decrease in seal strength can be prevented. This prevents the bag from rupturing during sterilization when the printed material 101 is formed into a bag (prevention of internal pressure rupture). It also prevents the bag from rupturing during loading during transportation (prevention of external pressure rupture).

[0127] (Retort packaging) As described above, the ink layer 2 irradiated with active energy rays tends to have a rougher surface (larger irregularities). Furthermore, when a dry laminate layer is formed on a rough surface, the adhesive in the dry laminate layer penetrates more into the ink layer 2, reducing the amount of adhesive remaining on the surface, and making its thickness more susceptible to the effects of the irregularities. As a result, areas with thinner layers may occur, and consequently, the anchoring effect against the irregular structure may not be fully exerted, potentially leading to a decrease in adhesive strength. On the other hand, the extruded resin layer 3 can form a thicker layer compared to the dry laminate layer, so its thickness is less affected by the irregularities. Therefore, it can fully exert an anchoring effect against the irregular structure, thereby increasing adhesive strength. A printed material 101 having such an extruded resin layer 3 has higher adhesive strength compared to a printed material with a dry laminate layer, thus suppressing the decrease in adhesive strength due to ink degradation during heat sterilization. This ensures the strength of the packaging material after retort processing.

[0128] (Easy-to-open packaging material) Because the printed material 101 has high adhesive strength, its tear resistance can be improved. When polyethylene is used as the base layer 1 of the printed material 101, the elastic modulus of the polyethylene can be improved by irradiation with active energy rays, and as a result, the tear resistance can be increased. By using a low-density resin, for example, for the resin used in the extruded resin layer 3 of the printed material 101, or the resin used in the sealant layer 7 described later, the tear resistance can be improved. As described above, by improving the tearability of the printed material 101, even if the edges of the printed material 101 are scratched, it becomes less likely that the material will tear poorly due to the stretching of the resin during opening from the scratched edge. By setting the molecular orientation angles of the substrate layer 1 and / or the extruded resin layer 3 of the printed material 101 to -40° to 40°, the difference between the molecular orientation angles of the substrate layer 1 and the extruded resin layer 3 is reduced, thereby improving tear resistance.

[0129] (Frozen food packaging material) Because the printed material 101 has high rigidity, protrusions are less likely to form when it deforms. This prevents pinholes caused by protrusions hardening and rubbing against each other, especially in a frozen environment.

[0130] (Self-supporting packaging material) Because the printed material 101 has high rigidity, the packaging using the printed material 101 has high self-supporting properties. As a result, the packaging has a good display design when placed in a store. Because printed material 101 has high rigidity, it can exhibit high self-supporting properties even with a thinner thickness than conventional materials. This results in packaging with a better display design in stores. Furthermore, it reduces the environmental impact.

[0131] (Contents) Since the printed material 101 does not use organic solvents in its manufacture, odor is suppressed. As a result, when the printed material 101 contains mildly flavored foods such as porridge or pet food for animals sensitive to odors, odor transfer can be suppressed. The active energy ray curing ink of printed material 101 has a higher crosslinking density, is less prone to swelling, penetration, and hydrolysis compared to gravure ink. As a result, printed material 101 is less likely to experience a decrease in adhesive strength even when exposed to acidic volatile components, compared to gravure printed material, thus suppressing the decrease in adhesive strength over time. Therefore, it can be applied to contents such as chlorous acid water, vinegar, and fragrances.

[0132] (Packaging manufacturing process: preheating) Because the ink in printed material 101 has high heat resistance, discoloration can be suppressed even when a preheating process is performed to improve the sealability when manufacturing packaging using printed material 101. Therefore, there is no need to restrict the temperature conditions of the manufacturing process.

[0133] (Packaging manufacturing process: high-speed filling) Since the heat resistance of the ink in printed material 101 can be improved by irradiation with active energy rays, redissolution of the ink can be suppressed even when the sealing temperature is increased and the filling speed is increased. Since the rigidity of the printed material 101 can be improved by irradiation with active energy rays, the occurrence of wrinkles due to thermal shrinkage can be suppressed even when the sealing temperature is increased and the filling speed is increased. If the printed material 101 contains polyethylene, irradiation with active energy rays increases the rigidity of the polyethylene, and even if the sealing temperature is increased and the filling speed is increased, the occurrence of wrinkles due to thermal shrinkage can be suppressed. The active energy ray curing ink (especially acrylic resin) of printed material 101 has a higher thermal conductivity compared to gravure ink (especially urethane-based resin), so the heat during filling and sealing is easily transferred to the sealing surface, resulting in good sealing performance. As described above, the printed material 101 can suppress sealing defects even when high-speed filling is performed.

[0134] The following describes a specific example in which the printed material comprises a base layer 1, an ink layer 2, and an extruded resin layer 3, in addition to another layer. However, the number and order of addition of the other layer are not limited to the following example and can be changed as appropriate.

[0135] [Second Embodiment] Figure 3 is a schematic cross-sectional view showing the layer structure of a printed material according to a second embodiment of the present invention. The printed material 102 shown in Figure 3 comprises, from top (front side), a base material layer 1, an ink layer 2, an anchor coat layer 4, and an extruded resin layer 3, in this order.

[0136] The printed material 102 is a laminate formed by reverse offset printing. The printed material 102 has the same configuration as the printed material 101, except that it further comprises an anchor coat layer 4 provided between the ink layer 2 and the extruded resin layer 3. The base layer 1, ink layer 2, and extruded resin layer 3 of the printed material 102 have the same configuration as those described in the first embodiment, and the printing method and the method of irradiation with active energy rays can also be the same as in the first embodiment. The extruded resin layer 3 can also function as a sealant layer.

[0137] <Anchor Coat Layer> The anchor coat layer 4 is a layer that enhances the adhesion between the ink layer 2 and the extruded resin layer 3. Therefore, by having the anchor coat layer 4 in the printed material 102, lifting between the ink layer 2 and the extruded resin layer 3 is further suppressed.

[0138] (Surface treatment layer) The surface treatment layer is a layer formed by surface treatment of the substrate layer 1 so that it has good adhesion properties. Examples of surface treatments include physical treatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and / or nitrogen gas, glow discharge treatment, and chemical treatments such as oxidation treatment using chemicals, as described in the first embodiment of the substrate layer 1 above.

[0139] (Easy adhesion layer) As the easy-adhesion layer, the same type as the easy-adhesion layer described in the base layer 1 of the first embodiment described above can be used.

[0140] By including an anchor coat layer 4 in the printed material 102, the adhesion between the main material of the ink layer 2 and the main material of the extruded resin layer can be improved, and lifting between layers can be suppressed.

[0141] The anchor coat layer 4 can also contain an acrylic component of the same type as the alkaline component (crosslinking agent) contained in the ink layer 2 as a crosslinking agent. This can increase the adhesion between the ink layer 2 and the anchor coat layer 4, thereby increasing the adhesive strength.

[0142] The anchor coat layer 4 can be formed using either an aqueous resin composition that is compatible with water (and therefore compatible with dampening solution) or a non-aqueous resin composition that is not compatible with water (and therefore not compatible with dampening solution). Such aqueous resin compositions and / or non-aqueous resin compositions can be formed using conventionally known anchor coat agents such as polyolefin-based anchor coat agents, epoxy-based anchor coat agents, vinyl-based anchor coat agents, imine-based anchor coat agents, and urethane-based anchor coat agents.

[0143] The thickness of the anchor coat layer 4 is not particularly limited, but can be, for example, 0.1 to 1.0 μm.

[0144] As described above, the printed material 102 of this embodiment includes an anchor coat layer 4, which further suppresses lifting between the ink layer 2 and the extruded resin layer 3.

[0145] <Application> The printed material 102 can be used for the same purposes as the printed material 101 of the first embodiment.

[0146] [Third Embodiment] Figure 4 is a schematic cross-sectional view showing the layer structure of a printed material according to the third embodiment of the present invention. The printed material 103 shown in Figure 4 is a laminate formed by reverse offset printing. The printed material 103 comprises, from the top (front side), a base material layer 1, an ink layer 2, an anchor coat layer 4a, an extruded resin layer 3a, an intermediate layer 5, an anchor coat layer 4b, and an extruded resin layer 3b, in this order.

[0147] The printed material 103 has the same configuration as the printed material 102, except that it comprises an intermediate layer 5, an anchor coat layer 4b, and an extruded resin layer 3b provided on the extruded resin layer 3a. The base layer 1, ink layer 2, extruded resin layers 3a, 3b, and anchor coat layers 4a, 4b of the printed material 103 have the same configuration as those described in the first and second embodiments, and the printing method and the method of irradiation with active energy rays can also be the same as those in the first and second embodiments. The extruded resin layer 3b can also function as a sealant layer.

[0148] <Middle class> The intermediate layer 5 may contain polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene; alicyclic polyolefin resins; polyamide resins such as nylon 6 and nylon 66; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polypropylene terephthalate, polybutyl succinate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, and polyethylene diphenylate; polycarbonate resins; polyarylate resins; polyacetal resins; polyphenylene sulfide resins; trifluoroethylene resins; tetrafluoroethylene-hexafluoropropylene copolymers; vinylidene fluoride resins; fluorine resins; acrylic resins; methacrylic resins; polyacetal resins; polyglycolic acid resins; polylactic acid resins, etc. The resins contained in the intermediate layer 5 may be the same as or different from the resins contained in the base layer 1.

[0149] The intermediate layer 5 may contain aluminum foil. Alternatively, the intermediate layer 5 may be an aluminum vapor-deposited resin film in which an aluminum vapor-deposited layer is formed on a resin film. By including aluminum foil or an aluminum vapor-deposited layer in the intermediate layer 5, the printed material 103 can be given a metallic luster and its barrier properties can be improved. The intermediate layer 5 may have the same configuration as the base layer 1 of the first embodiment.

[0150] The thickness of the intermediate layer 5 is preferably 5 to 200 μm, more preferably 6.5 to 100 μm, even more preferably 7 to 50 μm, and particularly preferably 7 to 35 μm.

[0151] The intermediate layer 5 may be colored, and may be white, gray, black, or the like.

[0152] When aluminum foil is used as the intermediate layer 5, it is preferable that the extruded resin layer 3 contains an ethylene-methacrylic acid copolymer. In this embodiment, an anchor coat layer 4b is used, but since the ethylene-methacrylic acid copolymer has high adhesion to aluminum foil, the adhesive strength between the intermediate layer 5 and the extruded resin layer 3b can be increased even without providing the anchor coat layer 4b.

[0153] The intermediate layer 5 may have a barrier layer or a printed layer.

[0154] <Barrier layer> The barrier layer 6 is, for example, a gas barrier layer that improves the oxygen barrier and water vapor barrier properties of the printed material 103. The barrier layer 6 preferably includes an inorganic compound layer, or an inorganic compound layer and a coating layer. When the barrier layer 6 includes an inorganic compound layer and a coating layer, it is preferable that the inorganic compound layer and the coating layer are laminated in that order from the side of the extruded resin layer 3a. When microwave heating by a microwave oven is anticipated, the barrier layer 6 is preferably an inorganic oxide layer, a resin-containing layer, or a combination thereof.

[0155] <Inorganic compound layer> The inorganic compound layer may be formed by coating, or by depositing the inorganic compound.

[0156] Examples of inorganic compounds contained in the inorganic compound layer include metal oxides such as silicon oxide, boron oxide, aluminum oxide, magnesium oxide, calcium oxide, potassium oxide, tin oxide, sodium oxide, titanium oxide, lead oxide, zirconium oxide, and yttrium oxide. The inorganic compound layer is preferably a vapor-deposited film made of a metal oxide. From the viewpoint of transparency and barrier properties, aluminum oxide, silicon oxide, and magnesium oxide are preferred as metal oxides. Furthermore, considering cost, aluminum oxide and silicon oxide are more preferred as metal oxides. Furthermore, from the viewpoint of excellent tensile stretchability during processing, silicon oxide is even more preferred as the metal oxide. By making the inorganic compound layer a vapor-deposited film made of a metal oxide, high barrier properties can be obtained with a very thin layer that does not affect the recyclability of the printed material 103.

[0157] Because vapor-deposited films made of metal oxides are transparent, they can improve the visibility of the contents compared to vapor-deposited films made of metal.

[0158] The thickness of the vapor-deposited film made of aluminum oxide is preferably 5 to 30 nm, and more preferably 7 to 15 nm. By setting the thickness of the vapor-deposited film made of aluminum oxide to be above the lower limit, sufficient gas barrier properties can be obtained. By setting the thickness of the vapor-deposited film made of aluminum oxide to be below the upper limit, it is possible to suppress the occurrence of cracks due to deformation caused by internal stress in the thin film and suppress the decrease in gas barrier properties. Although it is still possible to use the printed material 103 even if the thickness of the vapor-deposited film exceeds the upper limit, the cost will increase due to the increase in material usage and the lengthening of the film formation time.

