JP6599744B2 - Shrink label - Google Patents

Description

  The present invention relates to a shrink label. More specifically, for example, the present invention relates to a shrink label that is suitable for use in containers such as beverages, foods, toiletries, and pharmaceuticals.

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

  The printing layer used for the shrink label is generally formed by a gravure printing method or a flexographic printing method. However, in recent years, an electrophotography using a toner from the viewpoints of a small lot and cost reduction. There has been proposed a method of forming the print layer by a printing machine of the type. As such a shrink label, for example, in a cylindrical shrink label provided with a heat shrinkable label base material and formed in a cylindrical body, it is located inside the cylindrical body among the surfaces of the label base material. A cylindrical shrink label having a toner print layer formed on the inner surface and a protective coating layer formed so as to cover the entire area of the toner print layer is known (for example, see Patent Document 1).

Japanese Patent Laying-Open No. 2015-13443

  In a shrink label, a toner print layer formed using toner tends to crack (ink crack) in the toner print layer during heat shrinkage such as shrink processing, and the ink crack is particularly likely to occur in heat treatment using a steam tunnel or the like. It was.

  Accordingly, an object of the present invention is to provide a shrink label that is less likely to cause ink cracking in the toner print layer during heat shrinkage.

  That is, this invention provides the shrink label characterized by having the label base material containing a heat-shrinkable film, a toner printing layer, and the printing layer (X) containing a cellulose resin in this order.

  It is preferable that the content of the cellulose resin in the printed layer (X) is 20% by weight or more.

  The shrink label preferably includes the label base material, a primer layer containing a binder resin, the toner printing layer, and the printing layer (X) in this order.

  The toner print layer contains a component having a functional group a, and a layer containing a component having reactivity with the functional group a on the side of the label substrate on which the toner print layer is provided (coating layer) (P)), and the coating layer (P) is preferably provided so as to overlap at least part of the toner print layer in the thickness direction.

  The toner printing layer contains a component having a functional group a, the toner printing layer is provided so as to be in contact with at least a part of the primer layer, and contains a component having reactivity with the functional group a. The layer (coating layer (P)) is preferably provided so as to be in contact with at least a part of the toner print layer.

  A printing layer other than the printing layer (X) may be provided between the toner printing layer and the printing layer (X) as the coating layer (P).

  The printing layer (X) may be the coating layer (P).

  The binder resin in the primer layer is preferably one or more resins selected from the group consisting of polyethylene resins, imine resins, polyamide resins, and urethane resins.

  The component having reactivity with the functional group a has a functional group reactive with the functional group a (functional group b), and the combination of the functional group a and the functional group b is a carboxy group and an isocyanate group, Carboxy group and epoxy group, carboxy group and aziridine group, carboxy group and carbodiimide group, carboxy group and oxazoline group, hydroxy group and isocyanate group, hydroxy group and aziridine group, silanol group and isocyanate group, amino group and isocyanate group, or amino group A group and an epoxy group are preferred.

  Since the shrink label of the present invention has the above-described configuration, ink cracks in the toner print layer are unlikely to occur during heat shrinkage. For this reason, the shrink label excellent in decorating property can be provided.

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

  The shrink label of this invention has the label base material containing a heat-shrinkable film, a toner printing layer, and the printing layer (X) containing a cellulose resin in this order. That is, the shrink label of the present invention has at least a region where the label base material, the toner print layer, and the print layer (X) overlap in the thickness direction. In the present specification, the “printing layer (X) containing a cellulose-based resin” may be simply referred to as “printing layer (X)”.

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

  The label substrate includes at least a heat-shrinkable film (shrink film). Although it does not specifically limit as said heat-shrinkable film, The heat-shrinkable film used as a label base material of a well-known thru | or usual shrink label can be used. The type of resin forming the heat-shrinkable film can be appropriately selected according to the required physical properties, application, cost, etc., and is not particularly limited. For example, polyester resin, polyolefin resin (for example, Polyethylene resins, polypropylene resins, etc.), polystyrene resins, polyvinyl chloride resins, polyamide resins, acrylic resins and the like. These resin may use only 1 type and may use 2 or more types. Furthermore, the same kind or different kinds of resins may be laminated to be used as a laminated film. Of these, polyester resins, polyolefin resins, and polystyrene resins are preferable. That is, the heat-shrinkable film comprises a polyester film made of a polyester resin, a polyolefin film made of a polyolefin resin, a polystyrene film made of a polystyrene resin, a polyester resin as an outer layer, and a polyolefin resin or a polystyrene resin. A heterogeneous laminated film having an inner layer is preferred. Examples of the polyester-based resin, polyolefin-based resin, and polystyrene-based resin include, for example, JP-A-2008-170822, JP-A-2008-170697, JP-A-2008-163215, and JP-A-2008-163231. The polyester resin, polyolefin resin, polystyrene resin, and the like described can be used.

  Examples of the polyester resin used for the polyester film include polyethylene terephthalate (PET) resin, poly (ethylene-2,6-naphthalenedicarboxylate) (PEN), and polylactic acid (PLA). Among them, polyethylene terephthalate (PET) resin is preferable. As the PET resin, polyethylene terephthalate (PET) using terephthalic acid as the dicarboxylic acid component and ethylene glycol as the diol component; terephthalic acid as the dicarboxylic acid component, ethylene glycol as the diol component, Copolyester (CHDM copolymerized PET) using 4-cyclohexanedimethanol (CHDM) as a copolymerization component, terephthalic acid as a dicarboxylic acid component, ethylene glycol as a main component as a diol component, neopentyl glycol (NPG) as a main component Copolyester (NPG copolymerized PET) used as copolymer component, terephthalic acid as dicarboxylic acid component, ethylene glycol as main component as diol component, diethylene glycol as copolymer component Diol-modified PET such as copolymer polyester; dicarboxylic acid such as copolymer polyester using terephthalic acid as the main component, isophthalic acid and / or adipic acid as the copolymer component, and ethylene glycol as the diol component. Modified PET etc. are mentioned.

  As a polystyrene-type resin used for the said polystyrene-type film, as a constituent monomer, for example, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, p-isobutylstyrene, pt- Examples thereof include resins containing one or more styrene monomers such as butyl styrene and chloromethyl styrene. Specifically, for example, general-purpose polystyrene (GPPS), styrene-butadiene copolymer (for example, SBS), styrene-butadiene-isoprene copolymer (SBIS), styrene-acrylic acid ester copolymer and the like can be mentioned. .

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

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

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

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

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

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

  Commercially available products can be used as the heat-shrinkable film used as the label substrate. For example, “Space Clean S7042”, “SV-808” manufactured by Toyobo Co., Ltd., “LX-10S”, “LX-18S”, “LX-61S” manufactured by Mitsubishi Plastics (polyester film) ; "Bon set" manufactured by CI Kasei Co., Ltd., "GMLS" manufactured by Gunze Co., Ltd. (polystyrene film); "FL" manufactured by Gunze Co., Ltd. (polyolefin film); "Ecology" manufactured by Mitsubishi Plastics Co., Ltd. (Polylactic acid film); “DL” manufactured by Mitsubishi Resin Co., Ltd., “HGS” manufactured by Gunze Co., Ltd. (the above is a laminated film in which the surface layer is a polyester resin and the center layer is a polystyrene resin).

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

  When the heat-shrinkable film is transparent, the haze (haze) value [based on JIS K 7136, converted to a thickness of 40 μm, unit:%] of the heat-shrinkable film is not particularly limited, but is preferably 10% or less. More preferably, it is 7% or less, and further preferably 5% or less. When the haze value exceeds 10%, the inside of the label base material (the side that becomes the container side when the shrink label is attached to the container) is printed, and in shrink label applications where printing is shown through the label base material When used as a product, the printing may become cloudy and the decorativeness may deteriorate. However, even if the haze value exceeds 10%, it may be opaque in applications other than the above-described applications that show printing through the label base material, and can be used sufficiently. Further, the opaque heat-shrinkable film is not particularly limited, and for example, a milk white film, a metal vapor deposition film, or the like can be used.

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

[Toner printing layer]
The toner print layer is an essential layer in the shrink label of the present invention, and is provided on at least one surface of the label base material. The toner print layer may be provided on the entire surface of at least one surface of the label base material, or may be provided partially. In the case where the shrink label of the present invention has a primer layer described later, the toner print layer is preferably formed in a region overlapping at least a part of the region where the primer layer is formed. From the viewpoint of further improving the adhesion of the primer layer, it is more preferably formed in the region where the primer layer is formed.

  When the surface of the toner printing layer is observed with an optical microscope or the like, the dot shape caused by the toner particles forming the layer can be confirmed.

  The toner print layer is formed of toner. The toner contains at least toner particles. The toner particles are particles that form the toner print layer, and examples thereof include particles containing a binder resin, a wax, a charge control agent (CCA), and, if necessary, a pigment or an additive. The binder resin (the binder resin contained in the toner particles) plays a role of binding the wax, the CCA, the pigment, the additive, and the like. The binder resin is not particularly limited, but includes, for example, acrylic resins, polyester resins, polystyrene resins (including styrene- (meth) acrylate copolymer resins, styrene-conjugated diene copolymers). Epoxy resin, urethane resin, polyolefin resin, polyamide resin, cellulose resin, vinyl chloride-vinyl acetate copolymer resin, isocyanate resin, rosin resin, polystyrene-polyester graft copolymer, etc. And a resin excellent in blocking resistance and low-temperature fixability is preferable. Examples of the acrylic resin, the urethane resin, and the polyamide resin include those exemplified and described as other thermoplastic resins described later. As said cellulose resin, the cellulose resin illustrated and demonstrated as a cellulose resin in the printing layer (X) mentioned later is mentioned, for example. As the (meth) acrylic acid ester constituting the styrene- (meth) acrylic acid ester copolymer resin, n-butyl acrylate, 2-ethylhexyl acrylate and the like are generally used. The component derived from the diol constituting the polyester resin is an alkylene oxide adduct of bisphenol A, and the dicarboxylic acid component (including a dicarboxylic acid anhydride) constituting the polyester resin is terephthalic acid. Isophthalic acid, trimellitic anhydride, etc. are generally used. In addition, as the binder resin in the case where the toner print layer is formed by pressure fixing, a polyolefin resin (particularly, polyethylene, ethylene-vinyl acetate (EVA)) is preferable. The CCA plays a role of adjusting the chargeability and is not particularly limited. Examples thereof include a negatively charged CCA such as a chromium complex and a positively charged CCA such as nigrosine. The wax plays a role of imparting to the toner low-temperature fixability and releasability during fixing. The wax is not particularly limited, and any of natural wax, petroleum wax, and synthetic wax may be used. In the present specification, “(meth) acryl” means “acryl”, “methacryl”, or both.

  Examples of the additive include a surface treatment agent, a crosslinking agent (or a structural unit derived from the crosslinking agent), a carrier agent for conveying the toner particles, a release agent, a fluidity improver, and a metal oxide (for example, , Silica, alumina, titania, and the like) which are hydrophobized by treating the surface of fine particles with a silane coupling agent.

  The toner print layer preferably contains a component having a functional group a (sometimes referred to as “component (A)”). More specifically, the toner print layer is preferably formed from a toner containing a component having a functional group a. Thereby, when the component (it may be called "component (B)") reactive with the functional group a exists in the shrink label of this invention, a component (B) couple | bonds with the said component (A). (Crosslinking) between the toner printing layer and a layer other than the toner printing layer in the shrink label of the present invention (for example, a printing layer (X), a primer layer described later, a printing layer (Y), etc.) It is estimated that the strength is improved, and the adhesion of the toner print layer tends to be improved. Further, since the toner print layer becomes relatively hard, ink cracking of the toner print layer during heat shrinkage tends to be less likely to occur.

  In the present specification, the component (A) includes, in addition to the unreacted component (A) itself, the component (A) combined (crosslinked) with other components (for example, the component (B)). Also included are structural units derived from component (A). In addition to the unreacted component (B) itself, the component (B) includes the component (B) in which the component (B) is bonded (crosslinked) to other components (for example, the component (A)). The structural unit derived from is also included.

  In the shrink label of the present invention, the component (A) may or may not be bonded (crosslinked) to the component (B), but is preferably bonded (crosslinked). In addition, when it has couple | bonded, it is not necessary for all the components (A) to have couple | bonded (bridge | crosslinked) with the said component (B).

