JP2019035830A - Shrink label - Google Patents

Abstract

To provide a shrink label in which a brightness feeling of a print layer containing metallic pigment is excellent even after thermal shrinkage, and ink cracks hardly occur in the print layer containing metallic pigment during thermal shrinkage.SOLUTION: A shrink label comprises: a label base material containing a thermal shrinkable film; a print layer (X) disposed on at least one surface of the label base material, which contains urethane resin and aluminum pigment; and a print layer (Y) disposed on the surface on which the print layer (X) is disposed of the label substrate such that a part thereof is overlapped with the print layer (X) in a surface extending direction, which contains acrylic resin as primary resin components, and which has lubricant whose content ratio is 0.7 mass % or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a shrink label.

  Currently, plastic containers such as PET bottles and metal bottles such as bottle cans are widely used as containers for beverages such as tea and soft drinks. In many cases, plastic labels are attached to these containers for display, decoration, and functionality. As such a plastic label, for example, a heat-shrinkable label in which a printing layer is provided on a shrink film (heat-shrinkable film) because of merits such as decoration, workability (followability to containers), and a large display area. (Shrink labels) are widely used.

  Among the plastic labels, for example, there is a plastic label having a metallic luster by providing a printed layer containing a metal pigment. A printing ink containing an aluminum pigment obtained by a wet ball mill method is known as an ink for forming a printing layer containing such a metal pigment. In recent years, aluminum flake pigments obtained by the so-called vapor deposition method, in which flakes are produced by pulverizing a vapor-deposited metal film as a printing ink for forming a printed layer having a particularly high-luminance metallic luster and exhibiting a sense of luminance. High-intensity printing inks that contain (sometimes referred to as “deposited aluminum pigments”) are known (see, for example, Patent Documents 1 to 3).

JP 2007-224243 A JP 2003-96334 A JP 2002-20668 A

  However, a shrink label having a metallic luster may have a reduced brightness after heat shrinkage even when the printed layer has a superior brightness feeling before heat shrinkage. In addition, when a shrink label having a printed layer containing a metal pigment is subjected to shrink processing as a cylindrical label, that is, when thermally contracted, a crack (ink crack) may occur in the printed layer. In the form of a cylindrical label, ink cracking during shrink processing in a shrink label having a printed layer containing a metal pigment on the inside of the label substrate is such that the inner surface of the label is a container when heat is applied during shrink processing, etc. It is thought that this occurs when the end of the one end in the cylindrical form in which the other end is overlapped with one end of the label contacts the inside of the other end.

  The present invention has been conceived under such circumstances, and an object of the present invention is to provide an excellent brightness feeling of a printed layer containing a metal pigment even after heat shrinkage, and the metal pigment during heat shrinkage. An object of the present invention is to provide a shrink label in which ink cracking is unlikely to occur in a printing layer containing the ink.

  As a result of intensive studies to achieve the above object, the present inventors have provided a printing layer containing a urethane-based resin and an aluminum pigment on at least one surface of a label substrate including a heat-shrinkable film. By providing a printing layer containing an acrylic resin as a main resin component and having a lubricant content of a specific amount or less so that at least a part of the layer overlaps in the surface spreading direction, even after heat shrinkage It has been found that a shrink label that is excellent in brightness and hardly causes ink cracking upon heat shrinkage can be obtained. The present invention has been completed based on these findings.

  That is, the present invention provides a label base material containing a heat-shrinkable film, a printed layer (X) containing a urethane resin and an aluminum pigment provided on at least one surface of the label base material, and the label It contains an acrylic resin as a main resin component provided on the surface of the base material on which the printed layer (X) is provided so that at least a part thereof overlaps with the printed layer (X) in the surface spreading direction. And a printed layer (Y) having a lubricant content of 0.7% by mass or less.

  The print layer (Y) is preferably provided so as to be at least partially in contact with the print layer (X).

  The layer on the surface of the heat-shrinkable film on which the printed layer (X) is provided is preferably a layer mainly composed of a polyester resin.

  The aluminum pigment is preferably a vapor-deposited aluminum pigment and / or a leafing type aluminum pigment, more preferably a vapor-deposited aluminum pigment.

  The printed layer (Y) may contain an aluminum pigment.

  The printing layer (X) preferably contains a plasticizer.

  The shrink label has a protective print layer provided to cover the print layer (X) and the print layer (Y) as a print layer other than the print layer (X) and the print layer (Y). It may be. The protective printing layer preferably contains an acrylic resin as a main resin component, and the content of the lubricant is greater than 0.7% by mass with respect to the total mass of the protective printing layer.

  Since the shrink label of the present invention has the above-described configuration, the printed layer containing the metal pigment is excellent in brightness even after heat shrinkage, and ink cracking hardly occurs in the print layer containing the metal pigment during heat shrinkage. Therefore, the label after the shrink label of the present invention is attached to the adherend is excellent in the decorativeness because it is excellent in brightness and ink cracking hardly occurs.

It is the schematic (partial sectional drawing) which shows one Embodiment of the shrink label of this invention. It is the schematic which shows an example of the cylindrical shrink label which is one Embodiment of the shrink label of this invention. FIG. 3 is a schematic view showing an example of a cylindrical shrink label that is an embodiment of the shrink label of the present invention (an enlarged view of the main part of the III-III ′ section in FIG. 2). FIG. 3 is a schematic view (an enlarged view of the main part of the III-III ′ cross section in FIG. 2) showing another example of a cylindrical shrink label that is an embodiment of the shrink label of the present invention.

  The shrink label of the present invention contains a label base material containing a heat-shrinkable film, a printing layer containing a urethane resin and an aluminum pigment, an acrylic resin as a main resin component, and a lubricant content of 0. Printing layer that is 7% by mass or less. In addition, in this specification, the printing layer containing the said urethane type resin and an aluminum pigment may be called "printing layer (X)." In addition, a printing layer containing an acrylic resin as the main resin component and having a lubricant content of 0.7% by mass or less may be referred to as “printing layer (Y)”.

[Label substrate]
The label base material in the shrink label of the present invention serves as a support for the printing layer (X) and the printing layer (Y), and has a major influence on the strength, rigidity and shrinkage characteristics of the label.

  The label substrate includes at least a heat-shrinkable film (shrink film). Although it does not specifically limit as said heat-shrinkable film, The heat-shrinkable film used as a label base material of a well-known thru | or usual shrink label can be used. The type of resin forming the heat-shrinkable film can be appropriately selected according to the required physical properties, application, cost, etc., and is not particularly limited. For example, polyester resin, polyolefin resin (for example, Polyethylene resin, polypropylene resin, etc.), polystyrene resin, polyvinyl chloride resin, polyamide resin, acrylic resin and the like. These resins may be used alone or in combination of two or more. Furthermore, the same kind or different kinds of resins may be laminated to be used as a laminated film. Of these, polyester resins, polyolefin resins, and polystyrene resins are preferable. For example, as the heat-shrinkable film, a polyester film made of a polyester resin, a polyolefin film made of a polyolefin resin, a polystyrene film made of a polystyrene resin, a polyester resin as an outer layer, a polyolefin resin or a polystyrene film A heterogeneous laminated film having a resin as an inner layer may be mentioned. Examples of the polyester-based resin, polyolefin-based resin, and polystyrene-based resin include, for example, JP-A-2008-170822, JP-A-2008-170697, JP-A-2008-163215, and JP-A-2008-163231. The polyester resin, polyolefin resin, polystyrene resin, and the like described can be used.

  Examples of the polyester resin include polyethylene terephthalate (PET) resin, poly (ethylene-2,6-naphthalenedicarboxylate) (PEN), polylactic acid (PLA), and the like. Among these, a PET resin is preferable. As the PET resin, terephthalic acid is used as a dicarboxylic acid component, polyethylene terephthalate (PET) using ethylene glycol as a diol component; terephthalic acid is used as a dicarboxylic acid component, and ethylene glycol is a main component (diol component). Component having the highest mass ratio), copolymer polyester using 1,4-cyclohexanedimethanol (CHDM) as a copolymer component (CHDM copolymer PET), terephthalic acid as a dicarboxylic acid component, and ethylene as a diol component Copolymer polyester (NPG copolymer PET) using glycol as the main component (component with the highest mass ratio of diol components), neopentyl glycol (NPG) as the copolymer component, and terephthalic acid as the dicarboxylic acid component Diol-modified PET such as copolymer polyester using ethylene glycol as the main component (the component having the highest mass ratio of diol components) and diethylene glycol as the copolymer component; terephthalic acid as the main component (dicarboxylic acid) as the dicarboxylic acid component Among these acid components, dicarboxylic acid-modified PET such as copolymerized polyester using isophthalic acid and / or adipic acid as a copolymerization component and ethylene glycol as a diol component. Further, as the polyester resin, a soft polyester resin such as polyethylene terephthalate to which a plasticizer is added may be used.

  Examples of the polystyrene resin include styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, p-ethyl styrene, p-isobutyl styrene, pt-butyl styrene, chloromethyl styrene as constituent monomers. Examples thereof include resins containing one or more styrene monomers. Specifically, for example, general-purpose polystyrene (GPPS), styrene-butadiene copolymer (for example, SBS), styrene-butadiene-isoprene copolymer (SBIS), styrene-acrylic acid ester copolymer and the like can be mentioned. .

  The polystyrene resin may be a polystyrene resin (modified polystyrene resin) into which a polar group has been introduced or a soft polystyrene resin. Examples of the polar group in the modified polystyrene resin include an acid anhydride group, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid chloride group, a carboxylic acid amide group, a carboxylic acid group, a sulfonic acid group, and a sulfonic acid ester. Group, sulfonic acid chloride group, sulfonic acid amide group, sulfonic acid group, isocyanate group, epoxy group, amino group, imide group, oxazoline group, hydroxyl group and the like. Examples of the soft polystyrene resin include styrene elastomers, styrene-diene copolymers, HIPS (high impact polystyrene) with many rubber components, and graft HIPS with many rubber components. The styrene elastomer may be a styrene-diene copolymer elastomer containing a diene component. In addition, HIPS with many said rubber components means HIPS in which the content rate of a rubber component exceeds 30 mass% with respect to the total mass (100 mass%) of HIPS. Further, the graft HIPS having a large amount of the rubber component means graft HIPS in which the content ratio of the rubber component exceeds 30% by mass with respect to the total mass (100% by mass) of the graft HIPS.

  Examples of the polyolefin resin include polyethylene resins such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), metallocene catalyst LLDPE (mLLDPE), and ethylene-vinyl acetate copolymer; polypropylene, propylene-α -Polypropylene resins such as olefin copolymers; cyclic olefin resins and the like. In particular, the polyolefin film preferably has a cyclic olefin resin as an outer layer, and preferably has a cyclic olefin resin as an outer layer and a polyethylene resin or a polypropylene resin as an inner layer (center layer).

