JP7092473B2 - Shrink label - Google Patents

Description

The present invention relates to shrink labels.

Currently, plastic bottles such as PET bottles and metal bottles such as bottle cans are widely used as beverage containers for tea and soft drinks. Plastic labels are often attached to these containers for display, decorativeness, and functionality. As such a plastic label, for example, a heat-shrinkable label having a print layer provided on a shrink film (heat-shrinkable film) has merits such as decorativeness, processability (followability to a container), and a wide display area. (Shrink label) etc. are widely used.

Among the above plastic labels, for example, there is a plastic label having a metallic luster by providing a printing layer containing a metal pigment. As an ink for forming a printing layer containing such a metal pigment, a printing ink containing an aluminum pigment obtained by a wet ball mill method is known. Further in recent years, as a printing ink for forming a printing layer having a particularly high-brightness metallic luster and exhibiting a feeling of brightness, an aluminum flake pigment obtained by a so-called vapor deposition method in which a vapor-deposited metal film is crushed to produce flakes. High-brightness printing inks containing (sometimes referred to as "vapor-deposited aluminum pigments") are known (see, for example, Patent Documents 1 to 3).

JP-A-2007-224243 Japanese Patent Application Laid-Open No. 2003-96334 Japanese Unexamined Patent Publication No. 2002-20668

However, even if the shrink label having a metallic luster has an excellent brightness feeling of the print layer in the state before the heat shrinkage, the brightness feeling may decrease after the heat shrinkage. Further, when a shrink label having a print layer containing a metal pigment is shrink-processed in the form of a tubular label, that is, when it is heat-shrinked, cracks (ink cracks) may occur in the print layer. Ink cracking during shrink processing in a shrink label having a printing layer containing a metal pigment inside the label base material in the form of a tubular label means that the inner surface of the label is a container when heat is applied such as during shrink processing. It is considered that this is caused by contacting the label, or by contacting the inside of the other end portion of the one end portion in the tubular form in which the other end portion is overlapped with the one end portion of the label.

The present invention has been conceived under such circumstances, and an object of the present invention is to have an excellent brightness feeling of a print layer containing a metal pigment even after heat shrinkage, and the metal pigment at the time of heat shrinkage. It is an object of the present invention to provide a shrink label in which ink cracking is less likely to occur in a printing layer containing the above.

As a result of diligent studies to achieve the above object, the present inventors have provided a printing layer containing a urethane resin and an aluminum pigment on at least one surface of a label base material containing a heat-shrinkable film, and further printed the same. 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 having excellent brightness and less likely to cause ink cracking during heat shrinkage can be obtained. The present invention has been completed based on these findings.

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

It is preferable that the print layer (Y) is provided so as to be in contact with at least a part of the print layer (X).

The surface layer of the heat-shrinkable film on the side where the print layer (X) is provided is preferably a layer containing a polyester resin as a main component.

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

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

The printed layer (X) preferably contains a plasticizer.

The shrink label has a protective print layer provided so as 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). You may have. The protective printing layer preferably contains an acrylic resin as a main resin component and has a lubricant content of more 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 structure, the print layer containing the metal pigment has an excellent brightness even after heat shrinkage, and the print layer containing the metal pigment is less likely to crack during heat shrinkage. Therefore, the label after the shrink label of the present invention is attached to the adherend has an excellent luminance feeling and is less likely to cause ink cracking, and thus has excellent decorativeness.

It is a schematic diagram (partial sectional view) which shows one Embodiment of the shrink label of this invention. It is a schematic diagram which shows an example of the cylindrical shrink label which is one Embodiment of the shrink label of this invention. It is a schematic diagram which shows an example of the cylindrical shrink label which is one Embodiment of the shrink label of this invention (the main part enlarged view of the cross section III-III' of FIG. 2). It is a schematic diagram which shows another example of the cylindrical shrink label which is one Embodiment of the shrink label of this invention (the main part enlarged view of the cross section III-III' of FIG. 2).

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, and an acrylic resin as a main resin component, and the content ratio of a lubricant is 0. It has a print layer of 7.7% by mass or less. In the present specification, the print layer containing the urethane resin and the aluminum pigment may be referred to as "print layer (X)". Further, a printed 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 a "printing layer (Y)".

[Label base material]
The label base material in the shrink label of the present invention serves as a support for the printed layer (X) and the printed layer (Y), and mainly affects the strength, rigidity and shrinkage characteristics of the label.

The label substrate contains at least a heat-shrinkable film (shrink film). The heat-shrinkable film is not particularly limited, but a heat-shrinkable film used as a label base material for a known or commonly used shrink label can be used. The type of resin forming the heat-shrinkable film can be appropriately selected depending on the required physical properties, applications, costs, etc., and is not particularly limited, but for example, a polyester resin or a polyolefin resin (for example, (Polyethylene resin, polypropylene resin, etc.), polystyrene resin, polyvinyl chloride resin, polyamide resin, acrylic resin, etc. may be mentioned. Only one kind of these resins may be used, or two or more kinds thereof may be used. Further, the same kind or different kinds of resins may be laminated and used as a laminated film. Of these, polyester-based resins, polyolefin-based resins, and polystyrene-based resins are preferable. For example, the heat-shrinkable film includes a polyester-based film made of a polyester-based resin, a polyolefin-based film made of a polyolefin-based resin, a polystyrene-based film made of a polystyrene-based resin, and a polyester-based resin as an outer layer, and a polyolefin-based resin or a polystyrene-based film. Examples thereof include a heterogeneous laminated film having a resin as an inner layer. Examples of the polyester-based resin, polyolefin-based resin, and polystyrene-based resin are described in JP-A-2008-170822, JP-A-2008-170697, JP-A-2008-163215, and JP-A-2008-163231. The polyester-based resin, polyolefin-based resin, polystyrene-based resin and the like described above can be used.

Examples of the polyester-based resin include polyethylene terephthalate (PET) -based resin, poly (ethylene-2,6-naphthalenedicarboxylate) (PEN), polylactic acid (PLA) and the like. Of these, PET-based resins are preferable. As the PET-based resin, polyethylene terephthalate (PET) using terephthalic acid as a dicarboxylic acid component and ethylene glycol as a diol component; terephthalic acid as a dicarboxylic acid component and ethylene glycol as a main component (diol component). Among them, the component with the highest mass ratio), a copolymerized polyester (CHDM copolymerized PET) using 1,4-cyclohexanedimethanol (CHDM) as a copolymerization component, terephthalic acid as a dicarboxylic acid component, and ethylene as a diol component. Copolymerized polyester (NPG copolymerized PET) using glycol as the main component (the component with the highest mass ratio among the diol components), neopentyl glycol (NPG) as the copolymerization component, and terephthalic acid as the dicarboxylic acid component, diol A diol-modified PET such as a copolymerized polyester using ethylene glycol as a main component (the component having the highest mass ratio among diol components) and diethylene glycol as a copolymerization component; terephthalic acid as a main component (dicarboxylic acid) as a dicarboxylic acid component. Examples thereof include dicarboxylic acid-modified PET such as a copolymerized polyester using isophthalic acid and / or adipic acid as the copolymerization component and ethylene glycol as the diol component (the component having the highest mass ratio among the components). 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 constituent monomers of the polystyrene-based resin include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, p-isobutylstyrene, pt-butylstyrene, and chloromethylstyrene. Examples thereof include resins containing one or more styrene-based monomers such as. Specific examples thereof include general-purpose polystyrene (GPPS), styrene-butadiene copolymer (for example, SBS, etc.), styrene-butadiene-isoprene copolymer (SBIS), styrene-acrylic acid ester copolymer, and the like. ..

Further, the polystyrene-based resin may be a polystyrene-based resin (modified polystyrene-based resin) into which a polar group has been introduced or a soft polystyrene-based resin. Examples of the polar group in the modified polystyrene-based resin include an acid anhydride group, a carboxylic acid group, a carboxylic acid ester group, a carboxylated compound group, a carboxylic acid amide group, a carboxylic acid base, a sulfonic acid group, and a sulfonic acid ester. Examples thereof include a group, a sulfonated compound group, a sulfonic acid amide group, a sulfonic acid base, an isocyanate group, an epoxy group, an amino group, an imide group, an oxazoline group, and a hydroxyl group. Examples of the soft polystyrene-based resin include styrene-based elastomers, styrene-diene-based copolymers, HIPS (high-impact polystyrene) having a large amount of rubber component, and graft HIPS having a large amount of rubber component. The styrene-based elastomer may be a styrene-diene-based copolymer elastomer containing a diene component. The HIPS having a large amount of rubber component means a HIPS in which the content ratio of the rubber component exceeds 30% by mass with respect to the total mass (100% by mass) of HIPS. Further, the graft HIPS having a large amount of rubber component means a 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-catalyzed LLDPE (mLLDPE), and ethylene-vinyl acetate copolymer; polypropylene and propylene-α. -Polyethylene resin such as olefin copolymer; cyclic olefin resin and the like can be mentioned. In particular, the polyolefin-based film preferably has a cyclic olefin resin as an outer layer, and for example, a cyclic olefin resin as an outer layer and a polyethylene-based resin or a polypropylene-based resin as an inner layer (center layer) is preferable.