  Although it does not specifically limit as said functional group a, For example, a carboxy group (a carboxylic anhydride shall also be included), a hydroxyl group, an oxazoline group, an isocyanate group, an epoxy group, an amino group, an aziridine group, a carbodiimide group, A hydrosilyl group, a silanol group, a mercapto group, a vinyl group, etc. are mentioned. Among these, a carboxy group, a hydroxy group, an amino group, and a silanol group are preferable, and a carboxy group is particularly preferable. The functional group a is preferably one in which no reaction occurs between the functional groups a in an environment near normal temperature and pressure.

  The component (A) is not particularly limited as long as it is a component constituting the toner printing layer. For example, the component that forms the toner particles, such as the binder resin, the wax, the CCA, the pigment, and the additive. Is mentioned. Among these, from the viewpoint of adhesion of the toner print layer, the component that forms the toner particles is preferable, and the binder resin that forms the toner particles is more preferable. That is, the toner print layer preferably contains a binder resin having a functional group a as a component having the functional group a, and more preferably contains a binder resin having a carboxy group.

  The component (A) may be reactive with the component (B) at room temperature, and is reactive with the component (B) by active energy rays such as ultraviolet rays and electron beams, heat, moisture, and the like. It may be a thing.

  As such a binder resin having a carboxy group, for example, a polyolefin resin having a carboxy group such as a polyethylene resin having a carboxy group; an acrylic resin having a carboxy group; a polystyrene resin having a carboxy group (carboxy group) Styrene- (meth) acrylic acid ester copolymer resin having a carboxy group); a urethane resin having a carboxy group; a polyester resin having a carboxy group; a polyamide resin having a carboxy group; a cellulose having a carboxy group A vinyl chloride-vinyl acetate copolymer resin having a carboxy group; an isocyanate resin having a carboxy group; a rosin resin having a carboxy group; Among these, a polyolefin resin having a carboxy group, a polystyrene resin having a carboxy group, and a polyester resin having a carboxy group are preferable, and a polyolefin resin having a carboxy group and a polystyrene resin having a carboxy group are more preferable.

  Examples of the binder resin having a carboxy group include a resin composed of a monomer having a carboxy group as an essential monomer component. Examples of the monomer having a carboxy group include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, and maleic acid. The binder resin having a carboxy group may be composed of monomers other than the monomer having a carboxy group as a monomer component.

  As the binder resin having a carboxy group, a binder resin composed of the unsaturated carboxylic acid as a monomer component is preferable. For example, an olefin-unsaturated carboxylic acid copolymer such as an ethylene-unsaturated carboxylic acid copolymer resin is preferable. Polymerization resin; (meth) acrylic acid ester-unsaturated carboxylic acid copolymer resin; styrene-unsaturated carboxylic acid copolymer resin (including styrene- (meth) acrylic acid ester-unsaturated carboxylic acid copolymer resin) Urethane resin composed of unsaturated carboxylic acid as monomer component; Polyester resin composed of unsaturated carboxylic acid as monomer component; Polyamide resin composed of unsaturated carboxylic acid as monomer component A cellulose resin composed of an unsaturated carboxylic acid as a monomer component Vinyl chloride-vinyl acetate copolymer resin composed of unsaturated carboxylic acid as monomer component; Isocyanate resin composed of unsaturated carboxylic acid as monomer component; Rosin resin composed of unsaturated carboxylic acid as monomer component, etc. Is mentioned. Of these, olefin-unsaturated carboxylic acid copolymer resins (particularly ethylene-unsaturated carboxylic acid copolymer resins) and styrene-unsaturated carboxylic acid copolymer resins are preferred. In the binder resin composed of the unsaturated carboxylic acid as a monomer component, a part of the carboxy group in the binder resin may be esterified.

  Specific examples of the binder resin having a carboxy group include olefin- (meth) acrylic acid copolymers such as ethylene- (meth) acrylic acid copolymer; ethylene- (meth) acrylic acid ester- (meth). Olefin- (meth) acrylic acid ester- (meth) acrylic acid copolymer such as acrylic acid copolymer; styrene- (meth) acrylic acid copolymer; styrene- (meth) acrylic acid ester- (meth) acrylic acid A copolymer is preferable, and an ethylene- (meth) acrylic acid copolymer and a styrene- (meth) acrylic acid copolymer are more preferable.

  As the toner, a powder toner or a liquid toner may be used. The toner is preferably a powder toner from the viewpoint of versatility. On the other hand, liquid toner can use toner particles having a particle diameter smaller than that of powder toner, and the thickness of the toner print layer can be reduced. There is a tendency to be excellent in following ability.

  When the toner is a powder toner, the average particle diameter (volume average particle diameter) of the toner particles contained in the powder toner is not particularly limited, but is preferably about 5 to 6 μm. When the toner is a liquid toner, the particle size (volume average particle size) of the toner particles contained in the liquid toner is not particularly limited, but is preferably about 1 to 2 μm. In addition, the said volume average particle diameter is a median diameter (D50) in volume reference distribution, for example, can be measured by a laser diffraction method.

  When the functional group a is an acidic functional group such as a carboxy group, the acid value of the toner print layer is not particularly limited, but is 500 mgKOH / g or less (for example, more than 0 mgKOH / g and 500 mgKOH / g or less). More preferably, it is 5-300 mgKOH / g, More preferably, it is 10-200 mgKOH / g, Most preferably, it is 20-100 mgKOH / g. When the acid value is 500 mgKOH / g or less, the stability of the toner is improved. In addition, in this specification, an acid value is calculated | required based on JISK5601-2-1 (titration method). Specifically, the acid value of the toner print layer conforms to the above JIS by using a toner to form a single toner print layer on one surface of a substrate such as a film and using the toner print layer as a sample. Can be measured. In addition, it can measure similarly about the acid value of the printing layer (X) mentioned later, the acid value of a coating layer (P), and the acid value of a primer layer.

  The toner print layer preferably does not contain a component (component (B)) having reactivity with the functional group a. Specifically, the content of the component (B) in the toner print layer is not particularly limited, but is preferably 5% by weight or less, more preferably 3% by weight with respect to the total amount (100% by weight) of the toner print layer. % Or less, more preferably 1% by weight or less, and particularly preferably 0% by weight. The toner print layer may contain the component (B). In this case, it is necessary to minimize the content of the component (B). When the content exceeds 5% by weight, the component (A) and the component (B) react with each other in the toner before application to the label base material, and toner particles aggregate or the viscosity in the case of liquid toner. May increase, making it difficult to apply toner.

  The toner print layer may be a print layer (design print layer) for giving indications such as product names, designs, illustrations, drawings, information on products (for example, handling precautions, etc.), such as white It may be a background print layer formed in a single color. The toner print layer may include a design print layer formed of a plurality of print layers and a background print layer. Further, the toner print layer may have a design print layer formed of a plurality of print layers without having a background print layer. In this case, a background printing layer different from the toner printing layer (for example, a background printing layer provided by a general-purpose printing method such as gravure printing or flexographic printing) may be provided, or the background printing layer is not provided and is transparent. A basic label may be used.

  In the present specification, the background print layer is a print layer that forms the background of the design print layer when the shrink label of the present invention is formed into a cylinder and is observed from the outside of the cylinder. For example, titanium oxide is used as a color pigment. It is formed by a white printed layer containing 20 to 60% by weight. Further, in the present specification, the design print layer is not particularly limited. For example, the design print layer is formed by overlapping a plurality of print layers having different color pigments so as to obtain a desired display such as a trade name, an illustration, and handling precautions. Yes.

  In this specification, the “outside” of the shrink label means the side that is not in contact with the adherend (the opposite side of the adherend) when the shrink label is attached to the adherend such as a container. The “inside” of the shrink label means the side (container side) in contact with the adherend.

  The thickness of the toner print layer is not particularly limited, but is preferably 0.1 to 15 μm, and more preferably 0.2 to 10 μm. The thickness of the toner print layer is the total thickness of the design print layer and the background print layer which are toner print layers.

[Print layer (X)]
The print layer (X) is an essential layer in the shrink label of the present invention, and is provided on at least one surface (the surface on which the toner print layer is provided) of the label base material.

  The print layer (X) may be provided on the entire surface of at least one surface of the label base material, or may be provided partially, but at least in the portion where the toner print layer is provided. Provided (that is, provided so that there is a region where the toner print layer and the print layer (X) overlap in the thickness direction), and provided so as to cover at least a portion where the toner print layer is provided. It is preferable that The print layer (X) is particularly preferably provided so as to overlap the entire area where the toner print layer is provided (particularly, so as to cover the entire area).

  The printing layer (X) contains a cellulose resin as an essential component. The shrink label of the present invention is provided with a printing layer (X) containing a cellulose-based resin on the surface side (the side opposite to the label base material of the toner printing layer) from the toner printing layer, so that heat shrinkage is achieved. Occasionally ink cracks are less likely to occur in the toner print layer. Also, the transparency after heat shrinkage tends to be excellent.

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

  Although the weight average molecular weight (Mw) of the said cellulose resin is not specifically limited, 10,000-150,000 are preferable, More preferably, it is 12,000-100,000. In addition, in this specification, although a weight average molecular weight (Mw) is not specifically limited, For example, it can measure by standard polystyrene conversion by GPC.

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

  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 K7121. The DSC measurement is not particularly limited. For example, the DSC measurement can be performed using a differential scanning calorimeter “DSC6200” manufactured by Seiko Instruments Inc. under a temperature rising rate of 10 ° C./min.

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

  The printing layer (X) is not particularly limited, but other than the cellulose resin, if necessary, a thermoplastic resin other than the cellulose resin (sometimes referred to as “other thermoplastic resin”), a pigment, a dye, or the like Other components such as coloring agents (coloring materials) and additives may be contained. The additives are not particularly limited, but are lubricants, plasticizers, anti-settling agents, dispersants, stabilizers, curing agents (crosslinking agents), antifoaming agents, fillers, antioxidants, ultraviolet absorbers, antistatic agents. Agents, color separation preventing agents, fragrances, deodorants, slip agents and the like. Only one type of the other components may be used, or two or more types may be used.

  The other thermoplastic resin is not particularly limited, and a thermoplastic resin used as a binder resin for known or commonly used printing layers and printing inks can be used. Examples of the other thermoplastic resins include acrylic resins, urethane resins, polyester resins, polyamide resins, vinyl chloride resins, vinyl acetate resins, polyolefin resins (for example, polyethylene resins, polybutadiene resins). Etc.), isocyanate resins, rosin resins, polyvinyl alcohol resins (PVA resins), imine resins and the like. Among these, acrylic resins, urethane resins, and polyamide resins are preferable from the viewpoint of improving adhesion to the label base material. That is, the printing layer (X) preferably contains a cellulose resin and, if necessary, at least one thermoplastic resin of an acrylic resin, a urethane resin, and a polyamide resin as a resin component. Especially, it is especially preferable that printing layer (X) contains a cellulose resin and acrylic resin. The other thermoplastic resin may be a hydrophilic resin, but is preferably an oleophilic resin that is difficult to dissolve in water and easily soluble in an organic solvent. Only one kind of the other thermoplastic resins 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 (copolymer) having at least a structural unit derived from an acrylic monomer. The monomer component constituting the acrylic resin may contain a monomer component other than the acrylic monomer.

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

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

  In addition, when the acrylic resin is a hydrophilic resin, it is preferable to use a monomer component having a hydrophilic group introduced as the monomer component constituting the acrylic resin. Examples of the hydrophilic group include a carboxy group, a hydroxy group, an ether group, an amide group, a phosphate ester group, a sulfonic acid group, an amino group, an imino group, a quaternary ammonium group, and a tertiary sulfonium group.

  As said acrylic resin, polyacryl polyol resin etc. are mentioned, for example. The polyacryl polyol resin is an acrylic resin having two or more hydroxy groups. The polyacryl polyol resin has, for example, a monomer component having a hydroxy group such as a hydroxy group-containing (meth) acrylic acid ester as an essential monomer component, and, if necessary, another monomer component (for example, an acrylic monomer) ) For polymerization.