  The heat-shrinkable film may have a single-layer structure or a laminated structure. That is, the heat-shrinkable film may be a single layer film or a laminated film in which a plurality of film layers are laminated according to required physical properties, applications, and the like. In the case of a laminated film, film layers made of the same kind of resin may be laminated, or film layers made of different resins may be laminated. In the case of a laminated film, a polyester-based resin is used as an outer layer, a laminated film containing a polyolefin-based resin or a polystyrene-based resin as an inner layer, and a polystyrene-based resin as an outer layer, and a polystyrene-based resin having a composition different from that of the polyolefin-based resin or outer layer A laminated film including a laminated film and a cyclic olefin resin as an outer layer, and a polyethylene film or a polypropylene resin as an inner layer is preferable.

  In the heat-shrinkable film, it is preferable that at least the surface layer on the side where the printing layer (X) is provided is a layer containing a polyester resin as a main component. In addition, the main component in the layer which comprises a heat-shrinkable film is resin with the highest mass ratio among resin which comprises the said layer. When the surface layer is a layer containing a polyester-based resin as a main component, the heat-shrinkable film is used when a printing ink for forming a printing layer (X) containing an aluminum pigment is applied to a label substrate. Since it is difficult to dissolve by printing ink, it is excellent in transparency and the like, and the shrink label of the present invention is excellent in heat shrinkability. When the heat-shrinkable film has a single-layer structure, the heat-shrinkable film having a single-layer structure corresponds to the surface layer. On the other hand, when the heat-shrinkable film is a laminated film, the outermost layer in the laminated film corresponds to the surface layer. The content ratio of the polyester resin in the layer containing the polyester resin as a main component is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more with respect to the mass of the surface layer. Especially preferably, it is 95 mass% or more.

  As the heat-shrinkable film, in particular, it has a base layer part and surface layers respectively provided on both sides of the base layer part, and each of the surface layers contains 50% by mass or more of a polyester resin, The layer constituting the base layer part is preferably a heat-shrinkable film having at least a layer containing 50% by mass or more of a polystyrene-based resin. By using the heat-shrinkable film having such a configuration, the shrink label of the present invention has an appropriate shrinkage rate even when it is thinned, has excellent rigidity, and is less likely to cause wrinkles and delamination after heat shrinkage. Nevertheless, the heat-shrinkable film is excellent in transparency, and is thereby more excellent in brightness when visually recognizing the printed layer (X) and the printed layer (Y) through the label substrate. In the present specification, the heat-shrinkable film having the above structure may be referred to as “heat-shrinkable film (A)”. Moreover, the layer containing 50 mass% or more of the polystyrene-based resin contained in the base layer portion may be referred to as “resin layer (A)”. The said base layer part is the part pinched | interposed into the surface layer in the said heat-shrinkable film (A).

  In the heat-shrinkable film (A), the base layer portion includes one or more layers, but preferably includes 3 to 65 layers (particularly 5 to 65 layers). In the configuration in which the base layer portion includes 3 to 65 layers (especially 5 to 65 layers), it is excellent in the appropriateness of shrinkage rate, rigidity, wrinkle after heat shrinkage and delamination delamination, transparency, and brightness. In particular, as the layer constituting the base layer portion, the resin layer (A) and the adhesive resin layer are alternately included in a total of 3 to 65 layers (particularly, 5 to 65 layers), and the outermost layer of the base layer portion is the above An adhesive resin layer is preferred. The adhesive resin layer is not particularly limited as long as it is an adhesive resin layer for imparting adhesion between the surface layer and the base layer portion. For example, the adhesive resin layer is a resin layer containing a polystyrene resin and / or a polyester resin as an essential component. Preferably there is. Examples of the laminated structure of the heat-shrinkable film (A) include [surface layer / resin layer (A) / surface layer] [surface layer / adhesive resin layer / resin layer (A) / adhesive resin layer / surface layer], [Surface layer / adhesive resin layer / resin layer (A) /... Adhesive resin layer / resin layer (A) / adhesive resin layer / surface layer] and the like.

  The above-mentioned thing is mentioned as a polyester-type resin in a surface layer. As the polyester resin, an aromatic polyester resin is preferable. The aromatic polyester-based resin means that 50 mol% or more (preferably 70 mol% or more) of all dicarboxylic acid components is 50 mol% or more (preferably 70 mol% or more) of aromatic dicarboxylic acids and / or all diol components. 70 mol% or more) is a polyester resin which is an aromatic diol. Furthermore, the aromatic polyester-type resin which is a polymer by the condensation reaction of the dicarboxylic acid containing aromatic dicarboxylic acid and the diol containing aliphatic diol, or a mixture thereof is preferable. Among the aromatic polyester resins, modified aromatic polyester resins containing a modifying component (copolymerization component) are preferable, and more preferably PET using EG as a diol component, CHDM copolymerized PET, dicarboxylic acid Modified aromatic polyester resin (2,2-dialkyl-1, 2,2-dialkyl-1,2) using terephthalic acid as a component, ethylene glycol as a diol component, and 2,2-dialkyl-1,3-propanediol as a copolymerization component 3-propanediol copolymerized PET) (in particular, NPG copolymerized PET).

  Examples of the polystyrene resin in the resin layer (A) include those described above. Among the polystyrene resins, styrene-diene copolymers are preferable, more preferably styrene-butadiene copolymers, still more preferably styrene-butadiene block copolymers, and particularly preferably styrene blocks at both ends. Styrene-butadiene block copolymer, most preferably SBS. The styrene-diene copolymer is not particularly limited, but the content ratio of the structural unit derived from the styrene monomer is 50 with respect to the total mass (100% by mass) of the styrene-diene copolymer. -95 mass% is preferable, More preferably, it is 60-90 mass%, More preferably, it is 70-90 mass%, Most preferably, it is 75-90 mass%. When the content is 50% by mass or more, the heat-shrinkable film is suitably hardened, the rigidity of the shrink label is appropriately increased, and the shrinkage property when the shrink label is attached is favorable, which is preferable. It is preferable for the content ratio to be 95% by mass or less because appropriate shrinkage stress and shrinkage characteristics can be obtained.

  The styrene-diene copolymer is not particularly limited, but the content ratio of the structural unit derived from diene is 5 to 50% by mass with respect to the total mass (100% by mass) of the styrene-diene copolymer. More preferably, it is 10-40 mass%, More preferably, it is 10-30 mass%, Most preferably, it is 10-25 mass%.

The content ratio of the structural unit derived from the styrene monomer and the content ratio of the structural unit derived from the diene are the compositions of the styrene-diene copolymer (each styrene-diene copolymer contained in each styrene-diene copolymer). The content of the structural unit and the content of each styrene-diene copolymer in all the styrene-diene copolymers contained in the resin layer (A) can be controlled. More specifically, for example, in the styrene-diene copolymer, the content of the structural unit derived from the styrene monomer is s ₁ (% by mass) and the content of the structural unit derived from the diene is d. The content ratio of styrene-diene copolymer (PS1) which is ₁ (mass%) and the structural unit derived from styrene monomer is s ₂ (mass%) and the content ratio of structural units derived from diene is It is a resin mixture composed only of styrene-diene copolymer (PS2) that is d ₂ (mass%), and the content ratio of PS1 in 100 mass% of the resin mixture (resin mixture of PS1 and PS2) is W _When the content ratio of ₁ (mass%) and PS2 is W ₂ (mass%), the content ratio of the structural unit derived from the styrene monomer in the resin mixture and the content of the structural unit derived from diene The ratio is generally It can be controlled as described below.
Content ratio (% by mass) of structural unit derived from styrene monomer = (s ₁ × W ₁ + s ₂ × W ₂ ) / 100
Content ratio (mass%) of structural units derived from diene = (d ₁ × W ₁ + d ₂ × W ₂ ) / 100

  The analysis / measurement of the constituent unit (constituent unit derived from a styrene monomer and constituent unit derived from a diene) or the content ratio of the constituent unit is not particularly limited. For example, nuclear magnetic resonance (NMR), gas chromatograph It can be performed by a tomograph mass spectrometer (GCMS) or the like. Analysis / measurement of other resin layers (adhesive resin layers, surface layers, etc.) and constituent units in the resin and the content ratio of the constituent units can be performed in the same manner.

  The adhesive resin layer is not particularly limited. For example, a resin layer containing a mixed resin of polystyrene resin and polyester resin in the highest mass ratio; a soft polystyrene resin, a polystyrene resin contained in the resin layer (A) A resin layer containing the highest mass proportion of one or more polystyrene resins selected from the group consisting of flexible polystyrene resins (specific flexible polystyrene resins) and modified polystyrene resins; the highest soft polyester resins Examples thereof include a resin layer contained in a mass ratio. The adhesive resin layer is selected from the group consisting of a resin layer containing a mixed resin of polystyrene resin and polyester resin in the highest mass ratio; a soft polystyrene resin, a specific flexible polystyrene resin, and a modified polystyrene resin, among others. A resin layer containing the one or more kinds of polystyrene-based resins in the highest mass ratio is preferable. When the adhesive resin layer is a resin layer containing a mixed resin of polystyrene resin and polyester resin in the highest mass ratio, the polystyrene resin of the resin layer (A) is composed of the polystyrene resin of the adhesive resin layer and the surface layer. The polyester resin is preferable because it can be bonded to the polyester resin of the adhesive resin layer, and the adhesion between the base layer portion and the surface layer is improved. In addition, the said adhesive resin layer may correspond to a resin layer (A).

  As a preferable aspect of the polyester-based resin and the polystyrene-based resin in the case where the adhesive resin layer is a resin layer containing the mixed resin in the highest mass ratio, those in the polyester-based resin in the surface layer described above and the resin layer described above It is the same as that in the polystyrene resin in (A). When the adhesive resin layer is a resin layer containing the mixed resin in the highest mass ratio, the content ratio of the mixed resin (that is, the total content ratio of the polystyrene resin and the polyester resin) is not particularly limited. From the viewpoint of improving the adhesion between the surface layer and the base layer part and suppressing delamination, the amount is preferably 50% by mass or more, more preferably 60%, based on the total mass (100% by mass) of the adhesive resin layer. It is 70% by mass or more, more preferably 70% by mass or more. Although the upper limit of the said content rate is not specifically limited, 100 mass% may be sufficient.

  Softness in the case where the adhesive resin layer is a resin layer containing at least one polystyrene resin selected from the group consisting of a soft polystyrene resin, a specific flexible polystyrene resin, and a modified polystyrene resin in the highest mass ratio. Examples of the polystyrene-based resin and the modified polystyrene-based resin include soft polystyrene-based resins and modified polystyrene-based resins exemplified and described as the polystyrene-based resins included in the resin layer (A). The hydrogenated soft polystyrene resin contained in the soft polystyrene resin is not particularly limited, but may be a hydrogenated styrene elastomer, a hydrogenated styrene-diene copolymer (particularly, a styrene having a large amount of hydrogenated diene components). Diene copolymers) are preferred.

