Laminate for laminate tube container

Abstract

To provide, while suppressing manufacture cost, a novel laminate for a laminate tube container having laminate strength not to be spoiled even if a glittering print layer is provided in a side seamed portion.SOLUTION: A laminate 100 for a laminate tube container in the present invention includes a glittering print layer 132 allowing a print layer 130 to exist throughout nearly entirely of a side seamed portion when sealant layers 110, 160 are partially superposed and heat-sealed together into a cylindrical laminate-tube container, as shown in Fig.1(a). The glittering print layer 132 contains a glittering pigment, polyurethane acrylate and a photo initiator but does not contain polyisocyanate. The outer sealant layer 110 and the inner sealant layer 160 consist of a polyethylene resin. Out of the print layers, at least one layer is in direct contact with a printed layer of a base material layer 140.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] Conventionally, laminated tube containers have been manufactured by various methods. For example, a laminated sheet is manufactured, and the outermost layer and the innermost layer at both ends are heat-sealed to manufacture a cylindrical body, and then a head consisting of a mouth and a shoulder is formed at one opening of the cylindrical body, and a cap is screwed onto the mouth to manufacture a laminated tube container. The location where the outermost layer and the innermost layer are heat-sealed is sometimes called a side seam. The laminated tube container manufactured in this manner can be filled with a semi-fluid content such as toothpaste from the open end of the cylindrical body, and the open end is hermetically sealed to form a bottom seal, thereby forming a tube-shaped packaged product.

[0003] It is also known to incorporate a substrate and a printed layer into the body of a laminated tube container in order to improve the distinctiveness or appearance of the laminated tube container.

[0004] Patent Document 1 discloses a laminated sheet for forming the body of a laminated tube container, which is formed into a cylindrical body so that the innermost layer of the laminated film becomes the inner peripheral layer of the body of the laminated tube container. This laminated film is composed of, from the innermost layer, a heat-sealable film (I), a barrier layer, a milky white polyethylene resin film, a transparent base film having a colored printing ink layer formed on one side, and a transparent heat-sealable film (II) laminated via adhesive layers.

[0005] For laminated tube containers having a printing layer, it has been proposed to print the entire surface including the side seam portion (also called "full print printing"). For example, Patent Document 2 discloses a laminate for a tube including a laminated surface layer, an adhesive layer, a UV ink layer, and a base laminate. The surface layer includes a polyolefin. The adhesive layer is formed of a two-component adhesive of a polyol having an ester portion and a polyisocyanate. The surface of the base laminate that contacts the UV ink layer is formed of a polyolefin. The UV ink layer is disposed at a location corresponding to the seal portion on the surface of the base laminate.

[0006] In addition, for printing to provide a plastic container with a luxurious feel, it is known to use a glittering print layer obtained by pearl ink or the like. Patent Document 3 discloses a laminate for a laminate tube having a surface layer, a glittering print laminate, and a substrate in this order. The glittering print laminate has a plurality of glittering print layers laminated on top of each other. Each of the plurality of glittering print layers contains an ultraviolet curable resin and an inorganic glittering pigment. The ultraviolet curable resin contains an aliphatic polyurethane acrylate and a photopolymerization initiator having less than three benzene rings and no amino group. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2013-223934 A [Patent Document 2] International Publication No. 2014 / 178403 [Patent Document 3] JP 2021-178446 A Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention provides a novel laminate for laminated tube containers, which reduces production costs and does not impair laminate strength even when a glittering printed layer is provided on a side seam portion. [Means for solving the problem]

