JP6392070B2 - Shrink label and laminate for shrink label - Google Patents

Description

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

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

  The printing ink for forming the printing layer is, for example, a printing ink containing a urethane acrylic resin (A) having a structural unit derived from polyester polyol, an acrylic resin (B), and titanium oxide (C). In the urethane acrylic resin (A), the content of the structural unit derived from the monomer having a (meth) acryloyl group is 1 to 40% by weight, and the acid value of the acrylic resin (B) is 1 to 40 mgKOH / g, and the weight ratio of the acrylic resin (B) content to the urethane acrylic resin (A) content in the non-volatile content of the printing ink is 50:50 to 99: 1, and the non-volatile content of the printing ink A printing ink having a titanium oxide (C) content of 70 to 81% by weight in a minute is known (see Patent Document 1). Moreover, as said shrink label, content of the structural unit derived from n-butyl acrylate is 3 to 20 weight% on the at least single side | surface side of a shrink film, and content of the structural unit derived from methyl methacrylate is 25 weight, for example. %, And an acrylic resin containing 95% by weight or more of a structural unit derived from (meth) acrylic acid ester, and a transparent content of the acrylic resin of 80% by weight or more. A shrink label having a printed layer is known (see Patent Document 2).

  By the way, when a shrink label provided with a printing layer is used as a label for a container for toiletries such as detergents and sprays, the contents of the container adhere to the shrink label, and thereby the printing layer of the shrink label dissolves. There was a case. In order to prevent this, a curing agent is added to the printing ink forming the printing layer to reduce the solubility of the printing layer, and resistance to chemical components contained in the contents of the container (for example, acid, alkali, organic) There is known a technique for improving the resistance to dissolution and the like in a solvent.

JP 2012-62415 A JP2012-184030A

  However, such a printing layer resistant to chemical components has a hard ink coating and is likely to whiten (shrink white) during shrink processing. In particular, in the case of a transparent tone label, it has been difficult to use a printing layer whose transparency has been reduced by shrinkage whitening as a printing layer for a label that requires transparency.

That is, an object of the present invention is to provide a shrink label having a novel printed layer which is stable and excellent in resistance to chemical components and hardly shrinks and whitens.
Another object of the present invention is to provide a shrink label having a novel printing layer excellent in blocking resistance and transparency. Another object of the present invention is to provide a shrink label laminate having an active energy ray-curable resin composition layer that forms a novel printed layer that is stable and excellent in resistance to chemical components and hardly shrinks and whitens. It is to provide. Another object of the present invention is to provide a shrink label laminate having an active energy ray-curable resin composition layer that forms a novel printed layer excellent in blocking resistance and transparency.

  As a result of intensive studies to achieve the above object, the present inventors have found that a shrink label has a urethane-based oligomer having an acrylic resin as a main chain and an active energy ray-polymerizable group on at least one surface of a shrink film. By having a printed layer obtained by curing the active energy ray-curable resin composition layer containing the polymer compound (X) as a side chain with active energy rays, it has excellent resistance to chemical components stably. In addition, the present inventors have found that a shrink label that is less likely to shrink and whiten can be obtained, thereby completing the present invention.

  That is, the present invention is a shrink label having a print layer on at least one surface of a shrink film, wherein the print layer is a urethane oligomer having an acrylic resin as a main chain and having an active energy ray polymerizable group. There is provided a shrink label, which is a printed layer obtained by curing an active energy ray-curable resin composition layer containing a polymer compound (X) as a side chain with active energy rays.

  Furthermore, the present invention provides the polymer compound (X), wherein the acrylic resin has a weight average molecular weight of 5,000 to 200,000, and the urethane oligomer has a weight average molecular weight of 200 to 10,000. Provide shrink labels.

  Further, in the present invention, the content ratio of the acrylic resin and the urethane oligomer (acrylic resin: urethane oligomer) (weight ratio) in the polymer compound (X) is 10: 1 to 2: 1. A shrink label as described above is provided.

  Further, the present invention provides an active energy containing a polymer compound (X) having an acrylic resin as a main chain and a urethane oligomer having an active energy ray polymerizable group as a side chain on at least one surface of a shrink film. A laminate for shrink labels having a line curable resin composition layer is provided.

  The shrink label of the present invention comprises an active polymer containing at least one surface of a shrink film containing a polymer compound (X) having an acrylic resin as a main chain and a urethane oligomer having an active energy ray polymerizable group as a side chain. It has a printed layer obtained by curing an energy ray-curable resin composition layer with active energy rays. As a result, the shrink label of the present invention is stable and excellent in resistance to chemical components. Therefore, when the shrink label is used as a container label for toiletries such as detergents and sprays, the printed layer in the shrink label is the container. Dissolution and corrosion are unlikely to occur due to the contents of Moreover, since the shrink label of the present invention is less likely to shrink and whiten, it can be preferably used for applications requiring transparency. Furthermore, when the printing layer is provided as the outermost layer of the shrink label, it is excellent in blocking resistance, and thus the adhesion (adhesion) between the shrink labels can be prevented.

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. 2 is a schematic view showing an example of a cylindrical shrink label that is an embodiment of the shrink label of the present invention (an enlarged view of the main part of the A-A ′ cross section in FIG. 1). FIG. 3 is a schematic view (an enlarged view of a main part of the A-A ′ cross section in FIG. 1) showing another example of a cylindrical shrink label that is an embodiment of the shrink label of the present invention. FIG. 3 is a schematic view (an enlarged view of a main part of the A-A ′ cross section in FIG. 1) showing another example of a cylindrical shrink label that is an embodiment of the shrink label of the present invention.

  The shrink label of the present invention is a shrink label having a printing layer on at least one surface of a shrink film, and the printing layer comprises a urethane oligomer having an acrylic resin as a main chain and an active energy ray polymerizable group. A printed layer obtained by curing an active energy ray-curable resin composition layer containing the polymer compound (X) as a side chain with active energy rays. In the present specification, the print layer may be referred to as “print layer of the present invention”. The shrink label of the present invention may contain a layer (other layer) other than the above-mentioned shrink film and the printed layer of the present invention within a range not impairing the effects of the present invention.

[Print layer of the present invention]
The printing layer of the present invention is an essential layer in the shrink label of the present invention, and is provided on at least one surface of the shrink film. The printing layer of the present invention comprises an active energy ray-curable resin composition layer containing, as an essential component, a polymer compound having an acrylic resin as a main chain and a urethane oligomer having an active energy ray polymerizable group as a side chain. It is a printed layer obtained by curing with active energy rays. In the present specification, the “polymer compound having an acrylic resin as a main chain and a urethane oligomer having an active energy ray polymerizable group as a side chain” is referred to as “polymer compound (X)”. There is. In the present specification, the acrylic resin that is the main chain of the polymer compound (X) may be referred to as “acrylic resin (M)”. Further, in the present specification, the urethane oligomer having the active energy ray polymerizable group may be referred to as “the urethane oligomer of the present invention”. Further, in the present specification, an active energy ray-curable resin composition layer containing, as an essential component, a polymer compound having an acrylic resin as a main chain and a urethane oligomer having an active energy ray polymerizable group as a side chain, That is, the active energy ray-curable resin composition layer containing the polymer compound (X) may be referred to as “the active energy ray-curable resin composition layer of the present invention”.

  The printing layer of the present invention is formed by curing the active energy ray-curable resin composition layer of the present invention by irradiation with active energy rays. Specifically, the active energy ray-polymerizable groups in the polymer compound (X) contained in the active energy ray-curable resin composition layer of the present invention are irradiated with each other by irradiation with active energy rays, or The printing layer of the present invention is formed by polymerization and bonding with other active energy ray polymerizable monomers or active energy ray polymerizable oligomers.

  In this specification, although the said active energy ray is not specifically limited, For example, visible light, an ultraviolet-ray, an electron beam etc. are mentioned. Of these, ultraviolet rays and electron beams are preferable.

<Active energy ray-curable resin composition layer of the present invention>
The active energy ray-curable resin composition layer of the present invention contains the polymer compound (X) as an essential component.

(Polymer compound (X))
The polymer compound (X) has a urethane oligomer having an active energy ray polymerizable group as a side chain in an acrylic resin (acrylic resin (M)) as a main chain. Although high molecular compound (X) is not specifically limited, it plays the role as the main resin component which forms the printing layer of this invention. As the polymer compound (X), only one type may be used, or two or more types may be used.

  Examples of the acrylic resin (M) 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 (M) may contain a monomer component other than the acrylic monomer.