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 may be a laminated film in which a plurality of film layers are laminated depending on required physical characteristics, applications, and the like. Further, in the case of a laminated film, a film layer made of the same type of resin may be laminated, or a film layer made of different resins may be laminated. In the case of a laminated film, a laminated film containing a polyester resin as an outer layer and a polyolefin resin or a polystyrene resin as an inner layer, or a polystyrene resin as an outer layer and a polystyrene resin having a composition different from that of the polyolefin resin or the outer layer as an inner layer. A laminated film containing a laminated film or a cyclic olefin resin as an outer layer and a polyethylene-based resin or a polypropylene-based resin as an inner layer are preferable.

In the heat-shrinkable film, it is preferable that at least the surface layer on the side where the print layer (X) is provided is a layer containing a polyester resin as a main component. The main component of the layer constituting the heat-shrinkable film is the resin having the highest mass ratio among the resins constituting the layer. When the surface layer is a layer containing a polyester resin as a main component, the heat-shrinkable film is used when the printing ink for forming the printing layer (X) containing an aluminum pigment is applied to the label base material. Since it is difficult to dissolve in printing ink, it has excellent transparency and the like, and the shrink label of the present invention has excellent heat shrinkage. 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 of 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, still more preferably 90% by mass or more, based on the mass of the surface layer. Particularly preferably, it is 95% by mass or more.

The heat-shrinkable film particularly has a base layer portion and surface layers provided on both sides of the base layer portion, and each of the surface layers contains 50% by mass or more of a polyester resin. As the layer constituting the base layer portion, it is preferable that the film is 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 the above structure, the shrink label of the present invention has an appropriate shrinkage rate even when 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 thus is more excellent in brightness when visually recognizing the print layer (X) and the print 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)". Further, the layer containing 50% by mass or more of the polystyrene-based resin contained in the base layer portion may be referred to as "resin layer (A)". The base layer portion is a portion sandwiched between the surface layers in the heat-shrinkable film (A).

In the heat-shrinkable film (A), the base layer portion contains one or more layers, but preferably contains 3 to 65 layers (particularly 5 to 65 layers). In a configuration in which the base layer portion includes 3 to 65 layers (particularly 5 to 65 layers), it is excellent in appropriate shrinkage rate, rigidity, suppression of wrinkles and delamination after heat shrinkage, transparency, and a feeling of 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. It is preferably an adhesive resin layer. The adhesive resin layer is not particularly limited as long as it is an adhesive resin layer for imparting adhesiveness between the surface layer and the base layer portion, and is, for example, a resin layer containing a polystyrene resin and / or a polyester resin as an essential component. It is preferable to have. 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 can be mentioned.

Examples of the polyester resin in the surface layer include those mentioned above. As the polyester-based resin, an aromatic polyester-based resin is preferable. The aromatic polyester resin has 50 mol% or more (preferably 70 mol% or more) of the total dicarboxylic acid component and / or 50 mol% or more (preferably 70 mol% or more) of the total diol component. 70 mol% or more) is a polyester resin which is an aromatic diol. Further, an aromatic polyester resin which is a polymer, a copolymer, or a mixture thereof by a condensation reaction between a dicarboxylic acid containing an aromatic dicarboxylic acid and a diol containing an aliphatic diol is preferable. Further, among the above aromatic polyester-based resins, modified aromatic polyester-based resins containing a modifying component (copolymerization component) are preferable, and PET, CHDM copolymerized PET, and dicarboxylic acid using EG as a diol component are more preferable. A modified aromatic polyester resin (2,2-dialkyl-1,3-propanediol) using terephthalic acid as a component, ethylene glycol as a main component, and 2,2-dialkyl-1,3-propanediol as a copolymerization component. 3-Propanediol copolymerized PET) (particularly NPG copolymerized PET).

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

The styrene-diene-based copolymer is not particularly limited, but the content ratio of the constituent unit derived from diene is 5 to 50% by mass with respect to the total mass (100% by mass) of the styrene-diene-based copolymer. Is preferable, more preferably 10 to 40% by mass, still more preferably 10 to 30% by mass, and particularly preferably 10 to 25% by mass.

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

The analysis / measurement of the above-mentioned structural unit (the structural unit derived from the styrene-based monomer and the structural unit derived from the diene) and the content ratio of the above-mentioned structural unit is not particularly limited, but for example, nuclear magnetic resonance (NMR) and gas chromatograph. It can be performed by a tograph mass spectrometer (GCMS) or the like. It should be noted that the analysis / measurement of the structural unit and the content ratio of the structural unit in the other resin layer (adhesive resin layer, surface layer, etc.) and the resin can be performed in the same manner.

The adhesive resin layer is not particularly limited, but is, for example, a resin layer containing a mixed resin of a polystyrene-based resin and a polyester-based resin in the highest mass ratio; a soft polystyrene-based resin and a polystyrene-based resin contained in the resin layer (A). A resin layer containing at least one polystyrene-based resin selected from the group consisting of a flexible polystyrene-based resin (specific flexible polystyrene-based resin) and a modified polystyrene-based resin in the highest mass ratio; the soft polyester-based resin is the highest. 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 a polystyrene resin and a polyester resin in the highest mass ratio; a soft polystyrene resin, a specific flexible polystyrene resin, and a modified polystyrene resin. It is preferable that the resin layer contains the above-mentioned one or more kinds of polystyrene-based resins in the highest mass ratio. When the adhesive resin layer is a resin layer containing a mixed resin of a polystyrene resin and a polyester resin in the highest mass ratio, the polystyrene resin of the resin layer (A) is the polystyrene resin of the adhesive resin layer and the surface layer. The polyester-based resin of No. 1 can be bonded to the polyester-based resin of the adhesive resin layer, respectively, and the adhesiveness between the base layer portion and the surface layer is improved, which is preferable. The adhesive resin layer may correspond to the resin layer (A).

When the adhesive resin layer is a resin layer containing the mixed resin in the highest mass ratio, the polyester-based resin and the polystyrene-based resin are preferable embodiments of the polyester-based resin in the above-mentioned surface layer and the above-mentioned resin layer. 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-based resin and the polyester-based resin) is not particularly limited. From the viewpoint of improving the adhesiveness between the surface layer and the base layer portion and suppressing delamination, the content 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 by mass% or more, more preferably 70% by mass or more. The upper limit of the content ratio is not particularly limited, but may be 100% by mass.

Softness when the adhesive resin layer is a resin layer containing one or more polystyrene-based resins selected from the group consisting of soft polystyrene-based resins, specific flexible polystyrene-based resins, and modified polystyrene-based resins in the highest mass ratio. Examples of the polystyrene-based resin and the modified polystyrene-based resin include the soft polystyrene-based resin and the modified polystyrene-based resin exemplified and described as the polystyrene-based resin contained in the resin layer (A). The hydrogenated soft polystyrene-based resin contained in the above-mentioned soft polystyrene-based resin is not particularly limited, but is not particularly limited, but is a hydrogenated styrene-based elastomer, a hydrogenated styrene-diene-based copolymer (particularly, styrene having a large amount of hydrogenated diene component-). Diene-based copolymer) is preferable.

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 one direction and a direction different from 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 it is preferable that all the film layers are oriented in at least one direction. If 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 in a direction orthogonal to one direction (biaxially oriented film) is often used, and among them, 1 Axial alignment films (including films stretched primarily in one direction and slightly stretched in a direction orthogonal to that direction, substantially unidirectionally stretched) are commonly used.

The film oriented in at least one direction can be obtained by stretching the 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 the unstretched film in one direction, and when it is a biaxially oriented film, the unstretched film is unidirectionally and one. It is obtained by stretching in a direction orthogonal to the direction. The shrink label of the present invention can be heat-shrinked mainly in the orientation direction of the heat-shrinkable film.

The heat-shrinkable film can be produced by a conventional method such as melt film formation or solution film formation. It is also possible to use a commercially available heat-shrinkable film. When producing a heat-shrinkable film having a laminated structure, a conventional method such as a coextrusion method or a dry laminating method can be used as the laminating method. As a method of orienting the heat-shrinkable film, for example, the longitudinal direction (the direction of the film production line; also referred to as the longitudinal direction or the MD direction) and the width direction (the direction orthogonal to the longitudinal direction; also referred to as the transverse direction or the TD direction). Can be used for stretching in two directions, stretching in one direction in the longitudinal direction or the width direction, and the like. 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 treatment of a film stretched substantially in one direction in the width direction is carried out at a temperature of about 70 to 100 ° C., for example 1.01 to 1.5 times in the longitudinal direction, preferably 1. It can be carried out by stretching about 05 to 1.3 times and then stretching about 3 to 8 times, preferably about 4 to 7 times in the width direction.

