Laminates, packaging materials, lid materials and labels

Abstract

To provide a laminate that exhibits superior adhesion between a first base material and an ink layer as well as excellent blocking resistance, and to provide a packaging material including the laminate, a lid material including the laminate, and a label including the laminate.SOLUTION: A laminate 1 comprises, in order toward one side in the thickness direction, a first base material 2, an easy-adhesion layer 3, a primer layer 4, and an ink layer 5. The primer layer 4 is composed of a primer composition. The primer composition contains a polyisocyanate compound and a radically polymerizable compound, and the content of the polyisocyanate compound is 15 to 50 pts.mass per 100 pts.mass of the total amount of the polyisocyanate compound and the radically polymerizable compound.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminate, a packaging material, a lid material, and a label. [Background technology]

[0002] 2. Description of the Related Art Conventionally, a printing method using an inkjet method is known.

[0003] As such a printing method, for example, an image recording method has been proposed that includes an undercoat composition application step of applying an undercoat composition onto a substrate, a first actinic energy ray irradiation step of irradiating the undercoat composition with a first actinic energy ray, an ink application step of applying ink onto the undercoat composition irradiated with the first actinic energy ray by an inkjet recording method, and a second actinic energy ray irradiation step of irradiating the ink with a second actinic energy ray (see, for example, Patent Document 1 listed below). Using such a printing method, it is possible to produce a laminate that includes a substrate, an undercoat layer, and an ink layer in that order toward one side in the thickness direction. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2021-105139 Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, in the laminate, improved adhesion between the substrate and the ink layer is required.

[0006] Furthermore, the laminate is required to have blocking resistance.

[0007] The present invention provides a laminate that has excellent adhesion between a first substrate and an ink layer and excellent blocking resistance, a packaging material including the laminate, a lid material including the laminate, and a label including the laminate. [Means for solving the problem]

[0008] The present invention [1] is a laminate comprising a first substrate, an easy-adhesion layer, a primer layer, and an ink layer in that order toward one side in the thickness direction, the primer layer being made of a primer composition, the primer composition containing a polyisocyanate compound and a radically polymerizable compound, and the content of the polyisocyanate compound being 15 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the total amount of the polyisocyanate compound and the radically polymerizable compound.

[0009] The present invention [2] further includes the laminate described in [1] above, which has a first adhesive layer and a second substrate arranged in that order toward one side in the thickness direction of the ink layer.

[0010] The present invention [3] further includes the laminate described in [2] above, which has a second adhesive layer and a third substrate arranged in that order toward one side in the thickness direction of the second substrate.

[0011] The present invention [4] further includes the laminate described in [2] above, which further includes a second adhesive layer and a third substrate on the other side of the thickness direction of the first substrate, in that order toward the other side of the thickness direction.

[0012] The present invention [5] further includes the laminate described in [2] above, which has, on one thickness-wise side of the second substrate, a third adhesive layer, a barrier layer, a second adhesive layer, and a third substrate, arranged in that order toward one thickness-wise side.

[0013] The present invention [6] further includes the laminate described in [2] above, which has, on the other side of the thickness direction of the first substrate, a third adhesive layer, a barrier layer, a second adhesive layer, and a third substrate, in that order toward the other side of the thickness direction.

[0014] The present invention [7] includes a packaging material comprising the laminate according to any one of the above [1] to [6].

[0015] The present invention [8] includes a lid material comprising the laminate according to any one of the above [1] to [6].

[0016] The present invention [9] includes a label comprising the laminate according to any one of the above [1] to [6]. [Effects of the Invention]

[0017] The laminate of the present invention includes an easy-adhesion layer between a first substrate and a primer layer. The primer composition forming the primer layer contains a polyisocyanate compound and a radically polymerizable compound, and the content of the polyisocyanate compound is within a predetermined range. This improves adhesion between the first substrate and the ink layer and blocking resistance.

[0018] The packaging material of the present invention includes the laminate of the present invention, which can improve adhesion between the first substrate and the ink layer, as well as blocking resistance.

[0019] The covering material of the present invention includes the laminate of the present invention, and therefore, the adhesion between the first substrate and the ink layer and the blocking resistance can be improved.

[0020] The label of the present invention includes the laminate of the present invention, which can improve adhesion between the first substrate and the ink layer, as well as blocking resistance. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 shows a cross-sectional view of a first embodiment of the laminate of the present invention. [Figure 2]2A to 2H show one embodiment of a method for manufacturing a laminate. FIG. 2A shows a first step of preparing a first substrate. FIG. 2B shows a second step of disposing an easy-adhesion layer on one thickness-wise surface of the first substrate. FIG. 2C shows a third step of disposing an uncured primer layer on one thickness-wise surface of the easy-adhesion layer. FIG. 2D shows a fourth step of semi-curing the uncured primer layer. FIG. 2E shows a fifth step of disposing an ink layer on one thickness-wise surface of the semi-cured primer layer. FIG. 2F shows a sixth step of fully curing the semi-cured primer layer. FIG. 2G shows a seventh step of disposing a first adhesive layer on one thickness-wise surface of the ink layer. FIG. 2H shows an eighth step of disposing a second substrate on one thickness-wise surface of the first adhesive layer. [Figure 3] 3A to 3D show cross-sectional views of second to fifth embodiments of the laminate of the present invention. FIG. 3A shows a cross-sectional view of the second embodiment of the laminate of the present invention. FIG. 3B shows a cross-sectional view of the third embodiment of the laminate of the present invention. FIG. 3C shows a cross-sectional view of the fourth embodiment of the laminate of the present invention. FIG. 3D shows a cross-sectional view of the fifth embodiment of the laminate of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0022] 1. First embodiment A first embodiment of the laminate of the present invention will be described with reference to FIG.

[0023] In Figure 1, the up-down direction of the paper surface is the up-down direction (thickness direction), and the upper side of the paper surface is the upper side (one side in the thickness direction), and the lower side of the paper surface is the lower side (the other side in the thickness direction). Also, the left-right direction and the depth direction of the paper surface are surface directions perpendicular to the up-down direction. Specifically, they conform to the directional arrows in each figure.

[0024] <Laminate> The laminate 1 has a film shape (including a sheet shape) with a predetermined thickness. The laminate 1 extends in a plane direction perpendicular to the thickness direction. The laminate 1 has a flat upper surface and a flat lower surface.

[0025] As shown in FIG. 1, the laminate 1 includes a first substrate 2, an easy-adhesion layer 3, a primer layer 4, an ink layer 5, a first adhesive layer 6, and a second substrate 7, arranged in this order toward one side in the thickness direction. Specifically, the laminate 1 comprises, in order toward one side in the thickness direction, a first substrate 2, an easy-adhesion layer 3 arranged directly on the upper surface (one side in the thickness direction) of the first substrate 2, a primer layer 4 arranged directly on the upper surface (one side in the thickness direction) of the easy-adhesion layer 3, an ink layer 5 arranged directly on the upper surface (one side in the thickness direction) of the primer layer 4, a first adhesive layer 6 arranged directly on the upper surface (one side in the thickness direction) of the ink layer 5, and a second substrate 7 arranged directly on the upper surface (one side in the thickness direction) of the first adhesive layer 6.