  In this specification, acrylic monomers are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid alkyl ester having a linear or branched alkyl group such as isononyl, decyl (meth) acrylate, dodecyl (meth) acrylate, etc .; (meth) acrylic acid; carboxyl group content such as carboxyethyl acrylate (Meth) acrylic acid ester; 2-hydroxymethyl (meth) acrylate 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) Hydroxyl group-containing (meth) acrylic esters such as acrylate, 2-hydroxy-3-phenoxypropyl acrylate, paracumylphenol EO-modified acrylate; alicyclic hydrocarbon groups such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate (Meth) acrylic acid ester having an aromatic hydrocarbon group such as phenyl (meth) acrylate and phenoxyethyl (meth) acrylate; N-methylo (Meth) acrylic acid amide derivatives such as ru (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, acryloylmorpholine; dimethylaminoethyl (Meth) acrylate dialkylaminoalkyl esters such as (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dipropylaminopropyl (meth) acrylate, etc. Is mentioned. The said acrylic monomer may use only 1 type and may use 2 or more types. “(Meth) acryl” means “acryl” and / or “methacryl” (either or both of acrylic and methacryl).

  Although it does not specifically limit as a monomer component (it may be called "other monomer component") which comprises acrylic resin (M) other than the said acrylic monomer, For example, crotonic acid, itaconic acid, fumaric acid, malein Carboxyl group-containing polymerizable unsaturated compounds such as acids or their anhydrides; Styrenic compounds such as styrene, vinyltoluene, and α-methylstyrene; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl halides such as vinyl chloride Vinyl ethers such as methyl vinyl ether; cyano group-containing vinyl compounds such as (meth) acrylonitrile; α-olefins such as ethylene and propylene;

  Content of acrylic monomer in the total amount (100% by weight) of monomer components constituting the acrylic resin (M), that is, a structural unit derived from the acrylic monomer in the acrylic resin (M) (100% by weight) The content of is not particularly limited, but is preferably 70% by weight or more (for example, 70 to 100% by weight), more preferably 80% by weight or more from the viewpoint of resistance to chemical components and printing ink stability.

  The weight average molecular weight (Mw) of the acrylic resin (M) is not particularly limited, but is preferably 5,000 to 200,000, more preferably 4 from the viewpoints of resistance to chemical components, printing ink viscosity, and printability. It is 10,000 to 190,000, more preferably 90,000 to 180,000. 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 polymer compound (X) can be produced using, for example, at least an acrylic resin constituting the acrylic resin (M) and a urethane oligomer constituting the urethane oligomer of the present invention. The weight average molecular weight of the polymer resin (M) is obtained by measuring the weight average molecular weight of the acrylic resin constituting the acrylic resin (M), which is the raw material of the polymer compound (X). Also good.

  The urethane oligomer of the present invention which is a side chain of the polymer compound (X) has an active energy ray polymerizable group. When the polymer compound (X) has the urethane oligomer of the present invention in the side chain, the flexibility of the printed layer is improved even after curing, and shrinkage whitening can be suppressed. In addition, since the urethane-based oligomer has an active energy ray-polymerizable group, the active energy ray-curable resin composition layer containing the polymer compound (X) is cured by irradiation with active energy rays, so that a stable chemical component A printed layer that is excellent in resistance to shrinkage and hardly shrinks and whitens can be obtained. The position of the active energy ray polymerizable group in the urethane oligomer of the present invention is not particularly limited, but from the viewpoint that the flexibility of the urethane oligomer can be fully utilized, the end of the urethane oligomer (bonded to the main chain). The end opposite the side) is preferred. That is, the urethane oligomer of the present invention preferably has an active energy ray polymerizable group at the terminal.

The active energy ray polymerizable group is not particularly limited as long as it is a group that can be polymerized by irradiation with active energy rays. Although it does not specifically limit as said active energy ray polymeric group, For example, (meth) acryloyl group, groups containing carbon-carbon unsaturated bonds, such as a vinyl group (group containing radically polymerizable group); epoxy group, oxetanyl And a group containing a cationically polymerizable group such as a group. Among these, a group containing a radical polymerizable group is preferable. The “(meth) acryloyl group” represents “acryloyl group [CH ₂ ═CHCO—]” and / or “methacryloyl group [CH ₂ ═C (CH ₃ ) CO—]”.

  The urethane-based oligomer of the present invention is not particularly limited as long as it is a urethane-based oligomer having an active energy ray polymerizable group. For example, it is an oligomer obtained by reacting a polyisocyanate compound and a polyol compound, and the active energy ray The thing which has a polymeric group is mentioned. That is, the urethane-based oligomer of the present invention is an oligomer having a structural unit derived from a polyisocyanate compound and a structural unit derived from a polyol compound and having an active energy ray polymerizable group.

  Examples of the polyisocyanate compound include known diisocyanates such as aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate. 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, trifunctional or higher functional polyisocyanates and polyisocyanate adducts can be used in combination with the diisocyanates. Among these, hexamethylene diisocyanate and isophorone diisocyanate are preferable from the viewpoint of suppressing discoloration (yellowing) of the printing layer. The said polyisocyanate compound may use only 1 type and may use 2 or more types.

  Examples of the polyol compound include polyester polyol, polyether polyol, polycarbonate polyol, polylactone polyol, polyolefin polyol, and polyhydric alcohol. Among these, polyester polyols and polyether polyols are preferable from the viewpoint of the flexibility of the printing layer. The said polyol compound may use only 1 type and may use 2 or more types.

  The polyester polyol is a polyester compound having two or more hydroxyl groups in the molecule (in one molecule), and among them, a polyester diol having two hydroxyl groups in the molecule is preferable. Although the said polyester polyol is not specifically limited, It is preferable that it is a polymer comprised by using dicarboxylic acid and diol as an essential structural component. That is, the polyester polyol preferably has at least a structural unit derived from a dicarboxylic acid and a structural unit derived from a diol. Moreover, said diol and trifunctional or more than trifunctional polyol compounds (polyether polyol, polyester polyol, etc.) can also be mixed and used as needed.

  Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, 2,5-dimethylterephthalic acid, 5-t-butylisophthalic acid, 4,4′-biphenyldicarboxylic acid, trans-3,3′-stilbene dicarboxylic acid, Trans-4,4′-stilbene dicarboxylic acid, 4,4′-dibenzyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalene Dicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,2,6,6-tetramethylbiphenyl-4,4′-dicarboxylic acid, 1,1,3-trimethyl-3-phenylindene-4,5-dicarboxylic acid 1,2-diphenoxyethane-4,4′-dicarboxylic acid, diphenyl ether dicarboxylic acid, 2,5-ant Aromatic dicarboxylic acids such as sendicarboxylic acid, 2,5-pyridinedicarboxylic acid, and substituted products thereof; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid , Undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, icosanedioic acid, docosanedioic acid, 1,12-dodecanedioic acid, and Aliphatic dicarboxylic acids such as these substitutes; 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid , Trans-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedi Carboxylic acid, and include alicyclic dicarboxylic acids such as substituted versions thereof. Among these, from the viewpoint of suppressing discoloration (yellowing) of the printing layer, aliphatic dicarboxylic acids and alicyclic dicarboxylic acids are preferable, and succinic acid, adipic acid, sebacic acid, dodecanedioic acid, cis-1,4 are more preferable. -Cyclohexanedicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid. The said dicarboxylic acid may use only 1 type and may use 2 or more types.

  Examples of the diol include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2 -Dimethyl-1,3-propanediol (neopentyl glycol), 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2,4-dimethyl-1,3-hexanediol, 1,10-decanediol, polyethylene glycol, polypropylene Aliphatic diols such as glycol; 1,2-cyclohexanedimethanol, 1,3-cyclohexane Cycloaliphatic diols such as sandimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol; 2,2-bis (4-β-hydroxyethoxyphenyl) propane And ethylene oxide adducts of bisphenol compounds such as bis (4-β-hydroxyethoxyphenyl) sulfone, and aromatic diols such as xylylene glycol. Of these, aliphatic diols are preferable, and neopentyl glycol (NPG) and ethylene glycol (EG) are more preferable. The said diol may use only 1 type and may use 2 or more types.

  In addition to the dicarboxylic acid and the diol, the polyester polyol includes oxycarboxylic acids such as p-oxybenzoic acid and p-oxyethoxybenzoic acid; monocarboxylic acids such as benzoic acid and benzoylbenzoic acid; trimellitic acid, etc. It may contain a structural unit derived from a polyhydric carboxylic acid; a monohydric alcohol such as polyalkylene glycol monomethyl ether; a polyhydric alcohol such as glycerin, pentaerythritol, or trimethylolpropane.