[0159] The thickness of the silicon dioxide vapor-deposited film is preferably 10 to 50 nm, and more preferably 20 to 40 nm. By setting the thickness of the silicon dioxide vapor-deposited film to be above the lower limit, sufficient gas barrier properties can be obtained. By setting the thickness of the silicon dioxide vapor-deposited film to be below the upper limit, it is possible to suppress the occurrence of cracks due to deformation caused by internal stress in the thin film and suppress the decrease in gas barrier properties. Although it is still possible to use the printed material 103 even if the thickness of the vapor-deposited film exceeds the upper limit, the cost will increase due to the increase in material usage and the lengthening of the film formation time.

[0160] Inorganic compound layers can be formed, for example, by vacuum deposition. Vacuum deposition can utilize either physical vapor deposition or chemical vapor deposition. Examples of physical vapor deposition include, but are not limited to, vacuum evaporation, sputtering, and ion plating. Examples of chemical vapor deposition include, but are not limited to, thermal CVD (Chemical Vapor Deposition), plasma CVD, and photoCVD.

[0161] In the vacuum deposition described above, resistance heating vacuum deposition, electron beam heating vacuum deposition, induction heating vacuum deposition, sputtering, reactive sputtering, dual magnetron sputtering, plasma chemical vapor deposition (PECVD), etc., are preferably used. However, considering productivity, vacuum deposition is preferred. For the heating means in vacuum deposition, it is preferable to use one of electron beam heating, resistance heating, or induction heating.

[0162] <Coating layer> The coating layer, like the inorganic compound layer, has gas barrier properties. The coating layer can be formed, for example, by coating. In this case, a coating solution containing resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, polyvinylidene chloride, polyacrylonitrile, and epoxy resins can be used. Organic particles or inorganic particles, inorganic layered compounds, curing agents, etc., may be added to this coating solution.

[0163] The coating layer may be an organic-inorganic composite layer comprising, for example, at least one of a metal alkoxide, a hydrolysate of a metal alkoxide, and a reaction product of a hydrolysate of a metal alkoxide, and a water-soluble polymer. This organic-inorganic composite layer may further contain a silane coupling agent, a hydrolysate of a silane coupling agent, a reaction product of a hydrolysate of a silane coupling agent, and the like.

[0164] Examples of metal alkoxides and their hydrolysates contained in the organic-inorganic composite layer include tetraethoxysilane [Si(OC2H5)4], triisopropoxyaluminum [Al(OC3H7)3], and other metal alkoxides with the general formula M(OR). n Examples include compounds represented by [the formula] and their hydrolysates. One of these may be used alone, or two or more may be used in combination.

[0165] The total content of metal alkoxides, their hydrolysates, or their reaction products used in forming the organic-inorganic composite layer is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 65% ​​by mass or more, from the viewpoint of oxygen barrier properties. The total content of metal alkoxides, their hydrolysates, and their reaction products is preferably 70% by mass or less.

[0166] The water-soluble polymer contained in the organic-inorganic composite layer is not particularly limited and includes, for example, polysaccharides such as polyvinyl alcohol polymers, starch, methylcellulose, and carboxymethylcellulose, and hydroxyl group-containing polymers such as acrylic polyol polymers. From the viewpoint of further improving oxygen barrier properties, it is preferable that the water-soluble polymer contains a polyvinyl alcohol polymer. The degree of polymerization of the water-soluble polymer is preferably, for example, 300 to 4500.

[0167] The polyvinyl alcohol-based polymer contained in the organic-inorganic composite layer can be obtained, for example, by saponifying (including partial saponification) polyvinyl acetate. This water-soluble polymer may have several percent to several tens of percent of acetate groups remaining.

[0168] The content of the water-soluble polymer used in forming the organic-inorganic composite layer is preferably 15% by mass or more, and more preferably 20% by mass or more. On the other hand, the content of the water-soluble polymer used in forming the organic-inorganic composite layer is preferably 50% by mass or less, and more preferably 45% by mass or less.

[0169] Examples of silane coupling agents used in organic-inorganic composite layers include silane coupling agents having organic functional groups. Examples of silane coupling agents include ethyltrimethoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, glycidooxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropylmethyldimethoxysilane. A silane coupling agent selected from these, its hydrolysate, or one of their reaction products may be used alone or in combination of two or more.

[0170] As a silane coupling agent, one having an epoxy group as an organic functional group is preferred. Examples of silane coupling agents having an epoxy group include γ-glycidooxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Silane coupling agents having an epoxy group may also have organic functional groups other than the epoxy group, such as vinyl groups, amino groups, methacrylic groups, and ureyl groups. A silane coupling agent selected from these, its hydrolysate, or one of their reaction products may be used alone or as a mixture of two or more.

[0171] Silane coupling agents having organic functional groups, their hydrolysates, and their reaction products enhance the oxygen barrier properties of the coating layer and the adhesion to adjacent layers through the interaction of their organic functional groups with the hydroxyl groups of water-soluble polymers. In particular, when the silane coupling agent, its hydrolysate, and their reaction products have epoxy groups and the water-soluble polymer is polyvinyl alcohol, the interaction between the epoxy groups and the hydroxyl groups of polyvinyl alcohol further enhances the oxygen barrier properties and the adhesion to adjacent layers.

[0172] The total content of the silane coupling agent, its hydrolysate, and their reaction products used in forming the organic-inorganic composite layer is preferably 1% by mass or more, and more preferably 2% by mass or more. On the other hand, the total content of the silane coupling agent, its hydrolysate, and their reaction products is preferably 15% by mass or less, and more preferably 12% by mass or less.

[0173] The thickness of the coating layer is preferably 50 to 1,000 nm, and more preferably 100 to 500 nm. By setting the thickness of the coating layer above the lower limit, sufficient gas barrier properties can be obtained, and by setting it below the upper limit, sufficient flexibility can be maintained.

[0174] The barrier layer 6 is preferably surface-treated, as is the case with the substrate layer 1 in the first embodiment described above. This improves the adhesion between the barrier layer 6 and adjacent layers. Nanocomposite materials may also be used for the barrier layer 6.

[0175] By including an anchor coat layer 4a in the printed material 103, when the main material of the ink layer 2 and the main material of the extruded resin layer 3a are different types of resins, adhesion between the ink layer 2 and the extruded resin layer 3a is made possible, and the function of suppressing the lifting of the extruded resin layer 3a can be effectively exerted. When the main material of the ink layer 2 and the main material of the extruded resin layer 3a are the same type of resin, the adhesion between the ink layer 2 and the extruded resin layer 3a can be improved, thereby further suppressing lifting between the ink layer 2 and the extruded resin layer 3a. By including an anchor coat layer 4b in the printed material 103, when the main material of the intermediate layer 5 and the main material of the extruded resin layer 3b are different types of resins, adhesion between the intermediate layer 5 and the extruded resin layer 3b is made possible, and lifting between the intermediate layer 5 and the extruded resin layer 3b can be suppressed. If the main material of the intermediate layer 5 is metal or the same type of resin as the main material of the extruded resin layer, the adhesion between the intermediate layer 5 and the extruded resin layer 3b can be improved, thereby further suppressing lifting between the intermediate layer 5 and the extruded resin layer 3b.

[0176] In the printed material 103, the content of the same type of resin (for example, polyethylene, etc.) may be 90% by mass or more. In this case, the printed material 103 can be composed as a highly recyclable monomaterial.

[0177] As described above, the printed material 103 of this embodiment provides the same effects as the printed material 102 of the second embodiment. In addition, it also provides the effects attributed to the intermediate layer 5.

[0178] <Application> The printed material 103 can be used for the same purposes as the printed material 101 of the first embodiment.

[0179] [Fourth Embodiment] Figure 5 is a schematic cross-sectional view showing the layer structure of a printed material according to the fourth embodiment of the present invention. The printed material 104 shown in Figure 5 is a laminate formed by reverse offset printing. The printed material 104 comprises, from the top (surface side), a base layer 1, an ink layer 2, an anchor coat layer 4a, an extruded resin layer 3a, an intermediate layer 5, an anchor coat layer 4b, an extruded resin layer 3b, and a sealant layer 7, in this order.

[0180] The printed material 104 has the same configuration as the printed material 103, except that it includes a sealant layer 7 provided on the extruded resin layer 3b. The base layer 1, ink layer 2, extruded resin layers 3a, 3b, anchor coat layers 4a, 4b, and intermediate layer 5 of the printed material 104 have the same configuration as those described in the first to third embodiments, and the printing method and the method of irradiation with active energy rays can also be the same as those in the first to third embodiments.

[0181] <Sealant layer> The sealant layer 7 may contain polyethylene, polypropylene, polyethylene terephthalate, polybutylene succinate (PBS), etc. The polyethylene may be low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), or very low-density polyethylene (VLDPE), but linear low-density polyethylene (LLDPE) is preferred. The polypropylene is preferably unstretched polypropylene (CPP). Unstretched polyethylene, polyethylene terephthalate, and polybutylene succinate are also preferred. Thus, the sealant layer 7 is preferably an unstretched film, but other stretched films such as heat-sealable stretched polypropylene (HSOPP) and heat-sealable polyethylene terephthalate (HSPET) can also be used.

[0182] From the perspective of reducing environmental impact, polyethylene may be biomass polyethylene derived from plants such as sugarcane, or polyethylene recycled by mechanical recycling and / or chemical recycling.

[0183] The sealant layer 7 preferably contains a biodegradable resin.

[0184] The sealant layer 7 may contain other additives.

[0185] The sealant layer 7 may be transparent or opaque. When the sealant layer 7 is transparent, the contents of the printed material 104 are easily visible when used as packaging. When the sealant layer 7 is opaque, the contents do not obstruct the visibility of information such as characters and images displayed on the ink layer 2 when used as packaging. When the sealant layer 7 is opaque, it is preferable that the sealant layer 7 be white, gray, black, etc. These white, gray, black, etc. sealant layers 7 can improve the visibility of information displayed on the ink layer 2. For example, the sealant layer 7 may contain titanium dioxide. In this case, the sealant layer 7 can be configured as a light-shielding sealant layer for retort packaging. This suppresses the hardening and deterioration of polyethylene due to light, and as a result, the decrease in seal strength is suppressed.

[0186] The printed material 104 can be subjected to heat sealing more reliably by further comprising a sealant layer 7.

[0187] The thickness of the sealant layer 7 can be set appropriately considering the shape of the packaging bag to be manufactured and the mass of the contents to be contained, but for example it can be 15 to 150 μm.

[0188] The sealant layer 7 can be formed together with the extruded resin layer 3b, for example, by extruding molten extruded resin from an extrusion laminating device between the anchor coat layer 4b and a resin film such as an unstretched polyethylene film, and then cooling and solidifying it.

[0189] Thus, when the printed material 104 includes a sealant layer 7, the extruded resin layer 3b, together with the anchor coat layer 4b, can function as a laminate layer that adheres the intermediate layer 5 and the sealant layer 7.

[0190] When the extruded resin layer 3b contains polyethylene and the sealant layer 7 contains unstretched polypropylene (CPP), a peel-off lid can be made using pseudo-adhesion.

[0191] The sealant layer 7 may further contain additives. Examples of additives include crosslinking agents, antioxidants, antiblocking agents, lubricants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins.

[0192] For example, when the sealant layer 7 contains an antistatic agent, and the antistatic function is activated when the antistatic agent is exposed on the surface, it has conventionally been difficult to control the amount of exposure of the antistatic agent. However, in this embodiment, by irradiating the sealant layer 7 with active energy rays after lamination, the crystallinity of the sealant layer 7 can be increased, thereby suppressing excessive exposure of the antistatic agent. By limiting the amount of exposure of the antistatic agent in this way, excessive slippage of the surface of the sealant layer 7 can be suppressed. Furthermore, an antistatic film can be laminated on the sealant layer 7. Conventionally, when the sealant layer 7 contained an antistatic agent, the antistatic agent sometimes migrated to the anchor coat layer 4b side instead of the sealing surface, resulting in a failure to achieve the desired antistatic performance. However, by increasing the crystallinity of the sealant layer 7 as described above, migration to the anchor coat layer 4b side can be suppressed, thereby enabling the stable expression of the antistatic function (function as an antistatic film).

[0193] In the printed material 104, the content of the same type of resin (for example, polyethylene, etc.) may be 90% by mass or more. In this case, the printed material 104 can be composed as a highly recyclable monomaterial.

[0194] As described above, the printed material 104 of this embodiment provides the same effects as the printed material 101 of the first embodiment. In addition, it also provides the effects attributed to the sealant layer 7.