[0026] The thickness of the laminate 1 is not particularly limited, but from the viewpoint of strength and ease of handling, it is, for example, 1 μm to 200 μm, or preferably 10 μm to 150 μm.

[0027] <First base material> The first substrate 2 ensures the mechanical strength of the laminate 1. In addition, in the fifth step described below, the first substrate 2 is a printing substrate on which the ink layer 5 is disposed.

[0028] The first substrate 2 is not particularly limited, and examples thereof include a plastic film and a metal film.

[0029] Examples of plastic films include olefin polymer films, polyamide polymer films, polyester polymer films, and vinyl polymer films.

[0030] Examples of olefin polymer films include polyethylene films and polypropylene films. Examples of polyethylene films include high-density polyethylene films (HDPE films) and linear low-density polyethylene films (LLDPE films). Examples of polypropylene films include unstretched polypropylene films (CPP films), uniaxially stretched polypropylene films, and biaxially stretched polypropylene films (OPP films).

[0031] Examples of polyamide polymer films include nylon films (eg, nylon 6, nylon 66).

[0032] Examples of polyester polymer films include polyethylene terephthalate films (PET films) and polybutylene terephthalate films, and a preferred polyester polymer film is polyethylene terephthalate film.

[0033] Examples of vinyl polymer films include polyvinyl chloride films, ethylene-vinyl acetate copolymer films, and ethylene-vinyl alcohol copolymer films.

[0034] The plastic film is preferably a polyamide polymer film or a polyester polymer film. The plastic film is more preferably a polyamide polymer film. That is, the printing substrate is more preferably a polyamide polymer film. If the plastic film is a polyamide polymer film, the flexibility of the polyamide polymer film can improve the adhesion between the first substrate 2 and the ink layer 5 even after high-temperature sterilization.

[0035] Examples of metal films include aluminum foil, metal vapor deposition films, silica vapor deposition films, alumina vapor deposition films, silica-alumina composite vapor deposition films, stainless steel, iron, copper, and lead.

[0036] The first substrate 2 is preferably a plastic film.

[0037] The first substrate 2 has a thickness of, for example, 1 μm to 100 μm, or preferably 10 μm to 70 μm.

[0038] <Easy adhesion layer> The adhesive layer 3 assists in adhesion between the first substrate 2 and the primer layer 4. The adhesive layer 3 is in contact with the upper surface of the first substrate 2 (one surface in the thickness direction).

[0039] The adhesive layer 3 is formed from an adhesive composition.

[0040] The adhesive composition contains a resin and, if necessary, particles.

[0041] Examples of resins include urethane resins, polyester resins, acrylic resins, and polyvinyls (for example, polyvinyl alcohol, polyvinyl chloride, and vinyl chloride-vinyl acetate copolymers).

[0042] The resins can be used alone or in combination of two or more kinds.

[0043] Examples of the particles include inorganic particles.

[0044] Examples of inorganic particles include silica, colloidal silica, hollow silica, alumina, alumina sol, diamond, magnesium fluoride, calcium fluoride, tin oxide, indium tin oxide, titanium oxide, zinc oxide, niobium oxide, neodymium oxide, lanthanum oxide, zirconium oxide, cerium oxide, magnesium oxide, and tantalum pentoxide.

[0045] The particles can be used alone or in combination of two or more kinds.

[0046] In addition, as the easy-adhesion composition, a liquid for forming an easy-adhesion layer described in JP 2022-034576 A, a urethane resin constituting an easy-adhesion layer described in JP 2021-047295 A, a composition containing a water-dispersed latex as a binder component described in JP 2015-190033 A, and a polymer described in JP 2015-202682 A can also be used.

[0047] The adhesive composition can also be diluted with a known solvent to prepare a diluted solution of the adhesive composition.

[0048] As will be described in detail later, the adhesive layer 3 can be formed by applying an adhesive composition (diluted solution of adhesive composition) to one surface in the thickness direction of the first substrate 2, and drying it as necessary.

[0049] <Primer layer> The primer layer 4 is in contact with the upper surface (one surface in the thickness direction) of the adhesive layer 3 .

[0050] The primer layer 4 is made of a primer composition.

[0051] The primer composition includes a polyisocyanate compound and a radical polymerizable compound.

[0052] [Polyisocyanate compounds] The polyisocyanate compound improves the adhesion to the first substrate 2 .

[0053] Examples of the polyisocyanate compound include polyisocyanate and polyisocyanate derivatives.

[0054] Examples of polyisocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.

[0055] Examples of aliphatic polyisocyanates include aliphatic diisocyanates. Examples of aliphatic diisocyanates include 1,6-hexamethylene diisocyanate (1,6-HDI), 1,5-pentamethylene diisocyanate (1,5-PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2-, 2,3-, or 1,3-butylene diisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate. A preferred example of the aliphatic polyisocyanate is 1,6-HDI.

[0056] Examples of alicyclic polyisocyanates include alicyclic diisocyanates. Examples of alicyclic diisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'-, 2,4'-, or 2,2'-methylenebis(cyclohexyl isocyanate), or mixtures thereof (H 12 MDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof (H6XDI), bis(isocyanatomethyl)norbornane (NBDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

[0057] Examples of aromatic polyisocyanates include aromatic diisocyanates, such as 4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate or a mixture thereof (MDI), 2,4- or 2,6-tolylene diisocyanate or a mixture thereof (TDI), o-tolidine diisocyanate, 1,5-naphthalene diisocyanate (NDI), m- or p-phenylene diisocyanate or a mixture thereof, 4,4'-diphenyl diisocyanate, and 4,4'-diphenyl ether diisocyanate.

[0058] Examples of araliphatic polyisocyanates include araliphatic diisocyanates, such as xylylene diisocyanate (1,2-, 1,3-, or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), and ω,ω′-diisocyanato-1,4-diethylbenzene.

[0059] The polyisocyanate is preferably an aliphatic polyisocyanate.

[0060] Examples of polyisocyanate derivatives include the above-mentioned polyisocyanate polymers (e.g., isocyanurate derivatives), allophanate derivatives, polyol derivatives (e.g., polyol-modified products (alcohol adducts) produced by the reaction of polyisocyanate with trihydric alcohols (e.g., trimethylolpropane)), biuret derivatives, urea derivatives, oxadiazinetrione derivatives, carbodiimide derivatives, uretdione derivatives, and uretonimine derivatives. Preferred examples of polyisocyanate derivatives include isocyanurate derivatives, allophanate derivatives, and biuret derivatives. From the viewpoint of improving adhesion between the first substrate 2 and the ink layer 5, more preferred examples of polyisocyanate derivatives include isocyanurate derivatives and biuret derivatives.