  Examples of the polyether polyol include alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, and polyether polyols containing cyclic ethers such as tetrahydrofuran as monomer components. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and alkylene oxide copolymers such as ethylene oxide-propylene oxide copolymers. As the polyether polyol, bisphenols (for example, bisphenol A, bisphenol F, bisphenol AD, etc.) and dihydroxybenzene compounds (for example, catechol, resorcin, hydroquinone, etc.) are used as initiators and monomer components. Examples thereof include polyether diol. The said polyether polyol may use only 1 type and may use 2 or more types.

  Examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, and lactone block copolymer diol. As for the said polylactone polyol, only 1 type may be used and 2 or more types may be used.

Examples of the polyhydric alcohol include 2-methyl-1,8-octanediol, diethylene glycol, dipropylene glycol, glycerin, hexanetriol, trimethylolpropane, trimethylolethane, and 1,4-cyclohexanediol in addition to the diol. 1,4-cyclohexanedimethanol, dimer acid diol, quadrol, bisphenol A, pentaerythritol, arabitol, sorbitol, and other dihydric or higher alcohols.

  The introduction of the active energy ray polymerizable group is not particularly limited. For example, an oligomer obtained by reacting a polyisocyanate compound and a polyol compound, a (meth) acrylate having a hydroxyl group, or a (meth) having an isocyanate group. It can be carried out by reacting with acrylate. Examples of the (meth) acrylate having a hydroxyl group include 2 to 10 carbon atoms (preferably 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate) and the like. And hydroxyalkyl (meth) acrylates having a hydroxyalkyl group having 4 to 10 carbon atoms. Examples of the (meth) acrylate having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate.

  The urethane oligomer of the present invention is not particularly limited, but may be introduced into the acrylic resin (M) as the main chain via a polyalkylene oxide chain such as a polypropylene oxide chain. All of the urethane oligomers of the present invention may be introduced into the acrylic resin (M) as the main chain via a polyalkylene oxide chain, or only some of the urethane oligomers of the present invention are polyalkylene oxide chains. It may be introduced into the acrylic resin (M) which is the main chain via

  The weight average molecular weight (Mw) of the urethane oligomer of the present invention (weight average molecular weight of the urethane oligomer of the present invention per one) is not particularly limited, but is 200 from the viewpoint of resistance to chemical components and suppression of shrinkage whitening. -10,000 are preferable, More preferably, it is 250-7,000, More preferably, it is 300-5,000. In addition, the polymer compound (X) can be produced using, for example, at least an acrylic resin constituting the acrylic resin (M) and a urethane oligomer constituting the urethane oligomer of the present invention. The weight average molecular weight of the urethane oligomer may be obtained by measuring the weight average molecular weight of the urethane oligomer constituting the urethane oligomer of the present invention, which is a raw material for the polymer compound (X). . When the urethane oligomer of the present invention is introduced into the acrylic resin (M) as the main chain via a polyalkylene oxide chain, the weight average molecular weight of the polyalkylene oxide chain is: Not included.

  Although high molecular compound (X) is not specifically limited, You may have side chains (other side chains) other than the urethane-type oligomer of this invention. Examples of the other side chain include a urethane oligomer having no active energy ray polymerizable group, and a urethane resin that may have an active energy ray polymerizable group (for example, a weight average molecular weight (Mw) of 1). And a resin having a urethane bond in the molecule). The other side chain may also be introduced into the acrylic resin (M) that is the main chain via a polyalkylene oxide chain. In the present specification, the oligomer may be, for example, a polymer having a degree of polymerization of about 2 to 100, and the resin may be, for example, a polymer having a degree of polymerization of about 100 or more.

  The content ratio of the acrylic resin (M) and the urethane oligomer of the present invention in the polymer compound (X) [acrylic resin (M): urethane oligomer of the present invention] (weight ratio) is not particularly limited. Is preferably 10: 1 to 2: 1, more preferably 9: 1 to 3: 1, and even more preferably 8: 1 to 3: 1. When the amount of the acrylic resin (M) is less than 10: 1, it is preferable because the flexibility of the printed layer is prevented from being lowered and shrinkage whitening can be more effectively suppressed. Moreover, the flexibility of the printing layer is improved, and ink cracking is less likely to occur, which is preferable. When the urethane oligomer is less than 2: 1, the heat resistance of the printing layer is improved, and ink cracking is less likely to occur, which is preferable. The content ratio is a total ratio of the total weight of the acrylic resin (M) in the polymer compound (X) and the weight of all the urethane oligomers of the present invention contained in the polymer compound (X). is there. Moreover, although high molecular compound (X) can be manufactured using the urethane type oligomer which comprises the acrylic resin which comprises acrylic resin (M) at least, and the urethane type oligomer of this invention, for example, it contains the above The ratio was obtained by measuring the weight of the acrylic resin constituting the acrylic resin (M) and the weight of the urethane oligomer constituting the urethane oligomer of the present invention, which is a raw material for the polymer compound (X). May be adopted.

  The total content of the acrylic resin (M) and the urethane oligomer of the present invention in the polymer compound (X) is not particularly limited, but is based on the total weight (100% by weight) of the polymer compound (X). 70% by weight or more (for example, 70 to 100% by weight) is preferable, more preferably 80% by weight or more, and still more preferably 90% by weight or more. When the content is 70% by weight or more, the resistance to chemical components and the stability of the printing ink are further improved, which is preferable.

  Although the weight average molecular weight (Mw) of high molecular compound (X) is not specifically limited, 5,200-300,000 are preferable, More preferably, it is 50,000-280,000, More preferably, it is 100,000-250,000. When the Mw is 5,200 or more, resistance to chemical components is further improved, which is preferable. When the Mw is 300,000 or less, the viscosity of the printing ink becomes good and the printability is further improved, which is preferable.

  The polymer compound (X) is not particularly limited, but the double bond equivalent in the polymer compound (X) is preferably 300 to 3,000 g / mol, more preferably 500 to 2,500 g / mol. More preferably, it is 600 to 2,000 g / mol. When the double bond equivalent is 300 g / mol or more, the printed layer has sufficient hardness, and thus the resistance to chemical components is further improved, which is preferable. It is preferable that the double bond equivalent is 3,000 g / mol or less because the printed layer does not become too hard and shrinkage whitening hardly occurs.

  The content of the polymer compound (X) in the active energy ray-curable resin composition layer (100% by weight) of the present invention, that is, the polymer compound (X) in the printed layer (100% by weight) of the present invention The content of the derived structural unit is not particularly limited, but is preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, particularly preferably 60% by weight or more, and most preferably 70% by weight. % Or more. When the content is 30% by weight or more, resistance to chemical components is further improved, which is preferable. The upper limit of the content may be 100% by weight or less than 100% by weight. Moreover, when the printing layer of this invention contains a color pigment, content of the said high molecular compound (X) is although it does not specifically limit, 15-50 weight% is more preferable, 15-35 weight% is further more preferable.

  The active energy ray-curable resin composition layer of the present invention is not particularly limited, but may contain an acrylic resin in addition to the polymer compound (X). In this specification, the acrylic resin may be referred to as “acrylic resin (N)” from the viewpoint of clearly distinguishing from the acrylic resin (M).

  The acrylic resin (N) is a resin composed of the acrylic monomer as an essential monomer component, that is, a resin including at least a structural unit (structural unit) derived from the acrylic monomer. The monomer component constituting the acrylic resin (N) may contain a monomer component other than the acrylic monomer. In the present specification, the acrylic resin (N) does not include the polymer compound (X).

  Although it does not specifically limit as a monomer component which comprises acrylic resin (N) other than the said acrylic monomer, The monomer component illustrated and demonstrated as another monomer component in the said acrylic resin (M), etc. are mentioned.

  Content of acrylic monomer in the total amount (100% by weight) of monomer components constituting the acrylic resin (N), that is, a structural unit derived from the acrylic monomer in the acrylic resin (N) (100% by weight) The content of is not particularly limited, but is preferably 50% by weight or more (for example, 50 to 100% by weight) from the viewpoint of improvement of transparency, suppression of shrinkage whitening, resistance to chemical components, and stability of printing ink, More preferably, it is 70 weight% or more, More preferably, it is 80 weight% or more.

  The weight average molecular weight (Mw) of the acrylic resin (N) is not particularly limited, but is preferably 10,000 to 100,000, more preferably 1 from the viewpoints of transparency of the printing layer, viscosity of the printing ink, and printability. 10,000 to 80,000.

  The glass transition temperature (Tg) of the acrylic resin (N) is not particularly limited, but is preferably 30 to 120 ° C., more preferably from the viewpoint of improving the transparency, wear resistance, and heat resistance of the printing layer of the present invention. Is 50-100 ° C.