  The hydroxyl value of the polyacryl polyol resin is not particularly limited, but is preferably 10 mg KOH / g or more (for example, 10 to 100 mg KOH / g), more preferably 15 to 80 mg KOH / g, and still more preferably 20 to 70 mg KOH / g. . The hydroxyl value can be measured by potentiometric titration according to JIS K 0070.

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

  The weight average molecular weight (Mw) of the acrylic resin is not particularly limited, but is preferably 20,000 to 250,000, more preferably 30,000 from the viewpoints of wear resistance and adhesion to the label base material and the toner print layer. ~ 200,000.

  Although the glass transition temperature (Tg) of the said acrylic resin is not specifically limited, 0-150 degreeC is preferable from a viewpoint of abrasion resistance and a heat resistant improvement, More preferably, it is 30-120 degreeC, More preferably, it is 40-100. ° C.

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

  The urethane-based resin is not particularly limited, and a known or commonly used printing layer or a polyurethane resin for printing ink can be used. Examples thereof include a resin obtained by reacting a polyisocyanate compound and a polyol compound.

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

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

  From the viewpoint of flexibility, the glass transition temperature (Tg) of the urethane resin is preferably −70 to 40 ° C., more preferably −60 to 30 ° C.

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

The polyamide-based resin is not particularly limited, and a known or commonly used printing layer or a polyamide-based resin for printing ink can be used. Examples of polyamide resins include polyamides obtained by polymerization of polyamines and polybasic acids, and polyamides obtained by polycondensation of aminocarboxylic acids (C _4-20 aminocarboxylic acids such as ω-aminoundecanoic acid). Polyamide obtained by ring-opening polymerization of lactam (C _4-20 lactam such as ε-caprolactam), polycondensation of polyvalent amine, polybasic acid and polyol component (diol such as ethylene glycol). Examples thereof include polyester amides, copolymers of the above-mentioned polyamide raw materials, and the like.

  Examples of the polybasic acid include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and maleic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; isophthalic acid, terephthalic acid and trimellitic acid Aromatic polybasic acids such as: polymerized fatty acids and the like. Of these, polymerized fatty acids are preferred. Polymerized fatty acids are obtained by polymerization of unsaturated fatty acids or esters thereof, and include monobasic fatty acids, dimerized polymerized fatty acids, trimerized polymerized fatty acids and the like.

  Examples of the polyvalent amine include aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, and methylaminopropylamine; aliphatic polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; cyclohexylenediamine, and isophoronediamine. And alicyclic polyamines such as xylylenediamine; aromatic polyamines such as phenylenediamine and diaminodiphenylmethane; and the like.

  A monocarboxylic acid, primary and secondary monoamine may be used in combination with the polybasic acid and the polyvalent amine in the polyamide resin. Examples of the monocarboxylic acid include acetic acid, propionic acid, lauric acid, palmitic acid, benzoic acid, cyclohexanecarboxylic acid, stearic acid, oleic acid, linoleic acid, and the like. Examples of the primary and secondary monoamines include ethylamine, propylamine, butylamine, octylamine, diethylamine, monoethanolamine, monopropanolamine, diethanolamine, and dipropanolamine.

  It does not specifically limit as said pigment, For example, the pigment used in a well-known printing layer can be used. Examples of the pigment include white pigments such as titanium oxide (titanium dioxide), indigo pigments such as copper phthalocyanine blue, red pigments such as condensed azo pigments, yellow pigments such as azo lake pigments, metal pigments such as aluminum, and carbon black Aluminum flakes, mica (mica), and other colored pigments can be selected and used according to the application. In addition to the above pigments, extender pigments such as alumina, calcium carbonate, barium sulfate, silica, and acrylic beads can also be used for the purpose of adjusting gloss.

  The lubricant is not particularly limited, and a lubricant used in a known or commonly used coating layer can be used. Examples of the lubricant include polyolefin waxes such as polyethylene wax and polyethylene oxide wax, various waxes (waxes) such as fatty acid amide, fatty acid ester, paraffin wax, polytetrafluoroethylene (PTFE) wax, carnauba wax, and the like. Examples thereof include resin beads. The said lubricant may use only 1 type and may use 2 or more types.

  When the toner print layer contains the component (A), the print layer (X) may contain the component (B). In this case, examples of the component (B) include the other thermoplastic resins and the additives. Especially, it is preferable that a component (B) is a hardening | curing agent. That is, it is preferable that the printing layer (X) further includes a curing agent as the component (B). In this case, the printing layer (X) corresponds to a coating layer (P) described later. In the present specification, the curing agent includes a structural unit derived from the curing agent in a state in which the curing agent is combined with other components, in addition to the curing agent before curing (before crosslinking).

  The print layer (X) is not particularly limited, but is preferably transparent. That is, the printing layer (X) is preferably a transparent printing layer. Note that the term “transparent” refers to a printed layer having such transparency that an adjacent layer can be visually recognized through the printed layer. When the printing layer (X) is transparent, it may be either colored or colorless, but is preferably colorless (that is, colorless and transparent).

  The content of the cellulose resin in the printing layer (X) is not particularly limited, but is preferably 20% by weight or more, more preferably 30% by weight with respect to the total weight (100% by weight) of the printing layer (X). More preferably, it is 40% by weight or more. When the content is 20% by weight or more, ink cracking of the toner print layer at the time of heat shrinkage tends to be less likely to occur. The content may be 100 wt% or less, but may be 95 wt% or less, 90 wt% or less, or 80 wt% or less in consideration of the case where a colorant, an additive, or the like is included. In particular, when a white pigment is included as a colorant, the content is preferably 70% by weight or less, more preferably 60% by weight or less.

  The content of the thermoplastic resin in the printing layer (X) (that is, the total content of the cellulose resin and the other thermoplastic resin) is not particularly limited, but the total weight (100 weight) of the printing layer (X). %) Is preferably 20% by weight or more, more preferably 30% by weight or more, and still more preferably 40% by weight or more. The content may be 100 wt% or less, but may be 95 wt% or less, 90 wt% or less, or 80 wt% or less in consideration of the case where a colorant, an additive, or the like is included. In particular, when a white pigment is included as a colorant, the content is preferably 75% by weight or less, and more preferably 65% by weight or less.

  The content of the cellulosic resin in the thermoplastic resin contained in the printing layer (X) is not particularly limited, but is 20% with respect to the total weight (100% by weight) of the thermoplastic resin in the printing layer (X). % Or more (for example, 20 to 100% by weight) is preferable, more preferably 30% by weight or more, still more preferably 40% by weight or more, and particularly preferably 45% by weight or more. When the printing layer (X) contains the other thermoplastic resin, the printing layer (X) contains 20 cellulose-based resins with respect to the total weight (100% by weight) of the thermoplastic resin in the printing layer (X). It is preferably a layer containing 95% by weight and 5-80% by weight of the other thermoplastic resin, more preferably 30-90% by weight of the cellulose-based resin, and 10-70% by weight of the other thermoplastic resin. A layer containing 40 to 85% by weight of a cellulose resin, more preferably 15 to 60% by weight of the other thermoplastic resin, particularly preferably 45 to 80% by weight of a cellulose resin, and the other thermoplastic resin. Is a layer containing 20 to 55% by weight.

  When the printing layer (X) does not contain a colorant and an additive or the content thereof is small, the content of the thermoplastic resin in the printing layer (X) is not particularly limited, but the total amount of the printing layer (X) is not limited. It is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 80% by weight or more with respect to the weight (100% by weight). The upper limit of the content may be 100% by weight, 98% by weight, 95% by weight, or 90% by weight.

  When the printing layer (X) contains a curing agent as the component (B), the content of the thermoplastic resin in the printing layer (X) is not particularly limited, but the total weight (100% by weight) of the printing layer (X) ) Is preferably 50 to 95% by weight, more preferably 55 to 90% by weight, and still more preferably 60 to 85% by weight. The content of the curing agent in this case is not particularly limited, but is preferably 3 to 40% by weight, more preferably 5 to 35% by weight, and still more preferably 10 to 30% by weight.

  When the printing layer (X) contains a white pigment as a colorant, the printing layer (X) can be used as a background printing layer. The content of the white pigment when the printing layer (X) contains a white pigment as a colorant is not particularly limited, but is 20 to 75% by weight with respect to the total weight (100% by weight) of the printing layer (X). Is more preferable, and 30 to 70% by weight is more preferable. Further, the content of the thermoplastic resin in this case is not particularly limited, but is preferably 20 to 75% by weight, more preferably 25 to 65% by weight based on the total weight (100% by weight) of the printed layer (X). %.

  When the printing layer (X) contains a white pigment as a colorant and a curing agent as the component (B), the content of the white pigment is not particularly limited, but the total weight (100% by weight) of the printing layer (X) ) To 10 to 70% by weight, more preferably 20 to 60% by weight. Further, the content of the thermoplastic resin in this case is not particularly limited, but is preferably 20 to 75% by weight, more preferably 25 to 65% by weight based on the total weight (100% by weight) of the printed layer (X). %. Further, the content of the curing agent in this case is not particularly limited, but is preferably 3 to 40% by weight, more preferably 5 to 35% by weight, based on the total weight (100% by weight) of the printed layer (X). More preferably, it is 10 to 30% by weight.

  When the printing layer (X) is the outermost surface of the shrink label of the present invention, the printing layer (X) preferably contains a lubricant. In this case, the content of the lubricant in the printing layer (X) is not particularly limited, but is preferably 1 to 15% by weight, more preferably 2 with respect to the total weight (100% by weight) of the printing layer (X). -10% by weight.

  The printing layer (X) is not particularly limited, but is preferably a solvent drying type printing layer formed with a solvent drying type printing ink.

  When the shrink label of the present invention has a layer containing the component (B) (that is, a coating layer (P) described later), the printed layer (X) is a component having reactivity with the component (B) (for example, The component which has the below-mentioned functional group c) may be contained. Although the component which has the reactivity with the said component (B) will not be specifically limited if it is a component contained in printing layer (X), For example, a cellulose resin, the said other component, etc. are mentioned.

  The acid value of the printing layer (X) is not particularly limited, but is preferably 40 mgKOH / g or less (for example, more than 0 mgKOH / g and 40 mgKOH / g or less), more preferably more than 0 mgKOH / g and 30 mgKOH / g or less. is there.

  Although the thickness of printing layer (X) is not specifically limited, 0.1-10 micrometers is preferable, More preferably, it is 0.2-5 micrometers.

[Primer layer]
In the shrink label of the present invention, a primer layer containing a binder resin is preferably provided between the label base material and the toner print layer. That is, the shrink label of the present invention preferably has the label base material, a primer layer containing a binder resin, the toner printing layer, and the printing layer (X) in this order. In this case, the shrink label of the present invention has at least a region in which the label base material, the primer layer, the toner printing layer, and the printing layer (X) overlap in the thickness direction. When the primer layer is provided between the label substrate and the toner print layer, the adhesion of the toner print layer to the label substrate tends to be improved.

  When the shrink label of the present invention has a primer layer, the primer layer is provided on at least one surface (the surface on which the toner print layer is provided) of the label base material. The primer layer may be provided on the entire surface of at least one surface of the label base material, or may be provided partially. In addition, the primer layer may be formed in a region that overlaps at least a part of the region in which the toner print layer is formed. From the viewpoint of further improving the adhesion of the toner print layer, the toner printing It is preferable that the layer is formed so as to overlap all the regions where the layer is formed.

  The primer layer contains a binder resin as an essential component. The said primer layer may contain other components, such as an additive, as needed.

  The binder resin is not particularly limited, and a known or commonly used binder resin for a printing layer can be used. Although the said binder resin is not specifically limited, It plays the role as the main resin component which forms the said primer layer, and forms a coating film when the primer coating agent which forms a primer layer is applied. The binder resin is not particularly limited, but acrylic resin, urethane resin, polyester resin, polyamide resin, cellulose resin, vinyl chloride resin, vinyl acetate resin, polyolefin resin (for example, polyethylene resin) And polybutadiene resins), isocyanate resins, rosin resins, polyvinyl alcohol resins (PVA resins), imine resins, and the like. Among these, acrylic resin, urethane resin, polyolefin resin, imine resin, and polyamide resin are preferable from the viewpoint of improving adhesion to the toner print layer, and more preferably, urethane resin, polyethylene resin, and imine. Resin and polyamide resin. Furthermore, a polyethylene-based resin, an imine-based resin, and an amide-based resin are particularly preferable in combination with a printing layer (X) containing a cellulose-based resin (particularly, a cellulose-based resin and an acrylic resin). The binder resin may be a hydrophilic resin, but may be an oleophilic resin that is difficult to dissolve in water and easily soluble in an organic solvent. For example, the polyolefin resin (polyethylene resin) and the imine resin are preferably hydrophilic resins. The polyamide resin is preferably a lipophilic resin. The urethane resin may be either a hydrophilic resin or a lipophilic resin. As the binder resin, only one kind may be used, or two or more kinds may be used. Examples of the acrylic resin, urethane resin, and polyamide resin include those exemplified and explained as the other thermoplastic resins described above.