The heat shrinkage rate (sometimes referred to as "heat shrinkage rate (90 ° C., 10 seconds)" at 90 ° C. for 10 seconds in the main shrinkage direction of the heat-shrinkable film 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) of the heat-shrinkable film in the direction orthogonal to the main shrinkage direction is not particularly limited, but is preferably -3 to 15%, more preferably -1 to 10%. .. The "main shrinkage direction" is the direction in which the heat shrinkage rate is the largest, and is generally the direction in which the film is mainly stretched. For example, a film stretched substantially in one direction in the width direction. In some cases, it is in the width direction.

As the heat-shrinkable film used as the label base material, a commercially available product can also be used. For example, "Space Clean S7042" and "SV-808" manufactured by Toyo Spinning Co., Ltd., "LX-10S", "LX-18S" and "LX-61S" manufactured by Mitsubishi Resin Co., Ltd. (all polyester films). "Bonset" manufactured by CI Kasei Co., Ltd., "GMLS" manufactured by Gunze Co., Ltd. (above, polystyrene film); "FL" manufactured by Gunze Co., Ltd. (polyester film); "Eco Rouge" manufactured by Mitsubishi Resin Co., Ltd. (Polylactic acid-based film); "DL" manufactured by Mitsubishi Chemical Co., Ltd., "HST" manufactured by Gunze Co., Ltd. (above, a laminated film in which the surface layer is a polyester resin and the center layer is a polystyrene resin) and the like can be mentioned. Further, the shrink film in the shrink label disclosed in Japanese Patent Application Laid-Open 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 slip layer, a heat insulating layer, a gas barrier layer, a light-shielding layer, and a metal or metal oxide vapor-deposited layer. Can be mentioned. Further, the surface of the heat-shrinkable film may be subjected to conventional surface treatments such as corona discharge treatment, primer treatment, and antistatic coating treatment, if necessary.

When the heat-shrinkable film is transparent, the haze value [JIS K 7136 compliant, thickness 40 μm conversion, unit:%] of the heat-shrinkable film is not particularly limited, but is preferably 10% or less. , More preferably 7% or less, still more preferably 5% or less. If the haze value exceeds 10%, print is applied to the inside of the label base material (the side that becomes the container side when the shrink label is attached to the container), and the shrink label (back printing) that shows printing through the label base material is printed. (Shrink label) In the application, when it is made into a product, printing may become cloudy and the decorativeness may be deteriorated. However, even when the haze value exceeds 10%, it may be opaque in applications other than the above-mentioned applications in which printing is shown through the label substrate (front printing shrink label), and it can be sufficiently used. The heat-shrinkable film on the opaque label substrate is not particularly limited, but for example, a milky white film, a metal-deposited film, or the like can be used.

The thickness of the heat-shrinkable film is not particularly limited, but is preferably 10 to 100 μm, more preferably 12 to 80 μm, and even more preferably 15 to 60 μm.

[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 substrate. Further, the print layer (X) may be provided on the entire surface of the surface of the label base material (the surface on the side where the print layer (X) is provided), or may be provided on a part of the surface. Further, the print layer (X) is not particularly limited, but may be a single layer or a plurality of layers. Further, the urethane resin and the aluminum pigment may be used alone or in combination of two or more.

The print layer (X) contains a urethane-based resin as a binder resin constituting the print layer (X). The binder resin plays a role as a main resin component forming the print layer (X), and forms a coating film when the printing ink forming the print layer (X) is coated. By including the urethane resin as the binder resin, the flexibility of the printed layer (X) is improved, and the followability of the printed layer (X) to the label substrate when the shrink label of the present invention is heat-shrinked is improved. Therefore, the brightness of the print layer (X) is remarkably excellent before and after heat shrinkage.

The urethane-based resin is not particularly limited, and a known or conventional urethane-based resin for a printing layer can be used. For example, a resin obtained by reacting a polyisocyanate compound with a polyol compound (that is, a polyisocyanate compound). And a copolymer of 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-phenylenediocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate and the like. Further, if necessary, trifunctional or higher functional polyisocyanates and polyisocyanate adducts can be mixed with the above diisocyanates and used.

Examples of the above-mentioned 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; polyetherdiols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and polytetramethylene glycol-polycaprolactone copolymer; propylene glycol, butanediol and hexanediol Polypolydiols obtained from diols such as adipic acid, sebacic acid, azelaic acid, isophthalic acid, terephthalic acid, fumaric acid and the like; polycaprolactone diols, polyvalerolactone diols, lactone block copolymerized diols and the like. Known diols such as lactone diol can be used. Further, if necessary, the above diols and a trifunctional or higher functional polyol compound (polyether polyol, polyester polyol, etc.) can be mixed and used.

The glass transition temperature (Tg) of the urethane resin is preferably −70 to 40 ° C., more preferably −60 to 30 ° C. from the viewpoint of flexibility. In the present specification, the glass transition temperature (Tg) of the resin can be measured by DSC (differential scanning calorimetry) in accordance with, for example, JIS K 7121. The DSC measurement is not particularly limited, but can be performed, for example, by using a differential scanning calorimeter "DSC6200" manufactured by Seiko Instruments Co., Ltd. at a heating rate of 10 ° C./min.

The mass average molecular weight (Mw) of the urethane resin is not particularly limited, but is preferably 10,000 to 100,000, more preferably 20,000 to 80,000, and even more preferably 30,000 to 70,000. In the present specification, the mass average molecular weight (Mw) is not particularly limited, but can be measured by, for example, GPC using polystyrene as a standard substance.

As the urethane-based resin, a commercially available product can also be used. For example, "Samplen IB series, LQ series" manufactured by Sanyo Chemical Industries, Ltd., "Uriano 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 the resin having the highest mass ratio among all the resins constituting the binder resin in the print layer (X). The content ratio of the urethane resin in the print layer (X) is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, based on the total mass of the print layer (X). When the content ratio is 10% by mass or more, the flexibility of the print layer (X) is further improved, and the feeling of 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 feeling of the print layer (X) can be further improved.

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

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

The aluminum pigment is preferably a vapor-deposited aluminum pigment. The vapor-deposited aluminum pigment is an aluminum flake produced by a vapor deposition method. The above-mentioned thin-film deposition method is a thin-film deposition metal in which aluminum is vapor-deposited on an appropriate support base material (film, etc.) to form a thin-film vapor film, which is then peeled off, crushed, and if necessary, classified into flakes. It is a method for producing a film fragment (deposited aluminum flake) (see, for example, Japanese Patent Application Laid-Open No. 2002-20668). According to the above-mentioned thin-film deposition method, aluminum flakes having a plate shape, a thinner thickness, and a higher aspect ratio can be obtained as compared with the case of manufacturing by a conventional ball mill method or the like. Therefore, in the print layer (X), the aluminum flakes are likely to be oriented in the direction parallel to the surface of the shrink label, the orientation is improved, and the incident light is likely to be specularly reflected. Therefore, the mirror glossiness of the print layer (X) is improved, and the excellent metallic luster is exhibited, so that the sense of brightness is further improved. As the vapor-filmed aluminum pigment, only one kind may be used, or two or more different kinds of thin-film vapor-deposited aluminum pigments may be mixed and used.

The D50 of the vapor-filmed aluminum pigment is not particularly limited, but is preferably 1 to 30 μm, more preferably 5 to 20 μm. When the D50 is 1 μm or more, the sense of brightness is improved, which is preferable. If the D50 exceeds 30 μm, blurring may occur when the printing ink is gravure-printed.

The thickness of the vapor-filmed aluminum pigment is not particularly limited, but is preferably less than 0.1 μm. The average thickness of the vapor-filmed aluminum pigment is not particularly limited, but is preferably 0.01 μm or more and less than 0.1 μm, and more preferably 0.01 to 0.07 μm. If the average thickness is less than 0.01 μm, the manufacturing efficiency may be industrially poor. 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 print layer (X) tends to be improved, and the sense of brightness tends to be further improved.

As the vapor-filmed aluminum pigment, a commercially available product can also be used. For example, "Metacine 71-0010" and "Metacine 41-0010" manufactured by Toyo Aluminum K.K., and "Metal Art A41010AE" manufactured by Ekart Co., Ltd. are available on the market.

The content ratio of the aluminum pigment in the print layer (X) is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, based on the total mass of the print layer (X). When the content ratio is 5% by mass or more, the brightness feeling of the print layer (X) is more excellent. When the content ratio is 70% by mass or less, the adhesion to the label base material and the printing layer (Y) is more excellent.