  In the present specification, the glass transition temperature (Tg) of the resin can be measured by DSC (differential scanning calorimetry) in accordance with, for example, JIS K7121. The DSC measurement is not particularly limited. For example, the DSC measurement can be performed using a differential scanning calorimeter “DSC6200” manufactured by Seiko Instruments Inc. under a temperature rising rate of 10 ° C./min.

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

  When the active energy ray-curable resin composition layer of the present invention contains the acrylic resin (N), the acrylic resin (N) in the active energy ray-curable resin composition layer (100% by weight) of the present invention. The content of the acrylic resin (N) in the printing layer (100% by weight) of the present invention is not particularly limited, but it is 0% from the viewpoint of improving transparency and suppressing shrinkage whitening. % Is preferably 50% by weight or less, more preferably 0% by weight or more and 30% by weight or less.

  The printed layer of the present invention is formed by curing the active energy ray-curable resin composition layer of the present invention by irradiation with active energy rays. The active energy ray-curable resin composition layer of the present invention that forms the printed layer of the present invention is, for example, applied with printing ink on at least one surface of a shrink film, and dried or dried and solidified as necessary. It is formed by doing.

  The printing ink is not particularly limited, but may be a solvent drying type printing ink or an active energy ray curable type printing ink. When using a solvent-drying type printing ink, the active energy ray-curable resin composition layer of the present invention is applied, for example, on at least one surface of a shrink film, and dried and solidified by heating or the like. Formed by removing the solvent. On the other hand, when an active energy ray curable printing ink is used, the active energy ray curable resin composition layer of the present invention is applied, for example, by applying the printing ink on at least one surface of a shrink film. It is formed by volatilizing a solvent or the like accordingly.

  When the active energy ray-curable resin composition layer of the present invention is formed with an active energy ray-curable printing ink, the active energy ray-curable resin composition layer of the present invention is not particularly limited. , An active energy ray polymerizable monomer and an oligomer (active energy ray polymerizable oligomer) which is a polymer having a low polymerization degree of the active energy ray polymerizable monomer may be included. Moreover, although the polymerization degree of the said active energy ray polymerizable oligomer is not specifically limited, About 2-20 are preferable, More preferably, it is about 5-15. When the active energy ray-curable resin composition layer contains an active energy ray polymerizable monomer and an active energy ray polymerizable oligomer together with the polymer compound (X), the active energy ray polymerizable monomer and the active energy ray are irradiated by active energy ray irradiation. Since the polymerizable oligomer and the polymer compound (X) are polymerized to form a polymer, the flexibility of the printing layer of the present invention is improved, and the shrink label of the present invention has sufficient heat shrinkability and transparency. It can be excellent in blocking resistance while holding.

  The active energy ray polymerizable monomer is a monomer having at least one active energy ray polymerizable functional group in the molecule. The active energy ray polymerizable functional group is preferably an active energy ray radical polymerizable group, and more preferably an ethylenically unsaturated group (active energy ray radical polymerizable ethylenically unsaturated group). More specifically, for example, a vinyl group, propenyl group, isopropenyl group, (meth) acryloyl group (acryloyl group, methacryloyl group) and the like can be mentioned.

  Examples of the active energy ray polymerizable monomer include monofunctional monomers and polyfunctional monomers. The monofunctional monomer is a monomer having only one active energy ray polymerizable functional group in the molecule. The polyfunctional monomer is a monomer having two or more active energy ray polymerizable functional groups in the molecule.

  Examples of the monofunctional monomer include known monofunctional monomers having an ethylenically unsaturated group, and are not particularly limited. For example, the acrylic monomer; carboxyl groups such as crotonic acid, itaconic acid, fumaric acid, and maleic acid Containing polymerizable unsaturated compounds or anhydrides thereof; styrene 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; cyano group-containing vinyl compounds such as (meth) acrylonitrile; α-olefins such as ethylene and propylene; N-acryloyloxyethyl hexahydrophthalimide and the like. Among these, from the viewpoint of the flexibility of the printed layer, the (meth) acrylic acid alkyl having a glass transition temperature (Tg) when the homopolymer is formed is, for example, -100 to 100 ° C, preferably -50 to 50 ° C. Esters are preferred.

  When the active energy ray-curable resin composition layer of the present invention contains an active energy ray-polymerizable monomer or active energy ray-polymerizable oligomer, the active energy ray-curable resin composition layer (100% by weight) of the present invention contains The total content of the active energy ray polymerizable monomer and the active energy ray polymerizable oligomer, that is, the structural unit derived from the active energy ray polymerizable monomer and the activity in the printing layer (100 wt%) of the present invention. The total content of the structural units derived from the energy beam polymerizable oligomer is not particularly limited, but is preferably 60% by weight or less (for example, more than 0% by weight and 60% by weight or less), more preferably 0% by weight. More than 50% by weight, more preferably more than 0% by weight and less than 30% by weight, particularly preferably more than 0% by weight and more than 20% by weight It is below. When the content is 60% by weight or less, the blocking resistance can be increased, which is preferable.

  The active energy ray-curable resin composition layer of the present invention is formed of an active energy ray-curable printing ink, and the active energy ray-curable resin composition layer of the present invention contains an active energy ray-polymerizable monomer. When the active energy ray-curable resin composition layer of the present invention is used, the polymer compound (X) is contained in an amount of 40% by weight or more, and the active energy ray polymerizable monomer is more than 0% by weight and 60% by weight. % Or less is particularly preferable. In this case, the active energy ray-curable resin composition layer of the present invention may be referred to as “active energy ray-curable resin composition layer (P)”.

  The content of the polymer compound (X) in the active energy ray-curable resin composition layer (100% by weight) of the present invention in the active energy ray curable resin composition layer (P), that is, the printing layer of the present invention. The content of the structural unit derived from the polymer compound (X) in (100 wt%) is 40 wt% or more (for example, 40 wt% or more and less than 100 wt%), preferably 50 wt% or more and 100 wt%. %, More preferably 60% or more and less than 100% by weight, still more preferably 70% or more and less than 100% by weight. When the content is 40% by weight or more, more stable resistance to chemical components is obtained, and transparency is improved, which is preferable.

  Content of the active energy ray-polymerizable monomer in the active energy ray-curable resin composition layer (100% by weight) of the present invention in the active energy ray-curable resin composition layer (P), that is, printing of the present invention. The content of the structural unit derived from the active energy ray polymerizable monomer in the layer (100 wt%) is more than 0 wt% and 60 wt% or less, preferably more than 0 wt% and 50 wt% or less. More preferably, it is more than 0% by weight and 40% by weight or less, more preferably more than 0% by weight and 30% by weight or less. When the content exceeds 0% by weight, heat shrinkability, transparency and printability are improved, which is preferable. When the content is 60% by weight or less, the blocking resistance can be increased, which is preferable.

  The active energy ray-polymerizable monomer in the active energy ray-curable resin composition layer (P) is not particularly limited, but is preferably a monofunctional monomer, more preferably acryloylmorpholine, 2-hydroxy-3-phenoxypropyl acrylate. , N-acryloyloxyethylhexahydrophthalimide, isobornyl acrylate, one or more monofunctional monomers selected from the group consisting of isobornyl acrylate. Acryloylmorpholine, 2-hydroxy-3-phenoxypropyl acrylate, N-acryloyloxyethyl hexahydrophthalimide, and isobornyl acrylate are commonly highly reactive by irradiation with active energy rays, and include these monofunctional monomers. The printed layer obtained by polymerizing and curing the energy ray curable resin composition layer is formed by reducing the uncured (unreacted) residual monomer in the printed layer, and curing these monofunctional monomers. Since the glass transition temperature (Tg) of the acrylic resin is relatively high, it has a common property that the blocking resistance of the printing layer can be improved, which is preferable. Furthermore, acryloylmorpholine, 2-hydroxy-3-phenoxypropyl acrylate, N-acryloyloxyethylhexahydrophthalimide, and isobornyl acrylate have a common chemical structure called acryloyl group, and acryloyl group is active energy ray-cured. There are important common chemical structural elements to polymerize by.

  Since the active energy ray-curable resin composition layer (P) contains the polymer compound (X), it is not necessary to contain a large amount of a monofunctional monomer for constituting the binder resin in the printing layer. A monofunctional monomer having a lower reactivity than the functional monomer hardly remains in the printed layer after curing, and is excellent in blocking resistance. In addition, the active energy ray-curable resin composition layer (P) has excellent blocking resistance without adding an anti-blocking agent such as silica, acrylic beads, titanium oxide, etc., and therefore retains the transparency of the printed layer. be able to. Therefore, when the active energy ray-curable resin composition layer (P) is used, the shrink label of the present invention can be excellent in blocking resistance while maintaining sufficient heat shrinkability and transparency. .