  Although the said primer layer is not specifically limited, In addition to binder resin, you may contain other components, such as coloring agents (coloring material), such as a pigment and dye, and an additive as needed. The additives are not particularly limited, but are lubricants, plasticizers, anti-settling agents, dispersants, stabilizers, curing agents (crosslinking agents), antifoaming agents, fillers, antioxidants, ultraviolet absorbers, antistatic agents. Agents, color separation preventing agents, fragrances, deodorants, slip agents and the like. Only one type of the other components may be used, or two or more types may be used.

  When the toner print layer contains the component (A), the primer layer may contain the component (B). In this case, the primer layer corresponds to a coating layer (P) described later. As said component (B), the said binder resin and the said additive are mentioned, for example. Especially, it is preferable that a component (B) is a hardening | curing agent. In this case, the primer layer contains a binder resin and a curing agent as component (B).

  The content of the binder resin in the primer layer is not particularly limited, but is preferably 50% by weight or more (for example, 50 to 100% by weight), more preferably, based on the total weight (100% by weight) of the primer layer. It is 60 to 99% by weight, more preferably 70 to 98% by weight, and particularly preferably 80 to 97% by weight.

  When the primer layer contains a curing agent as the component (B), the content of the binder resin is not particularly limited, but is preferably 50 to 95% by weight with respect to the total weight (100% by weight) of the primer layer, More preferably, it is 55 to 90 weight%, More preferably, it is 60 to 85 weight%. The content of the curing agent in this case is not particularly limited, but is preferably 3 to 40% by weight, more preferably 5 to 35% by weight, and still more preferably 10 to 30% by weight.

  When the shrink label of the present invention has a layer containing the component (B) (that is, a coating layer (P) described later), the primer layer is a component having reactivity with the component (B) (for example, described later). A component having a functional group c) may be contained. Especially, it is preferable that the said primer layer contains the component which has a reactivity with a component (B). That is, the primer layer is preferably formed of a primer coating agent containing a component having reactivity with the component (B). Although the component which has the reactivity with the said component (B) will not be specifically limited if it is a component contained in the said primer layer, For example, the said binder resin, said other component, etc. are mentioned. Among these, the binder resin is preferably a component having reactivity with the component (B) (for example, a binder resin having a functional group c). When the primer layer contains a component having reactivity with the component (B), the component (B) tends to improve the adhesion between the primer layer, the coating layer (P) and the toner printing layer. There is. Moreover, there is a tendency that ink cracks during heat shrinkage are less likely to occur. In addition, when the said primer layer contains the component which has a reactivity with a component (B), it is preferable that the said primer layer does not contain a component (B) substantially. Here, “substantially does not contain” means that it is not actively contained other than contained by migration from other layers. Specifically, the content of component (B) is, for example, 1% by weight or less, preferably 0.5% by weight or less, based on the total weight (100% by weight) of the layer.

  The primer layer contains no component (B), contains a component having a functional group c described below as a component having reactivity with the component (B), and the functional group c is an acidic functional group such as a carboxy group. In this case, the acid value of the primer layer is not particularly limited, but is preferably 500 mgKOH / g or less (for example, more than 0 mgKOH / g and 500 mgKOH / g or less), more preferably 5 to 300 mgKOH / g, and still more preferably 10 to 10 mgKOH / g. 200 mg KOH / g, particularly preferably 30 to 100 mg KOH / g.

  When the shrink label of the present invention is a back printed shrink label, the primer layer is preferably transparent, although not particularly limited. In addition, when the shrink label of the present invention is a front printed shrink label, the primer layer may be transparent or opaque.

  The primer layer is not particularly limited, but is preferably a solvent-drying primer layer formed by a solvent-drying primer coating agent.

  Although the thickness of the said primer layer is not specifically limited, 0.1-10 micrometers is preferable, More preferably, it is 0.2-3 micrometers.

  When the toner print layer contains the component (A), the shrink label of the present invention has a coating layer containing the component (B) on the side of the label substrate on which the toner print layer is provided. Is preferred. In the present specification, the “coating layer containing the component (B)” may be referred to as “coating layer (P)”. The coating layer (P) is preferably provided so as to overlap at least a part of the toner printing layer in the thickness direction. In this case, in the shrink label of the present invention, the component (B) moves from the coating layer (P) to each layer, and each layer in the shrink label of the present invention (the primer layer, the toner print layer, the print layer (X ) Etc.)), it is assumed that a crosslinked structure is formed in at least one of the layers or between the layers, and it is considered that this improves the interlayer strength between the respective layers and improves the adhesion of the toner print layer to the label substrate. It is done. In addition, ink cracking tends to be less likely to occur in the toner print layer during heat shrinkage. Examples of the crosslinked structure include a structure in which the component (A) and the component (B) in the toner print layer are combined.

[Coating layer (P)]
The coating layer (P) contains a component (B) (a component having reactivity with the functional group a). Examples of the coating layer (P) include a printing layer (X), the primer layer, the printing layer (X), and a coating layer other than the primer layer. In the present specification, the printing layer (P) other than the printing layer (X) and the primer layer may be referred to as “printing layer (Y)”.

  In the shrink label of the present invention, the coating layer (P) may be provided on either side of the toner print layer, but may be provided on the surface of the toner print layer opposite to the label substrate. preferable. That is, the shrink label of the present invention preferably has a label substrate, a toner print layer, and a coating layer (P) in this order. When the coating layer (P) is provided on the surface of the toner printing layer opposite to the label substrate, the coating layer (P) is formed on the surface (particularly the surface) of the toner printing layer in the production of the shrink label of the present invention. The coating layer (P) is considered to be because the component (B) in the coating agent impregnates the toner print layer with the solvent of the coating agent when the coating agent for forming the coating is applied. There is a tendency that the adhesion of the toner printing layer is improved. In addition, ink cracking tends to be less likely to occur in the toner print layer during heat shrinkage. The coating layer (P) is preferably a printing layer (Y).

  The coating layer (P) preferably contains a resin. The coating layer (P) may contain other components such as additives as necessary. The resin is not particularly limited, and a resin used as a binder resin for a known or conventional printing layer can be used. For example, the resins exemplified and described as the binder resin contained in the primer layer described above can be used. Can be mentioned. Moreover, as said other component, the component illustrated and demonstrated as another component which may be contained in the above-mentioned primer layer is mentioned, for example.

(Ingredient (B))
The component (B) has a functional group reactive with the functional group a (sometimes referred to as “functional group b”). The functional group b in the component (B) can be appropriately selected depending on the type of the functional group a. For example, a carboxy group (including a carboxylic acid anhydride), a hydroxy group, an oxazoline group, Examples thereof include an isocyanate group, an epoxy group, an amino group, an aziridine group, a carbodiimide group, a hydrosilyl group, a silanol group, a mercapto group, and a vinyl group. Note that the functional group a and the functional group b are preferably not the same functional group. The said functional group b may have only 1 type and may have 2 or more types. The functional group b is preferably one that does not react between the functional groups b in an environment near normal temperature and pressure.

  When the functional group a is a carboxy group, the functional group b is preferably an isocyanate group, an epoxy group, an aziridine group, a carbodiimide group, or an oxazoline group. From the viewpoint of further improving the adhesion of the toner print layer, an aziridine group, A carbodiimide group is more preferable, and an aziridine group is more preferable. When the functional group a is a hydroxy group or a silanol group, the functional group b is preferably an isocyanate group. When the functional group a is an amino group, the functional group b is preferably an isocyanate group or an epoxy group.

  The combination of the functional group a and the functional group b is important, and the functional group a and the functional group b may be reversed. As a combination of the functional group a and the functional group b, a carboxy group and an isocyanate group, a carboxy group and an epoxy group, a carboxy group and an aziridine group, a carboxy group and a carbodiimide group, a carboxy group and an oxazoline group, a hydroxy group and an isocyanate group, Hydroxyl group and aziridine group, silanol group and isocyanate group, amino group and isocyanate group, amino group and epoxy group are preferred, carboxy group and aziridine group, carboxy group and carbodiimide group, more preferably carboxy group and aziridine group is there. The primer layer, the toner print layer, the print layer (X), and the print layer (Y) may contain a component that promotes the reactivity between the functional group a and the functional group b.

  Although it will not specifically limit as a component (B) if it is a component (for example, resin, other components, etc.) contained in a coating layer (P), A hardening | curing agent is preferable especially. When the component (B) is a curing agent, the curing agent has the functional group b. Such a curing agent is not particularly limited as long as it is a compound having two or more functional groups b in the molecule. When the functional group a is a carboxy group, examples of the curing agent include an isocyanate curing agent, an epoxy curing agent, an aziridine curing agent, a carbodiimide curing agent, and an oxazoline curing agent. Among these, an aziridine-based curing agent is preferable from the viewpoint of further improving the adhesion of the toner print layer to the label base material. The said hardening | curing agent may use only 1 type, and may use 2 or more types.

  Examples of the isocyanate curing agent include known aromatic, aliphatic and alicyclic diisocyanates. Examples of the diisocyanates include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, and isophorone diisocyanate. If necessary, tri- or higher functional polyisocyanates and polyisocyanate adducts can be mixed with the diisocyanates. Only one kind of the isocyanate curing agent may be used, or two or more kinds may be used. It is also possible to use the above-mentioned isocyanate curing agent and commercial products. For example, “Coronate Series” manufactured by Tosoh Corporation is available on the market.

  Examples of the aziridine-based curing agent include trimethylolpropane tris [3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (1- (2-methyl) aziridinylpropionate)], N , N′-toluene-2,4-bis (1-aziridinecarboxylate), N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxylate), triethylenemelamine, bisisoprotaloyl-1 -(2-methylaziridine), tri-1-aziridinylphosphine oxide, tetramethylolmethane-tri-β-aziridinylpropionate, 2,2′-bishydroxymethylbutanol-tris [3- (1- Aziridinyl) propionate], 1,6-hexamethylenediethylene urea, N, N′-diphenyl Tan-4,4'-bis (1-aziridine carboxyamide), N, N'-hexamethylene-1,6-bis (1-aziridine carboxyamide) or the like. The said aziridine type hardening | curing agent may use only 1 type, and may use 2 or more types. A commercial item can also be used for the aziridine-based curing agent. For example, “Chemite Series” manufactured by Nippon Shokubai Co., Ltd. is available on the market.

  Examples of the carbodiimide-based curing agent include dicyclohexylmethane carbodiimide, dicyclohexyl carbodiimide, tetramethylxylylene carbodiimide, urea-modified carbodiimide, and the like. The said carbodiimide type hardening | curing agent may use only 1 type, and may use 2 or more types. A commercial item can also be used for the said carbodiimide type hardening | curing agent. For example, “Carbodilite series” manufactured by Nisshinbo Chemical Co., Ltd. is available on the market.

  The oxazoline-based curing agent has two or more oxazoline groups in the molecule and may be a low molecular compound or a polymer. Examples of the low molecular compound oxazoline-based curing agent include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl- 2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2,2′-bis- (2-oxazoline), 2,2′-methylene- Bis- (2-oxazoline), 2,2′-ethylene-bis- (2-oxazoline), 2,2′-trimethylene-bis- (2-oxazoline), 2,2′-tetramethylene-bis- (2 -Oxazoline), 2,2'-hexamethylene-bis- (2-oxazoline), 2,2'-octamethylene-bis- (2-oxazoline), 2,2'-ethyl -Bis- (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline) 2,2′-m-phenylene-bis- (4,4′-dimethyl-2-oxazoline), 2,2 ′-(1,3-phenylene) -bis- (2-oxazoline), bis- (2 -Oxazolinylcyclohexane) sulfide, bis- (2-oxazolinyl norbornane) sulfide and the like. Examples of the polymer oxazoline-based curing agent include a polymer having an addition-polymerizable oxazoline as an essential component as a constituent component. Examples of the addition polymerizable oxazoline include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2 -Isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like. The said oxazoline type hardening | curing agent may use only 1 type, and may use 2 or more types. A commercial item can also be used for the said oxazoline type hardening | curing agent. For example, “Epocross Series” manufactured by Nippon Shokubai Co., Ltd. is available on the market.