[0009] As a result of intensive research, the present inventors have found that the above problems can be solved by the following means, and have completed the present invention. That is, the present invention is as follows: Aspect 1 is composed of a laminate having an outer sealant layer, an outer adhesive layer, one or more printed layers, a substrate layer, an inner adhesive layer, and an inner sealant layer in this order, a part of the outer sealant layer and a part of the inner sealant layer are overlapped and heat-sealed to form a side seam portion to form a cylindrical laminated tube container, the printed layer including a glittering printed layer that is present over substantially the entire side seam portion, The photoluminescent print layer is made of an ultraviolet-curable flexographic photoluminescent ink, and the ultraviolet-curable flexographic photoluminescent ink contains a photoluminescent pigment, a polyurethane acrylate, and a photopolymerization initiator, but does not contain a polyisocyanate; The photopolymerization initiator has less than three benzene rings and does not have an amino group, The outer sealant layer and the inner sealant layer are made of a polyethylene resin, The base layer has a printable layer, and at least one of the printable layers is in direct contact with the printable layer. Laminated body for laminated tube containers. <Mode 2> A laminate for a laminated tube container as described in Mode 1, wherein the printed layer further has an undercoat printed layer in direct contact with the base layer, and a portion of the outer sealant layer and a portion of the inner sealant layer are overlapped and heat sealed to form a side seam portion, so that when the laminated tube container is made into a cylindrical laminated tube container, the undercoat printed layer is present over almost the entire side seam portion. <Aspect 3> The laminate for laminated tube containers according to aspect 2, wherein the undercoat printing layer contains polyisocyanate. <Aspect 4> A laminate for laminated tube containers according to aspect 2 or 3, wherein the glossy printed layer is in direct contact with the base printed layer. Aspect 5: The laminate for laminate tube containers according to any one of Aspects 1 to 4, wherein the content of the glittering pigment is from 1% by mass to 30% by mass, based on the mass of the ultraviolet curable flexographic glittering ink. Aspect 6: The laminate for laminate tube containers according to any one of Aspects 1 to 5, wherein the content of the photopolymerization initiator is from 1% by mass to 30% by mass, based on the mass of the ultraviolet curable flexographic photoluminescent ink. <Aspect 7> The laminate for laminated tube containers according to any one of Aspects 1 to 6, wherein the printable layer is made of a polyethylene-based resin. <Aspect 8> The laminate for laminated tube containers according to any one of Aspects 1 to 7, wherein the outer adhesive layer is a two-component curing dry lamination adhesive. Aspect 9: A laminate for a laminate tube container according to any one of aspects 1 to 8, A part of the outer sealant layer and a part of the inner sealant layer are overlapped and heat-sealed to form a side seam portion, thereby forming the laminated tube container laminate into a cylindrical shape. Laminated tube container. Effect of the Invention

[0010] According to the present invention, it is possible to provide a novel laminate for laminated tube containers, which reduces manufacturing costs and does not impair laminate strength even when a glossy printed layer is provided on a side seam portion. [Brief description of the drawings]

[0011] [Figure 1]Fig. 1(a) is a side cross-sectional view of one embodiment of the laminate for a laminate tube container of the present invention, and Fig. 1(b) is a side cross-sectional view of another embodiment of the laminate for a laminate tube container of the present invention. [Diagram 2] Fig. 2(a) is a schematic side view of one embodiment of the laminated tube container of the present invention. Fig. 2(b) is a schematic cross-sectional view of one embodiment of the laminated tube container of the present invention taken along line IIb-IIb in Fig. 2(a). Fig. 2(c) is an enlarged view of the part surrounded by line IIc in Fig. 2(b). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] <Laminate for Laminated Tube Containers> As shown in FIG. 1(a), the laminated tube container laminate 100 of the present invention has the following features: The laminate includes an outer sealant layer 110, an outer adhesive layer 120, one or more printed layers 130, a substrate layer 140, an inner adhesive layer 150, and an inner sealant layer 160, in that order. When a part of the outer sealant layer 110 and a part of the inner sealant layer 160 are overlapped and heat sealed to form a side seam portion to form a cylindrical laminated tube container, the printed layer 130 includes a glittering printed layer 132 that is present over substantially the entire side seam portion, The photoluminescent print layer 132 is made of an ultraviolet-curing flexographic photoluminescent ink, and the ultraviolet-curing flexographic photoluminescent ink contains a photoluminescent pigment, a polyurethane acrylate, and a photopolymerization initiator, but does not contain a polyisocyanate; The photopolymerization initiator has less than three benzene rings and does not have an amino group, The outer sealant layer 110 and the inner sealant layer 160 are made of a polyethylene resin, The base layer 140 has a printable layer, and at least one of the printable layers is in direct contact with the printable layer.