(Other ingredients)
The active energy ray-curable resin composition layer of the present invention is not particularly limited, but other than the polymer compound (X), the acrylic resin (N), the active energy ray polymerizable monomer, and the active energy ray polymerizable oligomer. These components (other components) may be contained within a range not impairing the effects of the present invention. Although it does not specifically limit as said other component, Resin other than polymer compound (X) and said acrylic resin (N) (for example, urethane acrylic resin, urethane resin, cellulose resin etc.), a color pigment, Dye, polymerization initiator (thermal polymerization initiator, photopolymerization initiator), antioxidant, anti-settling agent, lubricant, pigment dispersant, silicone oil, curing agent, wax, plasticizer, stabilizer, antifoaming agent, filling Agents, ultraviolet absorbers, color separation preventing agents, fragrances, deodorants, antiblocking agents (for example, inorganic particles such as silica and titanium oxide; resin beads such as acrylic beads) and the like. Only 1 type may be used for the said other component, and 2 or more types may be used for it.

  Although it does not specifically limit as said photoinitiator, A well-known thru | or usual photoinitiator can be used. The photopolymerization initiator is not particularly limited, but a photoradical polymerization initiator is preferable. The radical photopolymerization initiator is not particularly limited, and examples thereof include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, α-ketol photopolymerization initiators, and aromatic sulfonyl chloride photopolymerization initiators. Examples include photoactive oxime photopolymerization initiators, benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, and thioxanthone photopolymerization initiators. Only 1 type may be used for the said photoinitiator, and 2 or more types may be used for it. Although content of the said photoinitiator is not specifically limited, 1-5 weight% is preferable with respect to the total weight (100 weight%) of the active energy ray-curable resin composition layer of this invention, More preferably 1 to 3% by weight.

  Commercially available products may be used as the photopolymerization initiator, and examples thereof include trade names “Dalcure Series” and “Irgacure Series” manufactured by BASF Japan Ltd.

  The color pigment is not particularly limited, and for example, a color pigment used in a known or conventional print layer can be used. For example, white pigments such as titanium oxide (titanium dioxide), indigo pigments such as copper phthalocyanine blue, carbon black, aluminum flakes, mica (mica), and other colored pigments can be selected and used according to the application. . In addition to the above color pigments, extender pigments such as alumina, calcium carbonate, barium sulfate, silica, and acrylic beads can also be used for the purpose of adjusting gloss. When the printing layer of the present invention contains a color pigment, the content of the color pigment is not particularly limited, but is preferably 5 to 100 parts by weight with respect to the total weight (100 parts by weight) of the polymer compound (X). More preferably, it is 10 to 70 parts by weight.

  Although the thickness of the printing 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 printing layer uniformly, and when partial “fading” occurs, decorativeness is impaired, or printing as designed becomes difficult There is. In addition, if the thickness exceeds 10 μm, a large amount of printing ink is consumed, which increases the cost, makes it difficult to apply uniformly, makes the printed layer brittle and easy to peel off, When the cylindrical shrink label is subjected to shrink processing, the printed layer may hardly follow the thermal shrinkage of the shrink film.

[Shrink film]
The shrink film in the shrink label of the present invention serves as a support for the printed layer of the present invention, and has a major influence on the strength, rigidity and shrink characteristics (shrinkage characteristics) of the label. Although the said shrink film (heat-shrinkable film) is not specifically limited, The shrink film used as a label base material of a well-known shrink label can be used. The type of resin that forms the shrink film can be appropriately selected according to the required physical properties, application, cost, and the like, and is not particularly limited. For example, a polyester resin, a polyolefin resin, a polystyrene resin, Examples of the resin include polyvinyl chloride resin, polyamide resin, aramid resin, polyimide resin, polyphenylene sulfide resin, and acrylic resin. These resins 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. The shrink film includes a polyester film made of a polyester resin, a polyolefin film made of a polyolefin resin, a polystyrene film made of a polystyrene resin, a polyester resin as an outer layer, and a polyolefin resin or a polystyrene resin as an inner layer. A heterogeneous laminated film is preferred. Examples of the polyester-based resin, polyolefin-based resin, and polystyrene-based resin include, for example, JP-A-2008-170822, JP-A-2008-170697, JP-A-2008-163215, and JP-A-2008-163231. The polyester resins, polyolefin resins, polystyrene resins, and the like described can be used.

  As the polyester resin used for the polyester film, polyethylene terephthalate (PET) resin, poly (ethylene-2,6-naphthalenedicarboxylate) (PEN), polylactic acid (PLA), and the like can be used. 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 copolymerized polyester; (in the dicarboxylic acid component, modified terephthalic acid as a main component with isophthalic acid and / or adipic acid) the dicarboxylic acid-modified PET, and the like.

  Polyolefin resins used for the polyolefin film include polyethylene resins such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and metallocene catalyst LLDPE (mLLDPE); polypropylene, propylene-α-olefin Examples thereof include polypropylene resins such as copolymers; ethylene-vinyl acetate copolymers; cyclic olefin resins. In particular, the polyolefin film is preferably one having a cyclic olefin resin as an outer layer. For example, it is preferable to use a cyclic olefin resin as an outer layer and a polyethylene resin or a polypropylene resin as an inner layer (center layer).

  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, styrene-butadiene-styrene copolymer (SBS), styrene-butadiene / isoprene-styrene copolymer (SBIS), styrene-acrylic acid ester copolymer and the like are preferably exemplified. .

  The shrink film may have a single layer structure or a laminated structure. That is, the shrink 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 laminated film having a cyclic olefin resin as an outer layer and a polyethylene resin or a polypropylene resin as an inner layer is preferable.

  The shrink film is preferably 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. When the shrink film is a laminated film, it is preferred 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 shrink film, in particular, 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. Films (including films that are stretched primarily in one direction and slightly stretched in a direction perpendicular to the one direction and substantially stretched in one direction) are 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 shrink film.

  The shrink film can be produced by a conventional method such as melt film formation or solution film formation. It is also possible to use a commercially available shrink film. The surface of the shrink film may be subjected to conventional surface treatment such as corona discharge treatment or primer treatment, if necessary. When a shrink film having a laminated structure is produced, a conventional method such as a co-extrusion method or a dry lamination method can be used as a lamination method. Examples of the method for orienting the shrink film include 2 in the longitudinal direction (film production line direction; also referred to as longitudinal direction or MD direction) and the width direction (direction perpendicular to the longitudinal direction; also referred to as lateral direction or TD direction). Stretching in the direction, stretching in one direction of the longitudinal direction or the width direction, and the like can be used. As the stretching method, for example, a roll method, a tenter method, a tube method, or the like can be used. For example, the stretching process of a film stretched substantially in one direction in the width direction is, for example, 1.01 to 1.5 times, preferably 1. After stretching about 05 to 1.3 times, the stretching can be performed by stretching 3 to 8 times, preferably about 4 to 7 times in the width direction.

  The shrinkage rate of the shrink film in the main shrinkage direction at 90 ° C. for 10 seconds (may be referred to as “heat shrinkage rate (90 ° C., 10 seconds)”) is not particularly limited, but is 20 to 90%. Preferably, it is 30 to 85%, more preferably 40 to 80%. The thermal shrinkage rate (90 ° C., 10 seconds) in the direction perpendicular to the main shrinkage direction of the shrink film is not particularly limited, but is preferably −3 to 15%. 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.

  When the shrink film is transparent, the haze value [based on JIS K 7136, converted to a thickness of 40 μm, unit:%] of the shrink film is not particularly limited, but is preferably 10% or less, more preferably It is 7% or less, more preferably 5% or less. When the haze value exceeds 10%, a shrink label (back printed shrink label) that prints on the inside of the shrink film (the side that becomes the container side when the shrink label is attached to the container) and shows the print through the shrink film ) When used as a product, printing may become cloudy and decorative properties may be reduced. 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 a shrink film, and can be used sufficiently. Moreover, although it does not specifically limit as an opaque shrink film, For example, a milk white film etc. can be used.

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

  A commercial item can also be used for the shrink film. 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).

[Other layers]
The other layers (layers other than the shrink film and the printing layer of the present invention) are not particularly limited. For example, printing layers other than the printing layer of the present invention, adhesive layers (pressure-sensitive adhesive layer, heat-sensitive adhesive) Agent layer, etc.), anchor coat layer, primer coat layer, coating layer, inner coat layer, antistatic layer, metal or metal oxide deposition layer, light shielding layer, heat insulating layer, barrier layer and the like.

[Shrink label]
The shrink label of the present invention has the printed layer of the present invention on at least one surface of the shrink film.