The print layer (X) may contain a resin other than the urethane resin as the 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. Examples of the acrylic resin include acrylic resins contained in the print layer (Y) described later. Among them, acrylic resins and cellulose resins are used from the viewpoint of improving the flexibility of the print layer (X) and further improving the followability of the print layer (X) to the label substrate when the shrink label is heat-shrinked. preferable. As the resin other than the urethane-based resin, only one kind may be used, or two or more kinds may be used.

The cellulosic resin is not particularly limited, and a known or conventional printing layer or a cellulosic resin for printing ink can be used. The cellulosic resin is not particularly limited, and is, for example, nitrocellulose (nitrated cotton); cellulose acetate butyrate (cellulose acetate butyrate: CAB), cellulose acetate (cellulose acetate), cellulose acetate propionate (cellulose propionate acetate). : A cellulosic resin esterified with a carboxylic acid such as CAP) can be mentioned. Examples of the carboxylic acid include acetic acid, fatty acid, propionic acid, acetic anhydride, and fatty acid anhydride. As the cellulosic resin, a cellulosic resin esterified with a carboxylic acid is preferable, and CAB and CAP are more preferable. As the cellulosic resin, only one kind may be used, or two or more kinds may be used.

The mass average molecular weight (Mw) of the cellulosic resin is not particularly limited, but is preferably 10,000 to 150,000, more preferably 12,000 to 100,000.

The glass transition temperature (Tg) of the cellulosic 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 cellulosic 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 the CAP is preferably 135 to 165 ° C, more preferably 140 to 160 ° C.

As the cellulosic resin, a commercially available product can also be used. For example, "CAP-482-20", "CAB-381-20", "CAB-381-0.5", "CAB-381-0.1", "CAB-551-0." Manufactured by Eastman Chemical Co., Ltd. 1 ”,“ CAB-551-0.01 ”,“ CAP-504-0.2 ”,“ CAP-482-0.5 ”, etc., KOREA CNC“ RS series ”,“ SS series ”, etc. are on the market. It is available at.

The printed layer (X) may contain a plasticizer. When the print layer (X) contains a plasticizer together with an aluminum pigment (particularly a vapor-deposited aluminum pigment), the plasticizer imparts flexibility to the print layer (X), and the deformation and orientation (arrangement) of the aluminum pigment during shrink processing. ) Suppresses the disorder and suppresses the deterioration of the metallic gloss of the printed layer (X) due to the shrink processing, so that the feeling of brightness after heat shrinkage is further improved. Further, when a plasticizer is contained, the print layer (X) becomes more flexible and tends to be more susceptible to ink cracking during heat shrinkage, but even in this case, the shrink label of the present invention is less likely to cause ink cracking. ..

As the plasticizing agent, known or conventional plasticizing agents can be used, for example, phthalic acid ester compounds such as diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, dihydroabiethyl phthalate, and dimethyl isophthalate; acetyl. Citrate ester compounds such as tributyl citrate; benzoic acid ester compounds such as trimethylol ethane tribenzoate, trimethylolpropane tribenzoate, glyceride tribenzoate, pentaerythrite tetrabenzoate; sucrose octaacetate, ketonic acid. Tricyclohexyl, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propronate)], 1,6-hexanediol bis [3- (2,5-di-t-butyl) -4-Hydroxyphenyl) propionate] and other fatty acid ester compounds; N-cyclohexyl-p-toluenesulfonic acid amide and other sulfonic acid ester compounds; phosphate ester compounds, hindered phenol compounds, triazole compounds, hydroquinone Examples include system compounds. Of these, dicyclohexyl phthalate (DCHP) and tributyl acetylcitrate (ATBC) are preferable, and ATBC is particularly preferable. As the plasticizer, only one kind may be used, or two or more kinds may be used.

As the plasticizer, a commercially available product can also be used. 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 print layer (X) contains a plasticizer, the content ratio of the plasticizer in the print layer (X) is preferably 5 to 35% by mass, more preferably 7 with respect to the total mass of the print layer (X). ~ 30% by mass. When the content ratio is 5% by mass or more, the effect of softening the print layer becomes more sufficient, the mirror glossiness of the print layer (X) after heat shrinkage is improved, and the brightness feeling after heat shrinkage is further improved. do. When the content ratio is 35% by mass or less, peeling, blocking, and deterioration of scratch resistance of the printed layer (X) can be further suppressed.

The printed layer (X) may contain other components other than the above-mentioned components (binder resin including urethane resin, aluminum pigment, and plasticizer) as long as the effects of the present invention are not impaired. .. Examples of the above other components include coloring pigments other than aluminum pigments (other coloring pigments), lubricants, anti-precipitation agents, dispersants, stabilizers, fillers, antioxidants, ultraviolet absorbers, antistatic agents, and colors. Examples include anti-parting agents, fragrances, deodorants and the like. As the coloring pigment, for example, a white pigment such as titanium oxide (titanium dioxide), an indigo pigment such as copper phthalocyanine blue, carbon black, mica, and other coloring pigments can be selected and used according to the intended use. In addition, as the coloring pigment, extender pigments such as alumina, calcium carbonate, barium sulfate, silica, and acrylic beads can also be used for the purpose of adjusting gloss.

It is preferable that the print layer (X) has a thin print layer from the viewpoint of exhibiting an excellent luminance feeling. The thickness of the print layer (X) is not particularly limited, but is preferably 0.05 to 3 μm, and more preferably 0.1 to 2 μm. When the thickness is 0.05 μm or more, it is possible to suppress a decrease in the permeation concentration due to being too thin. 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) and the printing layer (X), and the feeling of brightness is further improved. improves. In addition, the amount of printing ink used can be reduced, which is preferable in terms of cost and environment. Further, the effects that it is easy to apply evenly, the strength of the print layer is high, and it is difficult to peel off can be obtained.

[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 is at least one surface (that is, that is) of the label base material. , The surface on which the print layer (X) is provided) is provided so that at least a part thereof overlaps with the print layer (X) in the surface spreading direction. The print layer (Y) does not need to be provided so as to be in contact with the print layer (X), but is provided so as to be in contact with at least a part (particularly, a portion where ink cracking is likely to occur) with the print layer (X). Is preferable. Further, the print layer (Y) may be provided on the entire surface of the surface of the label base material (the surface on the side where the print layer (Y) is provided), or may be provided on a part of the surface. Further, the print layer (Y) is not particularly limited, but may be a single layer or a plurality of layers.

The print layer (Y) contains an acrylic resin as a binder resin as a main resin component. That is, the print layer (Y) contains an acrylic resin as the resin having the highest mass ratio among all the resins constituting the binder resin in the print layer (Y). The binder resin plays a role as a main resin component forming the printing layer (Y), and forms a coating film when the printing ink forming the printing layer (Y) is coated. The print layer (Y) is a harder print layer than the print layer (X) because the content ratio of the lubricant is not more than a specific value and the acrylic resin is contained as the main resin component. Therefore, by providing such a print layer (Y) so that at least a part thereof overlaps with the print layer (X) in the surface spreading direction, the heat feeling of the print layer (X) is sufficiently exhibited. It is possible to prevent the relatively flexible print layer (X) from coming into contact with the container and / or the print layer (X) inside the other end from coming into contact with the end of one end during shrinkage, thereby printing. Ink cracking of the layer (X) can be suppressed. Only one kind of the acrylic resin may be used, or two or more kinds may be used.

Examples of the acrylic resin include a polymer composed of an acrylic monomer as an essential monomer component, that is, a polymer having at least a structural unit derived from the acrylic monomer (copolymer). 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. , (Meta) s-butyl acrylate, (meth) t-butyl acrylate, (meth) hexyl 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 acrylate, dodecyl (meth) acrylate [preferably (meth) acrylate C _1-12 alkyl ester, etc.]; Meta) 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 ( Hydroxy group-containing (meth) acrylic acid ester such as meta) acrylate, 6-hydroxyhexyl (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate [preferably (meth) acrylic acid hydroxy C _{1 -8} Alkyl esters, etc.]; (Meta) acrylic acid cycloalkyl esters such as (meth) acrylic acid cyclohexyl, (meth) acrylic acid isobornyl; N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, (Meta) acrylic acid amide derivatives such as N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate , Dimethylaminopropyl (meth) acrylate, dipropylaminopropyl (meth) acrylate and other (meth) acrylic acid dialkylaminoalkyl esters, etc., monomers having a (meth) acryloyl group (monomer having at least an acryloyl group or a methacryloyl group) ). As the acrylic monomer, only one kind may be used, or two or more kinds may be used.

The monomer component constituting the acrylic resin other than the acrylic monomer is not particularly limited, but is, for example, a carboxy group-containing polymerizable unsaturated compound such as crotonic acid, itaconic acid, fumaric acid, maleic acid or an anhydride thereof; Styrene-based 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. Containing vinyl compound; examples thereof include ethylene and propylene.