[0061] The polyisocyanate compound is preferably a polyisocyanate derivative. The polyisocyanate compound is more preferably a derivative of an aliphatic polyisocyanate. The polyisocyanate compound is further preferably an isocyanurate derivative of 1,6-hexamethylene diisocyanate, an allophanate derivative of 1,6-hexamethylene diisocyanate, or a biuret derivative of 1,6-hexamethylene diisocyanate. The polyisocyanate compound is particularly preferably an isocyanurate derivative of 1,6-hexamethylene diisocyanate or a biuret derivative of 1,6-hexamethylene diisocyanate.

[0062] The polyisocyanate compound may be diluted with a known solvent as needed. From the viewpoint of reducing the environmental load, the polyisocyanate compound is preferably used as it is without being diluted with a known solvent.

[0063] The polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0064] The content of the polyisocyanate compound is 15 to 50 parts by mass, preferably 20 to 45 parts by mass, more preferably 25 to 45 parts by mass, even more preferably 30 to 45 parts by mass, and particularly preferably 35 to 45 parts by mass, relative to 100 parts by mass of the total amount of the polyisocyanate compound and the radical polymerizable compound.

[0065] Specifically, the content of the polyisocyanate compound is 15 parts by mass or more, preferably 20 parts by mass or more, more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, particularly preferably 35 parts by mass or more, and 50 parts by mass or less, preferably 45 parts by mass or less, relative to 100 parts by mass of the total amount of the polyisocyanate compound and the radical polymerizable compound.

[0066] When the content of the polyisocyanate compound is equal to or greater than the above lower limit, the adhesion between the first substrate 2 and the ink layer 5 can be improved.

[0067] On the other hand, if the content of the polyisocyanate compound is less than the above lower limit, the adhesion between the first substrate 2 and the ink layer 5 decreases.

[0068] Furthermore, when the content of the polyisocyanate compound is equal to or less than the upper limit, blocking resistance can be improved.

[0069] On the other hand, if the content of the polyisocyanate compound exceeds the upper limit, the blocking resistance decreases.

[0070] [Radical polymerizable compounds] The radical polymerizable compound improves the adhesion to the ink layer 5 .

[0071] Examples of the radically polymerizable compound include a monofunctional polymerizable compound having one radically polymerizable group, and a polyfunctional polymerizable compound having two or more radically polymerizable groups.

[0072] Examples of the radical polymerizable group include a (meth)acryloyl group (an acryloyl group or a methacryloyl group) and a vinyl group. A preferred example of the radical polymerizable group is a (meth)acryloyl group.

[0073] Examples of the monofunctional polymerizable compound include monofunctional (meth)acrylates.

[0074] Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates having an alkyl moiety with 1 to 12 carbon atoms. Examples of alkyl (meth)acrylates having an alkyl moiety with 1 to 12 carbon atoms include alkyl (meth)acrylates having an alkyl moiety with 1 to 4 carbon atoms and alkyl (meth)acrylates having an alkyl moiety with 5 to 12 carbon atoms. Examples of alkyl (meth)acrylates having an alkyl moiety with 1 to 4 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and t-butyl (meth)acrylate. Examples of alkyl(meth)acrylates having an alkyl moiety with 5 to 12 carbon atoms include n-amyl(meth)acrylate, isoamyl(meth)acrylate, n-hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, and octadecyl(meth)acrylate.

[0075] Examples of polyfunctional polymerizable compounds include polyfunctional (meth)acrylates, such as difunctional (meth)acrylates, trifunctional (meth)acrylates, and tetrafunctional or higher polyfunctional (meth)acrylates.

[0076] Examples of bifunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate.

[0077] Examples of trifunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris(acryloyloxyethyl)isocyanurate.

[0078] Examples of tetrafunctional or higher polyfunctional (meth)acrylates include ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0079] In addition, as the radical polymerizable compound, the radical polymerizable compound described in JP 2021-105139 A can also be used.

[0080] Alternatively, commercially available products may be used as the radical polymerizable compound, such as Uvijet MK702 (manufactured by Fujifilm Corporation).

[0081] The radical polymerizable compounds can be used alone or in combination of two or more kinds.

[0082] The content of the radical polymerizable compound is 50 parts by mass to 85 parts by mass, preferably 55 parts by mass to 80 parts by mass, more preferably 55 parts by mass to 75 parts by mass, even more preferably 55 parts by mass to 70 parts by mass, and particularly preferably 55 parts by mass to 65 parts by mass, relative to 100 parts by mass of the total amount of the polyisocyanate compound and the radical polymerizable compound.

[0083] Specifically, the content of the radical polymerizable compound is 50 parts by mass or more, preferably 55 parts by mass or more, and 85 parts by mass or less, preferably 80 parts by mass or less, more preferably 75 parts by mass or less, even more preferably 70 parts by mass or less, and particularly preferably 65 parts by mass or less, relative to 100 parts by mass of the total amount of the polyisocyanate compound and the radical polymerizable compound.

[0084] When the content of the radical polymerizable compound is equal to or greater than the above lower limit, blocking resistance can be improved.

[0085] Furthermore, if the content of the radical polymerizable compound is equal to or less than the above upper limit, the adhesion between the first substrate 2 and the ink layer 5 can be improved.

[0086] The primer composition may contain additives in appropriate proportions as needed, such as a polymerization initiator (e.g., a radical polymerization initiator), a surfactant, an ultraviolet absorber, and an antioxidant.

[0087] Furthermore, the primer composition preferably does not contain a colorant, which will be described later.

[0088] The primer composition may be diluted with a known solvent as needed. From the viewpoint of reducing the environmental load, the primer composition is preferably used as is without being diluted with a known solvent.

[0089] As will be described in detail later, the primer layer 4 is obtained by applying a primer composition to one surface in the thickness direction of the adhesive layer 3 and then curing the primer composition. That is, the primer layer 4 includes a cured product of the primer composition.

[0090] The thickness of the primer layer 4 is in the range of, for example, 0.1 μm to 10.0 μm, or preferably 1.0 μm to 5.0 μm.

[0091] <Ink layer> The ink layer 5 is in contact with the upper surface (one surface in the thickness direction) of the primer layer 4.

[0092] The ink layer 5 is made of an ink composition.

[0093] [Coloring agent] The ink composition includes a colorant.

[0094] Examples of the colorant include dyes and pigments, and preferably, the colorant is a pigment.

[0095] Examples of the pigment include known pigments. More specifically, examples of the pigment include those described in "Dictionary of Pigments" edited by Seijiro Ito (published in 2000), "Industrial Organic Pigments" by W. Herbst and K. Hunger, and JP-A Nos. 2002-12607, 2002-188025, 2003-26978, and 2003-342503.

[0096] The colorants can be used alone or in combination of two or more.

[0097] The content of the colorant is appropriately selected depending on the color and intended use, but is, for example, 0.01% by mass to 30% by mass relative to the ink composition.

[0098] The ink composition may also contain a radically polymerizable compound, if necessary.

[0099] The radical polymerizable compound may be any of the radical polymerizable compounds listed above for the primer composition.

[0100] As the radical polymerizable compound, the same radical polymerizable compound as that of the primer composition described above is preferably selected.

