JP2017068101A - Shrinkable label - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a shrinkable label in which a metal layer or a printing layer is easy to follow thermal shrinkage of a label base material.SOLUTION: There is provided a shrinkable label which has a label base material containing a heat shrinkable film, a layer (A layer) that is a metal layer or a printing layer provided on at least one surface of the label base material, and a coating layer provided so as to overlap at least a part of the A layer in the thickness direction, where the coating layer contains a binder resin and polyrotaxane.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a shrink label. More specifically, the present invention relates to a shrink label in which a metal layer or a printed layer easily follows the heat shrinkage of a label substrate.

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

  For example, a shrink label having a metallic luster is known as the shrink label. As a technique for imparting a metallic luster to a shrink label, there are a method of directly depositing a metal on a label base material to provide a vapor deposition layer (vapor deposition method), and a method called a cold stamp method (for example, see Patent Document 1). In the cold stamp method, an adhesive is applied to a label base material in advance corresponding to a pattern of a predetermined shape, and a transfer foil film is pressed thereon to transfer the metal foil to a portion where the adhesive is applied. Is.

  By the way, 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, a toner is used from the viewpoint of a small lot and a low cost. A method of forming the print layer with an electrophotographic printer has been proposed (see, for example, Patent Document 2).

JP, 2014-063083, A JP 2002-144694 A

  However, the metal layer provided by the vapor deposition method, the cold stamp method, or the like hardly follows the shrinkage of the heat-shrinkable film that is the label base material of the shrink label when the shrink label is thermally shrunk. For this reason, before and after shrink processing, the metal layer was whitened (shrinkage whitened) and the like, and the metallic luster and brightness were liable to decrease.

  Also, the toner print layer formed using toner is difficult to follow the shrinkage of the heat-shrinkable film as the label base material when the shrink label is thermally shrunk. For this reason, cracking (ink cracking) is likely to occur in the toner print layer during shrink processing of the shrink label, and ink cracking is particularly likely to occur in the heat treatment by the steam tunnel. For this reason, there is a demand for a shrink label in which the metal layer and the toner printing layer have good followability to the heat shrinkage of the heat shrinkable film.

  Accordingly, an object of the present invention is to provide a shrink label in which the metal layer or the printing layer is excellent in the ability to follow the thermal shrinkage of the label substrate.

  That is, the present invention includes a label base material including a heat-shrinkable film, a layer (A layer) that is a metal layer or a printed layer provided on at least one surface of the label base material, and the A layer in the thickness direction. And a coating layer provided so as to overlap at least a part of the coating layer, wherein the coating layer contains a binder resin and a polyrotaxane.

  The coating layer preferably contains 0.1 to 70% by weight of polyrotaxane with respect to the total amount of the coating layer.

  The shrink label has a configuration in which the A layer is the printing layer, the label base material, the printing layer, and the protective printing layer are provided in this order, and the protective printing layer is the coating layer. May be.

  In the shrink label, the A layer is a toner printing layer, the toner printing layer contains a component having a functional group A, and the coating layer is crosslinked as a component having reactivity with the component having the functional group A. You may have the structure containing an agent.

  The shrink label has a configuration in which the A layer is a metal layer, the label base material, the anchor coat layer, and the metal layer are provided in this order, and the anchor coat layer is the coating layer. Also good.

  The shrink label may have a configuration in which the A layer is a metal layer, the label base material, the adhesive layer, and the metal layer are provided in this order, and the adhesive layer is the coating layer. .

  Since the shrink label of the present invention has the above-described configuration, the metal layer or the printed layer is excellent in the ability to follow the thermal contraction of the label substrate. For this reason, the shrink label of the present invention having a metal layer is less likely to cause shrinkage whitening of the metal layer, the metal gloss is hardly lowered before and after shrink processing, and is excellent in the shine and decoration of the shrink label. Moreover, since the shrink label of this invention which has a printing layer does not generate | occur | produce an ink crack easily at the time of shrink processing, it can provide the shrink label which is excellent in decorating property.

It is the schematic (partial sectional drawing) which shows an example of the shrink label of this invention whose A layer is a metal layer. It is the schematic (partial sectional drawing) which shows an example of the shrink label of this invention whose A layer is a toner printing layer. It is the schematic which shows an example of the cylindrical shrink label which is one Embodiment of the shrink label of this invention. FIG. 4 is a schematic view (an enlarged view of a main part of the A-A ′ cross section in FIG. 3) illustrating an example of a cylindrical shrink label that is an embodiment of the shrink label of the present invention in which the A layer is a metal layer. FIG. 4 is a schematic view (an enlarged view of the main part of the A-A ′ cross section in FIG. 3) showing an example of a cylindrical shrink label that is an embodiment of the shrink label of the present invention in which the A layer is a toner print layer.

  The shrink label of this invention has at least the label base material containing a heat-shrinkable film, the layer (A layer) which is a metal layer or a printing layer, and the coating layer containing binder resin and a polyrotaxane. In addition, in this specification, the said coating layer containing binder resin and a polyrotaxane may be called "the coating layer of this invention." Further, the metal layer and the print layer may be collectively referred to as “A layer”. The shrink label of this invention may contain layers (other layers) other than the said label base material, A layer, and the coating layer of this invention within the range which does not impair the effect of this invention.

[Coating layer of the present invention]
The coating layer of this invention is an essential layer in the shrink label of this invention, and is provided in the at least one surface of the label base material. The coating layer of the present invention is a layer (coating layer) containing a binder resin and a polyrotaxane as essential components. Since the coating layer of the present invention has the above-described configuration, the A layer is excellent in the followability to the thermal contraction of the label base material.

(Binder resin)
It does not specifically limit as said binder resin, The binder resin for well-known thru | or usual coating layers can be used. The binder resin does not include the polyrotaxane. Although the said binder resin is not specifically limited, it plays the role as the main resin component which forms the coating layer of this invention. Examples of the binder resin include acrylic resins, urethane resins, polyester resins, polyamide resins, cellulose resins (including nitrocellulose resins), vinyl chloride-vinyl acetate copolymer resins, chlorinated polypropylene, Examples thereof include modified olefin resins such as ethylene-vinyl acetate copolymer. Among them, from the viewpoint of improving the flexibility of the coating layer of the present invention and further improving the followability of the A layer to the label base material when the shrink label is thermally shrunk, an acrylic resin, a urethane resin, and a cellulose type Resin is preferable, and urethane resin is more preferable. As the binder resin, only one kind 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; carboxyl group-containing (meth) acrylic such as carboxyethyl acrylate Esters; 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, diethylene glycol mono ( Hydroxyl group-containing (meth) acrylic acid esters such as (meth) acrylate and dipropylene glycol mono (meth) acrylate [preferably (meth) acrylic acid hydroxy C _1-8 alkyl ester and the like]; (meth) acrylic acid cyclohexyl, (meta ) (Meth) acrylic acid cycloalkyl esters such as isobornyl acrylate; N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide (Meth) acrylic acid amide derivatives such as N, N-diethyl (meth) acrylamide; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate And monomers having a (meth) acryloyl group (monomers having at least an acryloyl group or a methacryloyl group) such as (meth) acrylic acid dialkylaminoalkyl esters such as dipropylaminopropyl (meth) acrylate. The said acrylic monomer may use only 1 type, and may use 2 or more types. In the present specification, “(meth) acryl” means “acryl”, “methacryl”, or both. The same applies to “(meth) acryloyl”, “(meth) acrylonitrile” and the like.

  The monomer component constituting the acrylic resin other than the acrylic monomer is not particularly limited. For example, a carboxyl group-containing polymerizable unsaturated compound such as crotonic acid, itaconic acid, fumaric acid, maleic acid, or the anhydride thereof; Styrenic compounds such as styrene, vinyl toluene and α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl halides such as vinyl chloride; vinyl ethers such as methyl vinyl ether; cyano groups such as (meth) acrylonitrile Contains vinyl compounds; ethylene, propylene, and the like.

  The content of the acrylic monomer in the total amount (100% by 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, More preferably, it is 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 from the viewpoint of wear resistance of the coating layer of the present invention and adhesion to the label substrate. Is 30,000 to 200,000. In addition, in this specification, although a weight average molecular weight (Mw) is not specifically limited, For example, it can measure by GPC using polystyrene as a standard substance.

  The glass transition temperature (Tg) of the acrylic resin is not particularly limited, but is preferably 30 to 120 ° C, more preferably 40 to 100 ° C, from the viewpoint of improving the wear resistance and heat resistance of the coating layer of the present invention. It is. In the present specification, the glass transition temperature (Tg) of the resin can be measured by DSC (differential scanning calorimetry) based on, for example, JIS K7121. The DSC measurement is not particularly limited. For example, the DSC measurement can be performed using a differential scanning calorimeter “DSC6200” manufactured by Seiko Instruments Inc. under a temperature rising rate of 10 ° C./min.

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

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

  Although the weight average molecular weight (Mw) of the said urethane type resin is not specifically limited, 10,000-100,000 are preferable, More preferably, it is 20,000-80,000, More preferably, it is 30,000-70,000.

  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 cellulose-based resin is not particularly limited. For example, nitrocellulose (nitrified cotton); cellulose acetate butyrate (cellulose acetate butyrate: CAB), cellulose acetate (cellulose acetate), cellulose acetate propionate (cellulose acetate propionate). : CAP) and the like, and a cellulose resin esterified with a carboxylic acid. Examples of the carboxylic acid include acetic acid, butyric acid, propionic acid, acetic anhydride, and butyric anhydride. As said cellulose resin, the cellulose resin esterified with carboxylic acid is preferable, More preferably, it is CAB. 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.

  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”, KOREA CNC “RS Series”, “SS Series” etc. Is available at

  The content (total amount) of the binder resin in the coating layer of the present invention is not particularly limited, but is preferably 20 to 99.9% by weight with respect to the total amount (100% by weight) of the coating layer of the present invention, More preferably, it is 30 to 95 weight%, More preferably, it is 35 to 90 weight%. When the content is 30% by weight or more, the adhesion of the coating layer to the label base material and the A layer is improved, and the coating layer is difficult to peel from the label base material. When the content is 99.9% by weight or less, the amount of polyrotaxane, coloring material, additive, etc. added is increased, and the coating layer can be easily designed.

(Polyrotaxane)
The polyrotaxane is composed of a plurality (two or more) of cyclic molecules, a linear molecule that makes the plurality of cyclic molecules skewered, and arranged at the end of the linear molecule to prevent detachment of the plurality of cyclic molecules. And a blocking group. That is, the polyrotaxane is a complex having a plurality of cyclic molecules, a linear molecule, and a blocking group, and the linear molecule has a plurality of cyclic molecules penetrating the plurality of cyclic molecules. It has a structure in which both ends of the linear molecule are blocked by blocking groups so that the molecule does not fall out of the linear molecule. The coating layer of the present invention is presumed that the polyrotaxane is included so that the cyclic molecules in the polyrotaxane can be moved freely on the linear molecules during heat shrinkage, but the layer A is a label base material. Excellent followability to heat shrinkage.

  In the present specification, in addition to the above complex, polyrotaxane includes a crosslinked product obtained by crosslinking the above complexes with a cyclic molecule portion or the like, and a weight obtained by polymerizing the above complex with another monomer or polymer. Mergers are also included.

  The linear molecule may be substantially linear, and may have a branched chain as long as the cyclic molecule as a rotor is rotatable and can exert a pulley effect. Moreover, although it is influenced also by the magnitude | size of a cyclic molecule, the length of a linear molecule is not specifically limited as long as a cyclic molecule can exhibit a pulley effect.

  As the linear molecule, a known or commonly used linear polymer can be used. The polymer is not particularly limited. For example, polyolefin resin, polyether resin, polyester resin, polyamide resin, acrylic resin, polysiloxane, polyene, polystyrene resin, polyvinyl chloride, polycarbonate resin, Examples include urethane resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose resins, polyacrylamides, polyvinyl acetal resins, polyamines, and the like.

  Examples of the polyolefin resin include α-olefin homo-copolymers and two or more copolymers, and examples thereof include polyethylene resins, polypropylene resins, and polyisoprenes. Examples of the polyether resin include polyethylene glycol, polypropylene glycol, polytetrahydrofuran and the like. Examples of the polyester resins include polyesters obtained by ring-opening polymerization of lactones such as ε-caprolactone, polyesters containing polyvalent carboxylic acids (particularly dicarboxylic acids) and polyols (particularly diols) as essential components, and polylactic acid polymers. Etc. Examples of the polysiloxane include polydimethylsiloxane. Examples of the polyene include conjugated polyenes such as polybutadiene and polyisoprene. Moreover, the said linear molecule | numerator may have aromatic rings, such as a benzene ring, in a molecule | numerator.