[0195] <Application> Printed material 104 can be used for the same purposes as printed material 101 in the first embodiment. In addition, because its heat resistance is further enhanced, it can be suitably used for boiled or retort foods (boiling or retort processing), resealed pouches (usually, the sealing of the sealant layer 7 between the welded and unsealed parts is performed by heating to 150°C or higher), cans, steam vents, and packaging that is retorted and then heated by the end consumer, such as by microwave heating, or subjected to moist heat.

[0196] [Fifth Embodiment] Figure 6 is a schematic cross-sectional view showing the layer structure of a printed material according to the fifth embodiment of the present invention. The printed material 105 shown in Figure 6 is a laminate formed by reverse offset printing. The printed material 105 comprises, from the top (front side), a base layer 1, an ink layer 2, an anchor coat layer 4a, an extruded resin layer 3a, an intermediate layer 5, a dry laminate layer 8, and a sealant layer 7, in this order.

[0197] The printed material 105 has the same configuration as the printed material 104, except that it includes a dry laminate layer 8 instead of the anchor coat layer 4b and the extruded resin layer 3b. The base layer 1, ink layer 2, extruded resin layer 3a, anchor coat layer 4a, and sealant layer 7 of the printed material 105 have the same configuration as those described in the first to fourth embodiments, and the printing method and the method of irradiation with active energy rays can also be the same as those in the first to fourth embodiments.

[0198] <Dry laminate layer> The adhesive used to form the dry laminate layer 8 may be a one-component curing adhesive, a two-component curing adhesive, or a non-curing adhesive. Furthermore, the adhesive may be a solvent-free adhesive or a solvent-based adhesive.

[0199] Examples of adhesives include polyether-based adhesives, polyester-based adhesives, silicone-based adhesives, polyamine-based adhesives, adhesives to which epoxy groups have been added, urethane-based adhesives, rubber-based adhesives, vinyl-based adhesives, epoxy-based adhesives other than those listed above, phenol-based adhesives, and olefin-based adhesives. Adhesives containing biomass components can also be preferably used. Polyamine-based adhesives and urethane-based adhesives are more preferred. Adhesives may have gas barrier properties. Adhesives may be used individually or in mixtures of two or more types. Specific examples of gas barrier adhesives include "Maxive®" manufactured by Mitsubishi Gas Chemical Company, Inc. and "Paslim®" manufactured by DIC Corporation.

[0200] The thickness of the dry laminate layer 8 is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, and even more preferably 1 to 5 μm.

[0201] The dry laminate layer 8 can be formed by applying and drying it on the sealant layer 7 using conventionally known methods such as the direct gravure roll coating method, gravure roll coating method, kiss coating method, reverse roll coating method, fontein method, and transfer roll coating method.

[0202] The printed material 105 may contain 90% by mass or more of the same type of resin (for example, polyethylene). In this case, the printed material 105 can be composed of a highly recyclable monomaterial.

[0203] As described above, the printed material 105 of this embodiment provides the same effects as the printed material 101 of the first embodiment and the printed material 104 of the fourth embodiment.

[0204] <Application> The printed material 105 can be used for the same purposes as the printed material 101 of the first embodiment and the printed material 104 of the fourth embodiment.

[0205] [Sixth Embodiment] Figure 7 is a schematic cross-sectional view showing the layer structure of a printed material according to the sixth embodiment of the present invention. The printed material 106 shown in Figure 7 is a laminate formed by reverse offset printing. The printed material 106 comprises, from the top (surface side), a coating layer 9, a substrate layer 1, an ink layer 2, and an extruded resin layer 3, in this order.

[0206] The printed material 106 has the same configuration as the printed material 101, except that it further comprises a coating layer 9 on the surface of the base material layer 1. The base material layer 1, ink layer 2, and extruded resin layer 3 of the printed material 106 have the same configuration as those described in the first embodiment, and the printing method and the method of irradiation with active energy rays can also be the same as those in the first embodiment.

[0207] <Coat layer> The printed material 106 includes a coating layer 9 as its outermost layer. The coating layer 9 is formed on at least a portion of the outer layer side of the transparent substrate layer 1. The coating layer 9 may be any transparent resin layer, and the resin is not particularly limited. When the printed material 106 is a metallic printed material having a metallic reflective layer, it is preferable to form the coating layer 9 in a position such that, when the printed material 106 is viewed from above, the coating layer 9 overlaps with at least a portion of the area having the metallic reflective layer. By arranging the coating layer 9 to overlap at least a portion of the area having the metallic reflective layer in the planar direction, the metallic luster based on the metallic reflective layer can be adjusted, and the design can be improved. Furthermore, by arranging the coating layer 9 to overlap at least a portion of the area having the metallic reflective layer in the planar direction, and by arranging the internal scattering layer to overlap at least a portion of the area having the coating layer 9, even if the surface is rubbed, the traces of abrasion will not be noticeable, and a decrease in design can be suppressed. The coating layer 9 may be arranged so as to overlap all of the areas having the metallic reflective layer in the planar direction, but from the viewpoint of creating a contrast in metallic luster depending on the presence or absence of the coating layer 9, it is preferable to arrange it so as to overlap only a part of the areas having the metallic reflective layer.

[0208] In printed material 106, the content of the same type of resin (for example, polyethylene, etc.) may be 90% by mass or more. In this case, printed material 106 can be composed as a highly recyclable monomaterial.

[0209] As described above, the printed material 106 of this embodiment provides the same effects as the printed material 101 of the first embodiment. In addition, it also provides the effects attributed to the coating layer 9.

[0210] <Application> The printed material 106 can be used for the same purposes as the printed material 101 of the first embodiment.

[0211] [Seventh Embodiment] Figure 8 is a schematic cross-sectional view showing the layer structure of a printed material according to the seventh embodiment of the present invention. The printed material 107 shown in Figure 8 is a laminate formed by offset printing on the front side. The printed material 107 comprises, from the top (surface side), an ink layer 2, a substrate layer 1, and an extruded resin layer 3 in that order.

[0212] The ink layer 2 of the printed material 107 has the same configuration as described in the first embodiment, and the printing method and the method of irradiating with active energy rays can also be the same as in the first embodiment.

[0213] When a dry laminate layer is laminated onto a base layer 1, the laminate of base layer 1 and the dry laminate layer has low rigidity, making it prone to lifting between the base layer 1 and the dry laminate layer. In contrast, the laminate of base layer 1 and the extruded resin layer 3 has higher rigidity compared to the laminate of base layer 1 and the dry laminate layer, making it less likely for lifting to occur between the base layer 1 and the extruded resin layer 3. This increase in rigidity suppresses lifting between the base layer 1 and the extruded resin layer 3. As a result, the printed material 107 has reduced appearance defects.

[0214] <Base material layer> As the base layer 1, a resin film having the same configuration as in the first to sixth embodiments can be used. On the other hand, since transparency is not required for the base layer 1 in the printed material 107, the degree of freedom for the base layer 1 is increased. For example, the base layer 1 may be colored or milky white.

[0215] In offset printing, one possible solution to improve white areas is to lower the viscosity of the ink to enhance leveling. However, lowering the viscosity may actually thin the ink layer 2, potentially preventing improved opacity. Nevertheless, if the substrate layer 1 is milky white, adhesion can be improved without reducing the ink viscosity. Furthermore, white printing becomes unnecessary, reducing the number of steps in the printing process. The opacity of the substrate layer 1 is preferably 40% or more, and more preferably 50% or more.

[0216] <Paper sheet> A paper sheet can also be used as the base layer 1. The paper sheet may comprise a paper layer and a coating layer. The paper layer may be made primarily from plant-derived pulp. Specific examples of paper sheets include fine paper, special fine paper, coated paper, art paper, cast coated paper, imitation paper, kraft paper, and glassine paper.

[0217] The printed material 107 may have an anchor coat layer between the paper sheet (base layer 1) and the extruded resin layer 3, in which case the coat layer may be provided on at least the side of the paper layer that is in contact with the anchor coat layer. If the paper sheet has a coat layer, the paper sheet only needs to have at least a paper layer and a coat layer. The coat layer may be provided on both sides of the paper layer. By providing a coat layer, it is possible to prevent the anchor coat layer from seeping into the paper layer, and it can also act as a sealer to fill in the irregularities of the paper layer, and the anchor coat layer can be formed uniformly without defects. As constituent materials of the coat layer, for example, various copolymers such as styrene-butadiene, styrene-acrylic, and ethylene-vinyl acetate, polyvinyl alcohol resin, cellulose resin, paraffin (wax), etc. may be used as binder resins, and clay, kaolin, calcium carbonate, talc, mica, etc. may be used as fillers. The coat layer may be a clay coat layer containing clay as at least as a filler.

[0218] If the paper sheet has a coating layer, the thickness of the coating layer can be set to 1.5 to 15 μm. The thickness of the coating layer may be 1.8 μm or more, 3 μm or more, 5 μm or more, or 6 μm or more. The thickness of the coating layer may be 12 μm or less, or 10 μm or less. By setting the thickness of the coating layer within the above range, the paper sheet can exhibit better water vapor barrier properties and oil resistance not only initially but also after being folded.

[0219] The thickness of the paper sheet can be set to 7 to 150 μm, or 30 to 100 μm. When the thickness of the paper sheet is within the above range, the paper sheet can obtain better water vapor barrier properties and oil resistance not only initially but also after being folded.

[0220] The ratio of the thickness of the coating layer to the thickness of the paper sheet can be set to 3-25%, or 5-20%. By setting the ratio within the above range, the paper sheet can exhibit better water vapor barrier properties and oil resistance not only initially but also after being folded.

[0221] The paper content is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the entire paper sheet. If the paper content is 50% by mass or more based on the entire paper sheet, the amount of plastic material used can be sufficiently reduced, the entire paper sheet can be said to be made of paper, and it has excellent recyclability.

[0222] The basis weight of paper sheets is 7-500 g / m². 2 Preferably, 30-200 g / m 2 This is preferable.

[0223] The paper sheet may include a vapor-deposited layer laminated to the paper layer or coating layer.

[0224] <Vapour-deposited layer> The vapor-deposited layer is a layer formed by depositing a metal or inorganic compound. For example, a vapor-deposited layer formed by depositing aluminum can be used. The vapor-deposited layer is made of aluminum oxide (AlO x ), silicon dioxide (SiO₂) x ) and other similar items may also be included.

[0225] In this embodiment as well, if the main material of the base layer 1 and the main material of the extruded resin layer 3 are different types of resin, an anchor coat layer similar to that described above may be provided. Note that if the main material of the base layer 1 is a paper sheet, has a vapor-deposited layer, or is the same type of resin as the main material of the extruded resin layer 3, it is not necessary to provide an anchor coat layer, but providing an anchor coat layer can further improve the adhesion between the base layer 1 and the extruded resin layer 3.

[0226] The printed material 107 may have an intermediate layer similar to the intermediate layer 5 of the third embodiment described above. When aluminum foil is used as the intermediate layer, even if pre-applied surface printing is performed, the resin (e.g., polyethylene, polypropylene, etc.) of the sealant layer (in this case, the extruded resin layer 3b) can be modified by EB irradiation. As a result, even if the printed material 107 contains aluminum foil, the puncture strength can be improved by PE modification.

[0227] In printed material 107, the content of the same type of resin (for example, polyethylene, etc.) may be 90% by mass or more. In this case, printed material 107 can be composed as a highly recyclable monomaterial.

[0228] As described above, the printed material 107 of this embodiment includes an extruded resin layer 3, which suppresses lifting between the base material layer 1 and the extruded resin layer 3, thus suppressing defects in appearance of the printed material 107.

[0229] <Application> The printed material 107 can be used for the same purposes as the printed material 101 of the first embodiment.

[0230] [Eighth Embodiment] Figure 9 is a schematic cross-sectional view showing the layer structure of a printed material according to the eighth embodiment of the present invention. The printed material 108 shown in Figure 9 is a laminate formed by offset printing on the front side. The printed material 108 comprises, from the top (surface side), an overcoat layer 10, an ink layer 2, a substrate layer 1, and an extruded resin layer 3, in this order.

[0231] The printed material 108 has the same configuration as the printed material 107, except that it includes an overcoat layer 10 on the ink layer 2. The base layer 1, ink layer 2, and extruded resin layer 3 of the printed material 108 have the same configuration as those described in the seventh embodiment, and the printing method and the method of irradiation with active energy rays can also be the same as those in the seventh embodiment.

[0232] The printed material 108 is obtained, for example, by applying ink to the substrate layer 1 by printing, then applying an overcoat layer 10 to the ink layer 2 before irradiation with active energy rays, and then irradiating the ink layer 2 with active energy rays while the substrate layer 1 and ink layer 2 are stacked, causing it to harden. Alternatively, for example, the opposite may be true: the overcoat layer 10 may be applied to the ink layer 2 after it has hardened, and then hardened. In this way, by making the hardening of the ink layer 2 and the hardening of the overcoat layer 10 separate processes, it is possible to add one more ink color in the offset printing process.