  The curing agent is not particularly limited, but may be water-soluble or water-insoluble (oil-soluble).

  Although the said hardening | curing agent is not specifically limited, Room temperature (For example, at least one part in the range of 10-40 degreeC, Preferably it is at least one part in the range of 12-35 degreeC, More preferably, it exists in the range of 15-30 degreeC. And at least a part of those having reactivity with the functional group a is preferred. It is preferable that the curing agent has reactivity with the functional group a at room temperature because the crosslinking reaction proceeds quickly and more sufficiently crosslinks. In addition, the said hardening | curing agent is not restricted to what has the reactivity with the functional group a at room temperature, Even if it has the reactivity with the functional group a by active energy rays, such as an ultraviolet-ray and an electron beam, heat | fever, moisture, etc. Good.

  Although the said hardening | curing agent is not specifically limited, From a viewpoint of suppressing discoloration of a coating layer (P), a non-aromatic hardening | curing agent (curing agent which does not contain an aromatic structure) is preferable.

  When a coating layer (P) contains a hardening | curing agent as a component (B), it is preferable that a coating layer (P) contains resin further. Resins (cellulosic resins, other thermoplastic resins, binder resins, etc.) contained in the coating layer (P) may be referred to as functional groups reactive with the functional groups b ("functional groups c"). May or may not be present. If the resin in the coating layer (P) has a functional group c appropriately, it is estimated that the resin in the coating layer (P) and the component (A) in the toner printing layer are cross-linked by the curing agent. However, the adhesion between the coating layer (P) and the toner printing layer tends to be improved. In addition, ink cracks tend to be less likely to occur in the toner print layer during heat shrinkage. On the other hand, the resin in the coating layer (P) has a functional group c from the viewpoint that the component (B) is not consumed by the reaction inside the coating layer (P) but is consumed by the reaction with the toner printing layer. Those that do not are also preferred.

  Examples of the functional group c include the functional groups exemplified and described as the functional group a. Moreover, as a combination of the functional group b and the functional group c, the combination illustrated and demonstrated as a preferable combination of the functional group a and the functional group b is preferable. The functional group c may be the same as or different from the functional group a, but is preferably the same. In addition, when the functional group c is different from the functional group a, the functional group c has the same reactivity as the functional group a so that the functional group a and the functional group b can easily react. It is preferred that it is lower than the functional group a. Especially, it is preferable that the functional group a and the functional group c are carboxy groups.

  When the said component (B) is an isocyanate type hardening | curing agent, as resin (except a cellulose resin) in a coating layer (P), acrylic resin (especially polyacryl polyol resin) is preferable. When the component (B) is an aziridine-based curing agent or a carbodiimide-based curing agent, the resin (excluding the cellulose-based resin) is an acrylic resin (particularly an acrylic resin having a carboxy group, a polyacryl polyol resin). A urethane resin (preferably a urethane resin using a polyester polyol as a polyol compound, a urethane resin using a polyether polyol as a polyol compound, more preferably a urethane resin using a polyester polyol as a polyol compound), Polyamide resins, particularly preferably acrylic resins.

  When the resin in the coating layer (P) has an acidic functional group c such as a carboxy group, the acid value of the coating layer (P) is not particularly limited, but the coating layer (P) forming the coating layer (P) is not limited. From the viewpoint of avoiding excessive progress of the crosslinking reaction in the working agent, it is preferably 40 mgKOH / g or less (for example, more than 0 mgKOH / g and 40 mgKOH / g or less), more preferably more than 0 mgKOH / g and 30 mgKOH / g. It is as follows.

[Print layer (Y)]
The printed layer (Y) overlaps at least a part of the toner printed layer in the thickness direction on at least one surface of the label base (the surface on which the toner printed layer and the printed layer (X) are provided). It is provided as follows. In particular, the print layer (Y) is preferably provided so as to overlap the entire surface of the region where the toner print layer is provided. When the shrink label of the present invention has a printing layer (Y), the adhesion of the toner printing layer to the label substrate tends to improve even if the primer layer and the printing layer (X) do not contain the component (B). There is. Further, in this case, it is not necessary that the primer layer and the printing layer (X) contain the component (B). Therefore, it is assumed that the primer layer and the printing layer (X) contain the component (B). Problems (eg, thickening of primer coating agent and printing ink, aggregation, reduction of pot life, etc.) can be made difficult to occur.

  The printing layer (Y) contains the component (B) as an essential component. The printing layer (Y) is a layer having a composition different from that of the primer layer, the toner printing layer, and the printing layer (X).

  The print layer (Y) preferably contains a binder resin as an essential component. The printing layer (Y) is not particularly limited, but may contain other components such as a colorant (coloring material) such as a pigment and a dye, an additive, and the like, in addition to the binder resin. The additives are not particularly limited, but are lubricants, plasticizers, anti-settling agents, dispersants, stabilizers, curing agents (crosslinking agents), antifoaming agents, fillers, antioxidants, ultraviolet absorbers, antistatic agents. Agents, color separation preventing agents, fragrances, deodorants, slip agents and the like. Only one type of the other components may be used, or two or more types may be used.

  As a component (B) in a printing layer (Y) layer, binder resin and the said additive are mentioned, for example. Especially, it is preferable that a component (B) is a hardening | curing agent. In this case, it is preferable that the printing layer (Y) further contains a binder resin.

  The binder resin is not particularly limited, and a known or conventional printing layer or binder resin for printing ink can be used. Although the said binder resin is not specifically limited, The role as a main resin component which forms a printing layer (Y) is borne. The binder resin is not particularly limited, but acrylic resin, urethane resin, polyester resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, polyolefin resin (for example, polyethylene resin, polybutadiene resin) Etc.), isocyanate resins, rosin resins, polyvinyl alcohol resins (PVA resins), imine resins, modified olefin resins such as chlorinated polypropylene and ethylene-vinyl acetate copolymers. Above all, the binder resin is preferably an acrylic resin, a urethane resin, or a polyamide resin. As the binder resin, only one kind may be used, or two or more kinds may be used.

  When the component (B) is any of the above additives, the binder resin is preferably one that has poor reactivity (particularly, no reactivity) with the component (B). Therefore, the binder resin depends on the component (B), but when the component (B) is an isocyanate curing agent, the resin in the printing layer (Y) is an acrylic resin (especially polyacrylic). Polyol resin) is preferred. When the component (B) is an aziridine-based curing agent or a carbodiimide-based curing agent, examples of the resin include acrylic resins (particularly acrylic resins having a carboxy group, polyacryl polyol resins), urethane resins (preferably A urethane resin using polyester polyol as the polyol compound, a urethane resin using polyether polyol as the polyol compound, more preferably a urethane resin using polyester polyol as the polyol compound), a polyamide resin, particularly preferably Acrylic resin. As said acrylic resin, the acrylic resin illustrated and demonstrated as said other thermoplastic resin is mentioned.

  The print layer (Y) may contain a component having reactivity with the component (B) (for example, the component having the functional group c), but it is preferable that the print layer (Y) does not substantially contain the component. The content of the component having reactivity with the component (B) in the printing layer (Y) is, for example, 1% by weight or less, preferably 0.5% with respect to the total weight (100% by weight) of the printing layer (Y). % By weight or less, more preferably 0% by weight.

  Although content of the binder resin in a printing layer (Y) is not specifically limited, 5-95 weight% is preferable with respect to the total weight (100 weight%) of a printing layer (Y), More preferably, it is 10-90. % By weight. When the printing layer (Y) does not contain a colorant and an additive or the content thereof is small, the content of the binder resin may be 30% by weight or more, 40% by weight or more, and 45% by weight or more. .

  Although content of the component (B) in a printing layer (Y) is not specifically limited, 1-60 weight% is preferable with respect to the total weight (100 weight%) of a printing layer (Y), More preferably, 3 ~ 50% by weight.

  When the printing layer (Y) contains a white pigment as a colorant, the printing layer (Y) can be used as a background printing layer. The printing layer (Y) when the printing layer (Y) contains a white pigment as a colorant is not particularly limited, but the binder resin is 10 to 10% with respect to the total weight (100% by weight) of the printing layer (Y). 60% by weight, preferably a layer containing 3 to 25% by weight of the curing agent as component (B) and 20 to 80% by weight of white pigment, more preferably 15 to 40% by weight of binder resin, component It is a layer containing 4 to 20% by weight of the curing agent as (B) and 40 to 80% by weight of a white pigment. Moreover, when a printing layer (Y) is the outermost surface of the shrink label of this invention, it is preferable that a printing layer (Y) contains 1 to 10 weight% of lubricants further.

  The printing layer (Y) is not particularly limited, but a solvent drying type printing layer formed with a solvent drying type printing ink, an active energy ray curable printing layer formed with an active energy ray curable printing ink, etc. Is mentioned. Among these, a solvent drying type printing layer is preferable.

  Although the thickness of a printing layer (Y) is not specifically limited, 0.1-10 micrometers is preferable, More preferably, it is 0.2-5 micrometers.

[Other layers]
The shrink label of the present invention is a layer other than the label base material, the primer layer, the toner print layer, the print layer (X), and the print layer (Y) within the range not impairing the effects of the present invention (others). Layer). The other layers are not particularly limited. For example, other printing layers, adhesive layers (pressure-sensitive adhesive layers, heat-sensitive adhesive layers, etc.), film layers, antistatic layers, metals and metal oxides A vapor deposition layer, a light shielding layer, a heat insulation layer, a barrier layer, etc. are mentioned.

  The other print layer is a print layer different from the primer layer, the toner print layer, the print layer (X), and the print layer (Y). The other print layer is preferably a print layer containing no component (B).

  Examples of the other print layer include a design print layer, a background print layer, a protective print layer, and an intermediate layer. The other printed layers are not particularly limited, but may be a single layer or a multilayer.

[Shrink label]
The shrink label of this invention has the said label base material, the said toner printing layer, and printing layer (X) in this order.

  In the shrink label of the present invention, each layer (primer layer, toner print layer, print layer (X), print layer (Y), etc.) may be a single layer or multiple layers. Moreover, when it is a multilayer, the composition of each layer in a multilayer, thickness, etc. may be the same and may differ.

  When the shrink label of the present invention has the primer layer, the toner print layer is preferably provided so as to be in contact with at least a part of the primer layer. In particular, it is preferable that the entire area of the toner print layer is provided so as to be in contact with the primer layer. Moreover, when the shrink label of this invention has a coating layer (P), it is preferable that the coating layer (P) is provided so that it may contact at least one part of the said toner printing layer.

  The shrink label of the present invention preferably has a toner printing layer on the inner side of the cylindrical shape (that is, the side in contact with the adherend with respect to the label base material) when the cylindrical shrink label is used.

  When the shrink label of this invention has a printing layer (Y), although the said primer layer and printing layer (X) may contain the component (B), it is preferable not to contain substantially.

  When the shrink label of the present invention has a print layer (Y), the print layer (Y) is on at least one surface of the label base material (the surface on which the toner print layer and the print layer (X) are provided), It is only necessary to be provided so as to overlap at least a part of the toner print layer in the thickness direction, and the provided position (position in the thickness direction) is not particularly limited. For example, an interlayer between a label substrate and a toner printing layer (if the primer layer is included, an interlayer between the label substrate and the primer layer, an interlayer between the primer layer and the toner printing layer, etc.), a toner printing layer and a printing layer (X) Or the surface of the printing layer (X) opposite to the side having the toner printing layer (for example, the surface of the printing layer (X)). In particular, the printing layer (Y) is preferably provided on the surface between the toner printing layer and the printing layer (X) and on the opposite side of the printing layer (X) from the side having the toner printing layer. More preferably, it is provided between the layer and the printing layer (X), and particularly preferably provided between the toner printing layer and the printing layer (X) and in contact with the toner printing layer. That is, when the shrink label of this invention has a printing layer (Y), it is preferable to have the said label base material, a toner printing layer, a printing layer (Y), and a printing layer (X) in this order. . Furthermore, from the viewpoint of further improving the adhesion of the toner print layer to the label base material, the print layer (Y) is preferably provided so as to be in contact with at least a part of the toner print layer.