  As the polymer constituting the linear molecule, polyether resins and polyester resins are preferable, and polyethylene glycol is particularly preferable.

  The ends (particularly both ends) of the linear molecule are blocked with a blocking group. Therefore, the compound that forms the linear molecule before it is blocked by the blocking group (sometimes referred to as “linear molecular precursor”) is a compound that forms a blocking group at both ends (“ It may preferably be referred to as a “blocking group precursor”) and has a group having reactivity. The reactive group can be appropriately selected depending on the type of reactive group of the blocking group precursor, and examples thereof include a hydroxy group, an amino group, a carboxy group, and a thiol group. . Among these, a carboxy group is preferable.

  The cyclic molecule is not particularly limited as long as it includes a linear molecule and exhibits a pulley effect, and a known or conventional cyclic substance can be used. Further, the cyclic molecule includes a molecule in which the ring is not completely closed, such as a “C” shape, in addition to a molecule in which the ring is closed.

  Examples of the cyclic molecule include cyclodextrin, crown ether (including benzocrown ether, dibenzocrown ether, and dicyclohexanocrown ether), derivatives or modified products thereof, and the like. Examples of the cyclodextrin include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, dimethylcyclodextrin, and glucosylcyclodextrin. Of these, α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin are preferable, and α-cyclodextrin is particularly preferable. The said cyclic molecule can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The cyclic molecule may have a reactive group. In this case, there is a tendency that cross-linking between the polyrotaxanes or between the polyrotaxane and the other polymer easily proceeds. The reactive group can be appropriately selected depending on the type of polymer to be crosslinked, and examples thereof include a hydroxy group, an amino group, a carboxy group, a thiol group, an aldehyde group, and an active energy ray polymerizable group. It is done. Moreover, the below-mentioned modifying group may have the group which has the said reactivity.

  The active energy ray-polymerizable functional group is not particularly limited as long as it is a group that can be polymerized by irradiation with active energy rays, and examples thereof include an active energy ray radical polymerizable group and an active energy ray cationic polymerizable group. It is done. Among them, an active energy ray radical polymerizable group is preferable, and a group containing a carbon-carbon unsaturated bond such as an ethylenically unsaturated group is more preferable. More specific examples of the ethylenically unsaturated group include a vinyl group, a propenyl group, an isopropenyl group, and a (meth) acryloyl group (acryloyl group, methacryloyl group). Moreover, as said active energy ray cationically polymerizable group, an epoxy group, an oxetanyl group, an oxolanyl group etc. are mentioned, for example.

  The number of cyclic molecules possessed by the polyrotaxane is not particularly limited as long as it is 2 or more.

  The polyrotaxane is not particularly limited, but preferably at least one of the linear molecule and the plurality of cyclic molecules has a modifying group, and more preferably at least one of the plurality of cyclic molecules has a modifying group. . By the modifying group, for example, various functions such as a function of bonding polyrotaxanes or a binder resin and a polyrotaxane, solubility, and the like can be imparted to the polyrotaxane.

  Examples of the modifying group include an organic group, such as an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group), a cycloalkyl group (for example, a cyclopropyl group, a cyclobutyl group). Group, cyclopentyl group, cyclohexyl group, cyclododecyl group, etc.), aryl group (eg, phenyl group, tolyl group, xylyl group, naphthyl group, etc.), cycloalkyl-alkyl group (eg, cyclohexylmethyl group, methylcyclohexyl group, etc.) ), An aralkyl group (for example, benzyl group, phenethyl group, etc.), a halogenated hydrocarbon group in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom (for example, chloromethyl group, 3-chloropropyl group, 3 , 3,3-trifluoropropyl groups, etc.) Or unsubstituted hydrocarbon group, and the like. In addition, the organic group has two or more of the monovalent substituted or unsubstituted hydrocarbon groups, an ether bond (—O—), a thioether bond (—S—), an ester bond (—CO—O—), an amide. Examples include a group bonded through a linking group such as a bond (—CO—NH—) and a carbonyl group (—CO—). Examples of the modifying group include a silyl group, a nitrate ester group, and a tosyl group.

As the modifying group, an organic group is preferable, and an organic group having 6 or more (more preferably 9 or more) carbon atoms is more preferable. The organic group is particularly preferably a group [—C ₃ H ₆ O— {CO— (CH ₂ ) ₅ —O} _p —H] in which a caprolactone-derived polyester is bonded via a propyloxy group. Note that p represents an integer of 1 or more. Examples of the propyloxy group include n-propyloxy group and isopropyloxy group.

  When the cyclic molecule is a cyclodextrin, it is preferable that the hydrogen atom of the hydroxy group in the cyclodextrin is substituted with the modifying group. That is, the cyclic molecule is preferably a cyclodextrin having at least a group in which a hydrogen atom of a hydroxy group is substituted with the modifying group.

  The cyclic molecule may have one modifying group per cyclic molecule or may have two or more modifying groups. Therefore, when the cyclic molecule is a cyclodextrin, the hydrogen atom of one hydroxy group in the cyclodextrin may be substituted with the modifying group, and the hydrogen atoms of two or more hydroxy groups may be substituted with the modifying group. May be substituted. In addition, when it has two or more modifying groups per cyclic molecule, the above two or more modifying groups may be only one kind or two or more different kinds. Further, the modifying groups in the plurality of cyclic molecules may be the same or different.

  As described above, the blocking group is disposed at the end (both ends) of the linear molecule and has a role of preventing the plurality of cyclic molecules from falling off. The blocking group is not particularly limited as long as the plurality of cyclic molecules can maintain a state in which the plurality of cyclic molecules are penetrated by the linear molecule, for example, a bulky group, an ionic group, etc. Is mentioned. Examples of the bulky group include a spherical group and a side wall-shaped group. In addition, when the blocking group is a group having the ionicity, the ionicity of the ionic group and the ionicity of the cyclic molecule interact with each other, for example, repel each other, thereby It is possible to maintain the state where the molecule is skewered into the linear molecule.

  Specific examples of the blocking group include dinitrophenyl groups such as 2,4-dinitrophenyl group and 3,5-dinitrophenyl group; cyclodextrinyl group; adamantyl group; trityl group; fluorescein group; And polycyclic aromatic hydrocarbon groups such as these, and derivatives or modified products thereof.

  The blocking group needs to have a role of blocking the end of the linear molecule. For this reason, it is preferable that the blocking group precursor has groups having reactivity with both ends of the linear molecular precursor. The reactive group can be appropriately selected depending on the type of the reactive group of the linear molecular precursor. Especially, it is preferable that the reactive group which the said linear molecular precursor has is a carboxy group, and the reactive group which the said blocking group precursor has is an amino group. That is, the linear molecule and the blocking group are preferably bonded by an amide bond.

  The polyrotaxane can be produced by a known or conventional method. For example, a plurality of cyclic molecules and a linear molecular precursor are mixed, and the opening of the cyclic molecule is penetrated by the linear molecular precursor in a skewered manner so that the linear molecular precursor is included in the cyclic molecule. Subsequently, the reactive group of the linear molecular precursor and the reactive group of the blocking group precursor are reacted to block both ends of the linear molecule with a blocking group. A polyrotaxane can also be used individually by 1 type, and can also be used in combination of 2 or more type. In addition, as a polyrotaxane, commercial items, such as a brand name "Celum superpolymer" series (made by Advanced Soft Materials Co., Ltd.), can also be used, for example.

  The content (total amount) of the polyrotaxane in the coating layer of the present invention is not particularly limited, but is preferably 0.1 to 70% by weight with respect to the total amount (100% by weight) of the coating layer of the present invention. Preferably it is 0.5 to 65% by weight, more preferably 0.8 to 63% by weight. When the content is 1% by weight or more, the followability of the A layer to the thermal contraction of the label base material is further improved. When the content is 70% by weight or less, blocking tends to hardly occur when the coating layer of the present invention is provided.

  In the shrink label of the present invention, when the A layer is a printing layer (particularly a toner printing layer), the coating layer of the present invention adjacent to the printing layer contains a component having reactivity with the components in the printing layer. Is preferred. In this case, the component in the printing layer and the component in the coating layer of the invention having reactivity with the component are bonded (crosslinked) during or after the formation of both layers, and the printing layer and the invention. This is presumed to be due to the improved adhesion of the coating layer, but the printed layer is excellent in the ability to follow the thermal shrinkage of the label substrate, and ink cracks in the printed layer are less likely to occur during shrink processing.

  In addition, when the component in a printing layer and the component in the coating layer of this invention have reactivity, both components have a functional group which is mutually reactive. In this specification, the functional group which the component which has the reactivity with the component in the coating layer of this invention in a printing layer has may be called "functional group A." In addition, when the functional group (that is, the functional group having reactivity with the functional group A) of the component having reactivity with the component in the printing layer in the coating layer of the present invention is referred to as “functional group B”. There is. Therefore, the coating layer of the present invention preferably contains a component having a functional group B (that is, a component having reactivity with the functional group A). The component having the functional group B may or may not be bonded (crosslinked) to the component having the functional group A in the printed layer in the shrink label of the present invention.

  In the present specification, the component having the functional group A includes the component having the functional group A in addition to the component having the unreacted functional group A itself (for example, the component having the functional group B). ) And bonded (crosslinked). In addition to the component itself having the unreacted functional group B, the component having the functional group B includes other components (for example, a component having the functional group A, a functional group described later). Also included are those bonded (crosslinked) to the component having C.

  The component having the functional group B in the coating layer of the present invention has a functional group having reactivity with the functional group A. The functional group 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, an isocyanate group, and an epoxy group. Amino group, aziridine group, carbodiimide group, hydrosilyl group, silanol group, mercapto group, vinyl group and the like. 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 in which no reaction occurs 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. A carbodiimide group is more preferred, and an aziridine group is more preferred. 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.

  Although it will not specifically limit if it is a component which comprises the coating layer of this invention as a component which has the said functional group B, For example, a crosslinking agent (curing agent) other than the said binder resin and the said polyrotaxane etc. are mentioned. Especially, the said binder resin and a crosslinking agent are preferable, More preferably, it is a crosslinking agent. In addition, the component which has the functional group B may be sufficient as the some component in the component which comprises the coating layer of this invention. In the present specification, the crosslinking agent includes those in a state where the crosslinking agent is bonded to other components in addition to the crosslinking agent before crosslinking.

  When the component having the functional group B is the binder resin, the binder resin has the functional group B. In this case, the adhesion between the printing layer and the coating layer of the present invention is improved by crosslinking the component having the functional group A described later and the binder resin in the coating layer of the present invention. Is likely to be relatively hard, but there is a tendency that ink cracks in the printed layer are less likely to occur. The binder resin having the functional group B may be reactive with the functional group A at room temperature. The binder resin has reactivity with the functional group A by active energy rays such as ultraviolet rays and electron beams, heat, moisture, and the like. You may have.

  When the component having the functional group B is the crosslinking agent, the coating layer of the present invention contains the binder resin (particularly, a binder resin that is not reactive with the functional group A) and the crosslinking agent. It is preferable. When the component having the functional group B is the crosslinking agent, the crosslinking agent has the functional group B. Such a crosslinking 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 crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a carbodiimide crosslinking agent, and an oxazoline crosslinking agent. Among these, from the viewpoint of making ink cracking of the printing layer less likely to occur, an aziridine-based crosslinking agent and an isocyanate-based crosslinking agent are preferable, and an isocyanate-based crosslinking agent is particularly preferable. Only 1 type may be used for the said crosslinking agent, and 2 or more types may be used for it.

  Examples of the isocyanate-based crosslinking 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. As for the said isocyanate type crosslinking agent, only 1 type may be used and 2 or more types may be used. It is also possible to use the above isocyanate-based cross-linking agents and commercial products. For example, “Coronate Series” manufactured by Tosoh Corporation is available on the market.

  Examples of the aziridine-based crosslinking 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. One kind of the aziridine-based crosslinking agent may be used, or two or more kinds thereof may be used. A commercial item can also be used for the aziridine-based crosslinking agent. For example, “Chemite Series” manufactured by Nippon Shokubai Co., Ltd. is available on the market.

  Examples of the carbodiimide-based crosslinking agent include dicyclohexylmethane carbodiimide, dicyclohexyl carbodiimide, tetramethylxylylene carbodiimide, urea-modified carbodiimide, and the like. The said carbodiimide type crosslinking 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 crosslinking agent. For example, “Carbodilite series” manufactured by Nisshinbo Chemical Co., Ltd. is available on the market.