[0233] <Overcoat layer> The overcoat layer 10 is a transparent layer for protecting the ink layer 2. The overcoat layer 10 may contain a transparent active energy ray curable resin. As the active energy ray curable resin, a transparent resin mainly composed of a prepolymer (including oligomers) and / or monomers containing radical polymerizable double bonds in the molecule that crosslink (cure) by irradiation with active energy rays such as electron beams can be used. Here, "main component" means that it is present in an amount of 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or more.

[0234] Specifically, examples of prepolymers and monomers include compounds having radically polymerizable unsaturated groups such as (meth)acryloyl groups and (meth)acryloyloxy groups, and cationic polymerizable functional groups such as epoxy groups in the molecule. Here, (meth)acryloyl group means acryloyl group and / or methacryloyl group.

[0235] Examples of prepolymers having radically polymerizable unsaturated groups include polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, triazine (meth)acrylate, and silicone (meth)acrylate. The weight-average molecular weight (Mw) of these is preferably around 250 to 100,000. The weight-average molecular weight (Mw) is measured using gel permeation chromatography (GPC) on a polystyrene basis.

[0236] Examples of monomers having radically polymerizable unsaturated groups include monofunctional monomers such as methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and phenoxyethyl (meth)acrylate. Examples of polyfunctional monomers include diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0237] Examples of prepolymers having cationic polymerizable functional groups include epoxy resins such as bisphenol-type epoxy resins and novolac-type epoxy compounds, and vinyl ether resins such as fatty acid-based vinyl ethers and aromatic vinyl ethers. Polyene / thiol-based prepolymers, which are combinations of polyenes and polythiols, are also preferred as prepolymers. Examples of thiols include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of polyenes include polyurethanes with allyl alcohol added to both ends, such as diols and diisocyanates.

[0238] Of these, acrylic resins are preferred as the transparent active energy ray curable resin. The transparent active energy ray curable resin may be used alone or as a mixture of two or more types.

[0239] The thickness of the overcoat layer 10 is preferably 0.1 to 10 μm. Setting the thickness of the overcoat layer 10 to above the lower limit improves various resistances such as scratch resistance, abrasion resistance, and weather resistance. Setting the thickness of the overcoat layer 10 to below the upper limit eliminates the need to use an unnecessarily large amount of resin material, thereby reducing costs.

[0240] In this embodiment as well, if the main material of the base layer 1 and the main material of the extruded resin layer 3 are different types of resin, an anchor coat layer similar to that described above may be provided. If the main material of the base layer 1 is a paper sheet, has a vapor-deposited layer, or is the same type of resin as the main material of the extruded resin layer 3, it is not necessary to provide an anchor coat layer, but providing an anchor coat layer can further improve the adhesion between the base layer 1 and the extruded resin layer 3.

[0241] In printed material 108, the content of the same type of resin (for example, polyethylene, etc.) may be 90% by mass or more. In this case, printed material 108 can be composed as a highly recyclable monomaterial.

[0242] As described above, the printed material 108 of this embodiment includes an extruded resin layer 3, which suppresses lifting between the base material layer 1 and the extruded resin layer 3, thus suppressing defects in appearance of the printed material 108.

[0243] <Application> Printed material 108 can be used for the same purposes as printed material 101 in the first embodiment.

[0244] [Ninth Embodiment] The printed matter of the ninth embodiment shows a mode particularly suitable for waterless offset printing among the reverse printing offset printings according to the second embodiment. Specifically, the printed matter 109 (not shown) of this embodiment, similar to FIG. 3, includes a base material layer 1, an ink layer 2, an anchor coat layer 4, and an extrusion resin layer 3 in this order from the upper side (front side). As offset printing, waterless offset printing without using dampening water is used, and as an active energy ray-curable ink, an ink for waterless offset printing is used, and an anchor coat layer 4 is provided between the ink layer 2 and the extrusion resin layer 3. The printed matter 109 has the same configuration as the printed matter 102 except that waterless offset printing is used as offset printing and an ink for waterless offset printing is used as the ink. The base material layer 1, the extrusion resin layer 3, and the anchor coat layer 4 included in the printed matter 109 have the same configuration as those described in the second embodiment, and the printing method and the active energy ray irradiation method can also adopt the same methods as those in the second embodiment (more specifically, the first embodiment).

[0245] <Offset printing> In this embodiment, among the watered offset printing and the waterless offset printing described in the above-mentioned second embodiment (more specifically, the first embodiment), waterless offset printing is used. As described above, waterless offset printing is a waterless printing method that performs printing without using dampening water by using a dedicated printing plate (for example, a printing plate in which a non-image portion is formed of silicone resin) as the printing plate 51 (see FIG. 2).

[0246] As in the printed matters 101 to 106 of the above-described first to sixth embodiments, in the aspect of the back printing of the present invention, by laminating the extrusion resin layer 3 on the ink layer 2, the appearance defects of the printed matters 101 to 106 can be suppressed due to the rigidity of the extrusion resin layer 3. From this, it is considered that if the extrusion resin layer 3 is reliably adhered to the ink layer 2, the functions of the extrusion resin layer 3 can be exhibited. In this regard, as the inventors further intensively studied, when adopting waterless offset printing, no matter which of the aqueous resin composition compatible with water and the non-aqueous resin composition incompatible with water, which were described in the second embodiment, is used to form the anchor coat layer 4, it was found that the adhesive strength between the ink layer 2 and the extrusion resin layer 3 can be enhanced.

[0247] <Ink> As the ink, among the inks described in the second embodiment (that is, the first embodiment), an ink suitable for waterless offset printing (an ink for waterless offset printing) is used. An ink for waterless offset printing can be determined when specific components such as silicone liquid, long-chain alkyl (meth)acrylate, or paraffin oil (for example, materials necessary for generating a boundary with a printing plate for waterless printing such as a printing plate in which a non-image portion is formed by a silicone resin) are detected in an intended blending amount.

[0248] Such an ink for waterless offset printing preferably contains one or more selected from the group consisting of silicone liquid, alkyl (meth)acrylate, vegetable oil, fatty acid ester derived from vegetable oil, hydrocarbon solvent, and fluorocarbon, and more preferably contains one or more selected from the group consisting of silicone liquid, alkyl (meth)acrylate, hydrocarbon solvent, and fluorocarbon.

[0249] These components have the effect of reducing ink adhesion to the silicone rubber, which is the non-image area of ​​the printing plate for waterless offset printing. The reason why ink adhesion to the silicone rubber is reduced is presumed to be as follows: The above components contained in the ink diffuse from within the ink upon contact with the surface of the silicone rubber, and can cover the surface of the silicone rubber in a thin film. It is presumed that the thin film thus formed prevents ink from adhering to the surface of the silicone rubber and prevents soiling of the silicone surface.

[0250] Of the above components, alkyl (meth)acrylate is preferred because it hardens when irradiated with active energy rays, thereby improving the water resistance of the cured ink film and simultaneously improving its sensitivity to active energy rays.

[0251] Examples of silicone liquids include dimethyl silicone, methylphenyl silicone, alkyl-modified silicone, polyether-modified silicone, aralkyl-modified silicone, fatty acid amide-modified silicone, fatty acid ester-modified silicone, fluoroalkyl-modified silicone, methyl hydrogen silicone, silanol-modified silicone, alcohol-modified silicone, amino-modified silicone, epoxy-modified silicone, epoxy polyether-modified silicone, phenol-modified silicone, carboxy-modified silicone, and mercapto-modified silicone.

[0252] Examples of alkyl (meth)acrylates include nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, and isooctadecyl (meth)acrylate. The alkyl group of the alkyl (meth)acrylate preferably has 5 to 24 carbon atoms, and more preferably 6 to 21 carbon atoms.

[0253] Examples of vegetable oils include soybean oil, linseed oil, safflower oil, tung oil, tall oil, and dehydrated castor oil. Examples of fatty acid esters derived from vegetable oils include esters of fatty acids having an alkyl main chain with approximately 15 to 20 carbon atoms, such as stearic acid, isostearic acid, hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, and eleostearic acid, and alkyl groups with approximately 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and 2-ethylhexyl.

[0254] Examples of hydrocarbon solvents include polyolefin oil, naphthenic oil, and paraffin oil.

[0255] Examples of fluorocarbons include 1,1,1,2,2-pentafluoroethane, 1,1,1,2,2,3,3,4,4-nonafluorobutane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluorooctane, and 1,1,1,2,3,3,3-heptafluoropropane. Examples include 1,1,1,2,3,3,4,4-octafluoro-2-trifluoromethylbutane, 1,1,1,2,3,3,4,4,5,5,6,6-dodecafluoro-2-trifluoromethylhexane, 1,1,2,2-tetrafluoroethane, 1,1,2,2,3,3,4,4-octafluorobutane, and 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane.

[0256] From the viewpoint of improving stain resistance, the content of one or more selected from the group consisting of silicone liquid, alkyl (meth)acrylate, vegetable oil, fatty acid ester derived from vegetable oil, hydrocarbon solvent, and fluorocarbon in the ink for waterless offset printing is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more. From the viewpoint of improving the storage stability of the ink for waterless offset printing, the content of one or more selected from the group consisting of silicone liquid, alkyl (meth)acrylate, vegetable oil, fatty acid ester derived from vegetable oil, hydrocarbon solvent, and fluorocarbon in the ink for waterless offset printing is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.

[0257] According to the printed material 109 of this embodiment, if the printed material 109 of the present invention is a printed material 109 that has been printed using waterless offset printing ink, by providing an anchor coat layer 4 between the ink layer 2 and the extruded resin layer 3, the adhesive strength between the ink layer 2 and the extruded resin layer 3 can be increased regardless of the type of resin composition used to form the anchor coat layer 4 (i.e., whether the resin composition used to form the anchor coat layer 4 is a water-compatible water-based resin composition or a water-incompatible non-water-based resin composition). As a result, the printed material 109 can more reliably demonstrate the effect of suppressing appearance defects caused by the rigidity of the extruded resin layer 3.

[0258] In the ninth embodiment, a configuration was described in which, in the printed material 102 of the second embodiment shown in Figure 3 (equipped with an anchor coat layer 4), waterless offset printing was used as the offset printing method and waterless offset printing ink was used as the ink. However, in the present invention, a configuration similar to the ninth embodiment can be adopted when the base layer, ink layer, anchor coat layer, and extruded resin layer are arranged in this order, thereby obtaining the same effects as the ninth embodiment. For example, in the printed materials 103 to 105 of the third to fifth embodiments shown in Figures 4 to 6 (each comprising a base layer 1, an ink layer 2, an anchor coat layer 4a, and an extruded resin layer 3a, respectively), waterless offset printing can be used as the offset printing method and waterless offset printing ink can be used as the ink. Furthermore, when adopting these configurations, a coat layer 9 similar to that of the sixth embodiment may be laminated on the base layer 1.

[0259] [Tenth Embodiment] The printed material of the tenth embodiment shows a configuration of the printed material 102 according to the second embodiment that is particularly suitable for offset printing with water, among reverse offset printing. Specifically, the printed material 110 (not shown) of this embodiment, like Figure 3, comprises a base material layer 1, an ink layer 2, an anchor coat layer 4, and an extruded resin layer 3 in this order from the top (surface side), and the anchor coat layer 4 is formed of a non-aqueous resin composition that is incompatible with water. The printed material 110 has the same configuration as the printed material 102 except that it uses a non-aqueous resin composition as a raw material for forming the anchor coat layer. The base material layer 1 and extruded resin layer 3 of the printed material 110 have the same configuration as those described in the second embodiment (more specifically, the first embodiment), and the printing method and the method of irradiation with active energy rays can also be the same as those of the second embodiment (more specifically, the first embodiment).

[0260] <Offset Printing> In the first embodiment described above, waterless offset printing is used as offset printing, and a waterless offset printing method is used as the ink. In the ninth embodiment, a non-aqueous resin composition is used as the raw material for forming the anchor coat layer 4. Therefore, the following will focus on the case where waterless offset printing is used. As described above, waterless offset printing is a printing method that uses dampening solution W (see Figure 2).

[0261] As shown in the printed materials 101 to 106 of the first to sixth embodiments described above, in the reverse printing embodiment of the present invention, by laminating the extruded resin layer 3 onto the ink layer 2, defects in the appearance of the printed materials 101 to 106 can be suppressed due to the rigidity of the extruded resin layer 3. From this, it is considered that if the extruded resin layer 3 is reliably adhered to the ink layer 2, the functions of the extruded resin layer 3 can be performed. In this regard, the inventors conducted further intensive research and found that, unlike the case of waterless offset printing in the ninth embodiment described above, when water-based offset printing is used, the adhesive strength between the ink layer 2 and the extruded resin layer 3 can be increased by forming the anchor coat layer 4 using the non-water-based resin composition among the water-based resin composition and non-water-based resin composition described above. In other words, by forming the anchor coat layer 4 with a non-water-based resin composition, the adhesive strength between the ink layer 2 and the extruded resin layer 3 can be increased regardless of whether water-based offset printing ink or waterless offset printing ink is used.