[0013] The glittering printing layer contains a glittering material, which is a material having a relatively large and flat shape. In a conventional laminated tube having such a glittering printing layer, when the glittering printing layer is laminated so as to be contained in the side seam portion, it was thought that it was necessary to contain polyisocyanate in the glittering printing layer in order not to impair the laminate strength. On the other hand, when polyisocyanate is contained in the ink constituting the glittering printing layer, the glittering printing ink is difficult to store due to its reactivity. Since the glittering material is relatively expensive, the difficulty in storing the glittering printing ink is a major problem in terms of cost.

[0014] In contrast, the inventors have discovered that a combination of polyurethane acrylate and photopolymerization initiator can produce a glossy printing layer that does not contain polyisocyanate and does not impair laminate strength even when laminated over the entire substrate layer.

[0015] As shown in FIG. 1( b ), the printing layer 130 may further include an underprinting layer 134 and another printing layer 136 .

[0016] Each component of the present invention will now be described.

[0017] <Outer sealant layer and inner sealant layer> The outer sealant layer and the inner sealant layer are made of a polyethylene resin.

[0018] In this specification, a polyethylene-based resin is a resin that contains more than 50 mol%, 60 mol% or more, 70 mol% or more, or 80 mol% or more of ethylene group repeating units in the main chain of the polymer, and is, for example, selected from the group consisting of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), derivatives thereof, and mixtures thereof.

[0019] The thickness of the outer sealant layer and the inner sealant layer is not particularly limited, and may be, for example, 50 μm or more, 60 μm or more, 70 μm or more, 80 μm or more, 85 μm or more, 90 μm or more, or 95 μm or more, and may be 200 μm or less, 190 μm or less, 180 μm or less, 170 μm or less, 160 μm or less, 150 μm or less, 140 μm or less, 130 μm or less, 125 μm or less, 120 μm or less, 115 μm or less, 110 μm or less, or 105 μm or less. The outer sealant layer and the inner sealant layer may be the same as or different from each other.

[0020] <Outer adhesive layer> The outer adhesive layer is a layer that is between the outer sealant layer and the printed layer or layers, thereby adhering them to one another.

[0021] For the adhesive layer, for example, a dry lamination adhesive, a hot melt adhesive, a water-soluble adhesive, an emulsion adhesive, a non-solvent lamination adhesive, a thermoplastic resin for extrusion lamination, etc. Among them, it is preferable to use a dry lamination adhesive, in particular a two-liquid curing type dry lamination adhesive.

[0022] <Printing layer> The printing layer may be one or more printing layers, at least one of which is in direct contact with the printable layer of the base layer.

[0023] When a portion of the outer sealant layer and a portion of the inner sealant layer are overlapped and heat sealed to form a side seam portion to form a cylindrical laminated tube container, these printed layers include a glossy printed layer that is present over almost the entire side seam portion.

[0024] Here, "substantially the entire side seam portion" means that it occupies 90% or more, 95% or more, 97% or more, 98% or more, or 99% or more of the area of ​​the side seam portion.

[0025] When a part of the outer sealant layer and a part of the inner sealant layer are overlapped and heat-sealed to form a side seam portion to form a cylindrical laminated tube container, the printed layer may have an underprinted layer that is present over substantially the entire side seam portion. In this case, the underprinted layer is in direct contact with the printed layer.

[0026] (Glitter printing layer) The photoluminescent print layer is a layer composed of an ultraviolet-curable flexographic photoluminescent ink. The ultraviolet-curable flexographic photoluminescent ink contains a photoluminescent pigment, a polyurethane acrylate, and a photopolymerization initiator, but does not contain a polyisocyanate.

[0027] The glittering printed layer is present over almost the entire side seam portion. When multiple glittering printed layers are present, one or more of the layers may be present over almost the entire side seam portion, and in particular, all of the glittering printed layers may be present over almost the entire side seam portion.

[0028] The glossy printed layer may be present over substantially the entire substrate layer.

[0029] When the glossy printed layer is a single layer, the thickness of the glossy printed layer is preferably 1 μm or more, 2 μm or more, or 3 μm or more, and 7 μm or less, or 6 μm or less, from the viewpoint of achieving glossiness.

[0030] When multiple glossy printing layers are present, the thickness of the glossy printing layers is preferably 10 μm or more, 15 μm or more, 20 μm or more, or 25 μm or more from the standpoint of design, and is preferably 40 μm or less, 35 μm or less, or 30 μm or less from the standpoint of suppressing yellowing.