  The oxazoline-based crosslinking 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 crosslinking 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-oxazolinylnorbornane) sulfide and the like. Examples of the polymer oxazoline-based crosslinking 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 crosslinking 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 crosslinking agent. For example, “Epocross Series” manufactured by Nippon Shokubai Co., Ltd. is available on the market.

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

  The cross-linking agent is not particularly limited, but may be room temperature (for example, at least part of the range of 10 to 40 ° C, preferably at least part of the range of 12 to 35 ° C, more preferably within the range of 15 to 30 ° C. That are reactive with the functional group A are preferred. It is preferable that the cross-linking agent has reactivity with the functional group A at room temperature because the cross-linking reaction proceeds quickly and more fully cross-links. In addition, the said crosslinking agent is not restricted to what has reactivity with the functional group A at room temperature, Even if it has 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 crosslinking agent is not specifically limited, From a viewpoint of suppressing discoloration of the coating layer of this invention, a non-aromatic crosslinking agent (crosslinking agent which does not contain an aromatic structure) is preferable.

  When the coating layer of this invention contains the said crosslinking agent as a component which has the said functional group B, content (the unreacted crosslinking agent and the crosslinking agent after reaction) of the said crosslinking agent in the coating layer of this invention Is not particularly limited, but is preferably 1 to 50% by weight, more preferably 3 to 45% by weight, and still more preferably 5 to 5% by weight based on the total weight (100% by weight) of the coating layer of the present invention. 40% by weight. When the content is 1% by weight or more, the adhesion to the label substrate or the toner print layer and the resistance to ink cracking of the toner print layer are improved, which is preferable. When the content is 50% by weight or less, the coating property of the coating agent of the present invention is improved, and when the coating layer of the present invention is provided on the outermost surface of the shrink label of the present invention, blocking prevention is achieved. It is preferable.

  In the present specification, the content of each component (for example, binder resin, polyrotaxane, pigment, cross-linking agent, etc.) contained in each layer is such that the total content in each layer is 100% by weight or less. , Can be appropriately selected from within the scope of the description.

  When the coating layer of the present invention contains the crosslinking agent as a component having the functional group B, the binder resin in the coating layer of the present invention may be reactive with the crosslinking agent. However, it does not have to be present. That is, the binder resin may or may not have a functional group reactive with the functional group B (sometimes referred to as “functional group C”). When the binder resin has a functional group C appropriately, it is estimated that the binder resin and the component having the functional group A in the printing layer are crosslinked by the crosslinking agent. There is a tendency that the adhesion between the layers is improved and ink cracking is less likely to occur.

  Examples of the functional group C include functional groups exemplified and described as the functional group A described later. 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 mentioned later is preferable. The functional group C may be the same as or different from the functional group A, but is preferably the same. Especially, it is preferable that the functional group A and the functional group C are carboxy groups.

  The coating layer of this invention may contain components other than binder resin, a polyrotaxane, and a crosslinking agent (curing agent) within the range which does not impair the effect of this invention. Although it does not specifically limit as said component, Coloring agents (coloring material), such as a pigment and dye, Additives (For example, lubricant (wax), a plasticizer, an anti-settling agent, a dispersing agent, a stabilizer, an antifoamer, a filling) Agent, antioxidant, ultraviolet absorber, antistatic agent, anti-coloring agent, fragrance, deodorant, anti-blocking agent (for example, inorganic particles such as silica and titanium oxide; resin beads such as acrylic beads), slip Agent) and the like. Moreover, when the coating layer of this invention is an active energy ray hardening-type coating layer, a polymerization initiator and a sensitizer are also mentioned as said additive. The said component may use only 1 type and may use 2 or more types.

  It does not specifically limit as said pigment, For example, the pigment used in a well-known coating 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.

  Further, when the coating layer of the present invention is a coating layer containing a colorant, the content of the colorant is not particularly limited, but with respect to the total weight (100% by weight) of the coating layer of the present invention, It is preferably 1 to 60% by weight, more preferably 3 to 55% by weight, and still more preferably 5 to 50% by weight.

  When the binder resin has an acidic functional group C such as a carboxy group, the acid value of the coating layer of the present invention is not particularly limited, but from the viewpoint of preventing the crosslinking reaction from proceeding excessively in the coating agent. 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. In addition, in this specification, an acid value is calculated | required based on JISK5601-2-1 (titration method). Specifically, the acid value of the coating layer of the present invention is the above-mentioned coating layer of the present invention formed as a single layer on one surface of a substrate such as a film, and the coating layer of the present invention as a sample. It can be measured according to JIS. In addition, the acid value of the toner print layer, the acid value of the primer layer, and the acid value of the protective print layer, which will be described later, can be similarly measured.

  The type of the coating layer of the present invention is not particularly limited, but is formed by a coating layer formed by a solvent drying type coating agent (solvent drying type coating layer) or an active energy ray curable coating agent. Coating layer (active energy ray-curable coating layer) and the like.

  As the coating layer of the present invention, for example, a design printing layer (color printing layer or the like) for giving a display of a product name, a design, an illustration, a figure, information on the product (for example, handling precautions, etc.), white, etc. A background printing layer formed in a single color, such as a protective printing layer provided to protect the film or printing layer, a primer layer provided to enhance the adhesion between the film and the printing layer, and the adhesion between the film and the metal layer An anchor coat layer, an adhesive layer (for example, an adhesive layer that provides adhesion between a label base material and a metal vapor deposition transfer layer described later) and the like are provided. When the A layer is a toner printing layer, the coating layer of the present invention is preferably a primer layer or a protective printing layer, and more preferably a protective printing layer. When the A layer is a metal direct vapor deposition layer described later, an anchor coat layer is preferable. When the A layer is a metal vapor deposition transfer layer described later, it is preferably an adhesive layer. 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 in a cylindrical shape and is observed from the outside of the cylindrical shape. It is formed by a white printed layer containing 20 to 60% by weight of titanium. 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.

  Although the thickness of the coating layer of this invention is not specifically limited, For example, 0.1-10 micrometers is preferable, More preferably, it is 0.3-5 micrometers. If the thickness is less than 0.1 μm, it may be difficult to provide a uniform coating layer, resulting in partial “blurring”, resulting in impaired decorativeness, or difficulty in printing as designed. There is a case. In addition, when the thickness exceeds 10 μm, a large amount of coating agent is consumed, which increases the cost, makes it difficult to apply uniformly, or makes the coating layer brittle and easy to peel off. There is.

[A layer]
The shrink label of this invention has A layer which is a metal layer or a printing layer as an essential layer. Both the metal layer and the toner printing layer have a common problem that the followability with respect to the heat shrinkage of the heat shrinkable film is inferior when used for a shrink label. In the shrink label of the present invention, by providing the coating layer of the present invention so as to overlap with at least a part of the metal layer or the printed layer in the thickness direction, both the metal layer and the printed layer are subjected to heat shrinkage. The followability to heat shrink of the conductive film can be made good.

(Metal layer)
The metal layer is a layer containing a metal or a metal compound as a main component (a component most frequently contained as a component in the layer), and is obtained by, for example, a foil (metal foil) obtained by rolling a metal or a vapor deposition method. Examples thereof include a metal layer (metal vapor deposition layer) and a metal compound layer (metal compound vapor deposition layer) obtained by a vapor deposition method. Further, the metal vapor deposition layer may be a vapor deposition layer (metal direct vapor deposition layer) obtained by directly depositing metal on a label base material, or a metal vapor deposition layer separately provided on an appropriate support is labeled. It may be a layer (metal vapor deposition transfer layer) obtained by transferring to a substrate. The metal layer may be one obtained by transferring the metal foil or the metal vapor-deposited layer to a label base material by a known or common technique such as hot stamping or cold stamping.

  In the shrink label, the metal layer is used as a glossy metal gloss layer, a gas barrier layer for preventing or reducing gas permeation, a light shielding layer for shielding light, and the like.

  Examples of the metal include aluminum, bronze (bronze), copper, zinc, brass, titanium, tin, gold, silver, and platinum. Among these, aluminum is preferable. As said metal compound, the said metal oxide (metal oxide), nitride, etc. are mentioned, for example, A metal oxide is preferable and aluminum oxide is especially preferable. The said metal or metal compound may use only 1 type, and may use 2 or more types. The metal may be an alloy of two or more of the above metals.

  Although the thickness of the said metal vapor deposition layer or the said metal compound vapor deposition layer is not specifically limited, 1 micrometer or less (for example, 10 nm-1000 nm) is preferable, and it is more preferable that it is 0.1 micrometer or less (for example, 15 nm-100 nm) especially. As for the thickness of the said metal foil, 1-200 micrometers is illustrated, for example.

(Print layer)
The print layer is not particularly limited, and examples thereof include known or commonly used print layers used in shrink labels. Examples of the printing layer include a solvent-drying printing layer, an ultraviolet curable printing layer, and a toner printing layer. Moreover, as said printing layer, the above-mentioned design printing layer, background printing layer, protective printing layer, primer printing layer, anchor coat printing layer etc. are mentioned, for example. Moreover, the said printing layer can be provided by the well-known thru | or usual printing method, for example, it is preferable to provide by the gravure printing method, the flexographic printing method, the electrophotographic method etc. Even if the shrink label of the present invention is a toner print layer, it has excellent followability to thermal contraction of the label substrate and can hardly cause ink cracking. preferable.

  The toner print layer is formed of toner. When the surface of the toner print 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 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. As said urethane type resin, the urethane type resin etc. which were illustrated and demonstrated as a binder resin in the coating layer of the above-mentioned this invention are 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.

  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.

  In addition, in the shrink label of this invention, it is preferable that the printing layer adjacent to the coating layer of this invention contains the component which has a reactivity with the component in the coating layer of this invention. That is, it is preferable that the printing layer adjacent to the coating layer of the present invention contains the component having the functional group A. In this case, the component in the printing layer and the component in the coating layer of the present invention having reactivity with the component are bonded (crosslinked) after the formation of both layers, and the printing layer and coating of the present invention are combined. It is presumed that the adhesiveness of the layer is improved, but the printed layer is excellent in the followability to the thermal contraction of the label base material, and ink cracking of the printed layer is less likely to occur during shrink processing. The component having the functional group A may or may not be bonded (crosslinked) to the component having the functional group B in the coating layer of the invention in the shrink label of the invention. .

  The functional group A is not particularly limited. For example, a carboxy group (including a carboxylic acid anhydride), a hydroxy 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.

  Note that a 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. That is, the combination of the functional group A and the functional group B includes carboxy group and 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, silanol group and isocyanate group, amino group and isocyanate group, amino group and epoxy group, more preferably carboxy group and aziridine group, carboxy group and carbodiimide group, still more preferably carboxy group and aziridine group. In addition, the component which accelerates | stimulates the reactivity of the said functional group A and the said functional group B may be contained in the printing layer or the coating layer of this invention.

  The component having the functional group A is not particularly limited as long as it is a component constituting the print layer. When the printing layer is a toner printing layer, it is not particularly limited, and examples thereof include components that form the toner particles such as a binder resin that forms the toner particles, the wax, the CCA, the pigment, and the additive. It is done. Among these, from the viewpoint of adhesion to the coating layer of the present invention, the component that forms the toner particles is preferable, and the binder resin that forms the toner particles is more preferable. That is, the binder resin is preferably a binder resin having a functional group A, and more preferably a binder resin having a carboxy group.

  The component having the functional group A may be reactive with the component having the functional group B at room temperature, and reacts with the functional group B by active energy rays such as ultraviolet rays and electron beams, heat, moisture, and the like. It may have a property.

  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, so that the toner print layer is thermally contracted during shrink processing. This is preferable because it is excellent in followability to a conductive film and can make ink cracking less likely to occur.

  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.

  When the printing layer is a toner printing layer, the toner printing layer preferably does not contain a component having reactivity with the functional group A. Specifically, the content of the component having reactivity with the functional group A in the toner print layer is not particularly limited, but is 5 wt% or less with respect to the total amount (100 wt%) of the toner print layer. It is preferably 3% by weight or less, more preferably 1% by weight or less, and particularly preferably 0% by weight. The toner print layer may contain a component having reactivity with the functional group A. In that case, the content of the component having reactivity with the functional group A needs to be minimized. When the content exceeds 5% by weight, the component having reactivity with the functional group A and the component having the functional group A are combined in the toner before application to the label base material, and the toner particles may aggregate. In the case of a liquid toner, the viscosity may increase and it may be difficult to apply the toner.