  When the shrink label of this invention does not have the said primer layer and printing layer (Y), it is preferable that printing layer (X) contains a component (B). Moreover, when the shrink label of this invention has the said primer layer and does not have a printing layer (Y), it is preferable that at least one of the said primer layer and printing layer (X) contains a component (B). In the latter case, only one of the primer layer and the printing layer (X) may contain the component (B), or both may contain the component (B). The layer containing the component (B) is provided so as to overlap at least a part of the toner print layer in the thickness direction.

  The shrink label of the present invention may be a front printed shrink label, a back printed shrink label, or a duplex printed shrink label. In the present specification, the front printed label is a label showing the toner print layer without passing through the label base material, and means a label having the toner print layer in front of the label base material when the label is viewed. The back printed label is a label showing the toner print layer through the label base material, and means a label having the toner print layer on the back side of the label base material when the label is viewed. Moreover, a double-sided printing label means the label which has a toner printing layer on the double-sided side of a label base material.

  When the shrink label of the present invention is a back printed shrink label, it is preferable that a background print layer is provided. In this case, at least one of the toner print layer, the print layer (X), and the print layer (Y) may be a background print layer, and the other layers (the other layers described above) are background print layers. May be. The background printing layer may be a single layer or may be provided in a plurality of layers by printing a plurality of times (for example, twice).

  When the background print layer is the above-mentioned other layers, the background print layer is not particularly limited, but the binder resin is 10 to 70% by weight and the white pigment is 20% with respect to the total weight (100% by weight) of the background print layer. It is preferably a layer containing -80% by weight, more preferably a layer containing 10-50% by weight of binder resin and 40-80% by weight of white pigment. Moreover, when a background printing layer is the outermost surface of the shrink label of this invention, it is preferable that a background printing layer contains 1-10 weight% of lubricants further.

  The shrink label of the present invention preferably has a crosslinked structure when the toner print layer contains the component (A). Examples of the cross-linked structure include a cross-linked structure in a layer or between layers such as a layer between the toner print layer and the print layer (X). Further, when the toner print layer contains the component (A) and has the primer layer, the layer between the toner print layer and the primer layer, and the layer between the toner print layer and the print layer (X), One or both preferably have a crosslinked structure. Moreover, when it has a printing layer (Y), the component (A) contained in the toner which forms a toner printing layer in the said interlayer, and the component (A) contained in the printing ink which forms a printing layer (Y) ( It is preferable to have a cross-linked structure formed by B). Further, when the primer layer and / or the printing layer (X) contains the component (B), the primer layer is formed between the layer and the component (A) contained in the toner forming the toner printing layer. It preferably has a crosslinked structure formed by the component (B) contained in the printing ink for forming the primer coating agent and / or the printing layer (X).

  Examples of the crosslinked structure include a bond formed by a carboxy group and an isocyanate group, an ester bond formed by a carboxy group and an epoxy group, a bond formed by a carboxy group and an aziridine group, and a carboxy group and a carbodiimide group. Bond formed by carboxy group and oxazoline group, urethane bond formed by hydroxy group and isocyanate group, bond formed by hydroxy group and aziridine group, urethane bond formed by silanol group and isocyanate group, amino Examples thereof include an amide bond formed by a group and an isocyanate group, and a crosslinked structure formed by a bond formed by an amino group and an epoxy group.

  The laminated structure of the shrink label of the present invention is not particularly limited. For example, from one surface of the shrink label, [label substrate / toner print layer / print layer (X)], [label substrate / primer layer / toner] [Print layer / Print layer (X)], [Label substrate / Toner print layer / Print layer (X) / Print layer (Y)], [Label substrate / Primer layer / Toner print layer / Print layer (X) / [Print layer (Y)], [Label substrate / toner print layer / print layer (Y) / print layer (X)], [label substrate / primer layer / toner print layer / print layer (Y) / print layer ( X)] (in the case of the back printed shrink label), [print layer (X) / toner print layer / label base material], [print layer (X) / toner print layer / primer layer / label base material], [ Printing layer (Y) / printing layer (X) / toner printing layer / label substrate], [printing (Y) / printing layer (X) / toner printing layer / primer layer / label substrate], [printing layer (X) / printing layer (Y) / toner printing layer / label substrate], [printing layer (X) / Printing layer (Y) / toner printing layer / primer layer / label base material] (in the case of front printing shrink label), and the like. In the above-described laminated structure, a laminated structure in which at least one of the primer layer, the printed layer (X), and the printed layer (Y) is a coating layer (P) is preferable, and the toner on the side opposite to the label base material A laminated structure in which the layer adjacent to the printing layer is the coating layer (P) is more preferable. In this case, the adhesion between the toner print layer and the label base material and the print layer (X) (if the primer layer is provided, the label print base material and the print layer via the toner print layer, the primer layer and the primer layer ( X) is excellent in adhesion), and ink cracking is less likely to occur in the toner print layer during heat shrinkage.

  When the shrink label of the present invention has a coating layer (P), the toner printing layer and the coating layer (P) are not necessarily provided directly adjacent to each other, but may be provided directly adjacent to each other. preferable. As such a shrink label, among the shrink labels having the laminated structure exemplified above, those having a laminated structure in which the toner printing layer and the coating layer (P) are provided directly adjacent to each other are preferable. Even when the toner printing layer and the coating layer (P) are not provided immediately adjacent to each other, that is, when another layer is provided between the toner printing layer and the coating layer (P), Since the component (B) in the coating agent for forming the coating layer (P) can be impregnated in the toner or the toner printing layer, the toner printing layer becomes hard, or the toner printing layer and the coating layer ( It is presumed that the adhesiveness of P) is improved, but there is a tendency that ink cracks are less likely to occur in the toner print layer during heat shrinkage.

  Among the above-described laminated structures, the laminated structure having the coating layer (P) is particularly preferably [label substrate / toner printing layer / printing layer (X) (coating layer (P))], [label Substrate / toner print layer / print layer (X) / print layer (Y)], [label substrate / toner print layer / print layer (X) (coating layer (P)) / print layer (Y)], [Label substrate / toner print layer / print layer (Y) / print layer (X)], [label substrate / toner print layer / print layer (Y) / print layer (X) (coating layer (P)) ], [Label substrate / primer layer / toner printing layer / printing layer (X) (coating layer (P))], [label substrate / primer layer (coating layer (P)) / toner printing layer / printing Layer (X)], [label substrate / primer layer (coating layer (P)) / toner printing layer / printing layer (X) (coating layer (P))], [label substrate / primer layer / toning layer] -Print layer / print layer (X) / print layer (Y)], [label substrate / primer layer / toner print layer / print layer (X) (coating layer (P)) / print layer (Y)], [Label substrate / primer layer (coating layer (P)) / toner printing layer / printing layer (X) / printing layer (Y)], [label substrate / primer layer (coating layer (P)) / toner Printing layer / printing layer (X) (coating layer (P)) / printing layer (Y)], [label substrate / primer layer / toner printing layer / printing layer (Y) / printing layer (X)], [ Label substrate / primer layer (coating layer (P)) / toner printing layer / printing layer (Y) / printing layer (X)], [label substrate / primer layer / toner printing layer / printing layer (Y) / Printing layer (X) (Coating layer (P))] [Label substrate / Primer layer (Coating layer (P)) / Toner printing layer / Printing layer (Y) / Printing layer (X) (Coating layer ( P) It is a.

  The preferable aspect of the shrink label of this invention is demonstrated using figures. FIG. 1 is a schematic view (partial sectional view) showing an example of a preferred embodiment of the shrink label of the present invention. The shrink label 1 of the present invention shown in FIG. 1 includes a label substrate 2, a primer layer 3, a toner printing layer 4 that is a design printing layer composed of a plurality of colors, a printing layer (Y) 5 that is a background printing layer, and a transparent Printing layer (X) 6 is included in this order. More specifically, in the shrink label 1 of the present invention shown in FIG. 1, the primer layer 3 is on the surface on one side of the label substrate 2 (so that the label substrate 2 and the primer layer 3 are directly adjacent). It is provided on the entire surface excluding the region to be the seal portion. In addition, the toner printing layer 4 is printed on the surface of the label substrate 2 on the side where the primer layer 3 is provided (the surface of the primer layer 3 on the side opposite to the label substrate 2). It is provided partially (on a part of the region where the primer layer 3 is provided) so that the layer 4 is directly adjacent. The printing layer (Y) 5 is provided on the surfaces of the toner printing layer 4 and the primer layer 3 so as to cover the entire area where the toner printing layer 4 is provided. In the region where the toner printing layer 4 is provided, the toner printing layer 4 and the printing layer (Y) 5 are provided so as to be directly adjacent to each other. In the region where the toner print layer 4 is not provided, the primer layer 3 and the print layer (Y) 5 are provided so as to be directly adjacent to each other. Further, in the printing layer (X) 6, the printing layer (Y) 5 and the printing layer (X) 6 are directly adjacent to the surface of the printing layer (Y) 5 (the surface opposite to the label substrate 2). And provided on the outermost surface of the shrink label 1 of the present invention. The printing layer (X) 6 is provided so as to cover the entire area where the toner printing layer 4 is provided. In the shrink label 1 of the present invention shown in FIG. 1, the primer layer 3 and the toner printing layer 4, the toner printing layer 4 and the printing layer (Y) 5, and the toner printing layer 4 and the printing layer (X) 6 are respectively , At least a part of which is provided to overlap. Therefore, the shrink label 1 of the present invention shown in FIG. 1 has a region in which the label base material 2 / toner print layer 4 / print layer (X) 6 are provided in this order. Specifically, it has a region where the label base material 2 / primer layer 3 / toner print layer 4 / print layer (Y) 5 / print layer (X) 6 are provided in this order.

  FIG. 1 shows the shrink label of the present invention having a laminated structure of “toner print layer 4 as design print layer / print layer (Y) 5 as background print layer / print layer (X) 6”. As a modified example of the above laminated structure, a laminated structure of “a toner printed layer as a design printed layer / a toner printed layer as a background printed layer / a printed layer (X) as a coating layer (P)” is also preferable. It can be illustrated as a shrink label.

  The shrinkage rate of the shrink label of the present invention in the main shrinkage direction at 90 ° C. for 10 seconds (sometimes referred to as “heat shrinkage rate (90 ° C., 10 seconds)”) is not particularly limited, but is 20 to 90. % Is preferable, more preferably 30 to 85%, still more preferably 40 to 80%. When the thermal shrinkage (90 ° C., 10 seconds) is less than 20%, the followability with respect to the shape of the container or the like to which the label is attached is insufficient during shrink processing, and a beautiful finish may not be obtained. Although the thermal contraction rate (90 degreeC, 10 second) of the direction orthogonal to the main shrinkage direction of the shrink label of this invention is not specifically limited, -3-15% (especially -1-10%) is preferable. The “main shrinkage direction” of the shrink label is the direction having the largest thermal shrinkage rate, and is generally the direction in which the shrink film is mainly stretched. When the shrink label is a cylindrical shrink label, Generally, the circumferential direction.

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

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

  Although not particularly limited, a toner print layer is provided in a region having a predetermined width from the upper and lower ends of the cylindrical shrink label (the upper and lower ends when the direction perpendicular to the circumferential direction in the cylindrical shrink label is the vertical direction). It is preferable not to be. The upper and lower ends of the cylindrical shrink label are likely to be internally folded at the time of shrink processing, but it is preferable because the generation of the toner print layer can be suppressed and the appearance can be improved by not providing the toner print layer here.

  FIG.2 and FIG.3 is the schematic which shows an example of the cylindrical shrink label which concerns on one Embodiment of the shrink label of this invention, respectively. The cylindrical shrink label 7 according to the present invention shown in FIG. 2 is formed into a cylindrical shape by superposing the other end on the outside of one end of the shrink label according to the present invention formed in a rectangular shape. The outer surface of the part is joined with a solvent or an adhesive to form a seal part 8. In the cylindrical shrink label of the present invention, the shrink film is at least oriented in the circumferential direction D of the cylindrical shrink label of the present invention and can be thermally contracted in that direction. In addition, it is preferable that the cylindrical shrink label of this invention is mounted | worn so that the circumferential direction may turn into a main contraction direction.