[0031] (Photochromic printing layer: Photochromic pigment) As the luster pigment, for example, a scaly metallic pigment, a pearl pigment, etc. can be used.

[0032] As the flaky metal pigment, for example, aluminum powder, particularly aluminum flakes, etc. can be used.

[0033] The pearl pigment can be synthetic mica, natural mica, or a pigment in which synthetic mica, natural mica, glass, or alumina flakes are coated with titanium oxide or silica.

[0034] The content of the glittering pigment in the glittering printing layer may be 1 mass% or more, 3 mass% or more, 5 mass% or more, 7 mass% or more, or 9 mass% or more, and may be 25 mass% or less, 22 mass% or less, 20 mass% or less, 17 mass% or less, 15 mass% or less, or 12 mass% or less, relative to the mass of the glittering printing layer.

[0035] In the glittering print layer, if the content of the pigment other than the inorganic glittering pigment is 3% by mass or less, 2% by mass or less, or 1% by mass or less, yellowing becomes noticeable, so the configuration of the present invention is more advantageous. This content may be 0% by mass or more than 0% by mass.

[0036] (Photo-glossy printing layer: polyurethane acrylate) As the polyurethane acrylate, for example, an aliphatic polyurethane acrylate and an aromatic polyurethane acrylate can be used, and among them, an aliphatic polyurethane acrylate is preferably used from the viewpoint of laminate strength. As these polyurethane acrylates, commercially available products can be used.

[0037] In the present invention, the term "aromatic polyurethane acrylate" refers to a polyurethane acrylate having a benzene ring, and the term "aliphatic polyurethane acrylate" refers to a polyurethane acrylate not having a benzene ring.

[0038] (Photo-initiator for photo-glossy printing layer) The photopolymerization initiator has less than three benzene rings, that is, two, one or zero benzene rings, and has no amino group.

[0039] Examples of such photopolymerization initiators include a mixture of oxyphenylacetic acid 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester and oxyphenylacetic acid 2-(2-hydroxyethoxy)ethyl ester, bis(2-phenyl-2-oxoacetic acid)oxybisethylene (Irgacure 754), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173), and the like.

[0040] The content of the photopolymerization initiator may be 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, or 5 parts by mass or more, and may be 10 parts by mass or less, 9 parts by mass or less, 8 parts by mass or less, 7 parts by mass or less, or 6 parts by mass or less, relative to 100 parts by mass of the aliphatic polyurethane acrylate.

[0041] (Underprinting layer) The underprinting layer is a layer of the printing layer that is in direct contact with the printed layer of the base material layer. When a part of the outer sealant layer and a part of the inner sealant layer are overlapped and heat sealed to form a side seam portion to form a cylindrical laminated tube container, the underprinting layer is present over almost the entire side seam portion.

[0042] The underprinting layer may be present over substantially the entire substrate layer.

[0043] The undercoat printing layer preferably contains polyisocyanate from the viewpoint of obtaining laminate strength. In this case, the content of polyisocyanate may be 1 mass% or more, 2 mass% or more, 3 mass% or more, or 4 mass% or more, and may be 25 mass% or less, 22 mass% or less, 20 mass% or less, 17 mass% or less, 15 mass% or less, 12 mass% or less, 10 mass% or less, 8 mass% or less, or 6 mass% or less, based on the mass of the undercoat printing layer.

[0044] As the polyisocyanate, for example, hexamethylene diisocyanate can be used.

[0045] From the viewpoint of obtaining sufficient laminate strength, it is preferable that the undercoat printed layer be in direct contact with the glittering printed layer.

[0046] For the underprinting layer, a composition in which a polyisocyanate is added to a commercially available ink can be used.

[0047] (other printed layers) The other printed layer may be an optional printed layer for the purpose of display, decoration, etc. The printed layer can be laminated by any printing means.

[0048] <Base material layer> The substrate layer is a non-permeable substrate on which the printing layer is laminated. The substrate layer may be a single layer, or may be a laminate in which multiple layers are laminated, and may include multiple layers of the same type.

[0049] The substrate layer may have, for example, a printable layer, a barrier layer, and a reinforcing layer. These layers may be laminated by any lamination means, for example, via an adhesive layer. The adhesive layer may be any of the adhesive layers listed for the outer adhesive layer.