  The toner print layer may be the design print layer or the background print layer. 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.

  Although the thickness of the said printing layer is not specifically limited, 0.1-15 micrometers is preferable, More preferably, it is 0.2-10 micrometers. In addition, the thickness of the said printing layer is the total thickness of the design printing layer which is a printing layer, and a background printing layer.

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

  The label substrate includes at least a heat-shrinkable film (shrink film). Although it does not specifically limit as said heat-shrinkable film, The heat-shrinkable film used as a label base material of a well-known thru | or usual shrink label can be used. The type of resin forming the heat-shrinkable film can be appropriately selected according to the required physical properties, application, cost, etc., and is not particularly limited. For example, polyester resin, polyolefin resin (for example, Polyethylene 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 includes a polyester-based film mainly composed of a polyester-based resin, a polyolefin-based film mainly composed of a polyolefin-based resin, a polystyrene-based film mainly composed of a polystyrene-based resin, and a polyester-based resin as an outer layer. And a heterogeneous laminated film having a polyolefin resin or polystyrene resin as an inner layer is preferable. 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, for example, a longitudinal direction (film production line direction; also referred to as longitudinal direction or MD direction) and a width direction (direction orthogonal to the longitudinal direction; also referred to as lateral direction or TD direction). Stretching in two directions, stretching in one direction of the longitudinal direction or 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 at 90 ° C. for 10 seconds (may be referred to as “heat shrinkage rate (90 ° C., 10 seconds)”) in the main shrink direction of the heat shrinkable film (before shrink processing) is not particularly limited. Is preferably 20% or more (for example, 20 to 90%), more preferably 30% or more (for example, 30 to 85%), still more preferably 40% or more (for example, 40 to 80%), and further preferably 45 % Or more (for example, 45 to 80%), particularly preferably 60% or more (for example, 60 to 80%). 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.

  The heat shrinkage rate (90 ° C., 10 seconds) in the direction perpendicular to the main shrinkage direction of the heat shrinkable film (before shrink processing) is not particularly limited, but is preferably −5 to 15%, more preferably. -3 to 10%.

  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. As a layer other than the heat-shrinkable film, for example, an anchor coat layer, a primer coat layer, a protective layer, an antistatic layer, a sliding layer, a heat insulating layer, a metal or a metal oxide vapor deposition that is not included in the coating layer. Layer and the like. Further, the surface of the heat-shrinkable film may be subjected to conventional surface treatment such as corona discharge treatment, primer treatment, antistatic coating treatment, etc., if necessary.

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

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

[Other layers]
The other layers (layers other than the label base material, the coating layer of the present invention, and the A layer) are not particularly limited. For example, an adhesive layer (a pressure-sensitive adhesive layer, a heat-sensitive adhesive layer, etc.), Examples include an anchor coat layer, a primer coat layer, a coating layer, an inner coat layer, an antistatic layer, a light shielding layer, a heat insulating layer, and a barrier layer.

[Shrink label]
The shrink label of this invention has A layer and the coating layer of this invention in the at least one surface of the said label base material. More specifically, the A layer is provided on at least one surface of the label base material. And the coating layer of this invention is provided in the said at least one surface of the said label base material so that it may overlap with at least one part of the said A layer in the thickness direction.

  The A layer is not particularly limited, but may be provided only on one side of the label substrate, or may be provided on both sides of the label substrate. The A layer may be provided on the entire surface of at least one surface of the label base material, or may be provided on a part thereof. Further, the A layer is not particularly limited, but may be a single layer or a multilayer.

  The coating layer of the present invention may be provided on the at least one surface of the label base so that at least a part thereof is adjacent to the A layer (that is, directly), or the coating layer of the present invention. It may be provided between the layer and the A layer via another layer. Especially, it is preferable that at least a part of the coating layer of the present invention is provided so as to be adjacent to the A layer.

  The coating layer of the present invention is not particularly limited as long as it is provided so as to overlap at least the portion where the A layer is provided in the thickness direction, and may be provided only on one side of the label base material, Although it may be provided on both sides of the label substrate, it is preferably provided on at least the side where the A layer is provided. Further, the coating layer of the present invention may be provided on the entire surface of at least one surface of the label substrate as long as it is provided so as to overlap at least the portion where the A layer is provided in the thickness direction. Although it may be provided in part, it is preferably provided at least in the entire region where the A layer is provided. Furthermore, the coating layer of the present invention is not particularly limited, but may be a single layer or a multilayer.

  Moreover, the coating layer of this invention may be provided in the label base material side of A layer, and may be provided in the opposite side to the label base material side of A layer. Examples of the configuration of the shrink label of the present invention in the former case include [label substrate / coating layer / A layer of the present invention] and the like. Examples of the configuration of the shrink label of the present invention in the latter case include [label base material / A layer / coating layer of the present invention] and the like. Further, the coating layer of the present invention is an A layer so that the structure of the shrink label of the present invention is, for example, [label substrate / coating layer of the present invention / A layer / coating layer of the present invention]. It may be provided on both sides.

  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 case where the A layer is a toner print layer, among them, as a back printed label from the viewpoint that ink breakage is less likely to occur during shrink processing even if the toner print layer has a cylindrical shape that is more likely to cause ink breakage. It is particularly useful to use. In this specification, the front printed label is a label that shows printing without passing through the label base material, and means a label having a design print layer in front of the label base material when the label is viewed. Moreover, a back printed label is a label which shows printing through a label base material, and means the label which has a design printing layer in the back | inner side rather than a label base material when seeing a label. Moreover, a double-sided printing label means the label which has a design printing layer on the both surfaces side of a label base material.

  When the A layer is a metal layer and the metal layer is a metal foil or a metal vapor-deposited transfer layer, [metal layer / adhesive layer (coating layer of the present invention) / label substrate], [protective printing layer / metal layer / Adhesive layer (coating layer of the present invention) / label base material], [Protective printing layer (coating layer of the present invention) / metal layer / adhesive layer / label base material], [Design printed layer / metal layer / adhesive layer] (Coating layer of the present invention) / Label substrate], [Design printing layer / Coating layer of the present invention / Metal layer / Adhesive layer / Label substrate], [Protective printing layer (Coating layer of the present invention) / Design printed layer / metal layer / adhesive layer / label substrate], [design printed layer / label substrate / adhesive layer (coating layer of the present invention) / metal layer] (in the case of front printed shrink labels), [ Label substrate / adhesive layer (coating layer of the present invention) / metal layer], [label substrate / design printing layer / adhesive layer (coating layer of the present invention) / metal layer], (back printing For Nkuraberu) and the like.

  The adhesive layer is preferably an active energy ray curable (particularly ultraviolet curable) coating layer. That is, the adhesive layer is preferably an active energy ray curable adhesive layer, and more preferably an ultraviolet curable adhesive layer. The adhesive layer (coating layer of the present invention) is not particularly limited, but the binder resin is 20-99.9% by weight and the polyrotaxane is 0.1% with respect to the total weight (100 parts by weight) of the adhesive layer. -50 wt% (more preferably 25-99.5 wt% binder resin, 0.5-40 wt% polyrotaxane, more preferably 30-99.2 wt% binder resin, 0.8-35 polyrotaxane % By weight).

  When the A layer is a metal layer and the metal layer is a metal direct vapor deposition layer or a metal compound vapor deposition layer, [metal layer / anchor coat layer (coating layer of the present invention) / label substrate], [protective printing layer ( Coating layer of the present invention) / metal layer / anchor coat layer / label substrate], [design printing layer / metal layer / anchor coat layer (coating layer of the present invention) / label substrate], [design printing layer / Coating layer / metal layer / anchor coat layer / label substrate of the present invention], [design printed layer / label substrate / anchor coat layer (coating layer of the present invention) / metal layer] (above, front printed shrink label ), [Label substrate / anchor coat layer (coating layer of the present invention) / metal layer], [label substrate / design printing layer / anchor coat layer (coating layer of the present invention) / metal layer] ( As mentioned above, in the case of a back printed shrink label, etc. are mentioned.

  The anchor coat layer is preferably a solvent drying type coating layer. Further, the anchor coat layer (the coating layer of the present invention) is not particularly limited, but the binder resin is 20 to 99.9% by weight and the polyrotaxane is 0% with respect to the total weight (100 parts by weight) of the anchor coat layer. 0.1-50 wt% (more preferably 25-99.5 wt% binder resin, 0.5-40 wt% polyrotaxane, more preferably 30-99.2 wt% binder resin, 0.8 polyrotaxane ~ 35 wt%) is preferably contained.

  The protective printing layer contains a binder resin as an essential component. The protective printing layer may contain a component having the functional group B. The protective printing layer containing the component having the functional group B may be referred to as “protective printing layer A”. Moreover, the protective printing layer which does not contain the component which has the said functional group B may be called "protective printing layer B". The said protective printing layer may contain other components, such as an additive, as needed.

  Examples of the protective printing layer (protective printing layer A and protective printing layer B) include those having the same composition as the protective printing layer having the composition described as the protective printing layer when the later-described A layer is a toner printing layer. It is done. Moreover, the preferable composition of the protective printing layer A and the protective printing layer B is also the same as the preferable composition described as the protective printing layer when the later-described A layer is a toner printing layer.

  In the above-described configuration, a protective printing layer may be provided on the surface of the outermost layer of the shrink label. Moreover, even if the shrink label of the present invention is a back printed shrink label, it is particularly useful as a back printed shrink label because it has excellent metallic gloss after heat shrinkage and excellent shrink label shine.

  The shrink label of the present invention when the A layer is a metal direct vapor deposition layer or a metal compound vapor deposition layer has a label substrate, an anchor coat layer, and a metal layer in this order among the layer configurations exemplified above, The anchor coat layer preferably has a layer structure that is the coating layer of the present invention. Moreover, the shrink label of this invention in case A layer is metal foil or a metal vapor deposition transfer layer has a label base material, an adhesive layer, and a metal layer in this order among the layer structures illustrated above, The above-mentioned The adhesive layer preferably has a layer configuration that is the coating layer of the present invention.

  A preferred configuration of the shrink label of the present invention when the A layer is a metal direct vapor deposition layer or a metal compound vapor deposition layer will be described with reference to the drawings. FIG. 1 is a schematic diagram (partial cross-sectional view) showing a preferred example of the shrink label of the present invention when the A layer is a metal direct vapor deposition layer or a metal compound vapor deposition layer. The shrink label 1 of the present invention shown in FIG. 1 has a label substrate 2, a design printing layer 3, an anchor coat layer 4, a metal direct vapor deposition layer or metal compound vapor deposition layer 5, and a protective printing layer 6. The shrink label 1 of the present invention shown in FIG. 1 is a back printed shrink label that shows printing through a label substrate 2. In FIG. 1, at least one of the anchor coat layer 4 and the protective printing layer 6 is the coating layer of the present invention.

  The design printing layer 3 is partially provided on the surface of one side of the label substrate 2 so that the label substrate 2 and the design printing layer 3 are directly adjacent to each other. The design print layer 3 is preferably formed by a plurality of print layers having different color pigments so as to have a desired design. The design print layer 3 may be transparent or opaque. Although the thickness of the design printing layer 3 is not specifically limited, 0.1-8 micrometers is preferable.

  The anchor coat layer 4 is formed on the surface on one side of the label substrate 2 (that is, the surface on which the design print layer 3 is provided), or the design print layer 3 and the anchor coat layer 4 or the label substrate 2 and the anchor coat. The design printing layer 3 is provided so as to cover the layer 4 so as to be directly adjacent thereto. The anchor coat layer 4 is a layer for improving the adhesion of the metal direct vapor deposition layer or the metal compound vapor deposition layer 5 to the label substrate 2 and the design print layer 3. The anchor coat layer 4 may be the coating layer of the present invention or may be a layer other than the coating layer of the present invention, but is preferably the coating layer of the present invention. The thickness of the anchor coat layer 4 is not particularly limited, but is preferably 0.1 to 10 μm.

  The metal direct vapor deposition layer or the metal compound vapor deposition layer 5 is formed on the surface of the label substrate 2 on one side (that is, the surface on which the design print layer 3 and the anchor coat layer 4 are provided) and the metal layer directly on the metal substrate. It is provided on the entire surface of the anchor coat layer 4 (the surface opposite to the label substrate 2) so that the vapor deposition layer or the metal compound vapor deposition layer 5 is directly adjacent. In addition, in FIG. 1, although provided in the whole surface of one side of the label base material 2, you may provide only in the part which wants to exhibit metal glossiness.