[0101] From the viewpoint of curability, the content of the radical polymerizable compound in the ink composition is, for example, 70% to 98% by mass, preferably 70% to 95% by mass, and more preferably 80% to 93% by mass.

[0102] The ink composition may contain additives in appropriate proportions as needed, such as the additives listed above for the primer composition.

[0103] The ink composition may be diluted with a known solvent as needed. From the viewpoint of reducing the environmental load, the ink composition is preferably used as is without being diluted with a known solvent.

[0104] The ink composition preferably comprises a colorant and a radically polymerizable compound.

[0105] As will be described in detail later, the ink layer 5 is formed by applying an ink composition to one surface of the semi-cured primer layer 4 in the thickness direction.

[0106] The thickness of the ink layer 5 is not particularly limited, and is, for example, 2 μm to 12 μm.

[0107] <First adhesive layer> The first adhesive layer 6 contacts the upper surface of the ink layer 5 (one surface in the thickness direction).

[0108] The first adhesive layer 6 is made of a known adhesive (for example, a two-component urethane adhesive).

[0109] The thickness of the first adhesive layer 6 is not particularly limited, and is, for example, 1.0 μm to 5.0 μm.

[0110] <Second base material> The second base material 7 is in contact with the upper surface (one surface in the thickness direction) of the first adhesive layer 6.

[0111] As the second substrate 7, the substrates listed above for the first substrate 2 can be used.

[0112] The second substrate 7 is preferably a plastic film.

[0113] The second substrate 7 has a thickness of, for example, 1 μm to 100 μm, or preferably 10 μm to 70 μm.

[0114] <Method of manufacturing laminate> The method for producing the laminate 1 includes the following steps: a first step of preparing a first substrate 2; a second step of disposing an easy-adhesion layer 3 on one thickness-wise surface of the first substrate 2; a third step of disposing an uncured primer layer 4a on one thickness-wise surface of the easy-adhesion layer 3; a fourth step of semi-curing the uncured primer layer 4a; a fifth step of disposing an ink layer 5 on one thickness-wise surface of the semi-cured primer layer 4b; a sixth step of completely curing the semi-cured primer layer 4b; a seventh step of disposing a first adhesive layer 6 on one thickness-wise surface of the ink layer 5; and an eighth step of disposing a second substrate 7 on one thickness-wise surface of the first adhesive layer 6. In steps 1 to 6 of this production method, each layer is sequentially disposed, for example, by a roll-to-roll process. Steps 1 to 6 of this production method can also be performed using a commercially available inkjet printer (e.g., Jet Press 540WV, manufactured by Fujifilm Corporation).

[0115] [1st step] In the first step, as shown in FIG. 2A, a first substrate 2 is prepared.

[0116] [Second process] In the second step, as shown in FIG. 2B, an easy-adhesion layer 3 is disposed on one surface of the first substrate 2 in the thickness direction.

[0117] To dispose the easy-adhesion layer 3 on one surface in the thickness direction of the first substrate 2, the easy-adhesion composition (diluted solution of the easy-adhesion composition) is applied to one surface in the thickness direction of the first substrate 2, and dried as necessary.

[0118] As for drying conditions, the drying temperature is, for example, 40° C. to 100° C., or preferably 60° C. to 90° C. The drying time is, for example, 10 seconds to 240 seconds, or preferably 30 seconds to 120 seconds.

[0119] As a result, the easy-adhesion layer 3 is disposed on one surface of the first base material 2 in the thickness direction.

[0120] [3rd step] In the third step, as shown in FIG. 2C, a primer layer 4a before curing is disposed on one surface of the adhesive layer 3 in the thickness direction.

[0121] To dispose the primer layer 4a before curing on one surface in the thickness direction of the adhesive layer 3, first, if necessary, a surface treatment is applied to one surface in the thickness direction of the adhesive layer 3. Examples of surface treatments include corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow discharge treatment, and saponification treatment. Corona treatment is preferred as the surface treatment.

[0122] Next, in the third step, a primer composition is applied to one surface in the thickness direction of the adhesive layer 3, and dried as necessary.

[0123] As for drying conditions, the drying temperature is, for example, 40° C. to 100° C., or preferably 60° C. to 90° C. The drying time is, for example, 10 seconds to 240 seconds, or preferably 30 seconds to 120 seconds.

[0124] As a result, the primer layer 4a (A stage) before curing is disposed on one surface of the adhesive layer 3 in the thickness direction.

[0125] [4th step] In the fourth step, as shown in FIG. 2D, the primer layer 4a before curing is semi-cured to form a semi-cured primer layer 4b (B stage). Semi-curing means that the polymerization rate of the radical polymerizable compound is, for example, 80% or less, preferably 70% or less, and, for example, 30% or more. The method for measuring the polymerization rate is in accordance with the method described in JP 2021-105139 A (the same applies below).

[0126] To semi-cure the primer layer 4a before curing, the primer layer 4a before curing is irradiated with active energy rays.

[0127] Examples of active energy rays include ultraviolet rays and electron beams, and preferably ultraviolet rays.

[0128] The amount of irradiation of the active energy rays is, for example, 3 mJ / cm from the viewpoint of semi-curing the primer layer 4a before curing. 2 ~100mJ / cm 2 , preferably 5 mJ / cm 2 ~20mJ / cm 2 is.

[0129] As a result, a part of the radically polymerizable compound in the primer composition is polymerized, and the primer layer 4a before curing is semi-cured.

[0130] [5th ​​step] In the fifth step, as shown in FIG. 2E, an ink layer 5 is disposed on one surface in the thickness direction of the semi-cured primer layer 4b.

[0131] An example of a method for disposing the ink layer 5 on one surface in the thickness direction of the semi-cured primer layer 4b is an inkjet method, in which an ink composition is ejected from an inkjet head and applied to one surface in the thickness direction of the semi-cured primer layer 4b.

[0132] Furthermore, in the fifth step, a plurality of ink compositions (specifically, ink compositions that contain different colorants and have different colors) can also be arranged in order.

[0133] As a result, the ink layer 5 is disposed on one surface in the thickness direction of the semi-cured primer layer 4b.

[0134] [6th step] 2F, in the sixth step, the semi-cured primer layer 4b is completely cured to form a completely cured primer layer 4 (C stage), as shown in FIG. 2F. "Completely cured" means that the polymerization rate of the radical polymerizable compound is, for example, more than 80%, preferably 90% or more.

[0135] To completely cure the semi-cured primer layer 4b, the semi-cured primer layer 4 is irradiated with active energy rays from the ink layer 5 side. The amount of irradiation light of the active energy rays is set to, for example, 105 mJ / cm from the viewpoint of completely curing the semi-cured primer layer 4b. 2 ~1000mJ / cm 2 , preferably 110 mJ / cm 2 ~200mJ / cm 2 is.