  3 is a cross-sectional view taken along the line A-A 'in FIG. 2, that is, an enlarged view of the main part in the vicinity of the seal portion 8 of the cylindrical shrink label 7 of the present invention. In FIG. 3, at the seal portion 8, both ends of the shrink label are joined with a solvent or an adhesive 9. Specifically, in the shrink label of the present invention, the primer layer 3 is provided in a region excluding a region having a predetermined width from the end 11 of the other end of one surface (the inner surface of the cylindrical body) of the label substrate 2. The primer layer 3 is formed on the surface of the primer layer 3 (the surface opposite to the label base material 2) except for the region having a predetermined width from the end 11 on the other end of the one side of the label base material 2. The toner print layer 4 is formed so as to have a smaller area than the layer 3, and a region having a predetermined width is removed from the end 11 at the other end of the one side of the label substrate 2 so as to cover the toner print layer 4. The printed layer (Y) 5 is formed over substantially the entire area, and the other end of one surface of the label substrate 2 is formed on the surface of the printed layer (Y) 5 (the surface opposite to the label substrate 2). The print layer (X) 6 is formed in a region excluding the region having a predetermined width from the end 11 of the portion so as to cover the entire surface of the print layer (Y) 5. To have. Therefore, in the shrink label of the present invention, the primer layer 3, the toner printing layer 4, the printing layer (Y) 5, and the printing layer (X) 6 are formed in a region having a predetermined width from the end 11 at the other end. The label base material 2 is exposed, and the label base material exposed surface is formed. Specifically, the cylindrical shrink label 7 of the present invention includes a label base material exposed surface formed on the inner surface side of the other end portion of the shrink label of the present invention and a label base material formed on the outer surface side of the one end portion. The exposed surface is joined with a solvent or an adhesive 9. In addition, even if it has the primer layer 3, the toner printing layer 4, the printing layer (Y) 5, the printing layer (X) 6 etc. among the said both ends, there is no influence on adhesiveness, You may have these layers. The primer layer 3, the toner print layer 4, the print layer (Y) 5, and the print layer (X) 6 may each be a single layer or a plurality of layers.

  In the cylindrical shrink label 7 of the present invention shown in FIG. 3, one end portion extends to a position where the end 10 overlaps the toner print layer 4 or the background print layer (Y) 5 as the background print layer. In addition, a region where the printing layers (Y) 5 which are background printing layers at one end and the other end overlap with each other via the label substrate 2 is formed. For this reason, since the cylindrical shrink label of the present invention can be seen continuously without the print layer (Y), which is a background print layer formed at one end and the other end, being interrupted at and near the seal portion, Excellent appearance. In the cylindrical shrink label of the present invention, the toner print layer 4 at the other end is formed in a region overlapping with one end (including the end 10), and the toner print layer 4 in the region is covered with the print layer (X). It has been broken. As described above, the cylindrical shrink label 7 of the present invention is configured so that the toner printing layer 4 is provided on a portion that contacts one end (particularly, a portion that contacts the end 10). Since the printing layer (X) 6 is provided so as to cover the layer 4, ink cracks are unlikely to occur in the toner printing layer. The cylindrical shrink label 7 of the present invention may have a structure that overlaps the end of one end and the printing layer (Y) on the other end as shown in FIG. 3, and the end of the one end is the other end. The end of the one end and the print layer on the other end side (Y) that extend to the area overlapping the exposed surface of the label base material and the end of the one end does not extend to the position overlapping the print layer (Y) on the other end side. ) May not be overlapped.

  The thickness of the design print layer (toner print layer) is, for example, 0.1 to 5 μm. The thickness of the background print layer (print layer (Y)) is, for example, 0.5 to 5 μm.

  Although the width | variety of the said seal | sticker part is not specifically limited, 0.2-10 mm is preferable, More preferably, it is 0.3-5 mm, More preferably, it is 0.4-2 mm.

  The shrink label of this invention has the label base material containing a heat-shrinkable film, a toner printing layer, and the printing layer (X) containing a cellulose resin in this order. As described above, the shrink label of the present invention employs a printing layer (X) that uses a cellulose-based resin that is not normally used as a binder resin for the protective layer as a layer for protecting the toner printing layer, thereby allowing heat shrinkage. This makes it difficult to cause ink cracks in the toner printing layer.

  In the conventional shrink label having a toner print layer, ink cracks are likely to occur in the toner print layer during shrink processing. In the back printed shrink label, ink cracking during shrink processing is caused by contact of the inner surface of the label with the container in the state where heat is applied during shrink processing or the inside of the other end is the end of one end. It is thought to be caused by contact with the surface. In shrink processing, shrinkage stress tends to be relatively strong near the seal portion of the cylindrical label. For these reasons, ink cracks are particularly likely to occur near the seal portion of the cylindrical label. Although it has been proposed to provide a protective layer on the inner side of the toner printing layer in the back printed shrink label, the ink cracking is not sufficiently suppressed even if the protective layer is simply provided. Further, the ink breakage was particularly likely to occur when the shrink processing was performed by hot water treatment using a steam tunnel or the like. For this reason, in order to prevent ink breakage in the vicinity of the seal portion, the current situation is that a transparent region without a print layer such as a toner print layer is provided in the vicinity of the seal portion. However, when a cylindrical shrink label having such a transparent region in the vicinity of the seal portion is attached to a beverage container, the interior of the container can be seen through the transparent region, so that the decorative property may be lacking. .

  On the other hand, in the shrink label of the present invention, ink cracking at the time of thermal shrinkage is less likely to occur than a conventional shrink label having a toner printing layer, and ink cracking is less likely to occur near the seal portion of the cylindrical label. For this reason, according to the shrink label of the present invention, it is easy to obtain a shrink label in which a toner print layer having no ink breakage exists in the vicinity of the seal portion even when the shrink processing is performed by hot water treatment. Moreover, there exists a tendency which is excellent in decorativeness by this.

[Manufacturing method and processing method of shrink label of the present invention]
The shrink label manufacturing method of the present invention includes a step of forming a toner print layer on at least one surface of a label substrate (toner print layer formation step), and a step of forming a print layer (X) on the one surface ( Printing layer (X) formation process) at least. In addition, other steps such as a step of forming a primer layer on the one surface (primer layer forming step) and a step of forming a printed layer (Y) on the one surface (printing layer (Y) forming step) are included. You may go out. The toner print layer formation step and the print layer (X) formation step are performed in this order. The primer layer forming step is preferably performed before the toner print layer forming step. The printing layer (Y) forming step is preferably performed after the toner printing layer forming step (preferably after the toner printing layer forming step and before the printing layer (X) forming step).

(Primer layer formation process)
In the primer layer forming step, it is formed by applying a coating agent (primer coating agent) for forming a primer layer on at least one surface of the label base material, followed by drying and solidifying. In addition, the primer layer containing a component (B) is formed using the primer coating agent containing a component (B).

  The method for applying the primer coating agent can be a known and commonly used method, and is not particularly limited. For example, gravure printing, flexographic printing, letterpress printing, silk screen printing, offset printing, etc. Examples thereof include a general-purpose printing method and a coating method using a known or conventional general-purpose coater such as a bar coater, a comma coater, or a spray coater. Among these, from the viewpoints of cost, productivity, etc., the gravure printing method and the flexographic printing method are preferable, and the gravure printing method is particularly preferable. In addition, when the applied primer coating agent is dried or dried and solidified by heating or the like, a general heating device that can be heated on a printing device can be preferably used. From the viewpoint of safety, a hot air heater or the like can be preferably used.

  A commercial item can be used for the said primer coat agent. Moreover, the primer coat agent containing a component (B) may use a commercial item, or mixes a component (B) with the primer coat agent of the commercial item which does not contain a component (B), for example. It can also be obtained. The primer coat agent preferably contains a binder resin having the functional group c.

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

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

  The primer coating agent may be aqueous, oily, or an emulsion system.

  Although the viscosity (23 ± 2 ° C.) of the primer coating agent is not particularly limited, for example, when applied by gravure printing, it is preferably 10 to 1000 mPa · s, more preferably 20 to 500 mPa · s. . The viscosity of the primer coating agent can be controlled by the type and blending amount (content) of the binder resin and other components, a thickener, a thinning agent, and the like. In the present specification, unless otherwise specified, “viscosity” is JIS Z using an E-type viscometer (conical plate-type rotational viscometer) at 23 ± 2 ° C. The value measured according to 8803 is meant.

  In order to control the content of the binder resin and other components in the primer layer, the content of each component such as the binder resin and other components in the non-volatile component of the primer coating agent is determined by the primer layer. What is necessary is just to prepare a primer coating agent so that it may become desired content in it. In general, the content (% by weight) of each component (nonvolatile component) in all the nonvolatile components of the primer coating agent is equal to the content (% by weight) of each component in the primer layer.

(Toner print layer forming process)
In the toner print layer forming step, an electrophotographic method is used by using the ink (toner) for forming the toner print layer on one side of the label base material (the side having the primer layer in the case of having a primer layer). Formed by a printing press. An electrophotographic printing machine, for example, applies a charge to the photosensitive drum, then draws the part where the toner is not desired to be drawn with a laser or the like to remove the charge, and attaches the toner to the photosensitive drum in a desired pattern. The toner is transferred onto the label substrate through a blanket to form the toner print layer. When the toner print layer is a multi-layer having a plurality of colors, the above formation method may be repeated to form a display by transferring each color to a label substrate, but each color toner is placed on a blanket. After transferring one color at a time and drying, the blanket on which all the colors are placed may be pressed against the label substrate and transferred to form a display. At this time, the toner transferred onto the label base material by a halogen heater or the like is heated and melted and fixed on the label base material.

  In the toner print layer forming step, it is preferable that a toner print layer (toner design print layer) which is a design print layer is formed.

  Commercially available products can be used for the electrophotographic printer. Examples of the commercially available products include “LP-S9000 series” manufactured by Seiko Epson Corporation, “SPC831 / 831M”, “SPC830 / 830M”, “SPC810-ME”, “SPC731 / 731M” manufactured by Ricoh Co., Ltd. “SPC730 / 730M”, “HP Indigo WS60000”, “HP Indigo WS6000”, “HP Indigo WS4600”, “HP Indigo WS4600”, Fuji Xerox Co., Ltd. “DocuPrintCt”, manufactured by Hewlett-Packard Company , “DocuPrint C3360”, “DocuPrint C3350”, and the like.

(Printing layer (X) formation process)
In the printing layer (X) formation step, the label base material is formed by applying the printing ink for forming the printing layer (X) to the side having the toner printing layer and drying and solidifying it.

  As a method for applying the printing ink, a gravure printing method, a flexographic printing method, and a letterpress rotary printing method are preferable from the viewpoints of cost, productivity, and the like, and a gravure printing method is particularly preferable. Moreover, when drying the applied printing ink by heating etc., the general heating apparatus which can be heated on a printing apparatus can be used preferably. From the viewpoint of safety, a hot air heater or the like can be preferably used.

  The said printing ink is manufactured by mixing a cellulose resin, the said solvent, and another component as needed, for example. The mixing can be performed by a known and commonly used mixing method, and is not particularly limited. For example, the above-described mixing apparatus or the like can be used. The mixing time (retention time) during mixing is not particularly limited, but is preferably 10 to 120 minutes. The obtained printing ink may be used after being filtered, if necessary. Each of the above components (cellulosic resin, solvent, and other components) may be used alone or in combination of two or more.

  The printing ink is not particularly limited, but may be aqueous, oily, or an emulsion system.

  The viscosity (23 ± 2 ° C.) of the printing ink is not particularly limited. For example, in the case of coating by gravure printing, 10 to 1000 mPa · s is preferable, and 20 to 500 mPa · s is more preferable. The viscosity of the printing ink can be controlled by the type and blending amount (content) of the cellulosic resin and other components, a thickener, a thinning agent, and the like.