  The protective printing layer 6 is formed on the surface on one side of the label substrate 2 (that is, the surface on which the design printing layer 3, the anchor coat layer 4, and the metal direct vapor deposition layer or the metal compound vapor deposition layer 5 are provided). Provided on the entire surface of the metal direct vapor deposition layer or metal compound vapor deposition layer 5 (the surface opposite to the anchor coat layer 4) so that the direct vapor deposition layer or metal compound vapor deposition layer 5 and the protective printing layer 6 are directly adjacent to each other. It has been. In addition, in FIG. 1, although provided so that the whole surface of the metal direct vapor deposition layer or the metal compound vapor deposition layer 5 may be covered, you may provide so that only one part may be covered. Further, the protective printing layer 6 may be partially provided on one surface of the label substrate 2 or may be provided on the entire surface. Although the thickness of the protective printing layer 6 is not specifically limited, 0.5-10 micrometers is preferable.

  In addition, in FIG. 1, although the case where A layer was a metal direct vapor deposition layer or a metal compound vapor deposition layer was demonstrated, when A layer is a metal foil or a metal vapor deposition transfer layer, the shrink label of this invention is in FIG. The metal direct vapor deposition layer or the metal compound vapor deposition layer 5 is preferably a metal foil or a metal vapor deposition transfer layer, and the anchor coat layer 4 is an adhesive layer.

  When the A layer is a toner print layer, the shrink label of the present invention has the toner print layer and the coating layer of the present invention on at least one surface of the label substrate. In this case, in the shrink label of the present invention, the toner print layer and the coating layer of the present invention preferably have a crosslinked structure. More specifically, in the toner print layer and the coating layer of the present invention, the component having the functional group A contained in the toner forming the toner print layer and the coating forming the coating layer of the present invention. It preferably has a cross-linked structure formed by the functional group A contained in the agent and a reactive component. If the A layer and the coating layer of the present invention have a crosslinked structure, it is assumed that the adhesion between the toner printing layer and the coating layer of the present invention is improved. The label substrate has excellent followability to heat shrinkage, and ink breakage of the toner printing layer is less likely to occur during shrink processing.

  Examples of the crosslinked structure in the layer A and the coating layer of the present invention include a bond formed by a carboxy group and an isocyanate group, an ester bond formed by a carboxy group and an epoxy group, and a carboxy group and an aziridine group. Bond, bond formed by carboxy group and carbodiimide group, bond formed by carboxy group and oxazoline group, urethane bond formed by hydroxy group and isocyanate group, urethane bond formed by silanol group and isocyanate group, amino group And an amide bond formed by an isocyanate group and a crosslinked structure formed by a bond formed by an amino group and an epoxy group.

  When the A layer is a toner print layer, a protective print layer may be provided on the surface of the toner print layer. In this case, the shrink label of the present invention preferably has a label substrate, a toner print layer, and a protective print layer in this order. Further, a toner printing layer may be provided on at least one side of the label base material via a primer layer. That is, a primer layer may be provided between the label base material and the toner print layer. Furthermore, the shrink label of the present invention may have an intermediate coating layer that imparts various functions to the shrink label of the present invention between the label substrate, the primer layer, the toner print layer, and the protective print layer. In addition, the outermost layer may have a layer other than these layers (a layer other than the primer layer, the toner printing layer, and the protective printing layer). In these configurations, the layers other than the primer layer and the protective printing layer may be the coating layer of the present invention, but at least one of the primer layer and the protective printing layer is the coating layer of the present invention. It is more preferable that at least the protective printing layer is the coating layer of the present invention. In addition, when the shrink label of this invention has a protective printing layer and the said protective printing layer is a coating layer of this invention, the followability of the toner printing layer with respect to the heat shrink of a heat-shrinkable film is more excellent.

  The primer layer is formed by applying a primer coating agent. The primer layer may be the coating layer of the present invention, or may be a coating layer other than the coating layer of the present invention (sometimes referred to as “other coating layer”). The primer layer is a layer used for improving adhesion to a label substrate such as a toner print layer, a coating layer of the present invention, and the other coating layers. 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, but in the vicinity of a portion that becomes a seal portion when a cylindrical shrink label is used. It is preferable that it is provided on the entire surface other than. In addition, when the shrink label of this invention has a primer layer, it is preferable that the toner printing layer is provided in the area | region in which the said primer layer is provided at least.

  The primer layer contains a binder resin as an essential component. The primer layer may contain a component having the functional group B. The primer layer containing the component having the functional group B may be referred to as “primer layer A”. Further, the primer layer not containing the component having the functional group B may be referred to as “primer layer B”. The said primer layer may contain other components, such as a polyrotaxane and an additive, as needed.

  The binder resin is not particularly limited, and a known or commonly used binder resin for a primer 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. Although it does not specifically limit as said binder resin, The binder resin etc. which were illustrated and demonstrated as binder resin contained in the coating layer of this invention are mentioned. Among these, acrylic resins, urethane resins, polyolefin resins, and imine resins are preferable from the viewpoint of improving adhesion to the toner print layer.

  The primer layer A contains a component having the functional group B. In particular, the primer layer A preferably contains a binder resin and a crosslinking agent as a component having the functional group B as essential components. Moreover, the primer layer A may contain the polyrotaxane and does not need to contain it.

  When the primer layer A contains a polyrotaxane, the primer layer A is 30 to 95% by weight of the binder resin, 0.1 to 70% by weight of the polyrotaxane, based on the total weight (100 parts by weight) of the primer layer, among others. 3 to 40% by weight of crosslinking agent (more preferably 35 to 90% by weight of binder resin, 0.5 to 55% by weight of polyrotaxane, 5 to 35% by weight of crosslinking agent, and more preferably 40 to 85% by weight of binder resin %, Polyrotaxane 0.8 to 60% by weight, and crosslinking agent 10 to 30% by weight).

  The primer layer B does not contain a component having the functional group B. The primer layer B contains the binder resin as an essential component. Moreover, the primer layer B may contain the polyrotaxane and does not need to contain it.

  When the primer layer B contains a polyrotaxane, the primer layer B is 30 to 99.9% by weight of the binder resin and 0.1 to 70% by weight of the polyrotaxane, based on the total weight (100 parts by weight) of the primer layer. (More preferably, the binder resin is 35 to 99.5% by weight, and the polyrotaxane is 0.5 to 60% by weight.) More preferably, the binder resin is 40 to 99.2% by weight, and the polyrotaxane is 0.8 to 65% by weight. It is preferable to contain.

  The primer layer (primer layer A and primer layer B) contains a component reactive with the component having reactivity with the functional group A (that is, a component having reactivity with the component having the functional group B). You may do it. Among these, the primer layer B preferably contains a component having reactivity with the component having the functional group B. The component having reactivity with the component having the functional group B is not particularly limited as long as it is a component constituting the primer layer, and examples thereof include the binder resin. When a component having reactivity with the functional group B is contained in the primer layer, the primer layer and the functional group B are contained by the component having the functional group B contained in a layer other than the primer layer in the shrink label of the present invention. It is preferable because the adhesion between the layer containing the component having a colorant and the toner print layer is further improved and ink cracking is less likely to occur.

  The component having reactivity with the functional group B in the primer layer has the functional group C. 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. Especially, it is preferable that the functional group A and the functional group C are carboxy groups.

  When the functional group C in the primer layer A is an acidic functional group such as a carboxy group, the acid value of the primer layer A is not particularly limited, but is 40 mg KOH / g or less (for example, more than 0 mg KOH / g and 40 mg KOH / g g or less), more preferably more than 0 mgKOH / g and 30 mgKOH / g or less.

  When the functional group C in the primer layer B is an acidic functional group such as a carboxy group, the acid value of the primer layer B is not particularly limited, but is 500 mgKOH / g or less (for example, more than 0 mgKOH / g and 500 mgKOH / g g or less), preferably 5 to 300 mgKOH / g, more preferably 10 to 200 mgKOH / g, and particularly preferably 30 to 100 mgKOH / 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.

  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.

  The protective printing layer is formed by printing a protective printing ink. The protective printing layer may be the coating layer of the present invention, or the other coating layer. The protective printing layer is provided on the surface of the toner printing layer (specifically, the surface opposite to the label substrate) to protect the toner printing layer, and the toner printing layer against heat shrinkage of the heat shrinkable film. Can be further improved, and ink cracking during shrink processing can be made less likely to occur. Moreover, when it contains a lubricant, it becomes the outermost layer of the shrink label and can also play a role of imparting slipperiness to the container or the like of the shrink label of the present invention. Moreover, when the said protective printing layer is a coating layer of this invention, the followable | trackability of the toner printing layer with respect to the heat shrink of a heat-shrinkable film is more excellent.

  The protective printing layer may be provided on the entire surface of the label base material on the side having the toner printing layer, or may be provided partially, but is provided on at least the entire surface of the region where the toner printing layer is provided. It is preferable that it is provided on the entire surface other than the vicinity of the portion that becomes the seal portion when a cylindrical shrink label is formed. Moreover, when the shrink label of this invention has a primer layer, it is preferable to provide in the whole surface of the area | region in which a primer layer and a toner printing layer are provided at least. In addition, the said protective printing layer is provided in the outermost surface of a shrink label, when making a shrink label excellent in slipperiness and abrasion resistance. That is, the shrink label of the present invention preferably has the protective printing layer on the outermost surface.

  The protective printing layer is not particularly limited, but may be a solvent drying type printing layer or an active energy ray curable printing layer. Among these, a solvent-dried printing layer is preferable.

  The protective printing layer contains a binder resin as an essential component. The protective printing layer may contain a component having the functional group B. That is, the protective printing layer may be the protective printing layer A or the protective printing layer B. The said protective printing 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. The binder resin is not particularly limited, but plays a role as a main resin component for forming the protective printing layer. Although it does not specifically limit as said binder resin, The binder resin etc. which were illustrated and demonstrated as binder resin contained in the coating layer of this invention are mentioned. Of these, acrylic resins, urethane resins, and polyamide resins are preferable from the viewpoint of preventing ink cracking during shrink processing.

  The protective printing layer A contains a component having the functional group B. In particular, the protective printing layer A preferably contains a binder resin, a polyrotaxane, and a crosslinking agent as a component having the functional group B as essential components. Further, the protective printing layer A may further contain a color pigment such as a white pigment or a lubricant.

  When the protective printing layer A is a protective printing layer containing a white pigment such as titanium oxide, the protective printing layer A is 30 to 70% by weight of the binder resin with respect to the total weight (100% by weight) of the protective printing layer A. 0.1 to 60% by weight of polyrotaxane, 5 to 60% by weight of white pigment, 3 to 25% by weight of crosslinking agent (more preferably, 35 to 65% by weight of binder resin, and 0.5 to 45% of polyrotaxane %, White pigment in an amount of 10 to 58% by weight, and a crosslinking agent in an amount of 5 to 20% by weight). Moreover, when the protective printing layer containing the said white pigment is the outermost surface of the shrink label of this invention, it is preferable that the protective printing layer A further contains 1 to 10 weight% of lubricants.

  On the other hand, when the protective printing layer A is a colorless and transparent protective printing layer containing no color pigment, the protective printing layer A contains 30 to 95 binder resin with respect to the total weight (100% by weight) of the protective printing layer A. % By weight, 0.1 to 60% by weight of polyrotaxane, 3 to 50% by weight of crosslinking agent (more preferably, 35 to 90% by weight of binder resin, 0.5 to 55% by weight of polyrotaxane, and 5 to 5% of crosslinking agent. 45 wt%, more preferably 38 to 85 wt% binder resin, 0.8 to 40 wt% polyrotaxane, and 10 to 40 wt% crosslinker). Moreover, when the said colorless and transparent protective printing layer is the outermost surface of the shrink label of this invention, it is preferable that the protective printing layer A contains 1-10 weight% of lubricants further.

  The protective printing layer B does not contain a component having the functional group B. The protective printing layer B preferably contains a binder resin and a polyrotaxane as essential components. Further, the protective printing layer B may further contain a color pigment such as a white pigment or a lubricant.

  When the protective printing layer B is a protective printing layer containing a white pigment such as titanium oxide, the protective printing layer B is 30 to 90% by weight of the binder resin with respect to the total weight (100% by weight) of the protective printing layer B. 0.1 to 60% by weight of polyrotaxane, 5 to 60% by weight of white pigment (more preferably, 35 to 85% by weight of binder resin, 0.5 to 55% by weight of polyrotaxane, and 10 to 58% by weight of white pigment. %) Is preferable. Moreover, when the protective printing layer containing the said white pigment is the outermost surface of the shrink label of this invention, it is preferable that the protective printing layer B contains 1 to 10 weight% of lubricants further.