The content ratio of the acrylic monomer in the total amount (100% by mass) of the monomer components constituting the acrylic resin, that is, the content ratio of the structural unit derived from the acrylic monomer in the acrylic resin (100% by mass) is particularly high. Although not limited, 80% by mass or more (for example, 80 to 100% by mass) is preferable, and more preferably 90% by mass or more (for example, 90 to 100%) from the viewpoint of adhesion to the label substrate or the printing layer (X). 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 wear resistance of the printed layer (Y) and adhesion to the label substrate and the printed layer (X). Is preferable, and more preferably 30,000 to 200,000.

The glass transition temperature (Tg) of the acrylic resin is not particularly limited, but is preferably 30 to 120 ° C., more preferably 40 to 100 ° C. from the viewpoint of improving wear resistance and heat resistance.

As the acrylic resin, a commercially available product may be used. As commercially available products, for example, "ARUFON series" manufactured by Toagosei Co., Ltd. and "Dianar series (BR series, LR series, etc.)" manufactured by Mitsubishi Rayon Co., Ltd. are available on the market.

The content ratio of the acrylic resin in the print 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 print layer (Y). It may be 95% by mass.

As described above, the content ratio of the lubricant in the printed layer (Y) is 0.7% by mass or less, preferably 0.5% by mass or less, most preferably 0.5% by mass, based on the total mass of the printed layer (Y). Is substantially free (eg, not positively added). If the content ratio exceeds 0.7% by mass, the hardness of the print layer (Y) tends to decrease, so that the effect of suppressing ink cracking may decrease.

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

The print layer (Y) may contain an aluminum pigment. When the print layer (Y) contains an aluminum pigment, the shrink label of the present invention has a two-layer structure in which the layer exhibiting metallic luster is a print layer (X) and a print layer (Y), and the metal layers are superimposed. A profound feeling and a sense of quality can be obtained.

Examples of the aluminum pigment that may be contained in the print layer (Y) include those exemplified and described as the aluminum pigment contained in the print layer (X). The aluminum pigment in the printed layer (Y) may be any of a leaving type aluminum pigment, a non-leaving type aluminum pigment, and a vapor-deposited aluminum pigment.

When the print layer (Y) is a print layer containing an aluminum pigment, the print layer (Y) is provided from the viewpoint of excellent brightness and less likely to cause ink cracking because the print layer (X) can exhibit a sense of brightness. It is preferable that the halftone dot area (halftone dot) of the area covered 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 the other regions may be less than 80%.

When the print layer (Y) contains an aluminum pigment, the content ratio of the acrylic resin in the print layer (Y) is preferably 15 to 70% by mass, more preferably 15% by mass, based on the total mass of the print layer (Y). It is 20 to 65% by mass. The content of the aluminum pigment in the print layer (Y) is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, based on the total mass of the print layer (Y).

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, a further back print layer is provided. It is possible to prevent the contents in the container from being seen through. The back printing layer is a printing layer that serves as a background for the design when observed from the outside of the cylinder, for example, when the shrink label is a tubular shrink label.

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). It is preferably 7 to 60% by mass. The content ratio of the white pigment in the print layer (Y) is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, based on the total mass of the print layer (Y).

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

The printed layer (Y) may contain other components other than the above-mentioned components (acrylic resin, aluminum pigment, and white pigment) as long as the effects of the present invention are not impaired. Examples of the above-mentioned other components include coloring pigments other than aluminum pigments and white pigments (other coloring pigments), anti-precipitation agents, dispersants, stabilizers, fillers, antioxidants, ultraviolet absorbers, antistatic agents, and the like. Examples include color separation inhibitors, fragrances, and deodorants. As the coloring pigment, for example, an indigo pigment such as copper phthalocyanine blue, carbon black, mica, and other coloring pigments can be selected and used according to the intended use.

The print layer (Y) is preferably made thicker from the viewpoint of protecting the print layer (X). The thickness of the print layer (Y) is not particularly limited, but is, for example, 0.1 to 10 μm.

[Shrink label]
As described above, the shrink label of the present invention has a label base material, a printing layer (X), and a printing layer (Y). The shrink label of the present invention may have a layer (other layer) other than the label base material, the print layer (X), and the print layer (Y). Examples of the other layers include a print layer other than the print layer (X) and the print layer (Y) (may be referred to as “other print layer”), an adhesive layer (pressure sensitive adhesive layer, heat sensitive). Adhesive layer, etc.), anchor coat layer, primer coat layer, coating layer, inner coat layer, antistatic layer, metal or metal oxide vapor deposition layer, light-shielding layer, heat insulating layer, barrier layer, slip layer, etc. (However, label Those not included in the substrate).

The other print layer is not particularly limited, and examples thereof include a known or conventional print layer used in a shrink label. Examples of the printing layer include a solvent-drying type printing layer formed by a solvent-drying type printing ink, an active energy ray-curable printing layer formed by an active energy ray-curable printing ink, and the like. Further, for example, in order to protect a design printing layer (color printing layer, etc.) such as drawings and designs such as product names, illustrations, handling precautions, a back printing layer formed of a single color such as white, a film, and a printing layer. Examples thereof include a protective printing layer provided in the above, a primer printing layer provided to enhance the adhesion between the film and the printing layer, and the like. The other printing layer is not particularly limited, but may be provided only on one side of the label base material or may be provided on both sides. Further, the other print layer may be provided on the entire surface of the surface of the label base material (the surface on the side where the other print layer is provided), or may be provided on a part of the surface of the label base material. Further, the above-mentioned other print layer is not particularly limited, but may be a single layer or a plurality of layers. In addition, the above-mentioned other printing layer can be provided by a well-known or conventional printing method. Above all, it is preferable that the other printing layer is provided by a gravure printing method or a flexographic printing method.

The other printing layer is not particularly limited, but preferably contains a binder resin as an essential component. Further, if necessary, it may contain coloring pigments such as blue, red, yellow, black and white, and additives such as lubricants, dispersants and defoamers. As the binder resin and the like, only one kind may be used, or two or more kinds may be used.

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

The shrink label of the present invention preferably has a design printing layer on the side of the label base material where the printing layer (X) and the printing layer (Y) are provided, as the other printing layer. When the design print layer is provided on the side where the print layer (X) and the print layer (Y) are provided, the shrink label of the present invention can be visually recognized between the design print layer and the print layer (X) through the label base material. Can be used as a back print shrink label. The design printing layer preferably contains a binder resin and a coloring pigment as essential components, and is generally formed of a plurality of printing layers having different coloring pigments so as to obtain a desired design. The thickness of the design print layer is not particularly limited, but is preferably 0.1 to 10 μm.

Further, the shrink label of the present invention preferably has a protective print layer provided so as to cover the print layer (X) and the print layer (Y) as the other print layer. By having the protective print layer, it is possible to suppress blocking when the shrink label is overlapped, and to impart slipperiness to the adherend when it 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 0.1 to 10% by mass) with respect to the total mass of the protective printing layer. Is 0.7% by mass or more, more preferably more than 0.7% by mass). The protective print layer may be a transparent layer or an opaque layer, but is preferably transparent from the viewpoint of luminance feeling. The protective printing layer contains, for example, an acrylic resin as a main resin component (that is, the acrylic resin is contained as the resin having the highest mass ratio among all the resins constituting the binder resin in the protective printing layer) and the lubricant. It is preferable that the layer has a content of more than 0.7% by mass (particularly, a transparent printing layer). The thickness of the protective print layer is, for example, 0.1 to 10 μm. By incorporating a lubricant in the design print layer, it can function as a protective print layer. In this case, it is not necessary to provide a protective print layer on the back surface of the design print layer.

The shrink label of the present invention may be a front print shrink label, a back print shrink label, or a double-sided print shrink label, but as described above, as a back print shrink label. It is especially useful to use. In addition, in this specification, a table printing label is a label which shows printing without passing through a label base material, for example, a label having a design printing layer in front of the label base material when looking at the label. The back print label is a label that shows printing through a label base material. For example, a label having a design printing layer behind the label base material when the label is viewed. The double-sided printing label means a label having a design printing layer on both sides of the label base material.

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

The thickness (total thickness) of the shrink label of the present invention is not particularly limited, but is preferably 10 to 120 μm, more preferably 15 to 90 μm, and even more preferably 20 to 65 μm.

The heat shrinkage rate (sometimes referred to as "heat shrinkage rate (100 ° C., 10 seconds)" of the shrink label (when not shrunk) of the present invention at 100 ° C. for 10 seconds (hot water treatment) in the main shrinkage direction is 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 in which the heat shrinkage rate is the largest, and generally coincides with the main shrinkage direction of the heat-shrinkable film. Generally, it is mainly in the stretched direction, and for example, in the case of a film stretched substantially in one direction in the width direction, it is in the width direction. The heat shrinkage rate (100 ° C., 10 seconds) of the shrink label (when not shrunk) of the present invention in the direction orthogonal to the main shrinkage direction is not particularly limited, but is preferably -5 to 25%, more preferably. It is -3 to 20%.