  The print layer of the present invention is not particularly limited. For example, design print layers (color print layers, etc.) such as product names, illustrations, handling precautions, etc., and background prints formed in a single color such as white It can be used for a protective printing layer provided for protecting a layer, a film or a printing layer, a primer printing layer provided for improving the adhesion between the film and the printing layer, and the like. Moreover, since the printing layer of this invention is excellent also in blocking resistance, it is preferable to be used as a layer of the outermost surface of a label (the innermost surface or outermost surface when it is set as a cylindrical shrink label). Although the printing layer of this invention is not specifically limited, You may be provided only in the single side | surface side of the shrink film, and may be provided in the both surfaces side of the shrink film. Moreover, the printing layer of this invention may be provided in the whole surface (for example, surface on the side in which the printing layer of this invention is provided) of the shrink film, and may be provided in part. Furthermore, the printing layer of the present invention is not particularly limited, but may be a single layer or a multilayer.

  The shrink label of the present invention is, for example, a cylindrical shrink label of a type in which both ends of the label are sealed with a solvent or an adhesive and attached to the container, and one end of the label is attached to the container, and the label is wound After that, it can be used as a wrapping type shrink label in which the other end is overlapped with one end to form a cylinder. The shrink label of the present invention is particularly preferably used for a cylindrical shrink label because it is stable and excellent in resistance to chemical components and is not easily contracted and whitened. That is, the shrink label of the present invention is preferably a cylindrical shrink label.

  1-4, an example of a cylindrical shrink label which is a preferred embodiment of the shrink label of the present invention will be described. The cylindrical shrink label 1 of the present invention shown in FIG. 1 is formed in a rectangular shape, and the shrink label of the present invention including the printed layer of the present invention is overlapped with the other end on the outer side of one end of the shrink label. A cylindrical body is formed in which the inner surface of the other end portion and the outer surface of the one end portion are joined with a solvent or an adhesive to form the seal portion 11. The tubular shrink label 1 is formed in a tubular shape so that the main shrinkage direction of the shrink film is the circumferential direction D of the tubular shrink label, and can be thermally shrunk in that direction.

  2 to 4 are enlarged cross-sectional views taken along the line A-A 'in FIG. 1, that is, the vicinity of the seal portion 11 of the cylindrical shrink label 1 of the present invention. Specifically, the shrink label of the present invention in FIGS. 2 to 4 is in a region excluding a region of a predetermined width from the end of the other end of one surface of the shrink film 21 (the surface on the inner surface side of the cylindrical body). A design printing layer 22 is formed, and a background printing layer 23 is formed over substantially the entire area excluding a region of a predetermined width from the other end of one surface of the shrink film 21 so as to cover the design printing layer 22. Has been. Further, as shown in FIG. 3, a protective printing layer 25 may be provided in a region excluding a region having a predetermined width from the other end of the surface of the background printing layer 23. As shown in FIG. 4, a protective printing layer 26 is provided in a region excluding a region having a predetermined width from one end of the other surface of the shrink film 21 (surface on the outer surface side of the cylindrical body). Also good. For this reason, in the shrink label of the present invention, the design print layer 22 and the background print layer 23 are not formed in the region having a predetermined width from the end of the other end, the shrink film 21 is exposed, and the film exposed surface is Is formed. Specifically, the cylindrical shrink label 1 of the present invention has a film exposed surface formed on the inner surface side of the other end portion of the shrink label of the present invention and a film exposed surface formed on the outer surface side of the one end portion. And bonded by a solvent or an adhesive. In addition, the printing layer of this invention can be used about a part or all of the said design printing layer, a background printing layer, and a protective printing layer. In addition, from the viewpoint that the shrink label of the present invention is excellent in blocking resistance, the background print layer 23 in the shrink label of the present invention shown in FIG. 2, and the protective print layer 25 in the shrink label of the present invention shown in FIG. In the shrink label of the present invention shown in FIG. 4, the background print layer 23 and the protective print layer 26 are the print layers of the present invention. Further, the design print layer 22 in the shrink label of the present invention shown in FIG. 2, the design print layer 22 and the background print layer 23 in the shrink label of the present invention shown in FIG. 3, and the design print layer in the shrink label of the present invention shown in FIG. Each of the print layers 22 of the present invention may be a print layer other than the print layer of the present invention.

  Although the design print layer is not particularly limited, for example, a plurality of print layers having different color pigments are stacked so as to obtain a desired display such as a trade name, an illustration, and handling precautions. The design print layer may be the print layer of the present invention, or may be a print layer other than the print layer of the present invention.

  The background print layer is a print layer serving as a background of the design print layer when the cylindrical shrink label of the present invention is observed from the outside of the cylinder, for example, white containing 20 to 60% by weight of titanium oxide as a coloring pigment. It is formed by a printing layer. In addition, content of the said titanium oxide is content with respect to the total weight (100 weight%) of a background printing layer. The background print layer may be the print layer of the present invention, or may be a print layer other than the print layer of the present invention.

  The thickness of the said design printing layer is 0.1-5 micrometers, for example, The thickness of the said background printing layer is 0.5-5 micrometers, for example, The printing layer formed by the design printing layer and the background printing layer As a whole, for example, it is formed to 1 to 10 μm.

  The protective printing layer is, for example, a printing layer containing 0.1 to 10% by weight of a lubricant, and may be a transparent layer or an opaque layer. It is preferable that the protective printing layer provided on the side surface can be visually checked at least on the design printing layer provided on the inner surface side of the cylinder. In addition, content of the said lubricant is content with respect to the total weight (100 weight%) of a protective printing layer. The protective printing layer may be the printing layer of the present invention, or may be a printing layer other than the printing layer of the present invention. The thickness of the protective printing layer is, for example, 0.1 to 10 μm.

  Although the width | variety of the said seal | sticker part is not specifically limited, 0.5-10 mm is preferable, More preferably, it is 1-5 mm.

  The shrink label of the present invention comprises an active energy ray-curable resin composition containing a polymer compound (X) having an acrylic resin (M) as a main chain and a urethane oligomer having an active energy ray polymerizable group as a side chain. The product has a printed layer obtained by curing with active energy rays. Thereby, a tough printed layer can be obtained while being flexible. For this reason, the shrink label of the present invention is less likely to cause shrinkage whitening of the printed layer, and is stable and excellent in resistance to chemical components.

  Moreover, when the printing layer of this invention is used as a layer of the outermost surface (the innermost surface or outermost surface at the time of setting it as a cylindrical shrink label), it is excellent also in blocking resistance. Furthermore, since the printing layer of the present invention contains a structural unit derived from the polymer compound (X), it is flexible yet tough, so it has abrasion resistance (scratch resistance), ink adhesion, and shrinkage. Excellent resistance to ink cracking and heat resistance during processing. Moreover, powder blowing can be reduced in the production process of shrink labels.

[Manufacturing method and processing method of shrink label of the present invention]
Examples of the shrink label manufacturing method and processing method (cylindrical shrink label processing method) of the present invention are shown below.

  The printed layer of the present invention is formed by curing the active energy ray-curable resin composition layer of the present invention by irradiation with active energy rays. Moreover, the active energy ray-curable resin composition layer of the present invention that forms the printed layer of the present invention is to apply printing ink on at least one surface of the shrink film, and to dry or dry solidify as necessary. It is formed by.

  When the printing ink is a solvent-drying type printing ink, the active energy ray-curable resin composition layer of the present invention is specifically formed by applying the solvent-drying type printing ink and drying and solidifying it. Is done. On the other hand, when the printing ink is an active energy ray-curable printing ink, the active energy ray-curable resin composition layer of the present invention is specifically applied with the active energy ray-curable printing ink, It is formed by drying as necessary. The above-described printing ink (solvent drying type printing ink and active energy ray curable type printing ink) may be applied, dried or dried and solidified during the manufacturing process of the shrink film (in-line coating). Although it may be performed after film formation (offline coating), offline coating is preferable from the viewpoint of productivity and workability. Moreover, you may provide layers other than the printing layer of this invention as needed.

  As a method for applying the printing ink, a gravure printing method and a flexographic printing method are preferable from the viewpoints of cost, productivity, and the like, and a gravure printing method is particularly preferable. In addition, when the applied printing ink is dried or dried and solidified by heating or the like, a general heating device that can be heated 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 printing layer of this invention is a design printing layer, application | coating of the said printing ink is performed for every color, and a design printing layer is formed by the printing layer of a some color.