[0136] This polymerizes a large portion of the radical polymerizable compound in the primer composition, completely curing the semi-cured primer layer 4b. Furthermore, if the ink composition contains a radical polymerizable compound, the radical polymerizable compound in the ink composition also polymerizes. That is, both the radical polymerizable compound in the primer composition and the radical polymerizable compound in the ink composition are cured. Furthermore, as described above, in this method, the uncured primer layer 4a is semi-cured in the fourth step, the ink layer 5 is disposed on one thickness-wise surface of the semi-cured primer layer 4b in the fifth step, and the semi-cured primer layer 4b is completely cured in the sixth step. Because the ink layer 5 is disposed on the semi-cured primer layer 4b in the fifth step, the fixation of the ink layer 5 can be improved compared to, for example, disposing the ink layer 5 on the completely cured primer layer 4. In particular, if the ink composition contains a radical polymerizable compound, the radical polymerizable compound in the semi-cured primer layer 4b becomes more compatible with the radical polymerizable compound in the ink layer 5, further improving the fixation of the ink layer 5.

[0137] [Step 7] In the seventh step, as shown in FIG. 2G, a first adhesive layer 6 is disposed on one surface of the ink layer 5 in the thickness direction.

[0138] To dispose the first adhesive layer 6 on one surface in the thickness direction of the ink layer 5, a known adhesive (for example, a two-component urethane adhesive) is applied to one surface in the thickness direction of the ink layer 5 and dried as necessary.

[0139] As a result, the first adhesive layer 6 is disposed on one surface of the ink layer 5 in the thickness direction.

[0140] [8th step] 2H, in the eighth step, the second substrate 7 is placed on one surface in the thickness direction of the first adhesive layer 6. Specifically, using a dry laminating device, the second substrate 7 is bonded to one surface in the thickness direction of the first adhesive layer 6, and then aging is performed as necessary.

[0141] As for the aging conditions, the aging temperature is, for example, 20° C. to 60° C., or preferably 30 to 50° C., and the aging time is, for example, 1 hour to 48 hours, or preferably 12 hours to 36 hours.

[0142] In this way, the second base material 7 is disposed on one surface of the first adhesive layer 6 in the thickness direction, and the laminate 1 is produced.

[0143] 2. Second to fifth embodiments In the second to fifth embodiments, the same components and steps as those in the first embodiment are denoted by the same reference numerals, and detailed descriptions thereof will be omitted. Furthermore, the second to fifth embodiments can achieve the same effects as those of the first embodiment, unless otherwise specified. Furthermore, the first embodiment can be combined with the second to fifth embodiments as appropriate.

[0144] 2-1. Second embodiment A second embodiment of the laminate of the present invention will be described with reference to FIG. 3A.

[0145] In the second embodiment, a second adhesive layer 8 and a third substrate 9 are further provided in this order toward one side in the thickness direction on one side of the second substrate 7. That is, in the second embodiment, the laminate 1 is provided with a first substrate 2, an easy-adhesion layer 3, a primer layer 4, an ink layer 5, an adhesive layer 6, the second substrate 7, the second adhesive layer 8, and a third substrate 9 in this order toward one side in the thickness direction.

[0146] <Second adhesive layer> The second adhesive layer 8 is in contact with the upper surface (one surface in the thickness direction) of the second base material 7.

[0147] The second adhesive layer 8 is made of a known adhesive (for example, a two-component urethane adhesive).

[0148] The thickness of the second adhesive layer 8 is not particularly limited, and is, for example, 1.0 μm to 5.0 μm.

[0149] <Third base material> The third base material 9 is in contact with the upper surface (one surface in the thickness direction) of the second adhesive layer 8.

[0150] As the third substrate 9, the substrates listed above as the first substrate 2 can be used.

[0151] The third substrate 9 is preferably a plastic film.

[0152] The third base material 9 has a thickness of, for example, 1 μm to 100 μm, or preferably 10 μm to 70 μm.

[0153] Preferably, from the viewpoint of heat resistance, the first substrate 2 is a polyester polymer (preferably polyethylene terephthalate), the second substrate 7 is a polyamide polymer (preferably nylon), and the third substrate 9 is an olefin polymer film.

[0154] In the second embodiment, after the eighth step described above, the laminate 1 is manufactured by arranging the second adhesive layer 8 and the third substrate 9 on one side of the second substrate 7 in the thickness direction. Specifically, the second adhesive layer 8 is disposed on one surface in the thickness direction of the second substrate 7, and then the third substrate 9 is disposed on one surface in the thickness direction of the second adhesive layer 8.

[0155] To dispose the second adhesive layer 8 on one surface in the thickness direction of the second substrate 7, a known adhesive is applied to one surface in the thickness direction of the second substrate 7, and dried as necessary.

[0156] As a result, the second adhesive layer 8 is disposed on one surface of the second base material 7 in the thickness direction.

[0157] Next, a third substrate 9 is placed on one surface in the thickness direction of the second adhesive layer 8. Specifically, using a dry laminating device, the third substrate 9 is bonded to one surface in the thickness direction of the second adhesive layer 8, and then aging is performed as necessary. The aging conditions are the same as those in the above-mentioned eighth step.

[0158] In this way, the third base material 9 is disposed on one surface of the second adhesive layer 8 in the thickness direction, and the laminate 1 is produced.

[0159] 2-2. Third embodiment A third embodiment of the laminate of the present invention will be described with reference to FIG. 3B.

[0160] In the third embodiment, a second adhesive layer 8 and a third substrate 9 are further provided in this order toward the other side in the thickness direction of the first substrate 2. That is, in the third embodiment, the laminate 1 is provided with the third substrate 9, the second adhesive layer 8, the first substrate 2, the easy-adhesion layer 3, the primer layer 4, the ink layer 5, the adhesive layer 6, and the second substrate 7 in this order toward one side in the thickness direction.

[0161] In the third embodiment, from the viewpoint of improving the adhesion between the first substrate 2 and the ink layer 5 even after high-temperature sterilization treatment, the first substrate 2 is a polyamide-based polymer (preferably nylon), the second substrate 7 is a polyester-based polymer (preferably polyethylene terephthalate), and the third substrate 9 is an olefin-based polymer film.

[0162] In the third embodiment, after the eighth step described above, the laminate 1 is manufactured by arranging the second adhesive layer 8 and the third substrate 9 on the other side of the first substrate 2 in the thickness direction. Specifically, the second adhesive layer 8 is disposed on the other surface in the thickness direction of the second substrate 7, and then the third substrate 9 is disposed on the other surface in the thickness direction of the second adhesive layer 8.

[0163] To dispose the second adhesive layer 8 on the other side in the thickness direction of the first substrate 2, a known adhesive is applied to the other surface in the thickness direction of the first substrate 2, and dried as necessary.

[0164] As a result, the second adhesive layer 8 is disposed on the other surface of the first base material 2 in the thickness direction.

[0165] Next, a third substrate 9 is placed on the other thickness-wise surface of the second adhesive layer 8. Specifically, using a dry laminating device, the third substrate 9 is bonded to the other thickness-wise surface of the second adhesive layer 8, and then aging is performed as necessary. The aging conditions are the same as those in the eighth step.