[0050] As such a substrate layer, for example, a substrate having the following layer structure can be used: ·LDPE(75μm) / Milk white LDPE(160μm) / LDPE(50μm) / PET(12μm) / LLDPE(100μm) ·LLDPE(55μm) / Transparent LDPE(80μm) / EAA(20μm) / AL(12μm) / EMAA(25μm) / PET(12μm)

[0051] (printed layer) The printable layer is not particularly limited as long as it is a layer that is impermeable to such an extent that the printing layer can be printed thereon, and may be, for example, a resin layer.

[0052] As the printable layer, for example, a thermoplastic resin such as a polyolefin resin, a vinyl polymer, a polyester, or a polyamide can be used alone or in a multi-layer structure of a combination of two or more types. Such a thermoplastic resin can be used in the form of a film or an extruded resin. The film may be a stretched film or a non-stretched film.

[0053] As the polyolefin resin, for example, a polyethylene resin or a polypropylene resin can be used. For the polyethylene resin, the description of the outer sealant layer and the inner sealant layer can be referred to.

[0054] In this specification, a polypropylene-based resin refers to a resin containing more than 50 mol%, 60 mol% or more, 70 mol% or more, or 80 mol% or more of propylene group repeating units in the main chain of the polymer, and examples thereof include polypropylene (PP) homopolymer, random polypropylene (random PP), block polypropylene (block PP), chlorinated polypropylene, acid-modified polypropylene, derivatives thereof, and mixtures thereof.

[0055] An example of the vinyl polymer is polyvinyl chloride (PVC).

[0056] Examples of polyester include polyethylene terephthalate (PET) and polybutylene terephthalate.

[0057] Examples of polyamides include nylons such as Nylon (registered trademark) 6 and Nylon MXD6.

[0058] (Barrier layer) As the barrier layer, for example, an inorganic material vapor deposition layer, a metal foil layer, an organic material coating layer, or the like can be used.

[0059] As the inorganic vapor deposition layer, for example, a silica vapor deposition film, an aluminum vapor deposition film, an alumina vapor deposition film, or a silica-alumina vapor deposition film can be used.

[0060] As the metal foil layer, for example, a simple metal foil such as aluminum foil, copper foil, or titanium foil, or an alloy foil such as aluminum alloy foil or stainless steel foil can be used.

[0061] As the organic coating layer, for example, a vinylidene chloride coating layer or a polyvinylidene fluoride coating layer can be used.

[0062] When an inorganic vapor deposition film or an organic coating layer is used as the barrier layer, the thickness of the barrier layer is preferably 100 nm or more, 200 nm or more, 300 nm or more, 500 nm or more, 700 nm or more, or 1 μm or more from the viewpoint of ensuring strength and barrier properties, and is preferably 5 μm or less, 4 μm or less, 3 μm or less, or 2 μm or less from the viewpoint of improving handleability as a laminate for a tube.

[0063] When a metal foil layer is used as the barrier layer, the thickness of the barrier layer is preferably 3 μm or more, 5 μm or more, 7 μm or more, 10 μm or more, or 15 μm or more from the viewpoint of ensuring strength and barrier properties, and is preferably 100 μm or less, 80 μm or less, 60 μm or less, 55 μm or less, 50 μm or less, 45 μm or less, 40 μm or less, or 35 μm or less from the viewpoint of improving handleability as a laminate for a tube.

[0064] (Reinforcement layer) The reinforcing layer may be a layer composed of a stretched film.

[0065] The reinforcing layer may be a stretched film made of, for example, a polyester resin, a polyamide resin, a polypropylene resin, or the like.

[0066] When the reinforcing layer is composed of a stretched film, the stretched film constituting the reinforcing layer may be, for example, a stretched film obtained by flat method stretching, and may be a uniaxially stretched film or a biaxially stretched film. The biaxially stretched film may be a sequentially biaxially stretched film or a simultaneous biaxially stretched film, or may be a stretched film obtained by carrying out these stretching operations multiple times.