  The heat-shrinkable film is a film oriented in at least one direction (for example, a film oriented in one direction or a film oriented in a direction different from one direction and one direction from the viewpoint of exhibiting shrink characteristics (heat shrinkability). ) Is preferable. When the heat-shrinkable film is a laminated film, it is preferable that at least one film layer in the laminated film is oriented, and that all the film layers are oriented in at least one direction. When all the film layers are non-oriented, sufficient shrink characteristics may not be exhibited. As the heat-shrinkable film, a film oriented in one direction (uniaxially oriented film) or a film oriented in one direction and a direction orthogonal to one direction (biaxially oriented film) is often used. An axially oriented film (including a film stretched substantially in one direction, mainly stretched in one direction and slightly stretched in a direction perpendicular to the one direction) is generally used.

  The film oriented in at least one direction can be obtained by stretching an unstretched film in at least one direction. For example, when the film oriented in at least one direction is a uniaxially oriented film, it is obtained by stretching an unstretched film in one direction. When it is a biaxially oriented film, the unstretched film is oriented in one direction and the one direction. It is obtained by stretching in a direction orthogonal to the direction. In addition, the shrink label of this invention can mainly heat-shrink in the orientation direction of a heat-shrinkable film.

  The heat-shrinkable film can be produced by a conventional method such as melt film formation or solution film formation. A commercially available heat-shrinkable film can also be used. In the case of producing a heat-shrinkable film having a laminated structure, a conventional method such as a coextrusion method or a dry lamination method can be used as a lamination method. Examples of the method for orienting the heat-shrinkable film include, for example, a longitudinal direction (film production line direction; also referred to as longitudinal direction or MD direction) and a width direction (direction orthogonal to the longitudinal direction; also referred to as lateral direction or TD direction). Stretching in two directions, stretching in one direction of the longitudinal direction or the width direction, and the like can be used. As the stretching method, for example, a roll method, a tenter method, a tube method, or the like can be used. For example, the stretching process of a film stretched substantially in one direction in the width direction is, for example, 1.01 to 1.5 times, preferably 1. After stretching about 05 to 1.3 times, the stretching can be performed by stretching 3 to 8 times, preferably about 4 to 7 times in the width direction.

  The heat shrinkage rate of the heat shrinkable film in the main shrinkage direction at 90 ° C. for 10 seconds (sometimes referred to as “heat shrinkage rate (90 ° C., 10 seconds)”) is not particularly limited, but is 30 to 90. % Is preferable, and more preferably 40 to 85%. The heat shrinkage rate (90 ° C., 10 seconds) in the direction perpendicular to the main shrinkage direction of the heat shrinkable film is not particularly limited, but is preferably −3 to 15%, more preferably −1 to 10%. . The “main shrinkage direction” is a direction having the largest thermal shrinkage rate, and is generally a direction mainly stretched, for example, a film stretched substantially in one direction in the width direction. In the case of the width direction.

  Commercially available products can be used as the heat-shrinkable film used as the label substrate. For example, “Space Clean S7042”, “SV-808” manufactured by Toyobo Co., Ltd., “LX-10S”, “LX-18S”, “LX-61S” manufactured by Mitsubishi Plastics (polyester film) ; "Bon set" manufactured by CI Kasei Co., Ltd., "GMLS" manufactured by Gunze Co., Ltd. (polystyrene film); "FL" manufactured by Gunze Co., Ltd. (polyolefin film); "Ecology" manufactured by Mitsubishi Plastics Co., Ltd. (Polylactic acid film); “DL” manufactured by Mitsubishi Chemical Co., Ltd., “HST” manufactured by Gunze Co., Ltd. (a laminated film having a surface layer of a polyester resin and a center layer of a polystyrene resin). Moreover, the shrink film in the shrink label of Unexamined-Japanese-Patent No. 2014-206736 can also be used.

  The label base material may have a layer other than the heat-shrinkable film. Examples of the layer other than the heat-shrinkable film include an anchor coat layer, a primer coat layer, a protective layer, an antistatic layer, a sliding layer, a heat insulating layer, a gas barrier layer, a light shielding layer, and a metal or metal oxide deposition layer. Can be mentioned. Further, the surface of the heat-shrinkable film may be subjected to conventional surface treatment such as corona discharge treatment, primer treatment, antistatic coating treatment, etc., if necessary.

  When the heat-shrinkable film is transparent, the haze (haze) value [based on JIS K 7136, converted to a thickness of 40 μm, unit:%] of the heat-shrinkable film is not particularly limited, but is preferably 10% or less. More preferably, it is 7% or less, and further preferably 5% or less. If the haze value exceeds 10%, the shrink label (printed on the back side) is printed on the inside of the label substrate (the side that becomes the container side when the shrink label is attached to the container) and the print is shown through the label substrate. In the case of (shrink label) applications, printing may become cloudy and decorative properties may be reduced when used as a product. However, even if the haze value exceeds 10%, it may be opaque in applications other than the above-described applications (print printed shrink labels) that show printing through the label base material, and can be used sufficiently. Moreover, it does not specifically limit as a heat-shrinkable film in an opaque label base material, For example, a milky white film, a metal vapor deposition film, etc. can be used.

  Although the thickness of the said heat-shrinkable film is not specifically limited, 10-100 micrometers is preferable, More preferably, it is 12-80 micrometers, More preferably, it is 15-60 micrometers.

[Print layer (X)]
The print layer (X) is a print layer containing a urethane resin and an aluminum pigment, and is provided on at least one surface of the label base material. The print layer (X) may be provided on both sides of the label base material. In addition, the printing layer (X) may be provided on the entire surface of the label base material (the surface on the side where the printing layer (X) is provided) or may be provided in part. Further, the printing layer (X) is not particularly limited, but may be a single layer or a multilayer. Moreover, only 1 type may be used for the said urethane type resin and the said aluminum pigment, respectively, and 2 or more types may be used for them.

  The printing layer (X) contains a urethane resin as a binder resin that constitutes the printing layer (X). The binder resin plays a role as a main resin component for forming the printing layer (X), and forms a coating film when the printing ink for forming the printing layer (X) is coated. By including a urethane-based resin as the binder resin, the flexibility of the printing layer (X) is improved, and the followability of the printing layer (X) to the label base material when the shrink label of the present invention is thermally contracted is improved. Therefore, the printed layer (X) is remarkably excellent in brightness before and after thermal contraction.

  The urethane-based resin is not particularly limited, and a known or conventional urethane resin for a printing layer can be used. For example, a resin obtained by reacting a polyisocyanate compound and a polyol compound (that is, a polyisocyanate compound) And a polyol compound).

  Examples of the polyisocyanate compound include one or a mixture of two or more known diisocyanates of aromatic, aliphatic and alicyclic groups. Examples of the diisocyanates include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, and isophorone diisocyanate. If necessary, tri- or higher functional polyisocyanates and polyisocyanate adducts can be mixed with the diisocyanates.

  Examples of the polyol compound include ethylene glycol, diethylene glycol, 1,3-propanediol, propylene glycol (1,2-propanediol), butanediol (1,3-butanediol, 1,4-butanediol, etc.), 1, Low molecular weight glycols such as 6-hexanediol and cyclohexanedimethanol; polyether diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol-polycaprolactone copolymer; propylene glycol, butanediol, hexanediol Polyester diols obtained from diols such as adipic acid, sebacic acid, azelaic acid, isophthalic acid, terephthalic acid, fumaric acid and the like; polycaprolacto Diol, polyvalerolactone diol, a known diols such as lactone diol, such as a lactone block copolymer diols can be used. Moreover, said diols and trifunctional or more than polyol compounds (polyether polyol, polyester polyol, etc.) can also be mixed and used as needed.

  From the viewpoint of flexibility, the glass transition temperature (Tg) of the urethane resin is preferably −70 to 40 ° C., more preferably −60 to 30 ° C. In the present specification, the glass transition temperature (Tg) of the resin can be measured by DSC (differential scanning calorimetry) based on, for example, JIS K7121. The DSC measurement is not particularly limited. For example, the DSC measurement can be performed using a differential scanning calorimeter “DSC6200” manufactured by Seiko Instruments Inc. under a temperature rising rate of 10 ° C./min.

  Although the mass mean molecular weight (Mw) of the said urethane type resin is not specifically limited, 10,000-100,000 are preferable, More preferably, it is 20,000-80,000, More preferably, it is 30,000-70,000. In addition, in this specification, although a mass average molecular weight (Mw) is not specifically limited, For example, it can measure by GPC using polystyrene as a standard substance.

  A commercial item can also be used for the said urethane-type resin. For example, “Samprene IB series, LQ series” manufactured by Sanyo Chemical Industries, Ltd., “Yuliano KL series” manufactured by Arakawa Chemical Industries, Ltd., etc. are available on the market.

  The print layer (X) preferably contains a urethane-based resin as a resin having the highest mass ratio among all resins constituting the binder resin in the print layer (X). As for the content rate of the urethane type resin in printing layer (X), 10-70 mass% is preferable with respect to the total mass of printing layer (X), More preferably, it is 20-60 mass%. When the content ratio is 10% by mass or more, the flexibility of the printed layer (X) is further improved, and the brightness after heat shrinkage is further improved. When the content ratio is 70% by mass or less, the content ratio of the aluminum pigment can be relatively increased, and the brightness of the printed layer (X) can be further improved.

  The aluminum pigment is not particularly limited, and may be a leafing type aluminum pigment, a non-leafing type aluminum pigment, or a vapor deposited aluminum pigment, but may be a vapor deposited aluminum pigment or a leafing type aluminum. Pigments are preferred.

  The non-leafing aluminum pigment has a property of being uniformly dispersed and arranged in a coating film (film) of printing ink. The leafing type aluminum pigment and the non-leafing type aluminum pigment are preferably aluminum pigments produced by ball milling (sometimes referred to as “ball mill method” or “wet ball mill method”).

  Among the above-described aluminum pigments, vapor-deposited aluminum pigments are preferable. The said vapor deposition aluminum pigment is the aluminum flakes manufactured by the vapor deposition method. The above-mentioned vapor deposition method is a vapor deposition metal in which aluminum is vapor-deposited on an appropriate support substrate (film, etc.) to produce a vapor-deposited aluminum film, which is then peeled off, pulverized, and classified as necessary to form a flake. This is a method for producing a film strip (evaporated aluminum flake) (see, for example, JP-A-2002-20668). According to said vapor deposition method, compared with the case where it manufactures by the conventional ball mill method etc., aluminum flakes with plate shape and thinner thickness and a higher aspect ratio can be obtained. For this reason, in the printed layer (X), the aluminum flakes are easily oriented in the direction parallel to the surface of the shrink label, the orientation is improved, and the incident light is easily regularly reflected. For this reason, the specular glossiness of the printed layer (X) is improved, and the brightness feeling is further improved by exhibiting excellent metallic luster. In addition, the said vapor deposition aluminum pigment may use only 1 type, and may mix and use 2 or more types of different vapor deposition aluminum pigments.