FIG. 1 is a schematic view (partial cross-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 has a label base material 2, a design printing layer 3 provided on one surface of the label base material 2, a printing layer (X) 4, and a printing layer (Y). 5 and a protective print layer 6. The design printing layer 3 is partially formed on one surface of the label base material 2 by a plurality of printing layers having different coloring pigments so as to obtain a desired design. The print layer (X) 4 is provided on one surface of the label base material 2 (the surface on which the design print layer 3 is provided) so as to be in contact with the label base material 2 and the design print layer 3. The print layer (Y) 5 is such that one surface of the label base material 2 (the surface provided with the design print layer 3 and the print layer (X) 4) is in contact with the print layer (X) 4. It is provided so as to overlap the print 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 end of the print layer (Y) 5 in the main shrinkage direction is the main shrinkage of the print layer (X) 4. It may be provided so as to be outside (for example, about 1 mm outside) from the direction end portion. The protective printing layer 6 is a printing layer (Y) 5 on one of the above surfaces of the label base material 2 (the surface provided with the design printing layer 3, the printing layer (X) 4, and the printing layer (Y) 5). It is provided so as to overlap the print layer (Y) 5 in the surface spreading direction so as to be in contact with the print layer (Y) 5. The protective print layer 6 is provided so as to cover the entire surface of the print layer (Y) 5. The protective print layer 6 has a main shrinkage direction end portion of the protective print layer 6 so as to cover the entire surface of the design print layer, the print layer (X), and the print layer (Y) even after heat shrinkage. It may be provided so as to be in contact with the label base material 2. The shrink label 1 of the present invention has a design print layer 3 having a protective print layer 6 inside, a design print layer 3 having a print layer (X) 4 inside, and a print layer (Y) inside. There is a design print layer 3 in which 5 is present. The design print layer 3 having the protective print layer 6 inside has no metallic luster when the label is visually recognized because the print layer containing the aluminum pigment does not exist in the background (the side opposite to the label base material). .. On the other hand, the design print layer 3 having the print layer (X) 4 inside is a transparent colored print layer, so that the design has a metallic luster when the label is visually recognized. Further, the design print layer 3 having the print layer (Y) 5 inside is a transparent colored print layer, so that when a print layer containing an aluminum pigment is used as the print layer (Y) 5, the label can be visually recognized. Sometimes the design has a metallic luster. Further, when the design print layer 3 contains a lubricant, the design print layer 3 also functions as a protective print layer, so that it is not necessary to provide a protective print layer in the inner region where the design print layer 3 exists. ..

The shrink label of the present invention is, for example, a tubular shrink label of a type in which both ends of the label are sealed with a solvent or an adhesive to form a cylinder and attached to a container, or one end of the label is attached to a container and the label is wound around. After that, it can be used as a shrink label of a winding method in which the other end is overlapped with one end to form a tubular shape. The shrink label of the present invention is particularly preferably used for a tubular shrink label because it is considered that the end of one end of the tubular label comes into contact with the inside of the other end during heat shrinkage as one of the causes of ink cracking. .. That is, the shrink label of the present invention is preferably used for a tubular shrink label. Hereinafter, the tubular shrink label using the shrink label of the present invention may be referred to as "the tubular shrink label of the present invention".

An example of a tubular shrink label, which is a preferred embodiment of the shrink label of the present invention, will be described with reference to FIGS. 2 to 4. The tubular shrink label 7 of the present invention shown in FIG. 2 is a shrink label of the present invention including a label base material, a printing layer (X), and a printing layer (Y) formed in a rectangular shape. This is a tubular body in which the other end is overlapped with the outside of one end to form a tubular shape, and the inner surface of the other end and the outer surface of the one end are joined with a solvent or an adhesive to form a sealing portion 8. The tubular shrink label 7 has a cylindrical shape so that the main shrinkage direction of the heat-shrinkable film is the circumferential direction D of the tubular shrink label, and the heat-shrinkable film can be heat-shrinkable in that direction.

FIG. 3 is an example of a cross section of III-III'in FIG. 2, that is, an enlarged view of a main part in the vicinity of the seal portion 8 of the tubular shrink label 7 of the present invention. In FIG. 3, in 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 (inner surface of the tubular body) of the label base material 2. 3 is formed, and the print layer (X) 4 is formed in substantially the entire region excluding the region of a predetermined width from the end 11 of the other end of one surface of the label base material 2, and the print layer (X) 4 is formed. On the surface of the label base material 2 (the surface opposite to the label base material 2), the printed layer (X) covers substantially the entire area excluding the region of a predetermined width from the end 11 of the other end of one surface of the label base material 2. The print layer (Y) 5 is formed so as to overlap with 4 in the surface spreading direction and both ends on one end side and the other end side are outside the ends of the print 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. Then, on the surface of the print layer (Y) 5 (the surface opposite to the label base material 2), an abbreviation for a region excluding a region having a predetermined width from the end 11 of the other end of one surface of the label base material 2. A protective print layer 6 is formed over the entire area so as to cover the print layer (X) 4 and the print layer (Y) 5. Further, the protective print layer 6 is provided so that both ends of the one end side and the other end side substantially coincide with both ends of the print layer (Y) 5.

FIG. 4 is another example of a cross section of III-III'in FIG. 2, that is, an enlarged view of a main part in the vicinity of the seal portion 8 of the tubular shrink label 7 of the present invention. The difference between the tubular shrink label 7 of the present invention shown in FIG. 4 and that shown in FIG. 3 is that the print layer (Y) 5 is partly on the surface of the print layer (X) 4 and the print layer (X) It is a point formed so as to overlap with 4 in the plane spreading direction. In FIG. 4, the print layer (Y) 5 is formed in the peripheral region of the print layer (X) 4 where the end 10 of one end contacts the inside of the other end during heat shrinkage. When the print layer (Y) 5 is partially provided on the print layer (X) 4 as shown in FIG. 4, the print layer (Y) 5 is a print layer containing an aluminum pigment or colorless and transparent from the viewpoint of decorativeness. It is preferably the print layer of. When the print layer (Y) 5 is a print layer containing an aluminum pigment, the print layer (Y) 5 has 80 to 100% halftone dots in the vicinity of the contact portion, and the halftone dots in the peripheral region thereof are the contact portion. It is preferable that the gradation decreases to 50% or less as the distance from the vicinity increases. With such a halftone dot configuration, ink cracking of the print layer (X) is less likely to occur, and the area where the print layer (Y) is formed is minimized, which is economically advantageous 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 print layer (Y) is provided and the area where the print layer (Y) is not provided is made inconspicuous by the above gradation, and the decorativeness is excellent.

The width of the seal portion 8 is not particularly limited, but is, for example, 0.2 to 10 mm.

In the tubular shrink label 7 of the present invention in FIGS. 3 and 4, one end portion extends to a position where the end portion 10 overlaps with the protective printing layer 6 at the other end portion, and the end portion and the other end portion are An area where the protective print layers 6 overlap each other is formed. Therefore, there is no region in which none of the print layers exists in the thickness direction. The tubular shrink label of the present invention may have a structure in which the end 10 of 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 of one end. Extends to a region that overlaps the exposed surface of the label substrate at the other end, and does not extend to a position where the end 10 of one end overlaps the protective printing layer 6 on the other end side. The structure may not overlap with the protective print layer 6 of the above.

[Manufacturing method and processing method of shrink label of the present invention]
The method for producing a shrink label of the present invention includes a step of forming a print layer (X) on at least one surface of a label base material (print layer (X) forming step) and a step of forming the print layer (X) on at least one surface of the label base material. At least a step of forming a print layer (Y) (a step of forming a print layer (Y)) is included. Further, the above-mentioned manufacturing method may include other steps (design print layer forming step, protective printing layer forming step, etc.).

(Design printing layer forming 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 printing layer forming step, the design printing layer is formed by applying the printing ink for forming the design printing layer on at least one surface of the label base material and solidifying it by drying, curing, or the like. As a method for applying the printing ink, a known and commonly used method can be used, and among them, gravure printing, flexographic printing, and digital printing are preferable. In the design printing layer forming step, the printing ink is generally applied a plurality of times for each color to form a multi-layered design printing layer.

When the design printing layer is the solvent-drying type printing layer, for example, a printing ink produced by mixing the binder resin, the solvent, and if necessary, the coloring pigment and other additives, is used in a printing machine. After coating with, 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 components constituting the binder resin,, if necessary, the coloring pigment, the solvent, and other additives are mixed. After applying the printing ink produced by the above using a printing machine, it is dried if necessary, and the above-mentioned monomer component is polymerized and cured by irradiation with an active energy ray (for example, ultraviolet rays).