  In order to control the content of the cellulose resin and other components in the printing layer (X), the content of each component such as the cellulose resin and other components in the non-volatile component of the printing ink, What is necessary is just to prepare printing ink so that it may become desired content in the said printing layer (X). In general, the content (% by weight) of each component (nonvolatile component) in all the nonvolatile components of the printing ink is equal to the content (% by weight) of each component in the printing layer (X).

(Printing layer (Y) formation process)
In the printing layer (Y) formation step, the printing ink for forming the printing layer (Y) is applied on at least one side of the label base material (on the side on which the toner printing layer and the printing layer (X) are provided). And is formed by drying, solidifying or curing.

  As a method for applying the printing ink, a gravure printing method, a flexographic printing method, and a letterpress rotary printing method are preferable from the viewpoints of cost, productivity, and the like, and a gravure printing method is particularly preferable. Moreover, when drying the applied printing ink by heating etc., the general heating apparatus which can be heated on a printing apparatus can be used preferably. From the viewpoint of safety, a hot air heater or the like can be preferably used.

  When the printing ink is a solvent-drying type printing ink, the printing layer (Y) is specifically formed by applying the solvent-drying type printing ink, evaporating the solvent, and solidifying it by drying. On the other hand, when the printing ink is an active energy ray-curable printing ink, the printing layer (Y) is specifically coated with the active energy ray-curable printing ink and dried as necessary. It is formed by curing by irradiation with active energy rays.

  When the printing ink is a solvent-drying printing ink, the printing ink includes, for example, the binder layer (binder resin contained in the printing layer (Y)), the solvent, and, if necessary, other components. It is manufactured by mixing. Mixing can be performed by a known or conventional mixing method, and for example, the above-described mixing apparatus or the like can be used. The mixing time (retention time) during mixing is not particularly limited, but is preferably 10 to 120 minutes. The obtained printing ink may be used after being filtered, if necessary. Each of the above components (binder resin, solvent, and other components) may be used alone or in combination of two or more.

  When the printing ink is an active energy ray-curable printing ink, the printing ink is a monomer component constituting the binder resin (a binder resin contained in the printing layer (Y)), and as necessary. The above-mentioned solvent, other components, etc. are produced by mixing as necessary. The mixing can be performed by a known and commonly used mixing method, and is not particularly limited. For example, the above-described mixing apparatus or the like can be used. The mixing time (retention time) during mixing is not particularly limited, but is preferably 10 to 120 minutes. The obtained printing ink may be used after being filtered, if necessary. Each of the above components (monomer component, solvent, and other components) may be used alone or in combination of two or more.

  The printing ink is not particularly limited, but may be aqueous, oily, or an emulsion system.

  The viscosity (23 ± 2 ° C.) of the printing ink is not particularly limited. For example, in the case of coating by gravure printing, 10 to 1000 mPa · s is preferable, and 20 to 500 mPa · s is more preferable. The viscosity of the printing ink can be controlled by the type and blending amount (content) of the binder resin, monomer component and other components, a thickener, a thickener and the like.

  In order to control the content of the binder resin and other components in the printing layer (Y), the binder resin in the non-volatile component of the coating agent or the monomer component constituting the binder resin, other components, etc. The printing ink may be prepared so that the content of each of the components becomes a desired content in the printing layer (Y). In general, the content (% by weight) of each component (nonvolatile component) in all the nonvolatile components of the printing ink is equal to the content (% by weight) of each component in the printing layer (Y).

  When manufacturing the shrink label which has a coating layer (P) and the said toner printing layer contains a component (A), the manufacturing method of the shrink label of this invention further includes the process (curing process) to harden | cure. You may go out. Examples of the curing in the curing step include curing by active energy ray irradiation, curing by heat (thermal curing), curing by moisture (moisture curing), two-component reaction type curing (two-component reaction curing), and the like. In addition, when hardening progresses at normal temperature etc., it is not necessary to perform hardening processing, such as active energy ray irradiation and a heating, separately. In addition, when a treatment such as drying, dry solidification, or active energy irradiation is performed at the time of forming the toner print layer, the print layer (X), or the print layer (Y), curing proceeds simultaneously with the layer formation by the above treatment. In this case, it is not necessary to perform a separate curing process. Although it does not specifically limit as said active energy ray, For example, visible light, an ultraviolet-ray, an electron beam etc. are mentioned.

  When curing by active energy ray curing or heat curing, the curing may be performed after laminating the toner printing layer and the coating layer (P) on one side of the label base material. Layer, the toner printing layer, the printing layer (X), the printing layer (Y), etc.) are preferably laminated. In addition, the said hardening may advance simultaneously with the said lamination | stacking, when it is not necessary to perform special hardening processes, such as moisture hardening and 2 liquid reaction hardening.

  In the two-component reaction curing, an operation other than mixing the two components is not particularly required, but a heating device or a humidity control device may be used to promote the curing reaction. In addition, the two-component reaction curing may proceed at a relatively low temperature (for example, 40 ° C. or lower, 30 ° C. or lower, or normal temperature) over time. In this case, for example, curing can be performed by performing an aging treatment for 8 to 48 hours in a constant temperature bath (or a constant temperature and humidity chamber) having the predetermined temperature.

  As described above, a shrink label in which the toner printing layer and the printing layer (X) are formed in this order on at least one surface of the label substrate can be produced.

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

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

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

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, in Table 1, the structure of the printing ink used by the Example and the comparative example, the evaluation result of the produced shrink label, etc. were shown. Table 2 shows details of raw materials in the printing inks used in Examples and Comparative Examples (trade name, manufacturer name, nonvolatile content, weight average molecular weight, etc.) and the like.

Examples 1-9, Comparative Examples 1-3
(Shrink label)
Emulsion containing a polyolefin resin having a carboxy group as a binder resin on one side of a polyester (PET) film (heat-shrinkable film) (trade name “LX-18S”, manufactured by Mitsubishi Plastics, Inc., thickness: 40 μm) The primer coating agent of the mold was applied and dried and solidified by gravure printing, and a primer layer was formed on the entire surface other than the vicinity of the seal portion. Next, a toner containing toner particles including a polyolefin resin having a carboxy group as a binder resin is printed with a digital printing machine of a photographic printing method, and a design printing layer with four process colors (CMYK) on the primer layer. Then, a toner print layer as a white background print layer was formed on substantially the entire surface of the region provided with the primer layer. Subsequently, the protective printing ink having the composition shown in Table 1 was applied, dried and solidified by gravure printing, and a protective printing layer was formed on the entire surface except for the vicinity of the portion to be the seal portion so as to cover the toner printing layer.

  As described above, a shrink label having a laminated structure of PET film (thickness: 40 μm) / primer layer (thickness: 1 μm) / toner printing layer (total thickness: 2 μm) / protective printing layer (thickness: 2 μm) is obtained. It was.

Example 10
A shrink label was produced in the same manner as in Example 2 except that an aqueous primer coating agent containing a polyethyleneimine resin as a binder resin was used as the primer coating agent.

Example 11
A shrink label was produced in the same manner as in Example 2 except that an oil-based primer coating agent containing a polyamide-based resin as a binder resin was used as the primer coating agent.

  In Examples and Comparative Examples, the ratio of the content of nonvolatile components in the binder resin and the curing agent (nonvolatile content) to the total weight (100% by weight) of the nonvolatile components in the protective printing ink is a shrink label. It is equal to the proportion of the content of the structural unit derived from the binder resin in the protective printing layer and the curing agent.

(Evaluation)
The following evaluation was performed about the shrink label obtained in Examples 1-11 and Comparative Examples 1-3. The evaluation results of Examples 1 to 9 and Comparative Examples 1 to 3 are shown in Table 1. For Examples 10 and 11, the same results as in Example 2 were obtained.

Ink cracking test (hot water immersion shrinkage test)
From the shrink labels obtained in Examples and Comparative Examples, a measurement sample of 210 mm (main shrinkage direction; width direction of shrink film) × 110 mm (perpendicular to main shrinkage direction; longitudinal direction of shrink film) was collected. . The measurement sample is further adjusted so that the main shrinkage direction of the measurement sample (the main shrinkage direction of the shrink film) is the circumferential direction and the surface on the side provided with the protective printing layer is the inner side. One end and the other end are overlapped to form a cylinder so that the protective printing layer on the side overlaps, and the shrink film on the one end and the other end is made of THF, and the width of the seal portion is 3 mm. The cylindrical shrink label was obtained (peripheral length: 200 mm).
A cylindrical glass bottle having a diameter of 62 mm (circumferential length of 194 mm) and a height of 108 mm was prepared. Furthermore, a 10 mm (main shrinkage direction) × 110 mm (perpendicular to the main shrinkage direction) shrink film (trade name “LX-18S”, manufactured by Mitsubishi Plastics, Inc., thickness: 45 μm) was prepared.
Alignment so that the width direction (main shrinkage direction) of the strip is the circumferential direction of the cylindrical glass bottle, and the upper and lower ends of the strip and the upper and lower ends of the cylindrical glass bottle were fixed with cellophane adhesive tape (upper and lower ends) The strip and the cylindrical glass bottle are not bonded at the center of the strip, except for). Next, the cylindrical shrink label is covered from above the cylindrical glass bottle (with a strip) so that the protective printing layer contacts the strip, and immersed in hot water at 90 ° C. for 30 seconds to heat the shrink label. Shrinkage (the strip also thermally shrinks in the width direction at this time) to obtain a labeled container.
Observe the appearance (outside) of the label of the container with the label, peel off the cylindrical shrink label, observe the toner printed layer inside the label, and crack the ink along the strip (in the height direction of the container). It was visually observed whether streaky ink peeling occurred). Evaluation was made according to the following criteria.
Good (○): No ink cracking can be confirmed from the outside or the inside of the peeled label. Available (△): Ink cracking cannot be confirmed from the outside, but when the label is peeled off, ink is printed inside the label. Cracks can be confirmed Defect (x): Ink cracks can be confirmed from the outside

  As can be seen from the evaluation results, the shrink labels (Examples) of the present invention did not cause ink cracks in the toner printing layer during shrink processing, or even if they occurred, confirmed the occurrence of ink cracks from the outside. could not. On the other hand, in the shrink label (comparative example) in which the protective printing layer does not contain a cellulose-based resin, ink cracking of the toner printing layer occurred during shrink processing, which could be confirmed from the outside.

DESCRIPTION OF SYMBOLS 1 Shrink label of this invention 2 Label base material 3 Primer layer 4 Toner printing layer 5 Printing layer (Y)
6 Print layer (X)
7 Cylindrical shrink label of the present invention 8 Seal portion 9 Solvent or adhesive 10 End of one end 11 End of other end

Claims (8)

A label base material comprising a heat-shrinkable film, and the toner printing layer, the printing layer containing a cellulose-based resin and (X), have a in this order,
The toner print layer contains a component having a functional group a, and a layer containing a component having reactivity with the functional group a on the side of the label substrate on which the toner print layer is provided (coating layer) (P)), and the coating layer (P) is provided so as to overlap at least part of the toner print layer in the thickness direction .   The shrink label according to claim 1, wherein the content of the cellulose resin in the printed layer (X) is 20% by weight or more.   The shrink label of Claim 1 or 2 which has the said label base material, the primer layer containing binder resin, the said toner printing layer, and the said printing layer (X) in this order. Before SL toner printing layer, the provided in contact with at least a portion of the primer layer, said coating layer (P) is provided in contact with at least a portion of the toner printed layer, wherein Item 5. The shrink label according to item 3. 5. The print layer according to claim 1, wherein a print layer other than the print layer (X) is provided between the toner print layer and the print layer (X) . The shrink label according to item 1 . The shrink label according to any one of claims 1 to 5 , wherein the printed layer (X) is the coating layer (P). The shrink label according to claim 3 or 4 , wherein the binder resin in the primer layer is one or more resins selected from the group consisting of polyethylene resins, imine resins, polyamide resins, and urethane resins. . The component having reactivity with the functional group a has a functional group reactive with the functional group a (functional group b), and the combination of the functional group a and the functional group b is a carboxy group and an isocyanate group, Carboxy group and epoxy group, carboxy group and aziridine group, carboxy group and carbodiimide group, carboxy group and oxazoline group, hydroxy group and isocyanate group, hydroxy group and aziridine group, silanol group and isocyanate group, amino group and isocyanate group, or amino group It is a group and an epoxy group, The shrink label of any one of Claims 1-7 .

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