[0262] <Ink> As the ink, an ink suitable for water-based offset printing (water-based offset printing ink) from the inks described in the first embodiment is used. The water-based offset printing ink preferably contains a surfactant. By containing a surfactant in the water-based offset printing ink, an appropriate amount of dampening solution (generally 10 to 20% by mass of the total ink amount) is absorbed and emulsified during water-based offset printing, increasing the repulsion of the non-image areas of the printing plate 51 (see Figure 2) to the dampening solution, and improving the ink's stain resistance.

[0263] The ratio of hydrophilic to hydrophobic groups in a surfactant is expressed by its HLB value. In this specification, "HLB value" refers to a value that represents the degree of affinity of a surfactant for water and oil. The HLB value ranges from 0 to 20, with values ​​closer to 0 indicating higher lipophilicity and values ​​closer to 20 indicating higher hydrophilicity. Considering that the surfactant dissolves in dampening solution, the HLB value of the surfactant is preferably 8 or higher, and more preferably 10 or higher. Furthermore, considering that the surfactant dissolves in ink for offset printing with water, the HLB value of the surfactant is preferably 18 or lower, and more preferably 16 or lower.

[0264] Specific examples of surfactants include polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene palmityl ether, polyoxypropylene alkyl ether, polyoxypropylene lauryl ether, polyoxypropylene oleyl ether, polyoxypropylene stearyl ether, polyoxypropylene cetyl ether, polyoxypropylene palmityl ether, polyoxyalkylene alkyl ether, polyoxyalkylene lauryl ether, polyoxyalkylene oleyl ether, polyoxyalkylene stearyl ether, polyoxyalkylene cetyl ether, polyoxyalkylene palmityl ether, sol Examples include mono, di, and trialkyl ethers of sorbitanic acid, mono, di, and trilauryl ethers of sorbitanic acid, mono, di, and trioleyl ethers of sorbitanic acid, mono, di, and tristearyl ethers of sorbitanic acid, mono, di, and tricetyl ethers of sorbitanic acid, mono, di, and tripalmyl ethers of sorbitanic acid, mono, di, and trialkyl ethers of polyoxyethylene sorbitanic acid, mono, di, and trilauryl ethers of polyoxyethylene sorbitanic acid, mono, di, and trioleyl ethers of polyoxyethylene sorbitanic acid, mono, di, and tristearyl ethers of polyoxyethylene sorbitanic acid, mono, di, and tricetyl ethers of polyoxyethylene sorbitanic acid, and mono, di, and tripalmyl ethers of polyoxyethylene sorbitanic acid, as well as polyether-modified silicone oils. Of these, those with an HLB value of 8 to 18 are preferred.

[0265] From the perspective of taking in dampening water during water-based offset printing and achieving a stable emulsified state, the surfactant content in the ink for water-based offset printing is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. Considering the perspective of suppressing the deterioration of print quality, such as the ink for water-based offset printing becoming over-emulsified due to excessive intake of dampening water during water-based offset printing and the halftone shape becoming distorted, the surfactant content in the ink for water-based offset printing is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0266] When the ink contains the above surfactant, any of the resins described in the first embodiment can be used as the resin contained in the ink.

[0267] When the ink does not contain a surfactant, examples of the resin contained in the ink include hydrophilic group-containing vinyl monomers in order to achieve both solubility in water and good dispersibility of the pigment. Specific examples of the hydrophilic group-containing vinyl monomers include (meth)acrylic acid, (meth)acrylic acid dimer, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, and the like. These may be used alone or in combination of two or more. The content of the hydrophilic group-containing vinyl monomer in the ink is preferably 20% by mass or more and less than 50% by mass, more preferably 25% by mass or more and less than 45% by mass, and even more preferably 30% by mass or more and less than 40% by mass. By setting the content of the hydrophilic group-containing vinyl monomer within the above range, it is possible to achieve both solubility in water of the ink (components other than the pigment) and good pigment dispersibility in the ink.

[0268] <Anchor coat layer> The anchor coat layer 4 is formed from a non-aqueous resin composition that is immiscible with water. Examples of non-aqueous resin compositions include those from the system of resin compositions listed in the second embodiment that are non-aqueous (specifically, those that use a non-aqueous solvent as the solvent), such as urethane-based anchor coat agents (one-component or two-component urethane resin compositions, etc.).

[0269] According to the printed material 110 of this embodiment, by providing an anchor coat layer 4 formed from a water-incompatible non-aqueous resin composition between the ink layer 2 and the extruded resin layer 3, the adhesive strength between the ink layer 2 and the extruded resin layer 3 can be increased regardless of the type of ink (i.e., whether the ink is for water-based offset printing or waterless offset printing). As a result, the printed material 110 can more reliably exhibit the effect of suppressing appearance defects caused by the rigidity of the extruded resin layer 3. In the printed material 110, it is particularly preferable that the offset printing is water-based offset printing, the ink is for water-based offset printing, an anchor coat layer 4 is provided between the ink layer 2 and the extruded resin layer 3, and the anchor coat layer is formed from a water-incompatible non-aqueous resin composition.

[0270] In the tenth embodiment, an example was described in which the anchor coat layer 4, formed from a non-aqueous resin composition, is used in the printed material 102 of the second embodiment shown in Figure 3 (which includes an anchor coat layer 4). However, in the present invention, the same configuration as the tenth embodiment can be adopted when the base layer, ink layer, anchor coat layer, and extruded resin layer are arranged in this order, thereby obtaining the same effects as the tenth embodiment. For example, in the printed materials 103 to 105 of the third to fifth embodiments shown in Figures 4 to 6 (each comprising a base layer 1, an ink layer 2, an anchor coat layer 4a, and an extruded resin layer 3a), an anchor coat layer 4a formed from a non-aqueous resin can be used. Furthermore, when adopting these configurations, a coat layer 9 similar to that of the sixth embodiment may be laminated on the base layer 1.

[0271] [Embodiment No. 11] The 11th embodiment is a package formed from printed materials according to the 1st to 10th embodiments. Figure 10 is a schematic diagram showing an example of a packaged product equipped with the package of the 11th embodiment of the present invention. The packaged product 200 shown in Figure 10 includes a packaging body 210 and contents contained therein (packaged goods, not shown).

[0272] The packaging 210 may be a standing pouch, for example, as shown in Figure 10. The packaging 210 can be formed using any of the printed materials 101 to 110 according to the first to tenth embodiments described above. According to the packaging 210 of this embodiment, since it is formed using the above-mentioned printed material, a packaging 210 with excellent appearance and durability can be obtained, in which the separation between the ink layer and / or base material layer and the extruded resin layer is suppressed.

[0273] Specifically, the packaging 210 includes a pair of main films and a bottom film, which are either any of the printed materials described in the first to tenth embodiments, or cut from thereto. The pair of main films and bottom films are overlapped so that their sealant layers (the extruded resin layer that functions as a sealant layer when the extruded resin layer is located on the furthest back side) face each other, and their periphery is heat-sealed to each other except for one end and the area near it. The bottom film is folded in half so that it forms a mountain fold when viewed from the sealant layer side (so that the sealant layer is on the outside), and at the position of the one end, it is sandwiched between the pair of main films so that the mountain fold faces the other end of the main film (the side opposite to the one end). The bottom film is heat-sealed to the pair of main films except for its central portion. The outer surfaces of the bottom film are bonded together at both sides of the bottom of the packaging 210. The packaging body 210 is provided with a notch 221 and an easy-open line 223 as an easy-open structure in the portion where the main film parts are heat-sealed together. The easy-open line 223 is a collection of small holes made by laser processing and is formed to extend from one side end of the packaging body 210 to the other side end. The notch 221 is formed on at least one of the left and right ends (both in the embodiment of Figure 10) such that the tip of the notch 221 is located on a virtual line extending from the end of the easy-open line 223.

[0274] The notch 221 may be a V-shaped notch as shown in Figure 10, or it may be a pentagonal (tortoise shell) notch as a pentagonal notch, a U-shaped notch as a U-shaped notch, an I-shaped cut as an I-shaped notch, or a notch-non (registered trademark) made of scratch processing. However, a notch with width, such as a notch, is preferable because it makes it easier to align the end of the easy-open line with the notch.

[0275] The portion of the packaging 210 where the easy-open line 223 is formed has lower tear strength than the portion where the easy-open line 223 is not formed. Therefore, when force is applied in the direction along the easy-open line 223, the packaging 210 is easily torn along the easy-open line 223. The easy-open line 223 has a plurality of discontinuously formed cuts in the direction of extension. A means for forming the easy-open line 223 is, for example, a laser processing machine.

[0276] The easy-open line 223 can be formed by irradiating the packaging 210 from the outside using a laser processing machine. Using a laser processing machine, it is possible to cut only specific layers by taking advantage of the fact that different materials absorb energy differently. For example, a carbon dioxide laser with a wavelength of 10.6 μm can be used, and the shape and depth of the easy-open line 223 can be adjusted relatively easily by adjusting the output and scanning speed of the laser head depending on the material. Alternatively, the easy-open line 223 can also be formed using a rotary cutter, a Pinnacle® die, or the like.

[0277] The shape of the cuts can be straight, curved, perforated, or dashed, and the number of cuts can be set appropriately so that they can function as easy-open lines 223, and may be one or more.

[0278] The easy-open structure may be provided so that the upper corner of the packaged product 200 can be used as an opening after it has been opened. In addition, the packaged body 210 may have an opening member or a lid attached.

[0279] If the pair of main film and bottom film in the packaging 210 do not have a sealant layer on the innermost side, the packaging 210 can be formed by using an adhesive or heat sealant instead of bonding with a sealant layer, and otherwise in the same manner as when a sealant layer is present.

[0280] Examples of packaging bodies 210 include packaging bodies for retort food, packaging bodies for boiling food, packaging bodies for microwave food, and packaging bodies for can labels. The packaging bodies of the present invention are not limited to the above-mentioned standing pouches, but can be formed in various other forms such as flat pouches and gusseted pouches with spouts. Furthermore, the shape of the packaging body is not limited to four-sided pouches, but may also be two-sided pouches, three-sided pouches, or gusseted pouches. In addition, as shown in Japanese Patent Application Publication No. 2022-132925, a bag-in-box can be made by sealing liquid in a packaging body and storing it in a cardboard or paperboard box.

[0281] The packaged items may be liquids, solids, or mixtures thereof, and examples include food products and pharmaceuticals. Specifically, these include confectionery such as cookies and rice crackers, food products such as pizza, noodles, broth, and coffee, health foods such as supplements, pharmaceuticals such as pesticides and medicines, animal products such as fish feed, pet food, and pet treats, vegetable seeds, and frozen foods. In addition, it can also be used for medical devices, industrial materials such as machine parts and precision materials. [Examples]

[0282] Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0283] [Test Example 1] (Production of printed materials) [Example 1] PET film (manufactured by Unitika Ltd., product name: Emblet PTM, thickness 12 μm) was used as the base layer. Using an offset printing press (COMEXI, CI-8, center drum type 8-color offset printing press), waterless offset printing was performed on the easily adhesive layer surface of the PET film using an ink containing electron beam curable resin. The ink used was an ink containing thermoplastic resin (manufactured by T&K TOKA Corporation, EB curing type ink). The ink colors used were black (K), cyan (C), magenta (M), yellow (Y), and white (W), as shown in Table 1. In Table 1, "CMY," etc., indicate that the colors were applied in that order from left to right, starting from the base layer side. As shown in Table 1, multiple laminates with different ink colors were prepared. In Table 1, "plain" indicates an area with an ink area ratio of 0%. The ink area ratio represents the ratio of the printed halftone area per unit area. For example, if the halftone dots to be printed are large and adjacent dots completely overlap, resulting in ink being printed across the entire unit area, the ink coverage ratio will be 100%.

[0284] After printing, the material was irradiated with an electron beam (EB) at a dose of 45 kGy from the ink layer side under a nitrogen atmosphere using an electron beam irradiation device (EC series, manufactured by ESI Corporation). Subsequently, the anchor coat resin A shown below was applied to the ink layer that had hardened on the substrate layer and dried to form an anchor coat layer (0.2 μm). An extruded resin layer (thickness 20 μm) was formed between the anchor coat layer and aluminum foil (barrier layer, manufactured by Toyo Aluminum Co., Ltd., 8079) by extruding polyethylene (Novatec LD LC600A, manufactured by Nippon Polyethylene Co., Ltd.) using an extrusion laminating device. Next, the anchor coat resin B shown below was applied to the aluminum foil and dried to form an anchor coat layer (1 μm). Then, the extruded resin was extruded between the aluminum foil and the PE film (sealant layer, manufactured by Nippon Polyethylene Co., Ltd., Novatec LD LC600A) in the same manner as above to form an extruded resin layer (thickness 20 μm), thereby forming the printed material of Example 1. The layer structure is as follows.