The solvent-drying type printing ink is produced, for example, by mixing a binder resin, a coloring pigment, a solvent, other additives and the like, if necessary. Mixing can be performed by a known and conventional mixing method, and is not particularly limited, and for example, a mixer such as a paint shaker, a butterfly mixer, a planetary mixer, a pony mixer, a dissolver, a tank mixer, a homomixer, a homodisper, or a roll mill. , Sand mills, ball mills, bead mills, line mills and other mills, kneaders and other mixing devices are used. The mixing time (residence time) at the time of mixing is not particularly limited, but is preferably 10 to 120 minutes. The obtained printing ink may be used after being filtered, if necessary. As each of the above components (binder resin, coloring pigment, solvent, and other additives), only one type may be used, or two or more types may be used.

As the solvent, water, an organic solvent, or the like usually used for printing inks used for gravure printing, flexographic printing, and the like can be used. Examples of the organic solvent include esters such as acetates (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; toluene. 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 and the like. The solvent can be removed by drying after applying the printing ink to the label base material. The solvent also includes the meaning of "dispersion medium".

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

The printing ink is produced by mixing, for example, a urethane resin, an aluminum pigment, a solvent, and other additives. The mixing can be carried out by a known and conventional mixing method, and examples thereof include those exemplified as a mixing device used for producing the printing ink for forming the above-mentioned design printing layer. The mixing time (residence time) at the time of mixing is not particularly limited, but is preferably 10 to 120 minutes. The obtained printing ink may be used after being filtered, if necessary. In addition, examples of the solvent include those exemplified as the solvent contained in the printing ink for forming the above-mentioned design printing layer. As each of the above components (urethane resin, aluminum pigment, solvent, and other additives), only one type may be used, or two or more types may be used.

(Printing layer (Y) forming step)
In the printing layer (Y) forming step, the printing layer (Y) is formed so that at least a part thereof overlaps with the printing layer (X) in the surface spreading direction on the surface on which the printing layer (X) of the label base material is formed. The print layer (Y) is formed by applying a composition (printing ink or the like) for forming the above and solidifying the composition by drying or the like.

The printing ink is produced by mixing, for example, an acrylic resin, a solvent, and other additives. The mixing can be carried out by a known and conventional mixing method, and examples thereof include those exemplified as a mixing device used for producing the printing ink for forming the above-mentioned design printing layer. The mixing time (residence time) at the time of mixing is not particularly limited, but is preferably 10 to 120 minutes. The obtained printing ink may be used after being filtered, if necessary. In addition, examples of the solvent include those exemplified as the solvent contained in the printing ink for forming the above-mentioned design printing layer. As each of the above components (acrylic resin, solvent, and other additives), only one type may be used, or two or more types may be used.

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

The printing ink is produced by mixing, for example, a binder resin, a lubricant, a solvent, and other additives. The mixing can be carried out by a known and conventional mixing method, and examples thereof include those exemplified as a mixing device used for producing the printing ink for forming the above-mentioned design printing layer. The mixing time (residence time) at the time of mixing is not particularly limited, but is preferably 10 to 120 minutes. The obtained printing ink may be used after being filtered, if necessary. In addition, examples of the solvent include those exemplified as the solvent contained in the printing ink for forming the above-mentioned design printing layer. As each of the above components (binder resin, lubricant, solvent, and other additives), only one type may be used, or two or more types may be used.

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 components of the printing ink forming each layer is determined. The printing ink may be prepared so as to have a desired content ratio in each of the above layers. In general, the content ratio (mass%) of each component (nonvolatile component) in all the non-volatile components of the printing ink is equal to the content ratio (mass%) of each component in each of the above layers.

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

(Manufacturing method of tubular shrink label)
The method for producing the tubular shrink label of the present invention is not particularly limited, but is, for example, as follows. A long shrink label of the present invention is slit to a predetermined width to obtain a long label body in which a plurality of shrink labels of the present invention are connected in the long direction (longitudinal direction). This long label body is laminated so that the heat-shrinkable direction (that is, the heat-shrinkable direction of the heat-shrinkable film) is the circumferential direction, and the other end is on the outside of one end to form a cylinder. A long tubular label continuum (long tubular shrink label) can be obtained by forming and sealing the overlapped portions in a strip shape with a predetermined width and joining both ends thereof. By cutting this long tubular shrink label in the circumferential direction, one tubular shrink label having a predetermined length in the height direction (the tubular shrink label of the present invention) can be obtained. When providing a perforation for cutting a label, a conventional method (for example, a method of pressing a disk-shaped blade in which a cut portion and a non-cut portion are repeatedly formed around the perforation, a method using a laser, etc.) is used. 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), before and after the process of processing into a cylindrical shape, and the like.

[Labeled container]
The shrink label of the present invention is not particularly limited, but is attached to a container and used as a labeled container. The shrink label of the present invention may be used for an adherend other than the container. For example, the shrink label of the present invention (particularly, a tubular shrink label) is placed (outerly fitted) around the container so that the shrink label of the present invention has a tubular shape, and is heat-shrinked by heat treatment to form a container. By mounting, a labeled container (a labeled container having the shrink label of the present invention) can be obtained. The above containers include, for example, soft drink bottles such as PET bottles, home delivery milk bottles, food containers such as seasonings, alcoholic beverage bottles, pharmaceutical containers, detergents, chemical product containers such as sprays, and toiletries. Includes containers, cup noodle containers, etc. The shape of the container is not particularly limited, and examples thereof include various shapes such as a bottle type such as a cylinder and a square shape, and a cup type. The material of the container is not particularly limited, and examples thereof include plastics such as PET, glass, and metal. The container to which the shrink label of the present invention is attached may be referred to as "the labeled container of the present invention".

The labeled container can be produced, for example, by fitting a tubular shrink label to a predetermined container and then heat-shrinking the tubular shrink label by heat treatment to bring it into close contact with the container (shrink processing). Examples of the heat treatment method include a method of passing through a hot air tunnel and 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. Further, dry steam at 101 to 140 ° C. can also be used. The heat treatment is not particularly limited, but is preferably carried out in a temperature range in which the temperature of the heat-shrinkable film is 85 to 100 ° C. (particularly 90 to 97 ° C.). Further, the treatment time of the heat treatment is preferably 4 to 20 seconds from the viewpoint of productivity and economy.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Table 1 shows the configurations and evaluation results of the shrink labels produced in Examples and Comparative Examples.

Example 1
(Production example 1 of silver ink)
Mixing solvent of vapor-deposited aluminum pigment (mixed solvent of ethyl acetate and isopropyl acetate) dispersion (manufactured by BASF, trade name "Metacine 71-0010", non-volatile content: 10% by mass) 15 parts by mass (as a vapor-deposited aluminum pigment, 1. 5 parts by mass), ethyl acetate solution of urethane resin (manufactured by Nippon Kako Paint Co., Ltd., trade name "FS-809-1", non-volatile content: 37% by mass) 7 parts by mass (2.6 as urethane resin) By mass), tributyl acetylcitrate (manufactured by Asahi Kasei Finechem Co., Ltd., trade name "ATBC", non-volatile content: 100% by mass), 2 parts by mass, and CAB resin (manufactured by Eastman Chemical Co., Ltd., trade name "CAB-381-" 20 ”, non-volatile content: 100% by mass) Add 40.1 parts by mass of ethyl acetate and 40 parts by mass of n-propyl acetate to 1.5 parts by mass to add a printing ink (silver ink (X1)) containing an aluminum pigment. Made. The content of the vapor-deposited aluminum pigment in the total non-volatile content (100% by mass) of the silver ink (X1) was 19.7% by mass, the content of the urethane resin was 34.2% by mass, and the plasticizer (ATBC). ) Was 26.3% by mass, and the content ratio of the cellulosic resin was 19.7% by mass. The content ratio of each component in the non-volatile content of the silver ink (X1) is equal to the content ratio of each component in the print layer formed by the silver ink (X1).

(Shrink label)
The silver ink (X1) obtained above is printed on one side of the heat-shrinkable film under the trade name "HST" (manufactured by Gunze Co., Ltd., corresponding to the heat-shrinkable film (A), thickness: 40 μm) on a desktop gravure. Using a machine (manufactured by Nissho Gravure Co., Ltd., trade name "GRAVO PROOF MINI") and a gravure plate (engraving 70 lines, angle 0), apply, dry and solidify by gravure printing on the entire surface, near the part that becomes the seal part. A silver-colored print layer (sometimes referred to as "silver-colored print layer (X1)") was formed on the entire surface other than the above. Next, a silver ink (Y1) (manufactured by Sakata Inks Co., Ltd., trade name "Etona") containing a non-leafing type aluminum pigment and containing an acrylic resin as a main resin component was applied onto the surface of the silver printing layer (X1). Using the same desktop gravure printing machine and gravure plate as above, the entire surface is coated, dried and solidified by gravure printing, and the entire surface other than the vicinity of the seal portion is covered with a silver printing layer (referred to as "silver printing layer (Y1)". May) formed. Next, a gravure ink for back printing (manufactured by DIC Co., Ltd., trade name "Fine Wrap GR Back Presser Nis") was applied onto the surface of the silver printing layer (Y1) using the same desktop gravure printing machine and gravure plate as above. Then, it was applied and dried by gravure printing on the entire surface to form a protective printing layer on the entire surface other than the vicinity of the portion to be the sealing portion. In this way, a shrink label having the composition of [label base material (40 μm) / silver print layer (X1) / silver print layer (Y1) / protective print layer] was produced.