[0067] The thickness of the reinforcing layer is preferably 5 μm or more, 7 μm or more, 10 μm or more, 12 μm or more, or 25 μm or more from the viewpoint of imparting practical time-dependent restoration property to the laminate tube, while the thickness of the reinforcing layer is preferably 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, 15 μm or less, or 12 μm or less from the viewpoint of not impairing short-term shape retention and not excessively increasing the total thickness of the laminate tube raw roll.

[0068] <Inner adhesive layer> The inner adhesive layer is a layer that lies between the substrate layer and the sealant layer, thereby adhering them to one another.

[0069] The inner adhesive layer may be any of the adhesive layers listed for the outer adhesive layer. In particular, the inner adhesive layer may be selected depending on the material of the base layer, particularly the material of the layer of the base layer closest to the innermost sealant layer.

[0070] Laminated tube container 2, a laminated tube container 200 of the present invention has the laminated tube container laminate 100. A part of the outer sealant layer 110 and a part of the inner sealant layer 160 are overlapped and heat sealed to form a side seam portion 210, thereby forming the laminated tube container laminate 100 into a cylindrical shape.

[0071] Although not shown, the laminated tube container of the present invention may have a head portion having a shoulder portion and a cap portion, and a tail seal portion located on the opposite side to the head portion.

[0072] The laminated tube container can be filled with contents such as medicines, cosmetics, and food, for example, toothpaste, moisturizing cream, and sunscreen.

[0073] The laminated tube container can be produced, for example, by a method including the following steps: A step of rolling the laminated tube laminate so that the base material, particularly the sealant layer of the base material, is on the inside, overlapping and heat-sealing the ends of the laminate to form a side seam portion, thereby obtaining a body portion; and A process of attaching a head having a shoulder portion and a cap portion to the periphery of the opening of the body portion to obtain a laminated tube container. EXAMPLES

[0074] The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these.

[0075] <<Preparation of Laminate>> Example As the substrate layer, a laminate having the following layer structure was prepared: LLDPE(55μm) / Transparent LDPE(80μm) / EAA(20μm) / AL / EMAA(25μm) / PET(12μm) In the above configuration, the LLDPE (55 μm) corresponds to the printing layer.

[0076] An LLDPE film (thickness 100 μm) was adhered as an inner sealant layer to the PET side of the above laminate using a two-component curing dry lamination adhesive.

[0077] Next, a 1 μm thick underprinting layer was laminated on the entire surface of the printing layer. The underprinting layer was made of a UV-curable flexographic black ink containing hexamethylene diisocyanate.

[0078] Next, a glittering printed layer (pearl printed layer) was laminated in a thickness of 5 μm in one pass over the entire surface of the base printed layer.

[0079] The glittering print layer was a composition obtained by mixing 85 parts by mass of an aliphatic polyurethane acrylate resin (EBECRYL270, Daicel Allnex), 10 parts by mass of a pearl pigment (Pyrisma, Merck), and 5 parts by mass of a photopolymerization initiator (Irgacure 184, IGM Resins BV) that has less than three benzene rings and does not have an amino group. The content of the photopolymerization initiator per 100 parts by mass of the aliphatic polyurethane acrylate was 6 parts by mass. The glittering print layer did not contain polyisocyanate.

[0080] The undercoat printing layer and the glittering printing layer were laminated by coating using flexographic printing under the following conditions, and then curing the coating by irradiating it with ultraviolet (UV) rays. Printing machine: Flexiproof Anilox roll: 180 lines / inch UV irradiation conditions: 160W

[0081] The glittering print layer and an LLDPE film as an outer sealant layer were bonded via a two-component curing dry lamination adhesive as an outer adhesive layer to produce a laminate for a laminate tube container of the example.

[0082] Comparative Example 1 A laminate for laminated tube containers in Comparative Example 1 was obtained in the same manner as in Example 1, except that a composition in which 5 parts by mass of hexamethylene diisocyanate was added to 95 parts by mass of the composition in Example 1 was used as the glossy printing layer.

[0083] Comparative Example 2 A laminate for laminate tube containers of Comparative Example 2 was obtained in the same manner as in Example 1, except that no glittering printed layer was laminated and no isocyanate was contained in the undercoat printed layer.

[0084] Comparative Example 3 A laminate for a laminate tube container of Comparative Example 3 was produced in the same manner as in Example 1, except that no glittering printed layer was laminated.