  Although D50 of the said vapor deposition aluminum pigment is not specifically limited, 1-30 micrometers is preferable, More preferably, it is 5-20 micrometers. When the D50 is 1 μm or more, the brightness feeling is improved, which is preferable. If the D50 exceeds 30 μm, blurring may occur when printing ink is gravure-printed.

  Although the thickness of the said vapor deposition aluminum pigment is not specifically limited, Less than 0.1 micrometer is preferable. Moreover, although the average thickness of the said vapor deposition aluminum pigment is not specifically limited, 0.01 micrometer or more and less than 0.1 micrometer are preferable, More preferably, it is 0.01-0.07 micrometer. If the average thickness is less than 0.01 μm, the production efficiency may be poor industrially. On the other hand, when the thickness and the average thickness are less than 0.1 μm, the orientation of the metal pigment in the printed layer (X) is improved, and the luminance feeling tends to be further improved.

  A commercial item can also be used for the said vapor deposition aluminum pigment. For example, “Metacene 71-0010”, “Metacene 41-0010” manufactured by Toyo Aluminum Co., Ltd., “Metal Ar A41010AE” manufactured by Ecart Co., etc. are available on the market.

  As for the content rate of the aluminum pigment in printing layer (X), 5-70 mass% is preferable with respect to the total mass of printing layer (X), More preferably, it is 10-50 mass%. When the content is 5% by mass or more, the brightness of the printed layer (X) is more excellent. Adhesiveness with a label base material and a printing layer (Y) is more excellent in the said content rate being 70 mass% or less.

  The print layer (X) may contain a resin other than the urethane resin as a binder resin. Examples of such resins include acrylic resins, polyester resins, polyamide resins, cellulose resins (including nitrocellulose resins), vinyl chloride-vinyl acetate copolymer resins, chlorinated polypropylene, and ethylene-acetic acid. Examples thereof include modified olefin resins such as vinyl copolymers. As said acrylic resin, acrylic resin contained in the below-mentioned printing layer (Y) is mentioned, for example. Among these, from the viewpoint of improving the flexibility of the printing layer (X) and further improving the followability of the printing layer (X) to the label base material when the shrink label is thermally shrunk, acrylic resins and cellulose resins are used. preferable. Only one type of resin other than the urethane-based resin may be used, or two or more types may be used.

  The cellulose resin is not particularly limited, and a known or commonly used printing layer or a cellulose resin for printing ink can be used. The cellulose-based resin is not particularly limited. For example, nitrocellulose (nitrified cotton); cellulose acetate butyrate (cellulose acetate butyrate: CAB), cellulose acetate (cellulose acetate), cellulose acetate propionate (cellulose acetate propionate). : CAP) and the like, and a cellulose resin esterified with a carboxylic acid. Examples of the carboxylic acid include acetic acid, butyric acid, propionic acid, acetic anhydride, and butyric anhydride. As said cellulose resin, the cellulose resin esterified with carboxylic acid is preferable, More preferably, they are CAB and CAP. Only 1 type may be used for the said cellulose resin, and 2 or more types may be used for it.

  Although the mass mean molecular weight (Mw) of the said cellulose resin is not specifically limited, 10,000-150,000 are preferable, More preferably, it is 12,000-100,000.

  The glass transition temperature (Tg) of the cellulose resin is not particularly limited, but is preferably 80 to 200 ° C, more preferably 100 to 165 ° C, from the viewpoint of making ink cracking less likely to occur during heat shrinkage. In particular, the glass transition temperature (Tg) of the cellulose resin esterified with the carboxylic acid is preferably 80 to 165 ° C, more preferably 100 to 165 ° C. The glass transition temperature (Tg) of CAB is preferably 80 to 165 ° C, more preferably 100 to 160 ° C. The glass transition temperature (Tg) of CAP is preferably 135 to 165 ° C, more preferably 140 to 160 ° C.

  A commercial item can also be used for the said cellulose resin. For example, “CAP-482-20”, “CAB-381-20”, “CAB-381-0.5”, “CAB-381-0.1”, “CAB-551-0. 1 ”,“ CAB-551-0.01 ”,“ CAP-504-0.2 ”,“ CAP-482-0.5 ”, etc.,“ RS Series ”,“ SS Series ”, etc. made by KOREA CNC Is available at

  The printing layer (X) may contain a plasticizer. When the printing layer (X) contains a plasticizer together with an aluminum pigment (particularly vapor-deposited aluminum pigment), the plasticizer imparts flexibility to the printing layer (X), and deformation and orientation (alignment) of the aluminum pigment during shrink processing. ) To suppress the deterioration of the metallic luster of the printed layer (X) due to shrink processing, and therefore, the brightness feeling after heat shrinkage is further improved. Further, when the plasticizer is contained, the printing layer (X) tends to be more flexible and more likely to cause ink cracking at the time of heat shrinkage. Even in this case, the shrink label of the present invention is less likely to cause ink cracking. .

  As the plasticizer, known or conventional plasticizers can be used. For example, phthalic acid ester compounds such as diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, dihydroabiethyl phthalate, and dimethyl isophthalate; acetyl Citric acid ester compounds such as tributyl citrate; Benzoic acid ester compounds such as trimethylol ethane tribenzoate, trimethylol propane tribenzoate, glyceryl tribenzoate, pentaerythritol tetrabenzoate; sucrose octaacetate, ketenoic acid Tricyclohexyl, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate)], 1,6-hexanediol bis [3- (2,5-di-t-butyl) -4-hydroxyphenyl) propionate] Fatty acid ester-based compounds; N- cyclohexyl -p- sulfonate ester compounds such as toluene sulfonic acid amide; phosphoric acid ester compounds, hindered phenol compounds, triazole compounds, and hydroquinone-based compounds. Among these, dicyclohexyl phthalate (DCHP) and tributyl acetylcitrate (ATBC) are preferable, and ATBC is particularly preferable. Only 1 type may be used for the said plasticizer, and 2 or more types may be used for it.

  A commercial item can also be used for the plasticizer. For example, “ATBC” manufactured by Asahi Kasei Finechem Co., Ltd. and “DCHP” manufactured by Wako Pure Chemical Industries, Ltd. are available on the market.

  When the printing layer (X) contains a plasticizer, the content of the plasticizer in the printing layer (X) is preferably 5 to 35% by mass, more preferably 7%, based on the total mass of the printing layer (X). -30 mass%. When the content is 5% by mass or more, the effect of softening the printed layer becomes more sufficient, the specular gloss of the printed layer (X) after heat shrinkage is improved, and the brightness feeling after heat shrinkage is further improved. To do. When the content ratio is 35% by mass or less, peeling of the printed layer (X), blocking, and deterioration of scratch resistance can be further suppressed.

  The printed layer (X) may contain other components other than the above-described components (binder resin including urethane resin, aluminum pigment, and plasticizer) within the range not impairing the effects of the present invention. . Examples of the other components include color pigments other than aluminum pigments (other color pigments), lubricants, anti-settling agents, dispersants, stabilizers, fillers, antioxidants, ultraviolet absorbers, antistatic agents, and colors. Parting prevention agents, fragrances, deodorants and the like can be mentioned. For example, white pigments such as titanium oxide (titanium dioxide), indigo pigments such as copper phthalocyanine blue, carbon black, mica (mica), and other colored pigments can be selected and used as the colored pigment. In addition to the above pigments, extender pigments such as alumina, calcium carbonate, barium sulfate, silica, and acrylic beads can be used for the purpose of adjusting gloss.

  The printing layer (X) preferably has a thin printing layer from the viewpoint of exhibiting excellent brightness. Although the thickness of printing layer (X) is not specifically limited, 0.05-3 micrometers is preferable, More preferably, it is 0.1-2 micrometers. When the thickness is 0.05 μm or more, a decrease in transmission density due to being too thin can be suppressed. When the thickness is 3 μm or less, the orientation of the aluminum pigment (particularly, the vapor-deposited aluminum pigment) is improved in the coating layer of the printing ink forming the printing layer (X) or the printing layer (X), and the brightness feeling is more improves. Moreover, the usage-amount of printing ink can be decreased and it is preferable at the surface of cost or an environment. Furthermore, the effect that it is easy to apply | coat uniformly, the intensity | strength of a printing layer is high, and it is hard to peel is acquired.

[Print layer (Y)]
The printing layer (Y) is a printing layer containing an acrylic resin as a main resin component and having a lubricant content of 0.7% by mass or less, and the at least one surface of the label substrate (that is, , The surface on which the printing layer (X) is provided) is provided so that at least a portion thereof overlaps with the printing layer (X) in the surface spreading direction. The printing layer (Y) is not necessarily provided so as to be in contact with the printing layer (X), but is provided so that the printing layer (X) is in contact with at least a part (particularly, a portion where ink cracking is likely to occur). It is preferable. Further, the printing layer (Y) may be provided on the entire surface of the label base material (the surface on the side on which the printing layer (Y) is provided) or may be provided in part. Further, the printing layer (Y) is not particularly limited, but may be a single layer or a multilayer.

  The printing layer (Y) contains an acrylic resin as a binder resin as a main resin component. That is, the printing layer (Y) includes an acrylic resin as a resin having the highest mass ratio among all resins constituting the binder resin in the printing layer (Y). The binder resin plays a role as a main resin component for forming the printing layer (Y), and forms a coating film when the printing ink for forming the printing layer (Y) is coated. The printing layer (Y) is a harder printing layer than the printing layer (X) because the content ratio of the lubricant is not more than a specific value and contains an acrylic resin as a main resin component. For this reason, by providing such a printing layer (Y) so that at least a part thereof overlaps with the printing layer (X) in the surface spreading direction, the printing layer (X) exhibits a brightness feeling while exhibiting sufficient heat. It is possible to prevent the relatively flexible printed layer (X) from coming into contact with the container and / or the inner printed layer (X) at the other end from coming into contact with the end of the one end when shrinking, thereby printing. Ink cracking of the layer (X) can be suppressed. The acrylic resin may be used alone or in combination of two or more.

  Examples of the acrylic resin include a polymer composed of an acrylic monomer as an essential monomer component, that is, a polymer (copolymer) having at least a structural unit derived from an acrylic monomer. The monomer component constituting the acrylic resin may contain a monomer component other than the acrylic monomer.

Examples of the acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. , S-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, ( (Meth) acrylic acid alkyl ester having a linear or branched alkyl group such as decyl (meth) acrylate and dodecyl (meth) acrylate [preferably (meth) acrylic acid C _1-12 alkyl ester and the like]; (Meth) acrylic acid; carboxy group-containing (meth) acrylic acid ester such as carboxyethyl acrylate Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, diethylene glycol mono (meth) Hydroxy group-containing (meth) acrylic acid esters such as acrylate and dipropylene glycol mono (meth) acrylate [preferably (meth) acrylic acid hydroxy C _1-8 alkyl ester and the like]; (meth) acrylic acid cyclohexyl, (meth) acrylic (Meth) acrylic acid cycloalkyl esters such as isobornyl acid; N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (Meth) acrylic acid amide derivatives such as (meth) acrylamide; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dipropylaminopropyl And monomers having a (meth) acryloyl group (monomers having at least an acryloyl group or a methacryloyl group), such as (meth) acrylate dialkylaminoalkyl esters such as (meth) acrylate. As for the said acrylic monomer, only 1 type may be used and 2 or more types may be used.