[0166] In this way, the third base material 9 is disposed on the other surface of the second adhesive layer 8 in the thickness direction, and the laminate 1 is produced.

[0167] 2-3. Fourth embodiment A fourth embodiment of the laminate of the present invention will be described with reference to FIG. 3C.

[0168] In the fourth embodiment, a third adhesive layer 10, a barrier layer 11, a second adhesive layer 8, and a third substrate 9 are further provided in this order toward one side in the thickness direction of the second substrate 7. That is, in the fourth embodiment, the laminate 1 is provided with a first substrate 2, an easy-adhesion layer 3, a primer layer 4, an ink layer 5, an adhesive layer 6, the second substrate 7, the third adhesive layer 10, a barrier layer 11, the second adhesive layer 8, and a third substrate 9 in this order toward one side in the thickness direction.

[0169] <Third adhesive layer> The third adhesive layer 10 contacts the upper surface of the second base material 7 (one surface in the thickness direction).

[0170] The third adhesive layer 10 is made of a known adhesive (for example, a two-component urethane adhesive).

[0171] The thickness of the third adhesive layer 10 is not particularly limited, and is, for example, 1.0 μm to 5.0 μm.

[0172] <Barrier layer> The barrier layer 11 prevents the ink from eluting from the ink layer 5 .

[0173] Examples of the barrier layer 11 include films in which aluminum oxide is vapor-deposited on a PET film, aluminum foil, metal vapor-deposited films, silica vapor-deposited films (e.g., silica vapor-deposited PET film), alumina vapor-deposited films, silica-alumina composite vapor-deposited films, stainless steel, iron, copper, and lead.

[0174] The barrier layer 11 has a thickness of, for example, 1 μm to 100 μm, or preferably 10 μm to 70 μm.

[0175] In the fourth embodiment, after the eighth step described above, the laminate 1 is manufactured by arranging the third adhesive layer 10, the barrier layer 11, the second adhesive layer 8, and the third substrate 9 on one side in the thickness direction of the second substrate 7. Specifically, the third adhesive layer 10 is arranged on one surface in the thickness direction of the second substrate 7, the barrier layer 11 is arranged on one surface in the thickness direction of the third adhesive layer 10, the second adhesive layer 8 is arranged on one surface in the thickness direction of the barrier layer 11, and then the third substrate 9 is arranged on one surface in the thickness direction of the second adhesive layer 8.

[0176] This completes the manufacture of the laminate 1. In the laminate 1, the barrier layer 11 can prevent the ink from eluting from the ink layer 5.

[0177] 2-4. Fifth embodiment A fifth embodiment of the laminate of the present invention will be described with reference to FIG. 3D.

[0178] In the fifth embodiment, a third adhesive layer 10, a barrier layer 11, a second adhesive layer 8, and a third substrate 9 are further provided in this order toward the other thickness direction side of the first substrate 2. That is, in the fifth embodiment, the laminate 1 is provided with a third substrate 9, a second adhesive layer 8, a barrier layer 11, a third adhesive layer 10, a first substrate 2, an easy-adhesion layer 3, a primer layer 4, an ink layer 5, an adhesive layer 6, and a second substrate 7 in this order toward one thickness direction side.

[0179] In the fifth embodiment, from the viewpoint of improving the adhesion between the first substrate 2 and the ink layer 5 even after high-temperature sterilization treatment, the first substrate 2 is a polyamide-based polymer (preferably nylon), the second substrate 7 is a polyester-based polymer (preferably polyethylene terephthalate), and the third substrate 9 is an olefin-based polymer film.

[0180] In the fifth embodiment, after the eighth step described above, the laminate 1 is manufactured by arranging the third adhesive layer 10, the barrier layer 11, the second adhesive layer 8, and the third substrate 9 on the other side in the thickness direction of the first substrate 2. Specifically, the third adhesive layer 10 is arranged on the other surface in the thickness direction of the first substrate 2, the barrier layer 11 is arranged on the other surface in the thickness direction of the third adhesive layer 10, the second adhesive layer 8 is arranged on the other surface in the thickness direction of the barrier layer 11, and the third substrate 9 is arranged on the other surface in the thickness direction of the second adhesive layer 8.

[0181] This produces the laminate 1. According to the laminate 1, similarly to the third embodiment, it is possible to improve the adhesion between the first substrate 2 and the ink layer 5 even after high-temperature sterilization treatment, and the barrier layer 11 can suppress elution of ink from the ink layer 5.

[0182] As will be described in detail later, the laminate 1 has excellent adhesion between the first substrate 2 and the ink layer 5, and excellent blocking resistance. Therefore, the laminate 1 can be suitably used, among others, in the production of packaging materials, lid materials (for example, top seal materials for cup containers), and labels (for example, in-mold labels). In other words, packaging materials, lid materials, and labels include the laminate 1.

[0183] 3. Effects The laminate 1 includes an easy-adhesion layer 3 between a first substrate 2 and a primer layer 4. The primer composition forming the primer layer 4 contains a polyisocyanate compound and a radically polymerizable compound, and the content of the polyisocyanate compound is within a predetermined range. This improves adhesion between the first substrate 2 and the ink layer 5 and blocking resistance.

[0184] Specifically, the laminate 1 includes an easy-adhesion layer 3 between the first substrate 2 and the primer layer 4. Therefore, the adhesion between the first substrate 2 and the ink layer 5 can be improved.

[0185] Furthermore, in the primer composition that forms the primer layer 4, if the amount of polyisocyanate compound is increased, the adhesion between the first substrate 2 and the ink layer 5 can be improved but the blocking resistance tends to decrease, and if the amount of polyisocyanate compound is decreased, the blocking resistance can be improved but the adhesion between the first substrate 2 and the ink layer 5 tends to decrease. In other words, there is a trade-off between the adhesion and the blocking resistance.

[0186] In contrast, in the primer composition that forms the primer layer 4, the content ratio of the polyisocyanate compound relative to 100 parts by mass of the total amount of the polyisocyanate compound and the radical polymerizable compound is adjusted to fall within a predetermined range, thereby achieving both the above-mentioned adhesion and blocking resistance.

[0187] The packaging material includes the laminate 1. Therefore, the adhesion between the first substrate 2 and the ink layer 5 and the blocking resistance can be improved.

[0188] The lid material includes the laminate 1. Therefore, the adhesion between the first substrate 2 and the ink layer 5 and the blocking resistance can be improved.

[0189] The label includes the laminate 1. Therefore, the adhesion between the first substrate 2 and the ink layer 5 and the blocking resistance can be improved.

[0190] 4. Variations In the modified examples, the same components and steps as those in the first to third embodiments are denoted by the same reference numerals, and detailed descriptions thereof will be omitted. Furthermore, the modified examples can achieve the same effects as those in the first to third embodiments, unless otherwise specified. Furthermore, the first to third embodiments and the modified examples can be combined as appropriate.