[0285] <Anchor coating resin A (water-based resin composition)> A water-based anchor coat (AC) composition with a solid content concentration of 1.5% by mass was prepared as anchor coat resin A by mixing a polybutadiene-based anchor coat (AC) agent (manufactured by Toyo Morton Co., Ltd., EL-451) with isopropanol (IPA) and water as solvents.

[0286] <Anchor coating resin B (non-aqueous resin composition)> By combining a polyether polyol (manufactured by Mitsui Chemicals, Inc., trade name: Takelac A3210) as the main agent, an aromatic polyisocyanate (manufactured by Mitsui Chemicals, Inc., trade name: Takenate A3) as the curing agent, and ethyl acetate as the solvent, an organic anchor coat (AC) composition with a solid content concentration of 16% by mass was prepared as anchor coat resin B.

[0287] <Layer configuration> PET#12 (substrate layer, 12μm) / ink (ink layer) / AC (anchor coat layer, 0.2μm) / EXPE (extruded resin layer, 20μm) / Al (barrier layer, 7μm) / AC (anchor coat layer, 1μm) / EXPE (extruded resin layer, 20μm) / PE#30 (sealant layer, 30μm)

[0288] [Comparative Example 1] In the same manner as in Example 1, an ink layer was formed on a PET film (substrate layer, 12 μm). Then, the dry laminating resin described below was applied to the ink layer that had hardened on the substrate layer, and an LLDPE film (sealant layer, manufactured by Futamura Chemical Co., Ltd., LL-XMTN, thickness 30 μm) was laminated on the applied dry laminating resin. A dry laminate layer (thickness 2 μm) was formed by storing it in a 40°C environment for 48 hours. In this way, the printed material of Comparative Example 1 was formed by bonding the ink layer and the LLDPE film via the dry laminate layer. The layer structure is shown below.

[0289] <Dry laminating resin> A polyether polyol (manufactured by Mitsui Chemicals, Inc., trade name: Takelac A953) was used as the main agent, an aromatic polyisocyanate (manufactured by Mitsui Chemicals, Inc., trade name: Takenate A93) was used as the curing agent, and ethyl acetate was used as the solvent. By mixing these together, an organic solvent-type adhesive composition with a solid content concentration of 33% by mass was prepared as a resin for dry lamination.

[0290] <Layer configuration> PET#12 (substrate layer, 12μm) / ink (ink layer) / adh (DL (dry laminate layer), 2μm) / LLDPE#30 (sealant layer, 30μm)

[0291] (evaluation) [Measurement of adhesive strength (laminate strength)] In accordance with JIS K 6854-2:1999, a tensile testing machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name: Strograph VE10D) was used to cut the printed materials of Example 1 and Comparative Example 1 into 15 mm wide strips to serve as measurement samples. After peeling the interlayers at the edges of the measurement samples (between the ink layer and the extruded resin layer for Example 1, and between the ink layer and the dry laminate layer for Comparative Example 1), the peel strength was measured at an angle of 90° (total 180°), a tensile speed of 300 mm / min, and at room temperature. This peel strength was determined as the adhesive strength at room temperature (20°C). The results are shown in Table 1. In Table 1, "plain" refers to the area with an ink area ratio of 0%, as described above.

[0292] [Measurement of buoyancy] The printed materials of Example 1 and Comparative Example 1 were cut into 150 mm x 200 mm rectangles to form test specimens. The test specimens were folded so that the sealant layer side was facing inward and the short sides overlapped, and a 1.5 kg rubber roller (Hiyama Shoten Co., Ltd., product name: Double Presser DP300) was rolled over them to create creases. The specimens were then folded again so that the short sides overlapped, and creases were created again with the same rubber roller. In the same manner, the specimens were folded two more times to create creases, for a total of four creases. After that, the folded test specimens were unfolded, and the intersections of the nine creases were observed using a microscope (Keyence Corporation, product name: VHX-6000). The number of creases between the substrate layer and / or ink layer and the sealant layer was counted, with each crease having a maximum length of 0.5 mm or more being counted as one crease. The number was evaluated according to the following criteria. The results are shown in Table 1. (Judgment criteria) A: No floats (0) B: One or two floats C: 3 or more floats

[0293] [Table 1]

[0294] As shown in Table 1, the printed material of Example 1 was found to have higher adhesive strength in all colors compared to the printed material of Comparative Example 1.

[0295] Furthermore, as shown in Table 1, the print material of Example 1 received an A rating for lifting for all colors, confirming that lifting was suppressed between the substrate layer and the extruded resin layer. On the other hand, the print material of Comparative Example 1 received a poor overall lifting rating, confirming that lifting occurred between the substrate layer and the dry laminate layer.

[0296] [Test Example 2] (Production of printed materials) [Example 2] Except for using a nylon (Ny) film (Kojin Film & Chemicals Co., Ltd., Bonil Q, 15 μm) as the base layer, the procedure was the same as in Example 1. As shown in Table 2, cyan (C), magenta (M), yellow (Y), and white (W) were applied in solid layers in order to the easily adhering layer surface of the Ny film, and a laminate was fabricated by irradiating with an electron beam (EB) at a dose of 45 kGy under the same irradiation conditions as in Example 1. After printing, the anchor coat resin C shown below was applied and dried to form an anchor coat layer (1.0 μm). Between the anchor coat layer and an LLDPE film (sealant layer, Futamura Chemical Co., Ltd., LL-XMTN, thickness 40 μm), polyethylene (Novatec LD LC600A, Nippon Polyethylene Co., Ltd.) was melted and extruded using an extrusion laminating device to form an extruded resin layer (thickness 20 μm), thereby forming the printed material of Example 2. The layer structure is as follows.

[0297] <Anchor coating resin C (non-aqueous resin composition)> By combining polyether polyol (manufactured by Mitsui Chemicals, Inc., trade name: Takelac A3210) as the main agent, aliphatic polyisocyanate (manufactured by Mitsui Chemicals, Inc., trade name: Takenate A3070) as the curing agent, and ethyl acetate as the solvent, an organic anchor coating (AC) agent with a solid content concentration of 15% by mass was prepared as anchor coating resin C.

[0298] <Layer configuration> Ny#15 (substrate layer, 15μm) / ink (ink layer) / AC (anchor coat layer, 1.0μm) / EXPE (extruded resin layer, 20μm) / LLPPE#40 (sealant layer, 40μm)

[0299] [Comparative Example 2] In the same manner as in Example 2, an ink layer was formed on a Ny film (substrate layer, 15 μm). Then, a dry laminating resin similar to that used in Comparative Example 1 was applied to the ink layer that had hardened on the substrate layer. An LLDPE film (sealant layer, manufactured by Futamura Chemical Co., Ltd., LL-XMTN, 60 μm thick) was laminated on the applied dry laminating resin and stored at 40°C for 48 hours to form a dry laminate layer (2 μm thick). By bonding the ink layer and the LLDPE film via the dry laminate layer in this way, the printed material of Comparative Example 2 was formed. The layer configuration is shown below. In order to minimize the influence on the loop stiffness test described later, the total thickness of the layer containing the same type of resin (in this case, PE) among the layers laminated on the opposite side of the substrate layer in the ink layer was set to the same value (60 μm) for both Example 2 and Comparative Example 2.

[0300] <Layer configuration> Ny#15 (substrate layer, 15μm) / ink (ink layer) / adh (DL (dry laminate layer), 2μm) / LLDPE#60 (sealant layer, 60μm)

[0301] [Example 3] Using the same PET film (substrate layer, 12 μm) as in Example 1, and in the same manner as in Example 1, cyan (C), magenta (M), yellow (Y), and white (W) were applied sequentially to the substrate layer as shown in Table 2, and a laminate was fabricated by irradiating with an electron beam (EB) at a dose of 45 kGy under the same irradiation conditions as in Example 1. After printing, the same anchor coat resin C as in Example 2 was applied and dried to form an anchor coat layer (0.2 μm), and an extrusion lamination was performed between the anchor coat layer and an LLDPE film (sealant layer, manufactured by Futamura Chemical Co., Ltd., LL-XMTN, thickness 50 μm) by melting and extruding polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec LD LC600A) using an extrusion laminating apparatus to form an extruded resin layer (thickness 20 μm), thereby forming the printed material of Example 3. The layer structure is as follows.

[0302] <Layer configuration> PET#12 (substrate layer, 12μm) / ink (ink layer) / AC (anchor coat layer, 0.2μm) / EXPE (extruded resin layer, 20μm) / LLPPE#50 (sealant layer, 50μm)

[0303] [Comparative Example 3] In the same manner as in Example 3, an ink layer was formed on a PET film (substrate layer, 12 μm). Then, a dry laminating resin similar to that used in Comparative Example 1 was applied to the ink layer that had hardened on the substrate layer. An LLDPE film (sealant layer, manufactured by Futamura Chemical Co., Ltd., LL-XMTN, 70 μm thick) was laminated onto the applied dry laminating resin and stored at 40°C for 48 hours to form a dry laminate layer (2 μm thick). By bonding the ink layer and the LLDPE film via the dry laminate layer in this way, the printed material of Comparative Example 3 was formed. The layer configuration is shown below. In order to minimize the influence on the loop stiffness test described later, the total thickness of the layer containing the same type of resin (in this case, PE) among the layers laminated on the opposite side of the substrate layer in the ink layer was set to the same value (70 μm) for both Example 3 and Comparative Example 3.

[0304] <Layer configuration> PET#12 (substrate layer, 12μm) / ink (ink layer) / adh (DL (dry laminate layer), 2μm) / LLDPE#70 (sealant layer, 70μm)

[0305] [Example 4] Using the same PET film (base layer, 12 μm) as in Example 1, and in the same manner as in Example 1, cyan (C), magenta (M), yellow (Y), and white (W) were applied in solid coats in order to the base layer, as shown in Table 2. A laminate was then fabricated by irradiating with an electron beam (EB) at a dose of 45 kGy under the same irradiation conditions as in Example 1. After printing, the same anchor coat resin A as in Example 1 was applied and dried to form an anchor coat layer (0.2 μm). Extrusion lamination was then performed between the anchor coat layer and an aluminum foil (7 μm) as in Example 1, by melting and extruding polyethylene (Novatec LD LC600A, manufactured by Nippon Polyethylene Co., Ltd.) using an extrusion laminating apparatus to form an extruded resin layer (thickness 15 μm). An anchor coat resin B, similar to that in Example 1, was applied to an aluminum foil and dried to form an anchor coat layer (1 μm). Between the anchor coat layer and an LLDPE film (sealant layer, manufactured by Futamura Chemical Co., Ltd., LL-XMTN, 30 μm thick), polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec LD LC600A) was melted and extruded using an extrusion laminating apparatus to form an extruded resin layer (15 μm thick), thereby forming the printed material of Example 4. The layer structure is as follows.

[0306] <Layer configuration> PET (substrate layer, 12 μm) / ink (ink layer) / AC (anchor coat layer, 0.2 μm) / EXPE (extruded resin layer, 15 μm) / Al (barrier layer, 7 μm) / AC (anchor coat layer, 1 μm) / EXPE (extruded resin layer, 15 μm) / LLDPE #30 (sealant layer, 30 μm)

[0307] [Comparative Example 4] In the same manner as in Example 4, an ink layer was formed on a PET film (substrate layer, 12 μm). Then, a dry laminating resin similar to that in Comparative Example 1 was applied to the ink layer that had hardened on the substrate layer, and an aluminum foil (7 μm) similar to that in Example 1 was laminated on the applied dry laminating resin. A dry laminating resin similar to that in Comparative Example 1 was further applied to the aluminum foil, and an LLDPE film (sealant layer, manufactured by Futamura Chemical Co., Ltd., LL-XMTN, thickness 60 μm) was laminated on the applied dry laminating resin. Each dry laminating layer (thickness 2 μm) was formed by storing the laminates at 40°C for 48 hours. In this way, the ink layer and the aluminum foil were bonded via the dry laminating layers, and the aluminum foil and the LLDPE film were bonded via the dry laminating layers, thereby forming the printed material of Comparative Example 4. The layer structure is shown below. Furthermore, in order to minimize the influence on the loop stiffness test described later, the total thickness of the layer containing the same type of resin (in this case, PE) among the layers laminated on the opposite side of the substrate layer in the ink layer was set to the same value (60 μm) in Example 4 and Comparative Example 4.