  Although it does not specifically limit as a monomer component which comprises acrylic resins other than the said acrylic monomer, For example, carboxy group containing polymerizable unsaturated compounds, such as crotonic acid, itaconic acid, fumaric acid, maleic acid, or its anhydride; Styrenic compounds such as styrene, vinyltoluene and α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl halides such as vinyl chloride; vinyl ethers such as methyl vinyl ether; cyano groups such as (meth) acrylonitrile Contains vinyl compounds; ethylene, propylene, and the like.

  The content of the acrylic monomer in the total amount (100% by mass) of the monomer component constituting the acrylic resin, that is, the content of the structural unit derived from the acrylic monomer in the acrylic resin (100% by mass) is particularly Although not limited, 80 mass% or more (for example, 80-100 mass%) is preferable from a viewpoint of adhesiveness with a label base material or printing layer (X), More preferably, 90 mass% or more (for example, 90-100). Mass%).

  The mass average molecular weight (Mw) of the acrylic resin is not particularly limited, but is 20,000 to 250,000 from the viewpoint of the wear resistance of the printing layer (Y) and the adhesion to the label base material and the printing layer (X). Is more preferable, and 30,000 to 200,000 is more preferable.

  Although the glass transition temperature (Tg) of the said acrylic resin is not specifically limited, From a viewpoint of abrasion resistance and a heat resistant improvement, 30-120 degreeC is preferable, More preferably, it is 40-100 degreeC.

  A commercial item may be used for the acrylic resin. As commercially available products, for example, “ARUFON series” manufactured by Toagosei Co., Ltd., “Dianar series (BR series, LR series, etc.)” manufactured by Mitsubishi Rayon Co., Ltd., etc. are available on the market.

  The content ratio of the acrylic resin in the printing layer (Y) is, for example, 8% by mass or more, may be 10% by mass or more, and the upper limit is 100% by mass with respect to the total mass of the printing layer (Y). It may be 95% by mass.

  As described above, the content ratio of the lubricant in the printing layer (Y) is 0.7% by mass or less, preferably 0.5% by mass or less, and most preferably based on the total mass of the printing layer (Y). Is substantially not contained (for example, not actively added). When the content ratio exceeds 0.7% by mass, the hardness of the printed layer (Y) tends to decrease, and thus the effect of suppressing ink cracking may decrease.

  Examples of the lubricant include lubricants used in known or conventional coating layers. For example, polyolefin wax such as polyethylene wax and polyethylene oxide wax, fatty acid amide, fatty acid ester, paraffin wax, polytetrafluoroethylene (PTFE). Various waxes (waxes) such as wax and carnauba wax, resin beads and the like can be mentioned. Other examples include organic or inorganic particles such as silica, alumina, calcium carbonate, barium sulfate, silica, and acrylic beads.

  The printing layer (Y) may contain an aluminum pigment. When the printing layer (Y) contains an aluminum pigment, the shrink label of the present invention has a two-layer structure of the printing layer (X) and the printing layer (Y), and the metal layer overlaps. A profound feeling and luxury can be obtained.

  Examples of the aluminum pigment that may be contained in the printing layer (Y) include those exemplified and described as the aluminum pigment contained in the printing layer (X). The aluminum pigment in the printing layer (Y) may be a leafing type aluminum pigment, a non-leafing type aluminum pigment, or a vapor deposition aluminum pigment.

  When the printing layer (Y) is a printing layer containing an aluminum pigment, the printing layer (Y) is provided from the viewpoint that the printing layer (X) can exhibit a feeling of brightness and is excellent in feeling of brightness and is less likely to cause ink cracking. It is preferable that the halftone dot area (halftone dot) of the region being formed is 80% or more. In this case, the halftone dot area in the region where ink cracking is likely to occur may be 80% or more, and the halftone dot area in other regions may be less than 80%.

  When the printing layer (Y) contains an aluminum pigment, the content of the acrylic resin in the printing layer (Y) is preferably 15 to 70% by mass, more preferably the total mass of the printing layer (Y). It is 20 to 65% by mass. Moreover, 5-30 mass% is preferable with respect to the total mass of a printing layer (Y), and, as for the content rate of the aluminum pigment in a printing layer (Y), More preferably, it is 10-25 mass%.

  The print layer (Y) may be a white print layer containing a white pigment such as titanium oxide (titanium dioxide). When the print layer (Y) is a white print layer, the print layer (Y) can function as a back print layer of the print layer (X). Therefore, when the adherend is a transparent container, an additional back print layer is provided. It is possible to prevent the contents in the container from being seen through. In addition, a back printed layer is a printed layer used as the background of a design when it observes from the outer side of a cylinder, when a shrink label is made into a cylindrical shrink label, for example.

  When the print layer (Y) is the white print layer, the content ratio of the acrylic resin in the print layer (Y) is preferably 5 to 80% by mass with respect to the total mass of the print layer (Y). Preferably it is 7-60 mass%. Moreover, 10-60 mass% is preferable with respect to the total mass of a printing layer (Y), and, as for the content rate of the white pigment in a printing layer (Y), More preferably, it is 15-55 mass%.

  On the other hand, when the printing layer (Y) is a colorless and transparent printing layer that does not contain a color pigment (including a metal pigment such as a white pigment and an aluminum pigment), the content ratio of the acrylic resin in the printing layer (Y) is: 50 mass% or more is preferable with respect to the total mass of a printing layer (Y), More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more. The upper limit may be 100% by mass.

  The printing layer (Y) may contain other components other than the above-described components (acrylic resin, aluminum pigment, and white pigment) within a range that does not impair the effects of the present invention. Examples of the other components include color pigments other than aluminum pigments and white pigments (other color pigments), anti-settling agents, dispersants, stabilizers, fillers, antioxidants, ultraviolet absorbers, antistatic agents, Examples include color separation preventing agents, fragrances, and deodorants. As the color pigment, for example, an indigo pigment such as copper phthalocyanine blue, carbon black, mica (mica), other color pigments, and the like can be selected and used according to the application.

  From the viewpoint of protecting the print layer (X), the print layer (Y) preferably has a thick print layer. Although the thickness of a printing layer (Y) is not specifically limited, For example, it is 0.1-10 micrometers.

[Shrink label]
The shrink label of this invention has a label base material, a printing layer (X), and a printing layer (Y) as mentioned above. The shrink label of this invention may have layers (other layers) other than a label base material, printing layer (X), and printing layer (Y). Examples of the other layers include printing layers other than the printing layer (X) and the printing layer (Y) (sometimes referred to as “other printing layers”), adhesive layers (pressure-sensitive adhesive layers, heat-sensitive properties). Adhesive layer, etc.), anchor coat layer, primer coat layer, coating layer, inner coat layer, antistatic layer, metal or metal oxide deposition layer, light shielding layer, heat insulating layer, barrier layer, sliding layer, etc. (however, label) And those not included in the substrate).

  The other print layer is not particularly limited, and examples thereof include known or commonly used print layers used in shrink labels. Examples of the printing layer include a solvent drying type printing layer formed with a solvent drying type printing ink, an active energy ray curable printing layer formed with an active energy ray curable printing ink, and the like. In addition, for example, to protect design print layers (color print layers, etc.) such as product names, illustrations, handling precautions, etc. and designs, back print layers formed in a single color such as white, films and print layers And a protective printing layer provided on the substrate, a primer printing layer provided to improve the adhesion between the film and the printing layer, and the like. Although the said other printing layer is not specifically limited, You may be provided only in the single side | surface side of the label base material, and may be provided in the double-sided side. Moreover, the said other printed layer may be provided in the whole surface of the surface of a label base material (the surface by which the other printed layer is provided), and may be provided in part. Furthermore, although the said other printed layer is not specifically limited, A single layer may be sufficient and a multilayer may be sufficient. The other print layers can be provided by a known or common printing method. Especially, it is preferable that the said other printing layer is provided by the gravure printing method or the flexographic printing method.

  Although the said other printing layer is not specifically limited, It is preferable that binder resin is included as an essential component. Furthermore, it may contain additives such as color pigments such as blue, red, yellow, black, white, lubricants, dispersants, antifoaming agents, etc., as necessary. Each of the binder resins may be used alone or in combination of two or more.

  The binder resin is not particularly limited, and for example, a resin used as a binder resin in a known or commonly used printing layer or printing ink can be used. Examples of the binder resin include acrylic resins, urethane resins, polyester resins, polyamide resins, cellulose resins (including nitrocellulose resins), vinyl chloride-vinyl acetate copolymer resins, and the like. Of these, acrylic resins and urethane resins are preferable. The color pigment is not particularly limited, and for example, a color pigment used in a known or conventional printing layer or printing ink can be used. For example, white pigments such as titanium oxide (titanium dioxide), indigo pigments such as copper phthalocyanine blue, carbon black, aluminum flakes, mica (mica), and other colored pigments can be selected and used according to the application. . In addition to the above pigments, extender pigments such as alumina, calcium carbonate, barium sulfate, silica, and acrylic beads can be used for the purpose of adjusting gloss.

  The shrink label of the present invention preferably has a design print layer on the side of the label substrate on which the print layer (X) and the print layer (Y) are provided as the other print layer. When the print layer (X) and the print layer (Y) are provided on the side where the design print layer is provided, the design print layer and the print layer (X) are visually recognized through the label substrate of the shrink label of the present invention. Can be used as a back printed shrink label. The design print layer preferably contains a binder resin and a color pigment as essential components, and is generally formed by a plurality of print layers having different color pigments so as to have a desired design. Although the thickness of the said design printing layer is not specifically limited, 0.1-10 micrometers is preferable.

  Moreover, it is preferable that the shrink label of this invention has a protective printing layer provided so that the printing layer (X) and the printing layer (Y) may be covered as said other printing layer. By having the protective printing layer, blocking when the shrink labels are stacked can be suppressed, or slipping with respect to the adherend can be imparted when the shrink label is attached to the adherend. The protective printing layer preferably contains a binder resin and a lubricant as essential components, and the content ratio of the lubricant is 0.1% by mass or more (for example, 0.1 to 10% by mass, preferably, based on the total mass of the protective printing layer) Is preferably 0.7% by mass or more, more preferably more than 0.7% by mass). The protective printing layer may be a transparent layer or an opaque layer, but is preferably transparent from the viewpoint of brightness. As the protective printing layer, for example, an acrylic resin is contained as a main resin component (that is, the acrylic resin is included as a resin having the highest mass ratio among all resins constituting the binder resin in the protective printing layer) and a lubricant. It is preferable that it is a layer (especially transparent printing layer) with more than 0.7 mass% content rate. The thickness of the protective printing layer is, for example, 0.1 to 10 μm. In addition, it can be made to function as a protective printing layer by making a design printing layer contain a lubricant. In this case, it is not necessary to provide a protective printing layer on the back surface of the design printing layer.