[0191] In the above description, in the first step, the first substrate 2 is prepared, and in the second step, an easy-adhesion layer 3 is arranged on one thickness-wise surface of the first substrate 2, thereby preparing a substrate with an easy-adhesion layer that has the first substrate 2 and the easy-adhesion layer 3 in order toward one thickness-wise surface; however, a commercially available product can also be used as is as the substrate with an easy-adhesion layer.

[0192] Examples of commercially available products include PTM (polyethylene terephthalate film with an easy-adhesion layer, manufactured by Unitika Ltd.) and ONMB (nylon film with an easy-adhesion layer, manufactured by Unitika Ltd.). [Example]

[0193] Specific numerical values ​​of blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the corresponding upper limit values ​​(numeric values ​​defined as "not more than" or "less than") or lower limit values ​​(numeric values ​​defined as "not less than" or "exceeding") of blending ratios (content ratios), physical property values, parameters, etc. described in the above "Description of the Invention." Furthermore, unless otherwise specified in the following description, "parts" and "%" are based on mass.

[0194] <Ingredient details> PET: Polyethylene terephthalate film (without adhesive layer), product name "E5101", thickness 12 μm, manufactured by Toyobo Co., Ltd. PET with easy-adhesion layer: polyethylene terephthalate film with easy-adhesion layer, product name "PTM", thickness 12 μm, manufactured by Unitika Ltd. NY: Nylon film (without adhesive layer), product name "ONBC", thickness: 15 μm, manufactured by Unitika Ltd. NY with easy-adhesion layer: Nylon film with easy-adhesion layer, product name "ONMB", thickness: 15 μm, manufactured by Unitika Ltd. CPP: Non-stretched polypropylene film, product name "ZK207", thickness: 60 μm, manufactured by Toray Advanced Film Co., Ltd. Transparent vapor-deposited PET: Silica-deposited polyethylene terephthalate film, product name "Techbarrier LS", thickness 12 μm, manufactured by Mitsubishi Chemical Corporation Takenate D170N: Isocyanurate derivative of hexamethylene diisocyanate, manufactured by Mitsui Chemicals, Inc. Takenate D165N: Biuret derivative of hexanemethylene diisocyanate, manufactured by Mitsui Chemicals Takenate D178NL: Allophanate derivative of hexanemethylene diisocyanate, manufactured by Mitsui Chemicals MK702: Product name "Uvijet MK702", manufactured by Fujifilm Uvijet MKA52: (Yellow (Y), manufactured by Fujifilm) Uvijet MK867: (Magenta (M) Fujifilm) Uvijet MK215: (Cyan (C) Fujifilm) Uvijet MKA04: (Black (K), Fujifilm) Uvijet MK021: (White (W), Fujifilm)

[0195] <Production of laminate> comparison example 6 (First embodiment) The laminate was produced using a UV inkjet printer (Jet Press 540WV, manufactured by Fujifilm Corporation), which will be described in detail below.

[0196] [Process 1 and Process 2] As a substrate, PET with an easy-adhesion layer was prepared.

[0197] [3rd step] A primer composition shown in Table 1 was applied to one surface in the thickness direction of the adhesive layer. As a result, a primer layer (thickness: 2 μm) before curing was disposed on one surface in the thickness direction of the adhesive layer.

[0198] [4th step] The primer layer before curing was irradiated with ultraviolet light to semi-cure the primer layer before curing. The UV irradiation dose is 14 mJ / cm 2 It was.

[0199] [5th ​​step] An ink composition was applied to one surface of the semi-cured primer layer in the thickness direction by an ink jet method to form an ink layer (thickness: 2.0 μm). Note that, as will be described in detail later, the composition of the ink composition was changed according to each evaluation method.

[0200] [6th step] The semi-cured primer layer was irradiated with ultraviolet light to completely cure the semi-cured primer layer. The ultraviolet light irradiation dose was 114 mJ / cm 2 It was.

[0201] [Step 7] A two-component urethane adhesive (Takelac A-648 (polyol, manufactured by Mitsui Chemicals) and Takenate A-77 (polyisocyanate, manufactured by Mitsui Chemicals)) was applied to one surface of the ink layer in the thickness direction, and a first adhesive layer (thickness: 3.6 μm) was formed. The amount of adhesive applied was 4.0 g / m. 2 It was.

[0202] [8th step] Using a dry laminating device, a second substrate was attached to one surface in the thickness direction of the first adhesive layer.

[0203] After the eighth step, a two-component adhesive (the same two-component adhesive as used in the seventh step) was applied to one surface of the second substrate in the thickness direction to form a second adhesive layer. The amount of adhesive applied was 4.0 g / m 2 Next, a third base material was attached to one surface of the second adhesive layer in the thickness direction using a dry laminating device, and then aging was performed (40°C, 1 day). In this way, a laminate was produced.

[0204] Comparative Example 1 Comparative Examples 5 and 7 Comparative Example 18 (Second Embodiment) comparison example 6A laminate was produced based on the same procedure as in Example 1, except that the first substrate and primer composition were changed based on Tables 1 and 2.

[0205] Comparative Example 1 9 Comparative Example 21 (Third embodiment) [1st process ~ 8th process] A laminate was produced based on the same procedure as in Comparative Example 6. However, the first substrate, second substrate, and primer composition were changed based on Table 2.

[0206] After the eighth step, a two-component adhesive (the same two-component adhesive as used in the seventh step) was applied to the other side of the first substrate in the thickness direction, and a second adhesive layer was disposed. The amount of adhesive applied was 4.0 g / m 2 Next, a third substrate was attached to the other surface of the second adhesive layer in the thickness direction using a dry laminating device, and then aging was performed (40°C, 1 day). In this way, a laminate was produced.

[0207] Comparative Example 22 (Fourth Embodiment) [1st process ~ 8th process] comparison example 6 A laminate was produced based on the same procedure as in Example 1, except that the first substrate, the second substrate, and the primer composition were changed based on Table 2.

[0208] After the eighth step, a two-component adhesive (the same two-component adhesive as used in the seventh step) was applied to one surface of the second substrate in the thickness direction, and a third adhesive layer was formed. The amount of adhesive applied was 4.0 g / m. 2 Next, using a dry laminating device, a barrier layer was attached to one surface of the third adhesive layer in the thickness direction, and then aging (40°C, 1 day) was performed. Next, a two-component adhesive (the same two-component adhesive as used in the seventh step) was applied to one surface of the barrier layer in the thickness direction, and the second adhesive layer was then placed. The amount of adhesive applied was 4.0 g / m 2Next, a third base material was attached to one surface of the second adhesive layer in the thickness direction using a dry laminating device, and then aging was performed (40°C, 1 day). In this way, a laminate was produced.

[0209] Example 18 (Fifth Embodiment) [1st process ~ 8th process] comparison example 6 A laminate was produced based on the same procedure as in Example 1, except that the first substrate, the second substrate, and the primer composition were changed based on Table 2.