  On the other hand, when the protective printing layer B is a colorless and transparent protective printing layer containing no color pigment, the protective printing layer B contains 30 to 7098 binder resin with respect to the total weight (100% by weight) of the protective printing layer B. It is preferable to contain 0.1% to 70% by weight of polyrotaxane (more preferably, 35 to 97% by weight of binder resin and 0.5 to 65% by weight of polyrotaxane). Moreover, when the said colorless and transparent protective printing layer is the outermost surface of the shrink label of this invention, it is preferable that the protective printing layer B contains 1-10 weight% of lubricants further.

  The protective printing layer (protective printing layer A and protective printing layer B) is a component having reactivity with the component having reactivity with the functional group A (that is, a component having reactivity with the component having the functional group B). ) May be contained. Among these, the protective printing layer B preferably contains a component having reactivity with the component having the functional group B. Although the component which has the reactivity with the component which has the said functional group B will not be specifically limited if it is a component which comprises the said protective printing layer, For example, the said binder resin etc. are mentioned. When the component having reactivity with the functional group B is contained in the protective printing layer, the component having reactivity with the functional group A in the layer other than the protective printing layer in the shrink label of the present invention, The adhesive strength between the layer containing the component having reactivity with the functional group A and the toner printing layer is further improved, and ink cracking tends to be less likely to occur, which is preferable.

  The component having reactivity with the functional group B in the protective printing layer has the functional group C. 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. Especially, it is preferable that the functional group A and the functional group C are carboxy groups.

  When the functional group C in the protective printing layer A is an acidic functional group such as a carboxy group, the acid value of the protective printing layer A is not particularly limited, but is 40 mg KOH / g or less (for example, more than 0 mg KOH / g and 40 mg KOH / G or less), more preferably more than 0 mgKOH / g and 30 mgKOH / g or less.

  When the functional group C in the protective printing layer B is an acidic functional group such as a carboxy group, the acid value of the protective printing layer B 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 5 to 300 mgKOH / g, still more preferably 10 to 200 mgKOH / g, and particularly preferably 30 to 100 mgKOH / g.

  Although the thickness of the said protective printing layer is not specifically limited, 0.1-10 micrometers is preferable, More preferably, it is 0.2-3 micrometers. When the thickness is 0.1 μm or more, the wear resistance is further improved, which is preferable. When the thickness is 10 μm or less, the transparency is improved, which is preferable.

  The laminated structure of the shrink label of the present invention when the A layer is a toner print layer is not particularly limited. For example, from one surface of the shrink label, [label substrate / primer layer (coating layer of the present invention) ) / Toner print layer], [label substrate / toner print layer / protective print layer (coating layer of the present invention)], [label substrate / primer layer / toner print layer / protective print layer (coating of the present invention) Layer)], [label substrate / primer layer (coating layer of the present invention) / toner printing layer / protective printing layer], [label substrate / primer layer (coating layer of the present invention) / toner printing layer / protection] And a laminated structure of the printing layer (coating layer of the present invention)]. Among them, the shrink label of the present invention preferably has a laminated structure having a protective printing layer which is the coating layer of the present invention, [label substrate / primer layer / toner printing layer / protective printing layer (coating layer of the present invention). ] Is more preferable. In this case, the followability of the toner print layer with respect to the thermal contraction of the label base material is further improved, and ink cracking is less likely to occur. In the laminated structure, the primer layer which is the coating layer of the present invention is preferably the primer layer A. Moreover, it is preferable that the protective printing layer which is a coating layer of this invention is the said protective printing layer A. FIG. In the above laminated structure, when both the primer layer and the protective printing layer are present, preferred combinations of the primer layer and the protective printing layer are the primer layer A and the protective printing layer B, the primer layer B and the protective printing layer A, and the primer. Layer A and protective printing layer A, more preferably primer layer B and protective printing layer A, primer layer A and protective printing layer A (that is, at least the protective printing layer is protective printing layer A). In this case, the adhesiveness between the toner printing layer, the primer layer, the label substrate via the primer layer, and the protective printing layer is excellent, and ink cracking is less likely to occur. An intermediate coating layer may be provided between the label substrate, the primer layer, the toner print layer, and the protective print layer.

  A preferred configuration of the shrink label of the present invention when the A layer is a toner print layer will be described with reference to the drawings. FIG. 2 is a schematic view (partial cross-sectional view) showing a preferred example of the shrink label of the present invention when the A layer is a toner printing layer. The shrink label 1 of the present invention shown in FIG. 2 includes a label substrate 2, a transparent primer layer 7, a design printing layer (toner design printing layer) 8a that is a toner printing layer composed of a plurality of colors, and a white that is a toner printing layer. The background print layer (toner background print layer) 8b and the transparent protective print layer (transparent protective print layer) 9 are included in this order. More specifically, in the shrink label 1 of the present invention shown in FIG. 2, the primer layer 7 is formed on one side of the label base 2 and on the surface of the label base 2 (the label base 2 and the primer layer 7 are To be directly adjacent). In addition, the toner design print layer 8a has the primer layer 7 and the toner design print layer 8a on the surface of the label substrate 2 on the side where the primer layer 7 is provided (the surface opposite to the label substrate 2). It is provided partially (in a part of the region where the primer layer 7 is provided) so as to be directly adjacent. The toner background print layer 8b is provided on the surfaces of the toner design print layer 8a and the primer layer 7 so as to cover the entire region where the toner design print layer 8a is provided. In the region where the toner design print layer 8a is provided, the toner design print layer 8a and the toner background print layer 8b are provided so as to be directly adjacent to each other. In the region where the toner design print layer 8a is not provided, the primer layer 7 and the toner background print layer 8b are provided so as to be directly adjacent to each other. The transparent protective printing layer 9 is provided on the surface of the toner background printing layer 8b (the surface opposite to the label substrate 2) so that the toner background printing layer 8b and the transparent protective printing layer 9 are directly adjacent to each other. It is provided on the outermost surface of the shrink label 1 of the present invention. The shrink label 1 of the present invention shown in FIG. 2 is a reverse print shrink label that shows printing through a label substrate 2. In FIG. 2, at least one of the primer layer 7 and the transparent protective printing layer 9 is the coating layer of the present invention.

  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 30 to 90. % Is preferable, more preferably 40 to 85%, and still more preferably 45 to 80%. When the heat shrinkage rate (90 ° C., 10 seconds) is less than 30%, followability with respect to the shape of a container or the like to which a 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 contraction direction of the shrink label of this invention is not specifically limited, -3-15% is preferable. The “main shrinkage direction” of the shrink label is the direction in which the heat shrinkage rate is the largest, and is generally the direction in which the heat shrinkable film is mainly stretched, and the shrink label is a cylindrical shrink label. Is generally in 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”.

  Further, when the A layer is a toner print layer, there is no particular limitation, but 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) are predetermined. It is preferable that a toner print layer is not provided in the width region. 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.

  An example of the cylindrical shrink label which is a preferable embodiment of the shrink label of the present invention will be described with reference to FIGS. The cylindrical shrink label 10 of the present invention shown in FIG. 3 is formed into a cylindrical shape by superposing the other end on the outside of one end of the shrink label of the present invention formed in a rectangular shape, and the inner surface and one end of the other end. This is a cylindrical body in which a seal part 11 is formed by joining the outer surface of the part with a solvent or an adhesive. The tubular shrink label 10 is formed into a tubular shape so that the main shrink direction of the heat-shrinkable film is the circumferential direction D of the tubular shrink label, and is heat shrinkable in that direction.

  4 and 5 are enlarged cross-sectional views taken along the line A-A 'of FIG. FIG. 4 shows an enlarged view of a main part in the vicinity of the seal portion of the cylindrical shrink label of the shrink label of the present invention shown in FIG. FIG. 5 shows an enlarged view of a main part in the vicinity of the seal portion of the cylindrical shrink label of the shrink label of the present invention shown in FIG.

  In FIG. 4, in the seal portion 11, both ends of the shrink label are joined with a solvent or an adhesive 12. Specifically, in the shrink label of the present invention, the design printing layer 3 is formed in a region excluding a region having a predetermined width from the other end portion of one surface (the surface on the cylindrical inner surface side) of the label substrate 2. An anchor coat 4 is formed over substantially the entire region excluding the region of a predetermined width from the end of the other end of the one surface of the label base 2 so as to cover the design print layer 3 formed. A metal direct vapor deposition layer or a metal compound vapor deposition layer 5 is formed in substantially the entire region where the layer 4 is provided, and the one side of the label substrate 2 is covered so as to cover the metal direct vapor deposition layer or the metal compound vapor deposition layer 5. The protective printing layer 6 is formed over substantially the entire region excluding the region having a predetermined width from the end of the other end. For this reason, in the shrink label of the present invention, the design print layer 3, the anchor coat layer 4, the metal direct vapor deposition layer or the metal compound vapor deposition layer 5, and the protective print layer 6 are provided in a region having a predetermined width from the other end. Not formed, the label base material 2 is exposed, a label base material exposed surface is formed, the seal portion 11 is formed on the inner surface side of the other end of the shrink label of the present invention, A label base material exposed surface formed on the outer surface side of the one end is joined with a solvent or an adhesive 12. That is, in the seal portion 11, it is preferable that the label base materials 2 are bonded to each other with a solvent or an adhesive 12. In addition, even if it has a printing layer such as a background printing layer, a design printing layer, an anchor coat layer, a metal direct vapor deposition layer, a metal compound vapor deposition layer, etc. Therefore, these layers may be included. In addition, the design print layer 3, the anchor coat layer 4, the metal direct vapor deposition layer or metal compound vapor deposition layer 5, and the protective print layer 6 may each be a single layer or multiple layers.

  In FIG. 5, in the seal portion 11, both ends of the shrink label are joined with a solvent or an adhesive 12. Specifically, in the shrink label of the present invention, the primer layer 7 is formed in a region excluding a region having a predetermined width from the other end of one surface of the label substrate 2 (the inner surface of the cylindrical body). The primer layer 7 is formed on the surface of the primer layer 7 (on the surface opposite to the label base material 2) from the other end of the one side of the label base material 2 except for a region having a predetermined width. The toner printing layer 8 is formed so as to have a smaller area, and the area of the label base material 2 excluding the area of a predetermined width from the other end of the one side of the label base material 2 is covered so as to cover the toner printing layer 8. A transparent protective printing layer 9 is formed over substantially the entire area. For this reason, in the shrink label of the present invention, the primer layer 7, the toner printing layer 8, and the transparent protective printing layer 9 are not formed in an area having a predetermined width from the other end, and the label base 2 is It is exposed and a label substrate exposed surface is formed. Specifically, the cylindrical shrink label 10 of the present invention includes a label substrate exposed surface formed on the inner surface side of the other end portion of the shrink label of the present invention and a label substrate formed on the outer surface side of the one end portion. The exposed surface is joined with a solvent or an adhesive 12. The toner printing layer 8 may be a single layer or a multilayer. The toner print layer 8 may be a design print layer, a background print layer, or a multilayer including both.

  In the cylindrical shrink label 10 of the present invention in FIG. 5, one end portion extends to a position where the end overlaps the transparent protective printing layer 9 at the other end, and the transparent protective printing at the one end portion and the other end portion. A region where the layers 9 overlap with each other via the label base 2 is formed. For this reason, there is no region where the transparent protective printing layer 9 does not exist in the thickness direction. The cylindrical shrink label of the present invention may have a structure that overlaps the end of one end and the transparent protective printing layer on the other end as shown in FIG. 5, and the end of the one end is a label on the other end. The end of one end and the transparent protective printing layer on the other end are overlapped, extending to the area overlapping the substrate exposed surface and not extending to the position where the end of one end overlaps the transparent protective printing layer on the other end. The structure which does not become good may be sufficient. The same applies to the cylindrical shrink label of the present invention in FIG.

  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.