  The shrink label of the present invention may be a front print shrink label, a back print shrink label, or a double-side print shrink label. It is particularly useful to use. In the present specification, the front printed label is a label that shows printing without passing through the label base material. For example, when the label is viewed, it means a label having a design print layer in front of the label base material. Moreover, a back printed label is a label which shows printing through a label base material, for example, when looking at a label, it means the label which has a design printing layer in the back | inner side rather than a label base material. Moreover, a double-sided printing label means the label which has a design printing layer on the both surfaces side of a label base material.

  The laminated structure of the shrink label of the present invention includes, for example, [label substrate / print layer (X) / print layer (Y)], [label substrate / print layer (X) from one surface of the shrink label. / Print layer (Y) / protective print layer], [label substrate (heat-shrinkable film / anchor coat layer) / print layer (X) / print layer (Y) / protective print layer], [label substrate / print Layer (X1) / printing layer (X2) / printing layer (Y) / protective printing layer], [label substrate / printing layer (X) / printing layer (Y1) / printing layer (Y2) / protective printing layer], [Label substrate / printing layer (X1) / printing layer (Y) / printing layer (X2) / protective printing layer] and the like. In addition, in the said laminated structure, you may have a design printing layer in the side by which the printing layer (X) and printing layer (Y) are provided of the label base material. The print layer (X1) and the print layer (X2) are two types of print layers (X) having different compositions, and the same applies to the print layer (Y1) and the print layer (Y2). As a combination of the printing layer (X1) and the printing layer (X2), for example, one is a printing layer (X) using an evaporated aluminum pigment and the other is a printing layer (X) using another aluminum pigment. The combination of two types of printing layers (X) from which the kind of aluminum pigment to be used differs is mentioned. The print layer (Y) may be any of a print layer containing an aluminum pigment, a white print layer, and a transparent print layer. As a combination of the print layer (Y1) and the print layer (Y2), for example, one is a print layer (Y) containing a vapor-deposited aluminum pigment and the other is a print layer (Y) containing another aluminum pigment, Is a printing layer (Y) containing an aluminum pigment and the other is a transparent printing layer.

  Although the thickness (total thickness) of the shrink label of this invention is not specifically limited, 10-120 micrometers is preferable, More preferably, it is 15-90 micrometers, More preferably, it is 20-65 micrometers.

  The shrinkage rate of the shrink label of the present invention (when unshrinked) in the main shrinkage direction at 100 ° C. for 10 seconds (hot water treatment) (sometimes referred to as “thermal shrinkage rate (100 ° C., 10 seconds)”) Although not particularly limited, it is preferably 40% or more, more preferably 45% or more, still more preferably 50% or more, still more preferably 60% or more, and particularly preferably 65% or more. The upper limit of the heat shrinkage rate (100 ° C., 10 seconds) is not particularly limited, but is preferably 90% and may be 85%. The “main shrinkage direction” is the direction having the largest heat shrinkage rate, and generally coincides with the main shrinkage direction of the heat shrinkable film. Generally, it is the direction mainly subjected to stretching treatment, for example, the width direction in the case of a film stretched substantially in one direction in the width direction. In addition, although the thermal contraction rate (100 degreeC, 10 second) of the direction orthogonal to the main shrinkage | contraction direction of the shrink label (at the time of non-shrink) of this invention is not specifically limited, -5-25% is preferable, More preferably -3 to 20%.

  FIG. 1 is a schematic view (partial sectional view) showing an embodiment of the shrink label of the present invention. The shrink label 1 of the present invention shown in FIG. 1 includes a label substrate 2, a design printing layer 3, a printing layer (X) 4, and a printing layer (Y) provided on one surface of the label substrate 2. 5 and a protective printing layer 6. The design print layer 3 is partially formed on one surface of the label substrate 2 by a plurality of print layers having different color pigments so as to have a desired design. The print layer (X) 4 is provided on the one surface (the surface on which the design print layer 3 is provided) of the label substrate 2 so as to come into contact with the label substrate 2 and the design print layer 3. The printed layer (Y) 5 is in contact with the printed layer (X) 4 on the one surface (the surface on which the design printed layer 3 and the printed layer (X) 4 are provided) of the label substrate 2. It is provided so as to overlap the printing layer (X) 4 in the surface spreading direction. Since the print layer (Y) 5 covers the entire surface of the print layer (X) even after heat shrinkage, the main shrinkage direction end of the print layer (Y) 5 is the main shrinkage of the print layer (X) 4. You may provide so that it may become an outer side (for example, about 1 mm outer side) rather than a direction edge part. The protective printing layer 6 has a printing layer (Y) 5 on the one surface (the surface on which the design printing layer 3, the printing layer (X) 4, and the printing layer (Y) 5 are provided) of the label substrate 2. So as to overlap with the printed layer (Y) 5 in the surface spreading direction. The protective printing layer 6 is provided so as to cover the entire surface of the printing layer (Y) 5. And since the protective printing layer 6 is made into the form which covers the whole surface of a design printing layer, a printing layer (X), and a printing layer (Y) even after heat shrink, the main shrinkage direction edge part of the protective printing layer 6 has the form. You may be provided so that the label base material 2 may be contacted. In addition, in the shrink label 1 of this invention, the design printing layer 3 in which the protective printing layer 6 exists inside, the design printing layer 3 in which the printing layer (X) 4 exists inside, and the printing layer (Y) inside Design printing layer 3 in which 5 is present. The design printing layer 3 having the protective printing layer 6 on the inner side has a design that does not have a metallic luster when the label is visually recognized because there is no printing layer containing an aluminum pigment on the background (opposite side of the label base material). . On the other hand, the design printing layer 3 in which the printing layer (X) 4 is present on the inner side has a metallic gloss when the label is visually recognized by being a transparent colored printing layer. Moreover, the design printing layer 3 in which the printing layer (Y) 5 exists inside is a transparent colored printing layer, and when a printing layer containing an aluminum pigment is used as the printing layer (Y) 5, the label is visually recognized. Sometimes it has a metallic luster design. In addition, when the design printing layer 3 contains a lubricant, the design printing layer 3 also functions as a protective printing layer, and thus it is not necessary to provide a protective printing layer in the inner region where the design printing layer 3 exists. .

  The shrink label of the present invention is, for example, a cylindrical shrink label of a type in which both ends of the label are sealed with a solvent or an adhesive and attached to the container, and one end of the label is attached to the container, and the label is wound After that, it can be used as a wrapping type shrink label in which the other end is overlapped with one end to form a cylinder. The shrink label of the present invention is particularly preferably used for the tubular shrink label because it is considered that one end of the tubular label contacts the inside of the other end during heat shrinkage. . That is, the shrink label of the present invention is preferably used for a cylindrical shrink label. Hereinafter, the cylindrical shrink label using the shrink label of the present invention may be referred to as “the cylindrical shrink label of the present invention”.

  An example of the cylindrical shrink label which is a preferable embodiment of the shrink label of the present invention will be described with reference to FIGS. The cylindrical shrink label 7 according to the present invention shown in FIG. 2 is formed in a rectangular shape and includes the label substrate, the print layer (X), and the print layer (Y). A cylindrical body in which a seal portion 8 is formed by superposing the other end portion on the outside of one end portion to form a cylinder, and joining the inner surface of the other end portion and the outer surface of the one end portion with a solvent or an adhesive. The tubular shrink label 7 is formed into a tubular shape so that the main shrink direction of the heat-shrinkable film is the circumferential direction D of the tubular shrink label, and is heat shrinkable in that direction.

  FIG. 3 is an example of a cross-sectional view taken along the line III-III ′ in FIG. In FIG. 3, at the seal portion 8, both ends of the shrink label are joined with a solvent or an adhesive 9. Specifically, the shrink label of the present invention has a design printing layer in a region excluding a region having a predetermined width from the end 11 of the other end of one surface (the inner surface of the cylindrical body) of the label substrate 2. 3 is formed, and a printing layer (X) 4 is formed in substantially the entire region excluding the region of a predetermined width from the end 11 at the other end of one surface of the label base 2, and the printing layer (X) 4 On the surface (the surface opposite to the label base material 2), the printing layer (X) over substantially the entire area excluding the predetermined width area from the end 11 at the other end of one surface of the label base material 2. The printing layer (Y) 5 is formed so as to overlap with the surface spreading direction 4 and both ends on one end side and the other end side are outside the both ends of the printing layer (X) 4. The print layer (Y) 5 may be any of a print layer containing an aluminum pigment, a colorless and transparent print layer, and a white print layer. And the abbreviation of the area | region except the area | region of predetermined width from the edge 11 of the other end part of one side of the label base material 2 on the surface (surface on the opposite side to the label base material 2) of the printing layer (Y) 5 A protective printing layer 6 is formed over the entire area so as to cover the printing layer (X) 4 and the printing layer (Y) 5. The protective printing layer 6 is provided so that both ends on one end side and the other end side substantially coincide with both ends of the printing layer (Y) 5.

  FIG. 4 is another example of a cross-sectional view taken along the line III-III ′ in FIG. The cylindrical shrink label 7 of the present invention shown in FIG. 4 is different from that shown in FIG. 3 in that the printing layer (Y) 5 is formed on a part of the surface of the printing layer (X) 4 and the printing layer (X). 4 is formed so as to overlap with the surface spreading direction. In FIG. 4, the print layer (Y) 5 is formed in a peripheral region on the print layer (X) 4 where the end 10 at one end contacts the inside of the other end during heat shrinkage. When the printing layer (Y) 5 is partially provided on the printing layer (X) 4 as shown in FIG. 4, the printing layer (Y) 5 is a printing layer containing an aluminum pigment or colorless and transparent from the viewpoint of decorativeness. It is preferable that it is a printing layer. When the printing layer (Y) 5 is a printing layer containing an aluminum pigment, the printing layer (Y) 5 has a halftone dot in the vicinity of the contact portion of 80 to 100%, and a halftone dot in the peripheral area is the contact portion. It is preferable that the gradation decreases to 50% or less as the distance from the vicinity increases. By adopting such a halftone dot configuration, ink cracking of the printing layer (X) is less likely to occur, and it is economically advantageous by minimizing the printing layer (Y) formation region, and the shrink label Since the thickness can be reduced, the followability to the adherend is excellent, and the boundary between the area where the printing layer (Y) is provided and the area where the printing layer (Y) is not provided is made inconspicuous by the gradation, and the decorativeness is excellent.

  Although the width | variety of the said seal | sticker part 8 is not specifically limited, For example, it is 0.2-10 mm.

  In addition, in the cylindrical shrink label 7 of this invention in FIG.3 and FIG.4, one end part has extended to the position where the end 10 overlaps with the protective printing layer 6 of the other end part, A region where the protective printing layers 6 overlap each other is formed. For this reason, there is no region in which no printed layer exists in the thickness direction. The cylindrical shrink label of the present invention may have a structure in which the end 10 at one end and the protective printing layer 6 on the other end side overlap as shown in FIGS. 3 and 4, or the end 10 at one end. Extends to a region overlapping the label substrate exposed surface at the other end, and does not extend to a position where the end 10 at one end overlaps the protective printing layer 6 at the other end. The protective printing layer 6 may have a structure that does not overlap.