[0085] "evaluation" (Ink reusability) The inks of the examples and comparative examples were prepared, left at room temperature for 8 hours, and then visually inspected for appearance. The evaluation criteria were as follows: A: No air bubbles were generated and it was reusable. B: Air bubbles were generated and the product could not be reused.

[0086] <Lamination strength> For the examples and comparative example 2 in which the ink reusability was evaluated as "A", the laminated tube container laminates produced were cut into 15 mm wide strips, and the outer sealant layer was peeled off to prepare test pieces. The laminate strength was measured using a tensile tester in accordance with JIS K 6854-3.

[0087] Table 1 shows the configurations and evaluation results of the examples and comparative examples.

[0088] [Table 1]

[0089] From Table 1, it can be seen that the laminate for laminated tube containers of the embodiment, which includes a photoluminescent printed layer composed of an ink containing a specific combination of polyurethane acrylate and photopolymerization initiator and which does not contain polyisocyanate, has good ink reusability and laminate strength.

[0090] In contrast, it can be seen that the inks of Comparative Examples 1 and 3, in which the inks for the glossy printing layer contain polyisocyanate, do not have good reusability.

[0091] Furthermore, from the results of Comparative Example 2, it can be seen that when polyisocyanate is omitted from an ink that is not composed of an ink containing a specific combination of polyurethane acrylate and photopolymerization initiator, sufficient laminate strength is not obtained. [Explanation of symbols]

[0092] 100 Laminated tube container laminate 110 Outer sealant layer 120 Outer adhesive layer 130 Printing layer 132 Glitter printing layer 134 Undercoat printing layer 136 Other Printing Layers 140 Base material layer 150 Inner adhesive layer 160 Inner sealant layer 200 Laminated tube container 210 Side seam

Claims

1. The laminate includes an outer sealant layer, an outer adhesive layer, one or more printed layers, a substrate layer, an inner adhesive layer, and an inner sealant layer, in that order. a part of the outer sealant layer and a part of the inner sealant layer are overlapped and heat-sealed to form a side seam portion to form a cylindrical laminated tube container, the printed layer including a glittering printed layer that is present over substantially the entire side seam portion, The photoluminescent print layer is made of an ultraviolet-curable flexographic photoluminescent ink, and the ultraviolet-curable flexographic photoluminescent ink contains a photoluminescent pigment, a polyurethane acrylate, and a photopolymerization initiator, but does not contain a polyisocyanate; the photopolymerization initiator has less than three benzene rings and has no amino group; The outer sealant layer and the inner sealant layer are made of a polyethylene resin, The base layer has a printable layer, and at least one of the printable layers is in direct contact with the printable layer. Laminated body for laminated tube containers.

2. The laminate for a laminated tube container as described in claim 1, wherein the printed layer further has an undercoat printed layer in direct contact with the base material layer, and a portion of the outer sealant layer and a portion of the inner sealant layer are overlapped and heat sealed to form a side seam portion, so that when the laminate is made into a cylindrical laminated tube container, the undercoat printed layer is present over almost the entire side seam portion.

3. The laminate for a laminate tube container according to claim 2 , wherein the undercoat print layer contains a polyisocyanate.

4. The laminate for a laminate tube container according to claim 2 or 3, wherein the glittering printed layer is in direct contact with the undercoat printed layer.

5. 3. The laminate for laminate tube containers according to claim 1, wherein the content of the glittering pigment is 1% by mass or more and 30% by mass or less based on the mass of the ultraviolet curable flexographic glittering ink.

6. 3. The laminate for laminate tube containers according to claim 1 or 2, wherein the content of the photopolymerization initiator is 1% by mass or more and 30% by mass or less with respect to the mass of the ultraviolet curable flexographic glitter ink.

7. 3. The laminate for a laminate tube container according to claim 1, wherein the printable layer is made of a polyethylene resin.

8. 3. The laminate for a laminate tube container according to claim 1, wherein the outer adhesive layer is a two-component curing dry lamination adhesive.

9. A laminate tube container laminate according to claim 1 or 2, A part of the outer sealant layer and a part of the inner sealant layer are overlapped and heat-sealed to form a side seam portion, thereby forming the laminated tube container laminate into a cylindrical shape. Laminated tube container.

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