  The solvent-drying printing ink is produced, for example, by mixing the polymer compound (X), a solvent, and, if necessary, the acrylic resin (N) and other components. The active energy ray-curable printing ink includes, for example, the polymer compound (X), if necessary, the acrylic resin (N), the active energy ray polymerizable monomer, and the active energy ray polymerizable oligomer. , By mixing solvent and other ingredients. Mixing can be carried out by a known or conventional mixing method, and is not particularly limited. For example, a mixer such as a paint shaker, butterfly mixer, planetary mixer, pony mixer, dissolver, tank mixer, homomixer, homodisper, A mill such as a roll mill, a sand mill, a ball mill, a bead mill, or a line mill, or a mixing device such as a kneader is used. The mixing time (retention time) during mixing is not particularly limited, but is preferably 10 to 120 minutes. The obtained printing ink may be used after being filtered, if necessary. Each of the above components (polymer compound (X), acrylic resin (N), active energy ray polymerizable monomer, active energy ray polymerizable oligomer, solvent and other components) may be used alone. Two or more kinds may be used.

  As said solvent (solvent), the organic solvent etc. which are normally used for printing ink can be used. Examples of the solvent include esters such as acetates (ethyl acetate, propyl acetate, butyl acetate, etc.); alcohols such as methanol, ethanol, isopropyl alcohol, propanol, and butanol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; toluene, xylene Aromatic hydrocarbons such as hexane, octane, etc .; Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Glycols such as ethylene glycol and propylene glycol; Ethylene glycol monopropyl ether, Propylene glycol monomethyl ether, Propylene Glycol ethers such as glycol monobutyl ether; Glycol ether esters such as propylene glycol monomethyl ether acetate It is. The solvent can be removed by drying after applying the printing ink to the shrink film. The solvent (solvent) also includes the meaning of “dispersion medium”.

  Although the viscosity (23 +/- 2 degreeC) of printing ink is not specifically limited, For example, when applying by gravure printing, 10-1000 mPa * s is preferable, More preferably, it is 20-500 mPa * s. The viscosity of the printing ink is determined by the types and blending amounts (contents), increase of polymer compound (X), acrylic resin (N), active energy ray polymerizable monomer, active energy ray polymerizable oligomer and other components. It can be controlled by a viscosity agent, a viscosity reducer, or the like. 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 active energy ray-curable resin composition layer of the present invention is formed. In addition, since the laminated body in this stage is before active energy ray irradiation, it has an acrylic resin as a main chain and a urethane oligomer having an active energy ray polymerizable group as a side chain on at least one surface of a shrink film. It is the laminated body for shrink labels which has the active energy ray-curable resin composition layer containing the high molecular compound (X) to do. The laminate for shrink label can obtain the shrink label of the present invention which is stable and excellent in resistance to chemical components and hardly shrinks and whitens by forming the printed layer of the present invention by irradiation with active energy rays. it can.

  Although irradiation of the active energy ray at the time of forming the printing layer of this invention is not specifically limited, It forms after forming the active energy ray curable resin composition layer of this invention, and forms the printing layer of this invention. In addition, the stage which performs the said active energy ray irradiation should just be after forming the active energy ray curable resin composition layer of this invention, for example, before manufacturing a cylindrical shrink label, the laminated body for shrink labels is manufactured. After forming into a cylindrical shape and before mounting the shrink label laminated body formed into the cylindrical shape on a container or the like, the shrink label laminated body formed into the cylindrical shape by performing shrink processing was attached to the container or the like It may be later. However, when the active energy ray-curable printing ink is used, the formed active energy ray-curable resin composition layer of the present invention has high fluidity, and therefore, the active energy ray for forming the printed layer of the present invention is not used. Irradiation is preferably performed after forming the active energy ray-curable resin composition layer of the present invention and before producing the cylindrical shrink label to form the printed layer of the present invention. In addition, when a plurality of active energy ray-curable resin composition layers are formed by applying a plurality of printing inks, irradiation with active energy rays is performed after all active energy ray-curable resin composition layers are formed. Alternatively, it may be performed each time one active energy ray-curable resin composition layer is formed. When a plurality of active energy ray-curable resin composition layers of the present invention are formed using a solvent-drying type printing ink, the active energy ray of the active energy ray is formed after all the active energy ray-curable resin composition layers are formed. Irradiation is convenient and preferable. On the other hand, when a plurality of active energy ray-curable resin composition layers of the present invention are formed using an active energy ray-curable printing ink, an active energy ray-curable printing ink is applied (one active energy). It is preferable to irradiate with active energy rays every time the linear curable resin composition layer is formed.

The active energy ray to be irradiated is not particularly limited, and examples thereof include visible light, ultraviolet rays, and electron beams. Of these, ultraviolet rays and electron beams are preferable. Specifically, the ultraviolet irradiation can be performed using, for example, an ultraviolet (UV) lamp, an ultraviolet LED, an ultraviolet laser, or the like. The active energy ray to be irradiated varies depending on the composition of the printing ink and is not particularly limited. However, from the viewpoint of curability, ultraviolet rays having a wavelength of 200 to 460 nm (near ultraviolet rays) are preferable, and the integrated light amount is 50 to 2000 mJ / cm. ² is preferred.

  Controlling the content of components such as polymer compound (X), acrylic resin (N), active energy ray polymerizable monomer, active energy ray polymerizable oligomer in the active energy ray curable resin composition layer of the present invention In order to do so, the printing ink may be prepared so that the content of each component in the non-volatile components of the printing ink becomes the desired content in the active energy ray-curable resin composition layer of the present invention. The same applies to the content of each component in the printed layer of the present invention. In general, the content (% by weight) of each component (nonvolatile component) in all the nonvolatile components of the printing ink is the content (% by weight) of each component in the active energy ray polymerizable composition layer of the present invention. ) And the content (% by weight) of each component in the printed layer of the present invention.

  As described above, the printed layer of the present invention is formed on the shrink film, and the shrink label of the present invention can be produced. Moreover, you may provide layers other than the printing layer of this invention as needed.

(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. After providing a printing layer of the present invention on a long shrink film, slitting to a predetermined width, a long label body in which a plurality of shrink labels of the present invention are continuous in the longitudinal direction (longitudinal direction) obtain. This long label is formed in a cylindrical shape by overlapping so that the heat shrinkable direction (that is, the shrinkage direction of the shrink film) is the circumferential direction, and the other end is outside the one end. Then, the overlapped portion is sealed in a band shape and both end portions 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 suitably selected after providing the printing layer of the present invention and before and after the process of processing into a cylindrical shape.

[Container with label]
Although the shrink label of this invention is not specifically limited, It mounts | wears with a container and is used as a labeled container. In addition, the shrink label of this invention may be used for adherends other than a container. For example, the shrink label of the present invention (particularly, the cylindrical shrink label) is placed around the container so that the shrink label of the present invention is in a cylindrical shape, and attached to the container by heat shrinking. A container (a labeled container having the shrink label of the present invention) is obtained. Examples of the container include beverage containers such as PET bottles, milk bottles and bottle cans; food containers such as seasonings; toiletries containers such as pharmaceutical containers, detergents and sprays. 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 plastic such as PET, glass, and metal.

  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 shrink film will be 85-100 degreeC (especially 90-97 degreeC). When the shrink label of the present invention can be heat-treated at a high temperature, it can be used for containers that require high shrinkage. Moreover, the processing time of heat processing has preferable 4 to 20 second from a viewpoint of productivity and economical efficiency.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, in Table 1, the structure of the shrink label produced by the Example and the comparative example, the evaluation result, etc. were shown. Table 2 shows the blending amounts of raw materials in the printing inks (background printing layer printing ink, protective printing layer printing ink) used in Examples and Comparative Examples. Table 3 shows details of raw materials in the printing inks used in Examples and Comparative Examples (trade name, manufacturer name, nonvolatile content, weight average molecular weight, etc.) and the like.

Example 1
(Printing ink for background printing layer)
13 parts by weight of acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name “Dyanal BR-113”) as a binder resin and cellulose resin (Eastman Chemical (Eastman Chemical), trade name “CAP-482”) 20 ") 0.5 parts by weight, titanium oxide 37 parts by weight, wax 1.5 parts by weight to ethyl acetate 13.5 parts by weight, n-propyl acetate 13.5 parts by weight, isopropyl alcohol (IPA) 21 parts by weight. It mixed and disperse | distributed using the mixer and obtained the printing ink for background printing layers (it may be called "the printing ink for background printing layers (a1)").

(Printing ink for protective printing layer)
As a solution of the polymer compound (X), 55 parts by weight of trade name “Acryt 8BR-500” (manufactured by Taisei Fine Chemical Co., Ltd.), photopolymerization initiator (trade name “Irgacure 127” manufactured by BASF Japan Ltd.) 5 Parts by weight and 1.5 parts by weight of wax are mixed in 19 parts by weight of toluene and 19.5 parts by weight of ethyl acetate, and dispersed using a mixer. (It may be referred to as “printing ink for protective printing layer (b1)”).