Example 2
A transparent printing layer (may be referred to as "transparent printing layer (Y2)") using the same desktop gravure printing machine and gravure plate as above, using an acrylic resin solution instead of the silver printing layer (Y1). A shrink label having the composition 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
Instead of the silver printing layer (X1), the same desktop gravure printing as above is performed using an ink containing a urethane resin containing aluminum particles as a main component (manufactured by DIC Co., Ltd., product name "Fine Wrap DH17 Silver"). The same as in Example 1 except that the silver print layer (sometimes referred to as "silver print layer (X2)") was formed by using the machine and the gravure plate [label base material (40 μm) / silver print layer ( A shrink label having the structure of [X2) / silver print layer (Y1) / protective print layer] was produced.

Comparative Example 1
(Shrink label)
As a heat-shrinkable film, the silver ink (X1) obtained above is applied to one side of the trade name "HST" (Gunze Co., Ltd., corresponding to the heat-shrinkable film (A), thickness: 40 μm) on a desktop gravure printing machine. (Made by Nissho Gravure Co., Ltd., trade name "GRAVO PROOF MINI") and gravure plate (engraving 70 lines, angle 0), applied by gravure printing on the entire surface, dried and solidified, except near the part that becomes the seal part A silver-colored printing layer (X1) was formed on the entire surface of the surface. Next, the gravure ink for back printing (manufactured by DIC Corporation, trade name "GR back presser varnish") is applied and dried by full-face gravure printing using the same desktop gravure printing machine and gravure plate as described above. A protective print layer was formed on the entire surface other than the vicinity of the portion to be the sealing portion. In this way, a shrink label having the composition of [label base material (40 μm) / silver printing layer (X1) / protective printing layer] was produced.

Comparative Example 2
The same desktop gravure printing as above using silver ink (manufactured by Dainichi Seika Kogyo Co., Ltd., product name "NT-High Ramic") containing urethane resin as the main resin component instead of the silver printing layer (Y1). The same as in Example 1 except that the silver print layer (sometimes referred to as "silver print layer (Z1)") was formed by using the machine and the gravure plate [label base material (40 μm) / silver print layer ( A shrink label having the composition of [X1) / silver print layer (Z1) / protective print layer] was produced.

Comparative Example 3
The same desktop gravure printing as above using silver ink (manufactured by Dainichi Seika Kogyo Co., Ltd., product name "NT-High Ramic") containing urethane resin as the main resin component instead of the silver printing layer (Y1). The same as in Example 3 except that the silver print layer (Z1) was formed using the machine and the gravure plate [label base material (40 μm) / silver print layer (X2) / silver print layer (Z1) / protective printing. A shrink label having the structure of [Layer] was produced.

(evaluation)
The shrink labels obtained in Examples and Comparative Examples were evaluated as follows. The evaluation results are shown in Table 1.

(1) Ink cracking test (hot water immersion shrinkage test)
For measurement of 210 mm (main shrinkage direction; width direction of heat shrinkable film) × 110 mm (orthogonal direction with respect 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 should be placed so that the main shrinkage direction of the measurement sample (main shrinkage direction of the heat-shrinkable film) is the circumferential direction, the surface on the side where the protective printing layer is provided is on the inside, and the end of one end and the other. One end and the other end are overlapped to form a cylinder so that the protective printing layer on the end side overlaps with each other, and the label base materials at the one end and the other end are separated by THF and the width of the sealing portion. Was sealed to be 3 mm, and a tubular shrink label was obtained (circumferential length: 200 mm).
In addition, a cylindrical glass bottle having a diameter of 62 mm (perimeter of 194 mm) and a height of 108 mm was prepared. Further, a strip of the same heat-shrinkable film as that used in Examples and Comparative Examples having a size of 10 mm (main shrinkage direction) × 110 mm (direction orthogonal to the main shrinkage direction) was prepared.
The width direction (main contraction direction) of the strip was aligned so that it was 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). In the center of the strip except, the strip and the cylindrical glass bottle are not adhered). Next, the above-mentioned tubular shrink label is put on the cylindrical glass bottle (with a strip) so that the protective printing layer comes into contact with the strip, and the shrink label is heated by immersing it in hot water at 90 ° C. for 20 seconds. It was shrunk (at this time, the strip was also heat-shrinked in the width direction) to obtain a labeled container.
Observe the appearance (outside) of the label of the obtained labeled container, 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 or not ink peeling) occurred. It was evaluated according to the following criteria.
Good (◎): Ink cracks cannot be confirmed from the outside or from the inside with the label peeled off. Usable (○): Ink cracks cannot be confirmed even when observed from the outside, but when the label is peeled off, ink is found inside the label. Cracks can be confirmed Defective (×): Ink cracks can be confirmed from the outside

(2) Luminance From the shrink labels obtained in Examples and Comparative Examples, a label piece having a size of 12 cm (longitudinal direction; orthogonal to the main contraction direction) × 12 cm (width direction; main contraction direction) was placed. I cut it out. Both ends of the label piece in the main shrinkage direction (width direction) [100 mm intervals excluding the parts chucked by the jig (10 mm each at both ends)] were fixed to a jig that can be fixed at 80 mm intervals (heat shrinkage). It is in a slack state before processing). The label piece having both ends fixed to the above jig was immersed in warm water at 90 ° C. for 20 seconds and heat-treated, and the label piece was heat-shrinked to a length of 80% as compared with that before the heat-shrinking treatment. 20% heat shrinkage in the main shrinkage direction (width direction)). In this way, a measurement sample was obtained by heat shrinking by 20% in the main shrinkage direction (width direction).
Using the gloss measuring instrument "UGV-5" manufactured by Suga Test Instruments Co., Ltd., the above measurement sample is used under the conditions of incident angle 60 ° / reflection angle 60 ° in accordance with JIS K 5600-4-7. The mirror glossiness of the surface of the silver print layer portion was measured. The surface on the heat-shrinkable film side was used as the measurement surface. Then, based on the obtained mirror glossiness, the sense of brightness was evaluated according to the following criteria.
Mirror gloss is 160 or more: Good mirror gloss (○)
Mirror gloss is 120 or more and less than 160: Usable mirror gloss (△)
Mirror gloss is less than 120: Mirror gloss is insufficient (×)
Good (◎): Mirror gloss is 160 or more and can be used (○): Mirror gloss is 120 or more and less than 160 Defective (×): Mirror gloss is less than 120

As can be seen from Table 1, the shrink labels (Examples 1 to 3) of the present invention had an excellent luminance feeling even after heat shrinkage, and ink cracking did not occur in the silver print layer after heat shrinkage. On the other hand, when the print layer (Y) is not provided (Comparative Example 1) or when a layer not containing an acrylic resin as a main component is used instead of the print layer (Y) (Comparative Examples 2 and 3). Ink cracking occurred in the silver print layer during heat shrinkage.

1 Shrink label of the present 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 One end end 11 The other end end

Claims (7)

A label substrate containing a heat-shrinkable film and
A printing layer (X) containing a urethane resin and an aluminum pigment provided on at least one surface of the label substrate, and a printing layer (X).
An acrylic resin as a main resin component provided on the surface of the label substrate on which the print layer (X) is provided so that at least a part thereof overlaps with the print layer (X) in the surface spreading direction. The printed layer (Y) containing 0.7% by mass or less of the lubricant and the printing layer (Y).
As a print layer other than the print layer (X) and the print layer (Y), it has a protective print layer provided so as to cover the print layer (X) and the print layer (Y) .
The protective printing layer contains a binder resin and a lubricant, and the content of the lubricant in the protective printing layer is more than 0.7% by mass with respect to the total mass of the protective printing layer.
A shrink label having a laminated structure of [label base material / print layer (X) / print layer (Y) / protective print layer ]. The shrink label according to claim 1, wherein the print layer (Y) is provided so as to be in contact with at least a part of the print layer (X). The shrink label according to claim 1 or 2, wherein the surface layer of the heat-shrinkable film on the side where the print layer (X) is provided is a layer containing a polyester 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 reefing type aluminum pigment. The shrink label according to any one of claims 1 to 4, wherein the printing layer (Y) is a printing layer containing an aluminum pigment, a white printing layer containing a white pigment, or a colorless and transparent printing layer. The shrink label according to any one of claims 1 to 5, wherein the printed layer (X) contains a plasticizer. The shrink label according to any one of claims 1 to 6, wherein the protective printing layer is a layer containing an acrylic resin as a main resin component.

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