[0308] <Layer configuration> PET#12 (substrate layer, 12μm) / ink (ink layer) / adh (DL (dry laminate layer), 2μm) / Al (barrier layer, 7μm) / adh (DL (dry laminate layer), 2μm) / LLDPE#60 (sealant layer, 60μm)

[0309] (evaluation) [Measurement of loop stiffness] The printed materials from Examples 2-4 and Comparative Examples 2-4 were cut into 180mm x 15mm rectangles to prepare test specimens. Using a loop stiffness measuring instrument (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name: Loop Stiffness Tester DA), the loop stiffness in the MD and TD directions was measured for the test specimens under the conditions of a test width of 100mm, a speed of 3.3mm / second, and a time of 3 seconds. The results are shown in Table 2 and Figure 11.

[0310] [Measurement of buoyancy] Using the same test specimens as those used for measuring loop stiffness in Examples 2-4 and Comparative Examples 2-4, the number of floats was counted in the same manner as in Test Example 1, and the results were evaluated using the same criteria as in Test Example 1. The results are shown in Table 2.

[0311] [Table 2]

[0312] As shown in Table 2 and Figure 11, the printed materials of Examples 2 to 4 were shown to have higher loop stiffness and rigidity (firmness) in both the MD and TD directions compared to the printed materials of the corresponding Comparative Examples 2 to 4.

[0313] Furthermore, as shown in Table 2, lifting between the ink layer and the extruded resin layer was suppressed in the printed materials of Examples 2 to 4, and the quality could be maintained when processed into packaging. On the other hand, lifting was observed between the ink layer and the dry laminate layer in the printed materials of the corresponding Comparative Examples 2 to 4, and they were not sufficiently durable for use as packaging.

[0314] [Test Example 3] (Sample preparation) As the base layer, the same PET film (base layer, 12 μm) as in Example 1 was used. Using an offset printing press (COMEXI, CI-8, center drum type 8-color offset printing press), a predetermined print was performed on the easily adhesive layer surface of the PET film using water-based offset printing with dampening solution, employing an ink containing an electron beam-curable resin. The ink used was a thermoplastic resin containing a copolymer of ethylene acrylic acid and ethylene methacrylic acid (T&K TOKA Corporation, EB-curable ink (water-based ink)). As shown in Table 3, black (K), cyan (C), magenta (M), yellow (Y), and white (W) were applied in solid colors in that order, and an EB-cured body was produced by irradiating it with an electron beam (EB) at an irradiation dose of 45 kGy under the same irradiation conditions as in Example 1.

[0315] As the base layer, a PET film (12 μm thick) having an easy-adhesion layer similar to that in Example 1 was used, and the corona-treated surface of the PET film was printed using gravure printing with an ink containing a urethane resin. The ink used was an ink containing a thermoplastic resin (Riogran, manufactured by Toyo Ink Co., Ltd.). As shown in Table 3, black (K), cyan (C), magenta (M), yellow (Y), and white (W) were applied in solid colors in that order to create a gravure printed body.

[0316] As the substrate layer, a general PET film without an easy-adhesion layer (Futamura Chemical Co., Ltd., FE2001, 12 μm thick) was used. On the corona-treated surface of the PET film, a predetermined print was performed using water-based offset printing with dampening solution and an ink containing an electron beam-curable resin, using an offset printing press (COMEXI Corporation, CI-8, center drum type 8-color offset printing press). The ink used was a thermoplastic resin containing a copolymer of ethylene acrylic acid and ethylene methacrylic acid (T&K TOKA Corporation, EB-curable ink (water-based ink)). As shown in Table 3, black (K), cyan (C), magenta (M), yellow (Y), and white (W) were applied in solid colors in that order, and an EB-cured body was produced by irradiating with an electron beam (EB) at an irradiation dose of 45 kGy under the same irradiation conditions as in Example 1.

[0317] (evaluation) <Measurement of color difference and ink detachment> Using aluminum foil, EB printed materials and gravure printed materials printed on the easy-adhesion layer of PET film having an easy-adhesion layer (hereinafter referred to as "easy-adhesion PET"), as well as EB printed materials printed on general PET film (hereinafter referred to as "general PET"), were sandwiched between aluminum foil on both the front and back surfaces so that the solid print areas of each printed material were in contact with the matte side of the aluminum foil. A thermal gradient tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name: HG-100-2) was used to perform a hot press treatment with the ink layer facing the heat source. The thermal gradient tester conditions were set to temperatures of 160°C, 200°C, and 240°C, a pressure of 0.20 MPa, and pressure time (time under pressure) of 2.0 seconds and 5.0 seconds. The ink layer of each printed material before and after the hot press treatment was measured using a spectrophotometer (manufactured by X-Rite, eXact Standard) to obtain the color difference. The results are shown in Table 3 and Figure 12. Furthermore, after the heat-pressure treatment, the surface of the aluminum foil in contact with the ink layer was observed using a microscope (Keyence Corporation, VHX-6000) to check for ink adhesion to the aluminum foil. If no ink adhered to the aluminum foil, it was evaluated as "no" ink detachment; if ink adhered to the aluminum foil, it was evaluated as "yes" ink detachment. The results are shown in Table 3.

[0318] [Table 3]

[0319] As shown in Table 3 and Figure 12, gravure printed materials tended to show increased color difference when subjected to heat pressure treatment, and this color difference increased further when the heat pressure treatment temperature was increased. Furthermore, when the heat pressure treatment temperature exceeded 200°C, the ink tended to detach. In contrast, EB printed materials generally showed a color difference of less than 2 even after heat pressure treatment, and no significant change in color difference was observed even when the heat pressure treatment temperature was increased. Also, as shown in Table 3, EB printed materials printed on general PET tended to show ink detachment when the heat pressure treatment temperature exceeded 200°C. In contrast, EB printed materials printed on easy-adhesion PET did not show ink detachment even when the heat pressure treatment temperature was increased, demonstrating excellent heat resistance and durability.

[0320] [Test Example 4] (Creation of printed materials) [EB print A] As the base layer, the same PET film as in Example 1 (Unitika Ltd., product name: Emblet PTM, thickness 12 μm) was used. Using an offset printing press (COMEXI, CI-8, center drum type 8-color offset printing press), a predetermined print was made on the easily adhesive layer surface of the PET film using water-based offset printing with dampening solution, with an ink containing an electron beam-curable resin. The ink used was a thermoplastic resin containing a copolymer of ethylene acrylic acid and ethylene methacrylic acid (Sakata Inx Corporation, EB-curable ink (water-based ink)). The base layer was coated with cyan (C), and an EB printed body A was prepared by irradiating it with an electron beam (EB) at an irradiation dose of 30 kGy under the same irradiation conditions as in Example 1.

[0321] [Gravure Printing Type A] As the base layer, a PET film (manufactured by Unitika Ltd., product name: Emblet PTM, thickness 12 μm) similar to that used in Example 1 was used, and a predetermined print was performed on the easily adhesive layer surface of the PET film using gravure printing with an ink containing a urethane resin. As the ink, an ink containing a thermoplastic resin (manufactured by Toyo Ink Co., Ltd., Rio Gran) was used. Gravure printed body A was prepared by solid coating the base layer with cyan (C).

[0322] [EB print B] Except for using the same nylon (Ny) film (Kojin Film & Chemicals Co., Ltd., Bonyl Q, 15 μm) as in Example 2 as the base layer, EB printed body B was prepared in the same manner as EB printed body A by applying a solid coat of cyan (C) to the easily adhering layer surface of the Ny film and irradiating it with an electron beam (EB) at an irradiation dose of 30 kGy under the same irradiation conditions as in Example 1.

[0323] [Gravure Printing Font B] Gravure print B was prepared in the same manner as gravure print A, except that the same nylon (Ny) film (Kojin Film & Chemicals Co., Ltd., Bonyl Q, 15 μm) as in Example 2 was used as the base layer, by solid coating cyan (C) onto the easily adhesive layer surface of the Ny film.

[0324] [EB print C] Except for using an OPP film (Futamura Chemical Co., Ltd., FOR, 30 μm) as the base layer, the same procedure as for EB printed material A was used. Cyan (C) was solidly applied to the corona-treated surface of the OPP film, and EB printed material C was prepared by irradiating it with an electron beam (EB) at an irradiation dose of 30 kGy under the same irradiation conditions as in Example 1.

[0325] [Gravure Printing Font C] Gravure print body C was prepared in the same manner as gravure print body A, except that the same OPP film (Futamura Chemical Co., Ltd., FOR, 30 μm) as EB print body C was used as the base layer, by solid coating cyan (C) onto the corona-treated surface of the OPP film.

[0326] (evaluation) <Solvent resistance test> The EB printed materials A-C and gravure printed materials A-C were cut into 40mm x 15mm rectangles to form test specimens. These specimens were immersed in ethyl acetate for 5 minutes, and the breakdown of the ink coating (ink layer) was observed visually and evaluated according to the following criteria. The results are shown in Table 4. (Judgment criteria) A: No ink breakdown B: The ink bleeds. C: Ink peels off

[0327] [Table 4]

[0328] As shown in Table 4, EB printed materials demonstrated excellent solvent resistance regardless of the type of substrate layer. In contrast, gravure printed materials showed inferior solvent resistance compared to EB printed materials, regardless of the type of substrate layer, and were particularly significantly inferior when the base layer was nylon or polypropylene.

[0329] [Test Example 5] We investigated the effect of differences in the constituent raw materials of the substrate layer on the mechanical properties (breaking strength, elongation at break) of the substrate layer after electron beam (EB) irradiation.

[0330] (Raw materials used) • High-density polyethylene (HDPE) film (manufactured by Tamapoly Co., Ltd., product name: HS51, thickness 30μm) • Biaxially oriented polyethylene (BOPE) film (manufactured by Guangdong Weifu Packaging Material Co. Ltd, product name: BOPE-TEN, thickness 25μm) • Stretched polypropylene (OPP) film (manufactured by Toyobo Co., Ltd., product name: Pyrene P2161, thickness 30 μm)

[0331] (EB irradiation method) HDPE film, BOPE film, and OPP film, used as substrate layers, were irradiated with electron beams (EB) from the corona-treated side at doses of 15, 30, 45, 60, 100, and 300 kGy, respectively, using an electron beam irradiation device (Hamamatsu Photonics K.K., low-energy electron beam irradiation device) under a nitrogen atmosphere.

[0332] <Measurement of breaking strength> Test specimens (measurement samples) were prepared by cutting each film, both unirradiated and after EB irradiation, to a width of 15 mm in accordance with JIS K 7127:1999. For each test specimen, the breaking strength in the flow direction (MD direction) was measured using a tensile testing machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name: Strograph VE10D) in accordance with JIS K 7161-1:2024, under the conditions of a chuck width (width of the test specimen) of 15 mm, an initial distance between chucks of 100 mm, and a test speed of 300 mm / min. The results are shown in Table 5.

[0333] <Measurement of elongation at break> Test specimens were prepared in the same manner as described in "Measurement of Breaking Strength" above. For each specimen, the elongation at break in the flow direction (MD direction) was measured using a tensile testing machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name: Strograph VE10D) in accordance with JIS K 7161-1:2024, under the conditions of a chuck width (width of the specimen) of 15 mm, an initial distance between chucks of 100 mm, and a test speed of 300 mm / min. The results are shown in Table 5.

[0334] [Table 5]

[0335] As shown in Table 5, polyethylene showed a tendency to suppress the decrease in tensile strength and elongation at break caused by EB irradiation compared to polypropylene. Furthermore, among polyethylenes, HDPE showed a moderate decrease in elongation at break while suppressing the decrease in tensile strength caused by EB irradiation, and therefore it was shown that it can suppress the elongation of the film due to EB irradiation and improve dimensional stability. Moreover, it is reasonably presumed that by using an HDPE film as the base layer and combining it with the extruded resin layer described above, the improvement in strength from the HDPE film and the improvement in rigidity from the extruded resin layer combine to obtain a laminate with appropriate strength.

[0336] [Test Example 6] As shown in Test Examples 1 and 2 above, laminating an extruded resin layer, which functions as an adhesive layer, onto the ink layer resulted in increased adhesive strength and suppressed lifting compared to cases where a dry laminate layer is laminated onto the ink layer or the substrate layer. Furthermore, based on these results, it is considered that a similar effect would be achieved when the extruded resin layer is laminated onto the substrate layer.

[0337] Here, when the extruded resin layer is laminated onto the ink layer, the anchor coat layer acts as an intermediary between them. Since the anchor coat layer inherently enhances the adhesive strength between the layers that are superimposed through it, the extruded resin layer should adhere more reliably to the ink layer. Furthermore, as shown in Test Examples 1 and 2 above, when forming the ink layer using waterless offset printing with ink for waterless offset printing, using either anchor coat resin A, which is a water-based resin composition, or anchor coat resins B and C, which are non-water-based resin compositions, will enhance the adhesive strength between the ink layer and the extruded resin layer and suppress lifting.