[Manufacturing method and processing method of shrink label of the present invention]
The manufacturing method of the shrink label of this invention is a process (printing layer (X) formation process) of forming a printing layer (X) in at least one surface of a label base material, and the said at least one surface of a label base material. It includes at least a step of forming the print layer (Y) (print layer (Y) formation step). Moreover, the said manufacturing method may include other processes (design printing layer formation process, protective printing layer formation process, etc.).

(Design printing layer formation process)
When the design print layer forming step is included, it is preferable to perform the design print layer forming step before the print layer (X) forming step. In the design print layer forming step, the design print layer is formed by applying a printing ink for forming the design print layer on at least one surface of the label base material and solidifying it by drying or curing. As a method for applying the printing ink, known and usual methods can be used, and among them, gravure printing, flexographic printing, and digital printing are preferable. In the design printing layer forming step, generally, the printing ink is applied a plurality of times for each color, and a design printing layer that is a multilayer is formed.

  When the design printing layer is the above solvent-drying type printing layer, for example, the printing ink produced by mixing the binder resin, the solvent, and, if necessary, the coloring pigment and other additives, After application using, the solvent is volatilized and provided. On the other hand, when the design printing layer is the active energy ray-curable printing layer, for example, the monomer component constituting the binder resin, and if necessary, the coloring pigment, the solvent, and other additives are mixed. After applying the printing ink produced by using a printing machine, it is dried as necessary, and the monomer component is polymerized and cured by irradiation with active energy rays (for example, ultraviolet rays).

  The solvent-drying type printing ink is produced, for example, by mixing a binder resin, a color pigment, a solvent, and other additives as necessary. Mixing can be performed by a known and common mixing method, and is not particularly limited. For example, a mixer such as a paint shaker, butterfly mixer, planetary mixer, pony mixer, dissolver, tank mixer, homomixer, homodisper, or roll mill A mixing device such as a mill such as a sand mill, a ball mill, a bead mill, or a line mill, or a kneader is used. The mixing time (retention time) during mixing is not particularly limited, but is preferably 10 to 120 minutes. The obtained printing ink may be used after being filtered, if necessary. Each of the above components (binder resin, color pigment, solvent, and other additives) may be used alone or in combination of two or more.

  As said solvent, the water normally used for the printing ink used for gravure printing, flexographic printing, etc., an organic solvent, etc. can be used. Examples of the organic solvent include esters such as acetate (eg, ethyl acetate, propyl acetate, butyl acetate); alcohols such as methanol, ethanol, isopropyl alcohol, propanol, and butanol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as xylene, aliphatic hydrocarbons such as hexane and octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, glycols such as ethylene glycol and propylene glycol, ethylene glycol monopropyl ether and propylene glycol monomethyl ether Glycol ethers such as propylene glycol monobutyl ether; glycol ether esters such as propylene glycol monomethyl ether acetate . The solvent can be removed by drying after applying the printing ink to the label substrate. The solvent includes the meaning of “dispersion medium”.

(Printing layer (X) formation process)
In the printing layer (X) forming step, when the design printing layer is formed on at least one surface of the label substrate, the printing layer (X) is removed except for the surface on which the design printing layer is formed. The composition to be formed (printing ink or the like) is applied and solidified by drying or the like to form the printed layer (X). When the design print layer is a transparent colored print layer, the print layer (X) is formed so as to cover the design print layer on the surface on which the design print layer is usually formed, but the design print layer is formed. The printed layer (X) may be partially formed except on the surface.

  The printing ink is produced, for example, by mixing a urethane resin, an aluminum pigment, a solvent, and other additives. Mixing can be performed by a well-known and commonly used mixing method, and examples thereof include those exemplified as a mixing apparatus used for producing printing ink for forming the above-described design printing layer. The mixing time (retention time) during mixing is not particularly limited, but is preferably 10 to 120 minutes. The obtained printing ink may be used after being filtered, if necessary. Moreover, what was illustrated as said solvent as a solvent contained in the printing ink for forming the above-mentioned design printing layer is mentioned. Each of the above components (urethane resin, aluminum pigment, solvent, and other additives) may be used alone or in combination of two or more.

(Printing layer (Y) formation process)
In the printing layer (Y) forming step, the printing layer (Y) is formed such that at least a part of the label base material overlaps with the printing layer (X) in the surface spreading direction on the surface of the label base material on which the printing layer (X) is formed. A printing layer (Y) is formed by applying a composition (printing ink or the like) that forms a solid and solidifying by drying or the like.

  The printing ink is produced, for example, by mixing an acrylic resin, a solvent, and other additives. Mixing can be performed by a well-known and commonly used mixing method, and examples thereof include those exemplified as a mixing apparatus used for producing printing ink for forming the above-described design printing layer. The mixing time (retention time) during mixing is not particularly limited, but is preferably 10 to 120 minutes. The obtained printing ink may be used after being filtered, if necessary. Moreover, what was illustrated as said solvent as a solvent contained in the printing ink for forming the above-mentioned design printing layer is mentioned. Each of the above components (acrylic resin, solvent, and other additives) may be used alone or in combination of two or more.

(Protective printing layer formation process)
When the protective printing layer forming step is included, the protective printing layer forming step is preferably performed after the printing layer (Y) forming step. In the protective printing layer forming step, the protective printing is performed so as to cover, for example, the printing layer (X) and the printing layer (Y) on the surface of the label base material on which the printing layer (X) and the printing layer (Y) are formed. A protective printing layer is formed by applying a composition for forming the layer (printing ink or the like) and solidifying it by drying or the like.

  The printing ink is produced, for example, by mixing a binder resin, a lubricant, a solvent, and other additives. Mixing can be performed by a well-known and commonly used mixing method, and examples thereof include those exemplified as a mixing apparatus used for producing printing ink for forming the above-described design printing layer. The mixing time (retention time) during mixing is not particularly limited, but is preferably 10 to 120 minutes. The obtained printing ink may be used after being filtered, if necessary. Moreover, what was illustrated as said solvent as a solvent contained in the printing ink for forming the above-mentioned design printing layer is mentioned. Each of the above components (binder resin, lubricant, solvent, and other additives) may be used alone or in combination of two or more.

  In order to control the content ratio of the binder resin and other components in each of the above layers, the content ratio of each component such as the binder resin and other components in the non-volatile component of the printing ink forming each layer, What is necessary is just to prepare printing ink so that it may become a desired content rate in each said layer. In general, the content (% by mass) of each component (non-volatile component) in all the non-volatile components of the printing ink is equal to the content (% by mass) of each component in each layer.

  As described above, the shrink label of the present invention can be produced.

(Manufacturing method of cylindrical shrink label)
Although the manufacturing method of the cylindrical shrink label of this invention is not specifically limited, For example, it is as follows. The long shrink label of the present invention is slit to a predetermined width to obtain a long label body in which a plurality of the shrink labels of the present invention are continuous in the long direction (longitudinal direction). This long label is stacked in a cylindrical shape so that the heat shrinkable direction (that is, the heat shrink direction of the heat shrinkable film) is the circumferential direction and the other end is outside the one end. Then, the overlapped portion is sealed in a band shape with a predetermined width, and both ends are joined to each other to obtain a long cylindrical label continuous body (long cylindrical shrink label). By cutting the long cylindrical shrink label in the circumferential direction, one cylindrical shrink label (the cylindrical shrink label of the present invention) having a predetermined length in the height direction can be obtained. In the case of providing a perforation for label excision, a conventional method (for example, a method of pressing a disk-shaped blade having a cut portion and a non-cut portion repeatedly formed around it, a method using a laser, etc.) Can be applied. The process of perforating can be appropriately selected after providing each layer such as the print layer (X) and the print layer (Y), and before and after the step of processing into a cylindrical shape.

[Container with label]
Although the shrink label of this invention is not specifically limited, It mounts | wears with a container and is used as a labeled container. In addition, the shrink label of this invention may be used for adherends other than a container. For example, the shrink label of the present invention (particularly, the cylindrical shrink label) is placed (externally fitted) around the container so that the shrink label of the present invention is in a cylindrical shape, and is thermally contracted by heat treatment. By mounting, a labeled container (a labeled container having the shrink label of the present invention) is obtained. Examples of the containers include soft drink bottles such as PET bottles, milk bottles for home delivery, food containers such as seasonings, bottles for alcoholic beverages, pharmaceutical containers, containers for chemical products such as detergents and sprays, and toiletries. Containers, cup noodle containers and the like are included. Although it does not specifically limit as a shape of the said container, For example, various shapes, such as bottle types, such as cylindrical shape and a square shape, and a cup type, are mentioned. The material of the container is not particularly limited, and examples thereof include plastics such as PET, glass, and metals. In addition, the container equipped with the shrink label of the present invention may be referred to as “the labeled container of the present invention”.

  The labeled container can be produced, for example, by externally fitting a cylindrical shrink label to a predetermined container, and then thermally shrinking the cylindrical shrink label by heat treatment so as to follow and closely adhere to the container (shrink processing). Examples of the heat treatment method include a method of passing through a hot air tunnel or a steam tunnel, a method of heating with radiant heat such as infrared rays, and the like. In particular, a method of treating with steam at 80 to 100 ° C. (passing through a heating tunnel filled with steam and steam) is preferable. Moreover, 101-140 degreeC dry steam can also be used. Although the said heat processing is not specifically limited, It is preferable to implement in the temperature range from which the temperature of a heat-shrinkable film will be 85-100 degreeC (especially 90-97 degreeC). Moreover, the processing time of heat processing has preferable 4 to 20 second from a viewpoint of productivity and economical efficiency.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, in Table 1, the structure and evaluation result of the shrink label produced by the Example and the comparative example were shown.

Example 1
(Silver ink production example 1)
15 parts by mass of a vapor-deposited aluminum pigment mixed solvent (mixed solvent of ethyl acetate and isopropyl acetate) (BASF Corporation, trade name “Metacene 71-0010”, nonvolatile content: 10% by mass) 5 parts by mass), ethyl acetate solution of urethane resin (manufactured by Nippon Kako Paint Co., Ltd., trade name “FS-8009-1”, nonvolatile content: 37% by mass), 7 parts by mass (2.6% as urethane resin) Parts by weight), tributyl acetyl citrate (manufactured by Asahi Kasei Finechem Co., Ltd., trade name “ATBC”, nonvolatile content: 100% by mass), and CAB resin (manufactured by Eastman Chemical Co., trade name “CAB-381- 20 ", non-volatile content: 100% by mass) To 1.5 parts by mass, 40.1 parts by mass of ethyl acetate and 40 parts by mass of n-propyl acetate were added. A printing ink containing a material (silver ink (X1)) was prepared. In addition, the content ratio of the vapor deposition aluminum pigment in the total nonvolatile content (100 mass%) of the silver ink (X1) is 19.7 mass%, the content ratio of the urethane resin is 34.2 mass%, and a plasticizer (ATBC). ) Was 26.3% by mass, and the cellulose resin was 19.7% by mass. In addition, the content rate of each component in the non volatile matter of the said silver ink (X1) is equal to the content rate of each component in the printing layer formed with the said silver ink (X1).