  In the shrink label of the present invention, an A layer which is a metal layer or a printed layer is provided on at least one surface of a label base material including a heat-shrinkable film, and at least a part of the A layer in the thickness direction. And a coating layer containing a binder resin and a polyrotaxane are provided. The shrink label of the present invention is provided with a coating layer containing a polyrotaxane adjacent to the A layer which is inferior in conformity to heat shrinkage, and thus the coating layer is thermally contracted by the label base material. Therefore, the layer A adjacent to the coating layer also easily follows the thermal contraction of the label substrate. For this reason, even when the shrink label of the present invention has a metal layer, shrinkage whitening of the metal layer is unlikely to occur, and the metallic luster and brightness are not easily lowered before and after shrink processing, and the shrink label is brilliant and decorative. Excellent. In addition, even when the shrink label of the present invention has a printing layer (particularly a toner printing layer), ink cracking is unlikely to occur in the printing layer (particularly the toner printing layer) at the time of shrink processing. Excellent.

[Manufacturing method and processing method of shrink label of the present invention]
When the A layer is a metal layer, the shrink label manufacturing method of the present invention forms a metal layer on at least one surface of the label base material (metal layer forming step), and forms the coating layer of the present invention. At least a coating step (coating layer forming step of the present invention). In addition, the order of a metal layer formation process and the coating layer formation process of this invention is not specifically limited. For example, in the shrink label of the present invention having a layer structure of [label base material / metal layer / coating layer of the present invention], in the order of the metal layer forming step and the coating layer forming step of the present invention, [label base material / In the shrink label of the present invention having the layer structure of [Coating layer / metal layer of the present invention], the order of the coating layer forming step and the metal layer forming step of the present invention is preferable. For example, when a metal layer is provided by a transfer method (particularly, hot stamping), the metal layer forming step and the coating layer forming step may be performed simultaneously. Moreover, the manufacturing method of the shrink label of this invention may have processes other than a metal layer formation process and the coating layer formation process of this invention.

  In the case of hot stamping, the metal layer forming step and the coating layer forming step are usually performed simultaneously. Specifically, the metal layer is formed by pressing the hot melt adhesive side of the laminate having the configuration of [Hot Melt Adhesive / Metal Layer / Releasing Support] to the label substrate with a hot hand or the like. Can be transferred to produce the shrink label of the present invention.

(Metal layer forming process)
In the metal layer forming step, a metal vapor deposition layer or a metal foil provided by directly depositing a metal or a metal compound on at least one surface of the label base material or by separately depositing a metal on an appropriate support is provided. A metal layer is formed by a transfer method for transferring to a label substrate. As the above-mentioned support, for example, a plastic film or the like whose surface has been peeled can be used. The transfer method can be performed by a known or common method such as a cold stamp. In addition, when the coating layer of this invention is already provided in the label base material, you may provide a metal layer so that it may adjoin at least one part of the coating layer of this invention.

(Coating layer forming step of the present invention)
In the coating layer forming step of the present invention, the coating layer is formed by applying a coating agent on at least one surface of the label substrate and solidifying it by drying or curing. In addition, the coating agent which forms the coating layer of this invention may be called "the coating agent of this invention." As a method for applying the coating agent of the present invention, a known and commonly used method can be used, and among them, gravure printing, flexographic printing, and digital printing are preferable. In addition, when the applied coating agent of the present invention 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. Application | coating of the coating agent of this invention may be performed in multiple times, and the coating layer which is a multilayer may be formed. In addition, when A layer is already provided in the label base material, you may provide the coating layer of this invention so that at least one part of A layer may adjoin.

  When the coating agent of the present invention is a solvent-drying type coating agent, the coating layer of the present invention specifically applies the solvent-drying type coating agent, volatilizes the solvent, and solidifies by drying. Is formed. On the other hand, when the coating agent of the present invention is an active energy ray-curable coating agent, the coating layer of the present invention is specifically applied by applying the active energy ray-curable coating agent. After drying according to the above, it is formed by curing by irradiation with active energy rays. In addition, when the coating layer of the present invention is an adhesive layer (that is, when the coating agent of the present invention is an adhesive), the active energy ray irradiation is performed after the metal layer is transferred (after bonding). You may go.

  When the coating agent of the present invention is a solvent-drying type coating agent, the coating agent of the present invention includes, for example, the binder resin (that is, the binder resin contained in the coating layer of the present invention), polyrotaxane, and solvent. And other additives, etc., if necessary. Mixing can be performed by a known and commonly used mixing method, and is not particularly limited. 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 coating agent may be used after filtration, if necessary. Each of the above components (binder resin, polyrotaxane, solvent, and other additives) may be used alone or in combination of two or more.

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

  When the coating agent of the present invention is an active energy ray-curable coating agent, the coating agent of the present invention is a single component constituting the binder resin (that is, the binder resin contained in the coating layer of the present invention). It is manufactured by mixing the monomer component, polyrotaxane, solvent, and other additives as necessary. The mixing can be performed by a known and common mixing method, and is not particularly limited, but 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 coating agent may be used after filtration, if necessary. Each of the above components (monomer component, polyrotaxane, solvent, and other additives) may be used alone or in combination of two or more.

  The coating agent of the present invention is not particularly limited, but may be aqueous, oily, or an emulsion system.

  The viscosity (23 ± 2 ° C.) of the coating agent of the present invention is not particularly limited. However, 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. It is. The viscosity of the coating agent of the present invention depends on the binder resin (or the monomer component constituting the binder resin), the type and blending amount (content) of the polyrotaxane and other components, the thickener, the thickener, etc. It is possible to control. In the present specification, unless otherwise specified, “viscosity” is JIS Z using an E-type viscometer (conical plate-type rotational viscometer) under the conditions of 23 ± 2 ° C. and the rotational speed of a cylinder of 50 rotations. The value measured according to 8803 is meant.

  As described above, the shrink label of the present invention is produced, in which the metal layer and the coating layer of the present invention are formed so as to overlap at least part of the metal layer in the thickness direction on at least one surface of the label base material. can do.

  When the A layer is a toner print layer, the shrink label manufacturing method of the present invention includes a step of forming the coating layer of the present invention on at least one surface of the label substrate (coating layer forming step of the present invention), and It includes at least a step of forming a toner print layer on at least one surface of the label substrate (toner print layer forming step). The order of the coating layer forming step and the toner printed layer forming step of the present invention is not particularly limited, but from the viewpoint of making ink cracking less likely, the coating layer forming step of the present invention is provided after the toner printed layer forming step. Is preferred. Moreover, the manufacturing method of the shrink label of this invention may have processes other than a toner printing layer formation process and the coating layer formation process of this invention.

  An example of the manufacturing method of the shrink label of the present invention in the case where the shrink label of the present invention is a shrink label having a primer layer, a toner print layer, and a protective print layer on one surface of the label substrate is shown below. . In such a method for producing a shrink label, a primer layer is formed on at least one surface of a label substrate (primer layer forming step), and a toner print layer is formed on the surface of the label substrate having the primer layer. At least a step (toner print layer forming step) and a step of forming a protective print layer on the surface of the label substrate having the primer layer and the toner print layer (protective print layer forming step). In addition, in the manufacturing method of this example, since at least one of the primer layer and the protective printing layer is a coating layer of the present invention, the primer layer forming step and the protective printing layer forming step At least one of them is the coating layer forming step of the present invention.

(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.

  The method for applying the primer coating agent is not particularly limited. For example, known or commonly used general-purpose printing methods such as gravure printing, flexographic printing, letterpress printing, silk screen printing, offset printing, bar coater, comma coater And a coating method using a known or conventional general-purpose coater such as 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 and solidified by heating or the like, a general heating device capable of heating on the printing device can be preferably used. From the viewpoint of safety, a hot air heater or the like can be preferably used.

  The primer coating agent is not particularly limited, but may be aqueous, oily, or an emulsion system.

  A commercial item can be used for the said primer coat agent. When the primer layer contains a polyrotaxane, the primer coating agent preferably contains a polyrotaxane. The primer coating agent containing a polyrotaxane may be a commercially available product, or may be obtained, for example, by mixing a polyrotaxane with a commercially available primer coating agent not containing a polyrotaxane. When the primer layer contains a component having the functional group C, the primer coating agent preferably contains a component having the functional group C. The primer coating agent containing a component having a functional group C may be a commercially available product, or, for example, a component having a functional group C in a commercially available primer coating agent not containing a component having a functional group C. It can also be obtained by mixing. The primer coating agent preferably contains a binder resin having the functional group C.

(Toner print layer forming process)
In the toner print layer forming step, the ink is formed on an at least one surface of the label substrate by an electrophotographic printer using the ink (toner) for forming the toner print layer. 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 a 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) as a design print layer and a toner print layer (toner background print layer) as a background print layer are formed.

  When the toner printing layer contains a component having a functional group A, the toner is not particularly limited as long as it contains a component having a functional group A, and a toner generally used for a copying machine is used. However, it is preferable to use a dedicated product suitable for the printing press. As the toner containing the component having the functional group A, a commercially available product may be used, or for example, the toner having the functional group A may be used.

  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.

(Protective printing layer formation process)
In the protective printing layer forming process, the printing ink (protective printing ink) for forming the protective printing layer is applied on the surface of the label base material having the primer layer and the toner printing layer, and then dried, solidified or cured. Is done.

  The method for applying the protective printing ink is preferably a gravure printing method, a flexographic printing method or a letterpress printing method from the viewpoints of cost, productivity, etc., among which the gravure printing method is particularly preferable. Moreover, when drying the applied protective printing ink by heating or the like, a general heating device capable of heating on the printing device can be preferably used. From the viewpoint of safety, a hot air heater or the like can be preferably used.

  When the protective printing ink is a solvent-drying type printing ink, the protective printing layer 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 protective printing ink is an active energy ray curable printing ink, the protective printing layer is specifically applied after the active energy ray curable printing ink is applied and dried as necessary. It is formed by curing by irradiation with active energy rays.

  When the protective printing ink is a solvent-drying type printing ink, the protective printing ink is, for example, the binder layer (a binder resin contained in the protective printing layer), if necessary, a polyrotaxane, the cross-linking agent, the above It is manufactured by mixing the lubricant, the solvent and the additive. Moreover, you may use the component which has the functional group B as the said binder resin, a polyrotaxane, the said crosslinking agent, the said lubricant, and the said additive. In particular, from the viewpoint that the protective printing layer preferably contains a component having the functional group B, at least one of the binder resin, polyrotaxane, the crosslinking agent, the lubricant, and the additive is functional. A component having a group B is preferred. Mixing can be performed by a known or conventional mixing method. 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 protective printing ink may be used after being filtered, if necessary. Each of the above components (binder resin, polyrotaxane, crosslinking agent, lubricant, solvent, additive, component having reactivity with functional group A) may be used alone or in combination of two or more. Also good.

  When the protective printing ink is an active energy ray-curable printing ink, the protective printing ink is a monomer component constituting the binder resin (a binder resin contained in the protective printing layer), a polyrotaxane, and the crosslinking agent. The lubricant, the solvent, and other additives are mixed as necessary. Moreover, you may use the component which has the functional group B as the said monomer component, a polyrotaxane, the said crosslinking agent, the said lubricant, and the said additive. In particular, from the viewpoint that the protective printing layer preferably contains a component having the functional group B, at least one component of the monomer component, polyrotaxane, the crosslinking agent, the lubricant, and the additive is The component having a functional group B is preferable. The mixing can be performed by a known and common mixing method, and is not particularly limited, but 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, polyrotaxane, crosslinking agent, lubricant, solvent, and other additives) may be used alone or in combination of two or more.

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

  The viscosity (23 ± 2 ° C.) of the protective printing ink is not particularly limited, but is preferably 10 to 1000 mPa · s, more preferably 20 to 500 mPa · s, for example, when applied by gravure printing. . The viscosity of the protective printing ink can be controlled by the type and blending amount (content) of each component of the binder resin, polyrotaxane, crosslinking agent, lubricant and additive, thickener, thinning agent, and the like.

  In order to control the content of components such as binder resin, polyrotaxane and lubricant in the protective printing layer, the binder resin in the non-volatile component of the protective printing ink or the monomer component constituting the binder resin, polyrotaxane and lubricant What is necessary is just to prepare protective printing ink so that content of each component of these etc. may become desired content in the said protective printing layer. In general, the content (% by weight) of each component (nonvolatile component) in all the nonvolatile components of the protective printing ink is equal to the content (% by weight) of each component in the protective printing layer.

  When the coating layer of the present invention contains a component having the functional group B, and the toner print layer contains a component having the functional group A, a curing step (curing) in the shrink label manufacturing method of the invention Step). 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), 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, drying and solidification, or active energy irradiation is performed at the time of forming the coating layer of the present invention or the toner printing layer, curing may proceed simultaneously with the layer formation by the above treatment. There is no need for 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.