[0338] Next, in Test Example 6, we investigated the effect of the anchor coat layer on the adhesion between the ink layer and the extruded resin layer when using water-based offset printing inks to form the ink layer by water-based offset printing.

[0339] (Preparation of test prints) [Test printout A] Using the same PET film (substrate layer, 12 μm) as in Example 1 of Test Example 1, and the same ink as in Test Example 3 (T&K TOKA Corporation, EB-curable ink (water-based ink)), the predetermined printing was performed on the easily adhesive layer surface of the PET film using an ink containing an electron beam-curable resin, in the same manner as in Test Example 3. Specifically, a PET film (Unitika Ltd., product name: Emblet PTM, thickness 12 μm) was used as the substrate layer, and the predetermined printing was performed on the easily adhesive layer surface of the PET film using an ink containing an electron beam-curable resin by water-based offset printing with dampening solution using an offset printing press (COMEXI Corporation, CI-8, center drum type 8-color offset printing press) with dampening solution. The ink used was a thermoplastic resin containing a copolymer of ethylene acrylic acid and ethylene methacrylic acid (T&K TOKA Corporation, EB-curable ink (water-based ink)). As shown in Table 6, the ink colors used were black (K), cyan (C), magenta (M), yellow (Y), and white (W). In Table 6, "CMY," etc., indicate that the colors were applied in that order from left to right, starting from the substrate layer. As shown in Table 6, multiple laminates with different ink colors were created. In Table 6, "plain" indicates an area with an ink area ratio of 0%. The ink area ratio represents the proportion of the printed halftone dot area per unit area. For example, if the halftone dots to be printed are large and adjacent halftone dots completely overlap, resulting in ink being printed across the entire unit area, the ink area ratio is 100%.

[0340] After printing, the print was irradiated with an electron beam (EB) at a dose of 45 kGy from the ink layer side under a nitrogen atmosphere using an electron beam irradiation device (EC series, manufactured by ESI Corporation). Subsequently, the anchor coat resin C described below was applied in the same manner as in Example 2 of Test Example 2 and dried to form an anchor coat layer (0.2 μm). Extrusion lamination was then performed between the anchor coat layer and an LLDPE film (sealant layer, manufactured by Futamura Chemical Co., Ltd., LL-XMTN, thickness 50 μm) by melting and extruding polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec LD LC600A) using an extrusion laminating device to form an extruded resin layer (thickness 20 μm), thereby forming the test print A. The layer structure is as follows.

[0341] <Anchor coating resin C (non-aqueous resin composition)> By combining polyether polyol (manufactured by Mitsui Chemicals, Inc., trade name: Takelac A3210) as the main agent, aliphatic polyisocyanate (manufactured by Mitsui Chemicals, Inc., trade name: Takenate A3070) as the curing agent, and ethyl acetate as the solvent, an organic anchor coating (AC) agent with a solid content concentration of 15% by mass was prepared as anchor coating resin C.

[0342] <Layer configuration> PET#12 (substrate layer, 12μm) / ink (ink layer) / AC (anchor coat layer, 0.2μm) / EXPE (extruded resin layer, 20μm) / LLPPE#50 (sealant layer, 50μm)

[0343] [Sample printed matter B] Test print B was formed in the same manner as test print A, except that anchor coat resin A, the same as in Example 1, was used instead of anchor coat resin C. The layer structure is as follows.

[0344] <Anchor coating resin A (water-based resin composition)> A water-based anchor coat (AC) composition with a solid content concentration of 1.5% by mass was prepared as anchor coat resin A by mixing a polybutadiene-based anchor coat (AC) agent (manufactured by Toyo Morton Co., Ltd., EL-451) with isopropanol (IPA) and water as solvents.

[0345] <Layer configuration> PET#12 (substrate layer, 12μm) / ink (ink layer) / AC (anchor coat layer, 0.2μm) / EXPE (extruded resin layer, 20μm) / LLPPE#50 (sealant layer, 50μm)

[0346] (evaluation) The adhesive strength and delamination were measured and evaluated in the same manner as in Test Example 1. Specifically, the adhesive strength and delamination were measured and evaluated as follows.

[0347] [Measurement of adhesive strength (laminate strength)] In accordance with JIS K 6854-2:1999, a tensile testing machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name: Strograph VE10D) was used to cut test print materials A and B into 15 mm wide strips to serve as measurement samples. After peeling the interlayer (between the ink layer and the extruded resin layer) at the edges of the measurement samples, the peel strength was measured at an angle of 90° (total 180°), a tensile speed of 300 mm / min, and at room temperature. This peel strength was determined as the adhesive strength at room temperature (20°C). The results are shown in Table 6. In Table 6, "plain" refers to the area with an ink area ratio of 0%, as described above.

[0348] [Measurement of buoyancy] The test print materials A and B were cut into 150mm x 200mm rectangles to form test specimens. The test specimens were folded so that the sealant layer side was facing inward and the short sides overlapped, and a 1.5kg rubber roller (Hiyama Shoten Co., Ltd., product name: Double Presser DP300) was rolled over them to create creases. The specimens were then folded again so that the short sides overlapped, and creases were created again with the same rubber roller. In the same manner, the specimens were folded two more times to create creases, for a total of four creases. After that, the folded test specimens were unfolded, and the intersections of the nine creases were observed using a microscope (Keyence Corporation, product name: VHX-6000). The number of creases between the substrate layer and / or ink layer and the sealant layer was counted, with each crease having a maximum length of 0.5mm or more being counted as one crease. The number was evaluated according to the following criteria. The results are shown in Table 6. (Judgment criteria) A: No floats (0) B: One or two floats C: 3 or more floats

[0349] [Table 6]

[0350] As shown in Table 6, when using inks for water-based offset printing, forming an ink layer by water-based offset printing, and providing an anchor coat layer between the ink layer and the extruded resin layer, it was shown that forming the anchor coat layer with a non-aqueous resin composition tends to result in higher adhesive strength and suppression of lifting compared to forming the anchor coat layer with an aqueous resin composition.

[0351] Furthermore, a comprehensive analysis of the results from Test Examples 1-6 suggests that, firstly, the extruded resin layer has higher rigidity than the dry laminate layer. Therefore, laminating the extruded resin layer onto the ink layer can increase adhesive strength and suppress lifting compared to laminating the dry laminate layer onto the ink layer. This is particularly noticeable when forming the ink layer using waterless offset printing. The reason for this is that waterless offset printing inks harden by irradiation with active energy rays (e.g., electron beams (EB)) without containing dampening water. As a result, the resin in the ink undergoes high crosslinking, and its surface forms a "hard shell" that is chemically inert and has low solvent permeability. It is presumed that adhesives for dry laminate layers cannot form strong chemical bonds or physical adhesion to this inert surface, resulting in almost no adhesive strength. In contrast, the resin composition for the anchor coat layer, regardless of whether it is water-based or non-water-based, is presumed to have been able to form strong chemical bonds and physical adhesion to the inert surface of the ink layer, resulting in high adhesive strength.

[0352] Furthermore, when comparing the types of resin compositions for the anchor coat layer when forming an extruded resin layer, it was found that when an ink layer is formed by waterless offset printing and an anchor coat layer is provided between the ink layer and the extruded resin layer, the resin composition for the anchor coat layer can be either a water-based resin composition or a non-water-based resin composition. On the other hand, when an ink layer is formed by water-based offset printing and an anchor coat layer is provided between the ink layer and the extruded resin layer, a non-water-based resin composition is preferred for the anchor coat layer.

[0353] The reason for this is presumed to be as follows: Ink for water-based offset printing is properly emulsified with dampening solution due to the process design. Offset printing, which uses active energy rays (for example, electron beams (EB)), does not require a heating and drying process. Therefore, if the substrate layer is a film that does not absorb the moisture from the ink, it is strongly presumed that the moisture incorporated into the ink layer through emulsification is unevenly distributed as "residual moisture" on the surface of the ink layer.

[0354] Here, the resin contained in the ink for water-based offset printing is essentially hydrophobic (oil-based), just like the ink for waterless offset printing. When a water-based resin composition (polybutadiene-based anchor coating resin A in Example 1) is applied to the surface of this hydrophobic resin, it is presumed that the following two inhibiting factors a) and b) will occur. a) Polarity mismatch: Water, acting as a medium, is present between the resin (hydrophobic) contained in the ink and the resin for the anchor coat (polybutadiene = hydrophobic), hindering their compatibility and adhesion. b) Physical inhibition by moisture: Residual moisture on the ink surface directly inhibits physical contact (hydrogen bonding and van der Waals forces) between the resin of the anchor coat and the resin contained in the ink. These inhibiting factors likely resulted in virtually no adhesive strength being achieved in combinations of water-based offset printing inks and water-based anchor coating resins, as seen in test print B.

[0355] In contrast, in combinations such as in Test Print A, where an ink for water-based offset printing is used and a non-aqueous resin composition (urethane-based anchor coat resin C in Example 2, urethane-based anchor coat resin B in Example 4) is used as the anchor coat resin, the non-aqueous resin composition is "oil-based," similar to dry laminating resins, and therefore has high compatibility with the hydrophobic resin in the ink (regardless of whether it is waterless or water-based offset printing). However, the biggest difference from dry laminating resins lies in the lamination process. Non-aqueous resin compositions such as anchor coat resins B and C are laminated onto the ink layer by extrusion of a molten resin at a high temperature (e.g., 300°C or higher) immediately after application. Therefore, even if "excessive residual moisture" exists on the surface of the ink layer, the "high heat during extrusion" instantly evaporates and removes the moisture before the curing agent (isocyanate) in the anchor coat resin causes curing failure. As a result, non-aqueous resin compositions such as anchor coating resins B and C are not inhibited by moisture and can adhere firmly (by hydrogen bonding) to the resin body in the ink layer, thus suppressing a decrease in strength.

[0356] Therefore, when forming an extruded resin layer on an ink layer formed by an offset printing ink irradiated with active energy rays, in order to ensure high adhesive strength between the ink layer and the extruded resin layer, regardless of various inhibiting factors such as the type of ink (inert surface of waterless offset printing ink, residual moisture of water-based offset printing ink), it is considered that an alternative technical means is extremely effective: either use a "waterless offset printing ink (which does not have problems with moisture or an inert surface)" (Examples 1-4), or use a "non-aqueous resin composition (which can processically avoid the effects of residual moisture) as the anchor coat resin" (Examples 2, 4, and Test Print A). [Industrial applicability]

[0357] The printed materials and packaging of the present invention are suitably usable, for example, as printed materials and packaging for foods that are heated or subjected to moist heat, such as boiled or retort foods, resealable pouches, and microwaveable foods, but they can also be used as printed materials and packaging for articles other than food. [Explanation of symbols]

[0358] 1 Base material layer 2 Ink Layers 3, 3a, 3b extruded resin layer 4, 4a, 4b Anchor coat layer 5. Middle Class 7. Sealant layer 8. Dry Laminate Layer 9 Coat Layers 10 Overcoat Layers 101~110 Printed matter 200 packaging products 210 Packaging

Claims

1. A printed material that has been offset printed using an active energy ray curable ink containing an active energy ray curable resin, An ink layer containing the aforementioned active energy ray curable ink, A substrate layer having affinity for the active energy ray curable resin, The ink layer and / or the extruded resin layer laminated on the substrate layer A printed material that includes the following features.

2. The printed material according to claim 1, wherein the active energy beam is an electron beam.

3. The printed article according to claim 2, wherein the ink layer substantially contains no polymerization initiator.

4. The printed material according to claim 1, wherein the thickness of the extruded resin layer is 3 to 100 μm.

5. The printed article according to claim 1, further comprising an anchor coat layer between the ink layer and / or the substrate layer and the extruded resin layer.

6. The aforementioned offset printing is waterless offset printing, which does not use dampening solution. The aforementioned active energy ray curing ink is an ink for waterless offset printing, The printed material according to claim 5, further comprising the anchor coat layer between the ink layer and the extruded resin layer.

7. The anchor coat layer is provided between the ink layer and the extruded resin layer. The printed article according to claim 5, wherein the anchor coat layer is formed of a non-aqueous resin composition that is incompatible with water.

8. The printed material according to claim 1, wherein the adhesive strength between the ink layer and / or the substrate layer and the extruded resin layer, as measured in accordance with JIS K 6854-3:1999, is 2 N / 15 cm or more.

9. The printed material according to claim 1, further comprising a sealant layer on the back side of the extruded resin layer.

10. A package formed by a printed material according to any one of claims 1 to 9.

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