(Shrink label)
As a heat-shrinkable film, trade name “HST” (manufactured by Gunze Co., Ltd., corresponding to heat-shrinkable film (A), thickness: 40 μm) is coated with the silver ink (X1) obtained above on a table gravure printing. Using the machine (Nissho Gravure Co., Ltd., trade name “GRAVO PROOF MINI”) and gravure plate (sculpture 70 lines, angle 0), coating, drying and solidifying by full gravure printing, near the part that becomes the seal part A silver print layer (sometimes referred to as “silver print layer (X1)”) was formed on the entire surface other than the above. Next, a silver ink (Y1) (trade name “Etona” manufactured by Sakata Inx Co., Ltd.) containing a non-leafing aluminum pigment and having an acrylic resin as a main resin component is placed on the surface of the silver print layer (X1). Using the same table-top gravure printing machine and gravure printing plate as described above, coating, drying and solidification are performed by full-surface gravure printing, and a silver-colored printing layer (referred to as a “silver-colored printing layer (Y1)”) is formed on the entire surface except the vicinity of the seal portion. Formed). Next, a gravure ink for back printing (manufactured by DIC Corporation, trade name “Fine Wrap GR Back Pressing Varnish”) is used on the surface of the silver printing layer (Y1) using the same tabletop gravure printing machine and gravure plate as above. Then, coating and drying were performed by full-surface gravure printing, and a protective printing layer was formed on the entire surface other than the vicinity of the portion to be the seal portion. In this manner, a shrink label having a configuration of [label base material (40 μm) / silver printing layer (X1) / silver printing layer (Y1) / protective printing layer] was produced.

Example 2
Instead of the silver print layer (Y1), an acrylic resin solution is used, and the same desktop gravure printing machine and gravure plate as described above are used to form a transparent print layer (sometimes referred to as “transparent print layer (Y2)”). A shrink label having a configuration of [label base material (40 μm) / silver printing layer (X1) / transparent printing layer (Y2) / protective printing layer] was produced in the same manner as in Example 1 except that the above was formed.

Example 3
In place of the silver print layer (X1), the same tabletop gravure printing as described above using an ink mainly composed of urethane resin containing aluminum particles (manufactured by DIC Corporation, product name “Fine Wrap DH17 Silver”) [Label substrate (40 μm) / silver print layer (in the same manner as in Example 1) except that a silver print layer (sometimes referred to as “silver print layer (X2)”) was formed using a press and a gravure plate. X2) / silver printing layer (Y1) / protective printing layer] was produced.

Comparative Example 1
(Shrink label)
As a heat-shrinkable film, the trade name “HST” (Gungze Co., Ltd., corresponding to heat-shrinkable film (A), thickness: 40 μm) is coated with the silver ink (X1) obtained above on a table gravure printing machine. (Product name “GRAVO PROOF MINI” manufactured by Nissho Gravure Co., Ltd.) and gravure plate (sculpture 70 lines, angle 0), other than the vicinity of the part that becomes a seal part by coating, drying and solidifying by full gravure printing A silver print layer (X1) was formed on the entire surface. Next, a gravure ink for back printing (manufactured by DIC Corporation, trade name “GR back press varnish”) was applied and dried by full gravure printing using the same table gravure printing machine and gravure plate as above, A protective printing layer was formed on the entire surface other than the vicinity of the seal portion. Thus, the shrink label which consists of a structure of [a label base material (40 micrometers) / silver printing layer (X1) / protective printing layer] was produced.

Comparative Example 2
In place of the silver printing layer (Y1), the same table-top gravure printing as described above using silver ink (product name “NT-Hyramic” manufactured by Dainichi Seika Kogyo Co., Ltd.) having urethane resin as the main resin component. [Label substrate (40 μm) / silver print layer (in the same manner as in Example 1) except that a silver print layer (sometimes referred to as “silver print layer (Z1)”) was formed using a press and a gravure plate. X1) / silver printed layer (Z1) / protective printed layer] to produce a shrink label.

Comparative Example 3
In place of the silver printing layer (Y1), the same table-top gravure printing as described above using silver ink (product name “NT-Hyramic” manufactured by Dainichi Seika Kogyo Co., Ltd.) having urethane resin as the main resin component. [Label substrate (40 μm) / Silver printing layer (X2) / Silver printing layer (Z1) / Protective printing] Except that the silver printing layer (Z1) was formed using a press and a gravure plate Shrink label having the structure of [Layer] was produced.

(Evaluation)
The following evaluation was performed about the shrink label obtained by the Example and the comparative example. The evaluation results are shown in Table 1.

(1) Ink crack test (hot water immersion shrinkage test)
For measurement of 210 mm (main shrinkage direction; width direction of heat-shrinkable film) × 110 mm (perpendicular to main shrinkage direction: longitudinal direction of heat-shrinkable film) from the shrink labels obtained in Examples and Comparative Examples A sample was taken. The measurement sample is further aligned with the end of one end so that the main shrinkage direction of the measurement sample (the main shrinkage direction of the heat-shrinkable film) is the circumferential direction and the surface on which the protective printing layer is provided is the inner side. One end and the other end are overlapped to form a cylinder so that the protective printing layer on the end side overlaps, and the label base material on the one end and the other end is made of THF, and the width of the seal portion. Was 3 mm to obtain a cylindrical shrink label (peripheral length: 200 mm).
A cylindrical glass bottle having a diameter of 62 mm (circumferential length of 194 mm) and a height of 108 mm was prepared. Furthermore, a strip of the same heat-shrinkable film as used in Examples and Comparative Examples of 10 mm (main shrinkage direction) × 110 mm (direction perpendicular to the main shrinkage direction) was prepared.
Alignment so that the width direction (main shrinkage direction) of the strip is the circumferential direction of the cylindrical glass bottle, and the upper and lower ends of the strip and the upper and lower ends of the cylindrical glass bottle were fixed with cellophane adhesive tape (upper and lower ends) The strip and the cylindrical glass bottle are not bonded at the center of the strip, except for). Next, the cylindrical shrink label is put on the cylindrical glass bottle (with a strip) so that the protective printing layer contacts the strip, and immersed in hot water at 90 ° C. for 20 seconds to heat the shrink label. Shrinkage (the strip also thermally shrinks in the width direction at this time) to obtain a labeled container.
Observe the appearance (outside) of the label of the obtained container with the label, peel off the label, observe the silver print layer inside the label, and crack the ink along the strip (streaks in the height direction of the container). It was visually observed whether ink peeling occurred. Evaluation was made according to the following criteria.
Good (◎): No ink cracks can be confirmed from the outside or from the inner side where the label is peeled off. Available (○): Ink cracks cannot be confirmed from the outside, but when the label is peeled off, ink is printed inside the label. Cracks can be confirmed Defect (×): Ink cracks can be confirmed from the outside

(2) Luminance sensation A label piece having a size of 12 cm (longitudinal direction; a direction perpendicular to the main contraction direction) × 12 cm (width direction; main main contraction direction) is obtained from the shrink labels obtained in the examples and comparative examples. Cut out. Both ends of the label piece in the main contraction direction (width direction) [100 mm intervals excluding portions chucked by the jig (each 10 mm at both ends)] were fixed to a jig that can be fixed at an interval of 80 mm (thermal contraction). It is in a slack state before processing). The label pieces fixed at both ends to the jig were immersed in 90 ° C. warm water for 20 seconds and heat-treated, and the label pieces were heat-shrinked to a length of 80% compared to before the heat-shrinking treatment ( 20% thermal shrinkage in the main shrinkage direction (width direction)). In this way, a measurement sample was obtained that was thermally contracted by 20% in the main contraction direction (width direction).
Using the gloss measuring device “UGV-5” manufactured by Suga Test Instruments Co., Ltd., in accordance with JIS K 5600-4-7, the conditions of the incident angle of 60 ° and the reflection angle of 60 ° were measured. The specular glossiness of the surface of the silver print layer portion was measured. The surface on the heat-shrinkable film side was measured as a measurement surface. And based on the obtained specular glossiness, the brightness | luminance feeling was evaluated on the following references | standards.
Specular gloss is 160 or more: Good specular gloss (○)
Specular gloss of 120 or more and less than 160: Usable specular gloss (△)
Specular gloss is less than 120: Specular gloss is insufficient (×)
Good (◎): Specular gloss is 160 or more Usable (○): Specular gloss is 120 or more and less than 160 Poor (x): Specular gloss is less than 120

  As can be seen from Table 1, the shrink labels (Examples 1 to 3) of the present invention were excellent in brightness even after heat shrinkage, and no ink cracking occurred in the silver print layer after heat shrinkage. On the other hand, when the printing layer (Y) is not provided (Comparative Example 1) or when a layer that does not contain an acrylic resin as a main component is used instead of the printing layer (Y) (Comparative Examples 2 and 3). During the heat shrinkage, ink cracks occurred in the silver print layer.

DESCRIPTION OF SYMBOLS 1 Shrink label of this invention 2 Label base material 3 Design printing layer 4 Printing layer (X)
5 Print layer (Y)
6 protective printing layer 7 cylindrical shrink label of the present invention 8 seal part D circumferential direction 9 solvent or adhesive 10 end of one end 11 end of the other end

Claims (7)

A label substrate containing a heat-shrinkable film;
A printing layer (X) containing a urethane-based resin and an aluminum pigment provided on at least one surface of the label substrate;
An acrylic resin as a main resin component provided on the surface of the label base material on which the printing layer (X) is provided so that at least a part thereof overlaps with the printing layer (X) in the surface spreading direction. And a printed layer (Y) having a lubricant content of 0.7% by mass or less.   The shrink label according to claim 1, wherein the printed layer (Y) is provided so as to be at least partially in contact with the printed layer (X).   The shrink label of Claim 1 or 2 whose layer of the surface by which the said printing layer (X) is provided of the said heat-shrinkable film is a layer which has a polyester-type resin as a main component.   The shrink label according to any one of claims 1 to 3, wherein the aluminum pigment is a vapor-deposited aluminum pigment and / or a leafing type aluminum pigment.   The shrink label of any one of Claims 1-4 in which the said printing layer (Y) contains an aluminum pigment.   The shrink label of any one of Claims 1-5 in which the said printing layer (X) contains a plasticizer.   As a printing layer other than the printing layer (X) and the printing layer (Y), a protective printing layer provided so as to cover the printing layer (X) and the printing layer (Y) is provided, and the protective printing layer Is a layer containing an acrylic resin as a main resin component and having a lubricant content ratio of more than 0.7% by mass with respect to the total mass of the protective printing layer. Shrink label.

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