  As described above, a shrink label in which a primer layer, a toner printing layer, and a protective printing layer are formed 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 process of perforating can be appropriately selected after providing each layer such as the coating layer of the present invention, before and after the process of processing into a cylindrical shape, and the like.

[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 home delivery, food containers such as seasonings, bottles for alcoholic beverages, pharmaceutical containers, containers for chemical products such as detergents and sprays, and toiletries. Containers, cup noodle containers and the like are included. Although it does not specifically limit as a shape of the said container, For example, various shapes, such as bottle types, such as cylindrical shape and a square shape, and a cup type, are mentioned. The material of the container is not particularly limited, and examples thereof include plastics such as PET, glass, and metals. In addition, the container equipped with the shrink label of the present invention may be referred to as “the labeled container of the present invention”.

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

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

Example 1
(Coating agent)
Urethane resin solution (trade name “Samprene IB-501”, manufactured by Sanyo Chemical Industries Co., Ltd.), polyrotaxane (trade name “Celum Superpolymer SH3400P”, manufactured by Advanced Soft Materials Co., Ltd.), and ethyl acetate. It mixed in the ratio shown in Table 1, and it dispersed using the mixer, and obtained the coating agent.

(Shrink label)
A tabletop gravure printing machine with the coating agent obtained above on one side of a polyester (PET) film (heat-shrinkable film) (trade name “LX-18S”, manufactured by Mitsubishi Plastics, Inc., thickness: 40 μm) (A trade name “GRAVO PROOF MINI” manufactured by Nissho Gravure Co., Ltd.) was applied, dried and solidified to form an anchor coat layer on the entire surface.
Subsequently, aluminum was vacuum-deposited on the surface of the anchor coat layer to form an aluminum vapor-deposited layer on the entire surface.
As described above, a shrink label having a laminated structure of PET film (thickness: 40 m) / anchor coat layer (thickness: 2 μm) / aluminum vapor deposition layer (thickness: 0.06 μm) was obtained.

Examples 2, 3 and Comparative Example 1
Shrink labels were produced in the same manner as in Example 1 except that the composition of the coating agent was changed as shown in Table 1.

Example 4
(Coating agent)
Table 1 shows the UV curable adhesive (trade name “CF Medium”, manufactured by T & K TOKA Corporation) and polyrotaxane (trade name “Celum Superpolymer SH3400P”, manufactured by Advanced Soft Materials Co., Ltd.). And dispersed using a mixer to obtain a coating agent.

(Printing ink for protective layer)
20 parts by weight of an acrylic resin (trade name “Dyanal BR-113”, manufactured by Mitsubishi Rayon Co., Ltd., nonvolatile content: 100% by weight) and 1.5 parts by weight of a lubricant, 38.5 parts by weight of isopropyl alcohol, ethyl acetate 20 parts by weight and 20 parts by weight of n-propyl acetate were mixed and dispersed using a mixer to obtain a protective layer printing ink.

(Shrink label)
On one side of a polyester (PET) film (heat-shrinkable film) (trade name “LX-18S”, thickness: 40 μm, manufactured by Mitsubishi Plastics, Inc.), the coating agent obtained above is applied to a flexographic printing system. Then, an adhesive layer (uncured) was formed on the entire surface other than the vicinity of the portion to be the seal portion.
Next, the aluminum vapor deposition layer side of the transfer substrate having an aluminum vapor deposition layer on the support is bonded to the surface of the adhesive layer, and after curing the adhesive layer by ultraviolet irradiation, the support is peeled off, An aluminum vapor deposition layer was formed on the entire surface other than the vicinity of the seal portion.
Then, the protective layer printing ink obtained above is applied to the surface of the aluminum vapor deposition layer using the tabletop gravure printing machine, dried and solidified, and a protective printing layer is formed on the entire surface other than the vicinity of the seal portion. Formed.
As described above, a shrink label having a laminated structure of PET film (thickness: 40 m) / adhesive layer (thickness: 2 μm) / aluminum vapor deposition layer (thickness: 0.025 μm) / protective printing layer (thickness: 1 μm) Obtained.

Comparative Example 2
A shrink label was produced in the same manner as in Example 4 except that the composition of the coating agent was changed as shown in Table 1.

Example 5
(Coating agent)
Urethane resin solution (trade name “Samprene IB-501”, manufactured by Sanyo Chemical Industries Ltd.), polyrotaxane (trade name “Celum Superpolymer SH3400P”, manufactured by Advanced Soft Materials Co., Ltd.), curing agent (trade name) “Fine wrap WPV curing agent” (manufactured by DIC Graphics Co., Ltd.) and ethyl acetate were mixed at a ratio shown in Table 1 and dispersed using a mixer to obtain a coating agent.

(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) A primer coat agent of a mold (containing no component having reactivity with a carboxy group) was applied and dried and solidified using the tabletop gravure printing machine, and a primer layer was formed on the entire surface other than the vicinity of the seal portion. Subsequently, a toner containing toner particles containing a polyolefin-based resin having a carboxy group as a binder resin was printed with a digital printing machine of a photographic printing system to form a toner printing layer on the primer layer. Subsequently, the coating agent obtained above was applied using the tabletop gravure printing machine, dried and solidified, and a protective printing layer was applied so as to cover the toner printing layer on the entire surface other than the vicinity of the seal portion. Formed.

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

Examples 6 and 7 and Comparative Example 3
A shrink label was produced in the same manner as in Example 5 except that the composition of the coating agent was changed as shown in Table 1.

(Evaluation)
The following evaluation was performed about the shrink label obtained by the Example and the comparative example. The evaluation results are shown in Table 1. In addition, “-” in Table 1 indicates that no evaluation was performed.

(1) Peel resistance (tape peel test)
The test was conducted in accordance with JIS K 5600-5-6 except that no cross cuts were made on the grid. On the surface opposite to the surface of the shrink film of the shrink labels obtained in the examples and comparative examples, an adhesive tape having a width of 18 mm (manufactured by Nichiban Co., Ltd., trade name “Cello Tape (registered trademark)”) is pasted. The pressure-sensitive adhesive tape was peeled off at 90 degrees.
In the area of 5 mm (main shrinkage direction) x 5 mm (perpendicular to the main shrinkage direction) on the surface to which the adhesive tape is applied, the peeled area (ratio) of the aluminum vapor deposition layer or toner print layer is visually observed. Judgment was made based on the following criteria.
Good peel resistance (○): No peeling (peeling area is 0%)
Level at which peel resistance can be used (△): Peeling area is less than 30% Peeling resistance is poor (x): Peeling area is 30% or more

(2) Metal gloss (brightness) (before heat shrink)
About the shrink label obtained by the Example and the comparative example, the part in which the aluminum vapor deposition layer was provided was made into JIS K using the gloss meter "micro-TRI-gloss" by a BYK-Gardner (BYK-Gardner) company make. Based on 5600-4-7, the specular gloss (before heat shrinkage) was measured under the conditions of an incident angle of 60 ° / reflection angle of 60 °. In addition, the shrink film surface was measured as a measurement surface. The brightness (before heat shrinkage) was evaluated according to the following criteria.
Good (○): Specular gloss is 150 or more Poor (×): Specular gloss is less than 150

(3) Metal gloss (brightness) (after 10% heat shrink)
From the shrink labels obtained in Examples and Comparative Examples, a label piece having a size of 150 mm (main shrinkage direction) × 100 mm (perpendicular to the main shrinkage direction) was cut out. The above-mentioned label piece was fixed to a jig capable of fixing a portion having a length of 100 mm in the main contraction direction of the label piece at an interval of 90 mm (fixed at a position of 25 mm from both ends in the main contraction direction of the label piece, and 100 mm therebetween) The length portion of each is 90 mm apart, and is in a sagging state before the heat shrink treatment). The label piece fixed to the jig was immersed in hot water at 90 ° C. for about 20 seconds and heat-treated, and the label piece was heat-shrinked so as to have a length of 90% compared to that before the heat-shrinking treatment ( 10% heat shrinkage in the main shrinkage direction). In this way, a measurement sample was obtained which was thermally contracted by 10% in the main contraction direction. The measurement sample was evaluated for luminance (after 10% heat shrinkage) in the same manner as in “(2) Metallic luster (brightness) (before heat shrinkage)”.

(4) Ink crack test (steam shrinkage test)
Samples for measurement measuring 252 mm (main shrinkage direction: width direction of shrink film) × 110 mm (direction perpendicular to main shrinkage direction: longitudinal direction of shrink film) were collected from the shrink labels obtained in the examples and comparative examples. . As shown in FIG. 5, 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 where the protective printing layer is provided is the inner side. One end and the other end are overlapped to form a cylinder so that the protective printing layer on the other end and the other end side does not overlap, and the shrink film between the one end and the other end is made of THF, Sealing was performed so that the width of the seal portion was 3 mm, and a cylindrical shrink label was obtained (peripheral length: 245 mm).
After the cylindrical shrink label obtained above was externally fitted to a container (substantially cylindrical PET container, trunk diameter: 70 mm), the tubular shrink label was thermally contracted by passing through a 90 ° C. steam tunnel. A container with a label was obtained (the heat shrinkage at the container body was 10%). The appearance (outside) of the label of the obtained container with a label was observed, and it was visually observed whether ink cracking occurred in the toner print layer. Evaluation was made according to the following criteria.
Good (○): Ink cracks cannot be confirmed. Bad (×): Ink cracks can be confirmed.

The description of the polyrotaxane described in Table 1 is shown below.
SH3400P: Product name “Celum Superpolymer SH3400P”, manufactured by Advanced Soft Materials, nonvolatile content: 100% by weight
SH2400P: Trade name “Celum Superpolymer SH2400P”, manufactured by Advanced Soft Materials, nonvolatile content: 100% by weight
SH1310P: Trade name “Celum Superpolymer SH1310P”, manufactured by Advanced Soft Materials, nonvolatile content: 100% by weight

  As can be seen from the evaluation results, the shrink labels (Examples 1 to 4) of the present invention having a metal layer have no peeling in the metal layer in the tape peeling test, and the luminance is the same as before the heat shrinkage even after 10% heat shrinkage. Was excellent, and the following property of the metal layer to the heat shrinkage of the shrink film was good. On the other hand, the shrink label (Comparative Examples 1 and 2) in which the anchor coat layer or the adhesive layer does not contain polyrotaxane has a lower brightness after 10% heat shrinkage than before heat shrinkage, and the metal layer against heat shrinkage of the shrink film. The following ability was inferior. Further, the shrink labels (Examples 5 to 7) of the present invention having a toner print layer did not peel off in the toner print layer in the tape peel test, and no ink cracking occurred in the toner print layer after 10% heat shrinkage. The followability of the toner printing layer to the thermal shrinkage of the shrink film was good. On the other hand, the shrink label in which the protective printing layer does not contain polyrotaxane (Comparative Example 3) causes ink cracking in the toner printing layer after 10% thermal shrinkage, and the followability of the toner printing layer to the thermal shrinkage of the shrink film is poor. It was.

DESCRIPTION OF SYMBOLS 1 Shrink label of this invention 2 Label base material 3 Design printing layer 4 Anchor coat layer 5 Metal direct vapor deposition layer or metal compound vapor deposition layer 6 Protective printing layer 7 Primer layer 8 Toner printing layer 9 Transparent protective printing layer 10 Cylindrical shape of this invention Shrink label 11 Sealing part 12 Solvent or adhesive

Claims (6)

  A label base material including a heat-shrinkable film, a layer (A layer) which is a metal layer or a printed layer provided on at least one surface of the label base material, and overlaps at least a part of the A layer in the thickness direction. A shrink label, comprising: a coating layer provided as described above, wherein the coating layer contains a binder resin and a polyrotaxane.   The shrink label according to claim 1, wherein the coating layer contains 0.1 to 70% by weight of polyrotaxane with respect to the total amount of the coating layer.   The shrink label according to claim 1 or 2, wherein the A layer is the printing layer, the label base material, the printing layer, and a protective printing layer are provided in this order, and the protective printing layer is the coating layer. .   The A layer is a toner printing layer, the toner printing layer contains a component having a functional group A, and the coating layer contains a crosslinking agent as a component having reactivity with the component having the functional group A. The shrink label of any one of claim | item 1-3.   The shrink label according to claim 1 or 2, wherein the A layer is a metal layer, has the label base material, the anchor coat layer, and the metal layer in this order, and the anchor coat layer is the coating layer.   The shrink label according to claim 1 or 2, wherein the A layer is a metal layer, has the label base material, an adhesive layer, and the metal layer in this order, and the adhesive layer is the coating layer.

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