[0210] After the eighth step, a two-component adhesive (the same two-component adhesive as used in the seventh step) was applied to the other surface of the first substrate in the thickness direction, and a third adhesive layer was formed. The amount of adhesive applied was 4.0 g / m. 2 Next, using a dry laminating device, a barrier layer was attached to the other surface of the third adhesive layer in the thickness direction, and then aging (40°C, 1 day) was performed. Next, a two-component adhesive (the same two-component adhesive as used in the seventh step) was applied to the other surface of the barrier layer in the thickness direction, and the second adhesive layer was then placed. The amount of adhesive applied was 4.0 g / m 2 Next, a third substrate was attached to the other surface of the second adhesive layer in the thickness direction using a dry laminating device, and then aging was performed (40°C, 1 day). In this way, a laminate was produced.

[0211] <Evaluation> [Print quality] In the production of the laminate to be used for evaluating print image quality, Uvijet MKA04 and Uvijet MK021 were used separately as ink compositions in the fifth step. Specifically, Uvijet MKA04 was applied to one surface of the semi-cured primer layer in the thickness direction by an inkjet method to print characters (specifically, a sample), and Uvijet MK021 was then applied to the entire surface of one surface of the semi-cured primer layer in the thickness direction. This produced a laminate.

[0212] ratio Comparative Example 1 - Comparative Example 18 The print quality of the laminate was evaluated after the sixth step and before the seventh step. Specifically, the characters were visually observed. The print quality was evaluated based on the following criteria. The results are shown in Tables 1 and 2. {standard} ○: Almost no ink bleeding was observed. △: Slight ink bleeding was observed. ×: Ink bleeding was observed.

[0213] [Blocking resistance] In the production of the laminate for evaluation of blocking resistance, Uvijet MK021 was used in the fifth step. Specifically, Uvijet MK021 was applied to the entire surface of one side of the semi-cured primer layer in the thickness direction by an inkjet method to form an ink layer. In this way, the laminate was produced.

[0214] For each example and comparative example, the blocking resistance of the laminate after the sixth step and before the seventh step was evaluated. Specifically, the laminate was wound into a roll, stored at room temperature for one week, and then unwound at a speed of 100 m / min. The blocking resistance was evaluated based on the following criteria. The results are shown in Tables 1 and 2. {standard} ○: No noise was made when unwinding. △: There was a noise when unwinding. x: The laminate broke when unwound.

[0215] [Adhesion] In the production of the laminate for evaluation of adhesion, Uvijet MKA52, Uvijet MK867, Uvijet MK215, and Uvijet MK021 were used separately as ink compositions in the fifth step. Specifically, Uvijet MKA52, Uvijet MK867, and Uvijet MK215 were applied in order to the entire surface of one side of the semi-cured primer layer in the thickness direction by an inkjet method, and then Uvijet MK021 was applied to the entire surface of one side of the semi-cured primer layer in the thickness direction to form an ink layer. This produced a laminate.

[0216] (Grid test) ratio Comparative Example 1 - Comparative Example 18 A cross-cut adhesion test was carried out on the laminate after the sixth step and before the seventh step in accordance with JIS K5600-5-6. An adhesion of 100 means that none of the cross-cut areas peeled off. An adhesion of 70 means that the area of ​​the unpeeled areas was 70%. Adhesion was evaluated based on the following criteria. The results are shown in Tables 1 and 2. {standard} ◯: Adhesion was 95 or more and 100 or less. △: Adhesion was 70 or more and 94 or less. ×: Adhesion was less than 70.

[0217] For the laminates of each Example and Comparative Example, the 180° peel strength of the first substrate and the second substrate was measured in accordance with JIS K 6854-3 at 24°C, a width of 15 mm, and a pulling speed of 300 mm / min. The results are shown in Tables 1 and 2.

[0218] Next, the laminates of each Example and Comparative Example were folded so that the third substrates faced each other, and the third substrates were heat-sealed together using a heat sealer at 220°C. The 180° heat seal strength was measured in accordance with JIS K 6854-3 at 24°C, a width of 15 mm, and a pulling speed of 300 mm / min. The results are shown in Tables 1 and 2.

[0219] <Retort test> For each of the laminates of the Examples and Comparative Examples, a bag measuring 13×17.5 cm (seal width 5 to 10 mm) was prepared with the third substrate facing inward, and filled with 130 g of water.

[0220] Then, the opening of the bag (the third substrates) was attached to a heat sealer and heat sealed at 220°C.

[0221] The bag was then placed on a tray measuring 210 x 520 x 105 mm and left to stand at 120°C for 30 minutes under a pressure of 0.35 MPa for hot water sterilization.

[0222] The appearance was then visually evaluated to check for the presence or absence of whitening. Those without whitening were rated as "Good." The results are shown in Table 2.

[0223] The 180° peel strength of the first and second substrates and the 180° peel strength of the heat seal (HS strength) were measured in accordance with JIS K 6854-3 at 24°C, with a width of 15 mm, and at a pulling speed of 300 mm / min. The results are shown in Table 2.

[0224] The failure modes are listed in Tables 1 and 2, along with the peel strength and heat seal strength. Details of the failure modes are as follows: Primer transfer: Peeling occurred between the first substrate and the primer layer. PET material damage: The PET film was damaged. Peel occurred between the PET / ad:PET and the second adhesive layer. CPP / CPP: Peeling occurred between CPP and CPP. CPP broken: The CPP film is damaged.

[0225] <Taste test> Example 1 8, Comparative Example 21 and Comparative Example 22 A bag measuring 13×17.5 cm (seal width 5 to 10 mm) was prepared with the third base material facing inward, and 130 g of water was filled therein.

[0226] The sealed bag was then boiled at 100°C for 45 minutes to sterilize it, after which the bag was opened and the water removed. Seven panelists then rated the taste of the water on a scale of 1 to 5 based on the following criteria. The average scores were then calculated. The results are shown in Table 2. {standard} 1 point: Tastes the same as pure water. 2 points: Close to pure water but with a slightly different taste. 3 points: Tastes different from pure water. 4 points: The taste is clearly different from pure water. 5 points: A rich taste that is clearly different from pure water.

[0227] [Table 1]

[0228] JPEG0007814691000002.jpg185159 [Explanation of symbols]

[0229] 1. Laminate 2 First base material 3 Easy adhesive layer 4 Primer layer 5 ink layers 6 First adhesive layer 7 Second base material 8 Second adhesive layer 9 Third base material 10 Third adhesive layer 11 Barrier layer

Claims

1. a first substrate, an easy-adhesion layer, a primer layer, an ink layer, a first adhesive layer, and a second substrate, arranged in this order toward one side in a thickness direction; The primer layer comprises a primer composition, The primer composition contains a polyisocyanate compound and a radical polymerizable compound, the content ratio of the polyisocyanate compound is 15 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total amount of the polyisocyanate compound and the radical polymerizable compound, The laminate further includes, on the other thickness-wise side of the first substrate, a third adhesive layer, a barrier layer, a second adhesive layer, and a third substrate, in that order toward the other thickness-wise side.

2. A packaging material comprising the laminate of claim 1.

3. A lid material comprising the laminate according to claim 1.

4. A label comprising the laminate of claim 1.

Images