(Shrink label)
Polyester (PET) film (heat-shrinkable film) (trade name “LX-18S”, manufactured by Mitsubishi Plastics, Inc., thickness: 40 μm) on one side of the printing ink for background printing layer (a1) with a viscosity of 15 mPa Diluted with a mixed solvent of ethyl acetate and IPA (mixing ratio [ethyl acetate: IPA] = [6: 4]) so as to be s, and a table gravure printing machine (manufactured by Nissho Gravure Co., Ltd., trade name “GRAVO”) Using PROOF MINI "), it was dried and solidified to form a background print layer (background print layer (A1)) on the entire surface other than the portion to be the seal portion. Next, the printing ink (b1) for the protective printing layer is diluted on the surface of the background printing layer (A1) with the above mixed solvent of ethyl acetate and IPA so that the viscosity becomes 18 mPa · s, and the table gravure printing machine (Product name "GRAVO PROOF MINI", manufactured by Nissho Gravure Co., Ltd.), dried and solidified to form an active energy ray-curable resin composition layer on the entire surface other than the seal portion, and shrink label A laminate was obtained.

  Then, from the surface side which apply | coated the active energy ray curable resin composition layer of the laminated body for shrink labels obtained above, a ultraviolet irradiation device (The product name "LIGHT HAMMER 10" by Fusion UV Systems Japan Co., Ltd.) , Lamp: H +, output: 80%), ultraviolet irradiation (UV irradiation) is performed under the condition of a conveyor speed of 30 m / min, and the active energy ray-curable resin composition layer is cured to provide a protective printing layer (protective printing) Layer (B1)) was formed.

  As described above, a shrink label having a laminated structure of PET film (thickness: 40 μm) / background printing layer (A1) (thickness: 1 μm) / protective printing layer (B1) (thickness: 2 μm) was obtained.

Example 2
A PET film (thickness: 40 μm) in the same manner as in Example 1 except that the protective printing layer printing ink (b2) having the composition shown in Table 2 was used instead of the protective printing layer printing ink (b1). A shrink label having a laminated structure of / background printing layer (A1) (thickness: 1 μm) / protective printing layer (B2) (thickness: 2 μm) was obtained.

Example 3
The active energy ray-curable resin composition was the same as in Example 1 except that the protective printing layer printing ink (b3) having the composition shown in Table 2 was used instead of the protective printing layer printing ink (b1). The layer was formed and the laminated body for shrink labels was obtained.

  Subsequently, from the surface side where the active energy ray-curable resin composition layer of the laminate for shrink labels obtained above was applied, an electron beam irradiation device (trade name “EBC-200” manufactured by NHV Corporation, Using a voltage of 150 kV and an electron beam density of 10 kGy, electron beam irradiation (EB irradiation) is performed at a conveyor speed of 30 m / min, and the active energy ray-curable resin composition layer is cured to provide a protective printing layer (protection) A printing layer (B3)) was formed.

  As described above, a shrink label having a laminated structure of PET film (thickness: 40 μm) / background printing layer (A1) (thickness: 1 μm) / protective printing layer (B3) (thickness: 2 μm) was obtained.

Example 4
A PET film (thickness: 40 μm) in the same manner as in Example 3 except that the protective printing layer printing ink (b4) having the composition shown in Table 2 was used instead of the protective printing layer printing ink (b3). A shrink label having a laminated structure of / background printing layer (A1) (thickness: 1 μm) / protective printing layer (B4) (thickness: 2 μm) was obtained.

Example 5
A PET film (thickness: 40 μm) in the same manner as in Example 1 except that the protective printing layer printing ink (b5) having the composition shown in Table 2 was used instead of the protective printing layer printing ink (b1). A shrink label having a laminated structure of / background printing layer (A1) (thickness: 1 μm) / protective printing layer (B5) (thickness: 2 μm) was obtained.

Example 6
A PET film (thickness: 40 μm) in the same manner as in Example 1, except that the protective printing layer printing ink (b6) having the composition shown in Table 2 was used instead of the protective printing layer printing ink (b1). A shrink label having a laminated structure of / background printing layer (A1) (thickness: 1 μm) / protective printing layer (B6) (thickness: 2 μm) was obtained.

Comparative Example 1
PET film (thickness: 40 μm) in the same manner as in Example 3 except that the active energy ray-curable resin composition layer was used as a protective printing layer (protective printing layer (B3 ′)) without performing electron beam irradiation. ) / Background printing layer (A1) (thickness: 1 μm) / protective printing layer (B3 ′) (thickness: 2 μm) was obtained as a shrink label.

Comparative Example 2
PET film (thickness: 40 μm) in the same manner as in Example 4 except that the active energy ray-curable resin composition layer was used as a protective printing layer (protective printing layer (B4 ′)) without electron beam irradiation. ) / Background printing layer (A1) (thickness: 1 μm) / protective printing layer (B4 ′) (thickness: 2 μm) was obtained as a shrink label.

Comparative Example 3
(Printing ink for protective printing layer)
67 parts by weight of urethane resin (trade name “Samprene IB-915”, manufactured by Sanyo Chemical Industries, Ltd.) as a binder resin and cellulose resin (trade name “CAP-482-20”, manufactured by Eastman Chemical Co.) 5 parts by weight, 1.5 parts by weight of wax, 5 parts by weight of a curing agent (trade name “CVL Hardener # 10” manufactured by DIC Corporation) are mixed with 17 parts by weight of ethyl acetate and 9 parts by weight of IPA, and a mixer is used. To obtain a protective printing layer printing ink (sometimes referred to as “protective printing layer printing ink (b7)”).

(Shrink label)
Polyester (PET) film (heat-shrinkable film) (trade name “LX-18S”, manufactured by Mitsubishi Plastics, Inc., thickness: 40 μm) on one side of the printing ink for background printing layer (a1) with a viscosity of 15 mPa -Diluted with the above mixed solvent of ethyl acetate and IPA so that it becomes s, and applied, dried and solidified using a desktop gravure printing machine (trade name “GRAVO PROOF MINI” manufactured by Nissho Gravure Co., Ltd.), and sealed A background printing layer (background printing layer (A1)) was formed on the entire surface other than the portion to be a part. Next, on the surface of the background printing layer (A1), the protective printing layer printing ink (b7) is diluted with a mixed solvent of ethyl acetate and IPA so as to have a viscosity of 18 mPa · s. (Product name “GRAVO PROOF MINI”, manufactured by Nissho Gravure Co., Ltd.) was applied, dried and solidified to form a protective printing layer (protective printing layer (B7)) on the entire surface other than the portion to be a seal portion.

  As described above, a shrink label having a laminated structure of PET film (thickness: 40 μm) / background printing layer (A1) (thickness: 1 μm) / protective printing layer (B7) (thickness: 2 μm) was obtained.

Comparative Example 4
A PET film (thickness: 40 μm) in the same manner as in Comparative Example 3 except that the protective printing layer printing ink (b8) having the composition shown in Table 2 was used instead of the protective printing layer printing ink (b7). A shrink label having a laminated structure of / background printing layer (A1) (thickness: 1 μm) / protective printing layer (B8) (thickness: 2 μm) was obtained.

Comparative Example 5
A shrink label having a laminated structure of PET film (thickness: 40 μm) / background printed layer (A1) (thickness: 1 μm) was obtained in the same manner as in Comparative Example 3 except that the protective printing layer (B7) was not provided. It was.

  The polymer compound (X), the monofunctional monomer, the acrylic resin, the urethane resin with respect to the total weight (100% by weight) of the non-volatile components in the background printing layer printing ink and the protective printing layer printing ink, Cellulosic resin, titanium oxide, photopolymerization initiator, wax, and the content ratio (nonvolatile content) of nonvolatile components of the curing agent are the polymer compound (X) in the background printing layer and the protective printing layer of the shrink label. It is equal to the proportion of the content of the structural unit derived from the above, the structural unit derived from the monofunctional monomer, acrylic resin, urethane resin, cellulose resin, titanium oxide, photopolymerization initiator, wax, and curing agent.

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

(1) 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. An adhesive tape having a width of 18 mm (manufactured by Nichiban Co., Ltd., trade name “Cerotape (registered trademark))” is pasted on the surface of the side provided with the printed layer of the shrink label obtained in Examples and Comparative Examples. The tape was peeled in the 90 degree direction.
In the area of 5 mm (main shrinkage direction) × 5 mm (perpendicular to the main shrinkage direction) on the surface of the protective print layer (background print layer in the case of Comparative Example 5) with the adhesive tape attached, the protective print layer ( In the case of Comparative Example 5, the peeled area (ratio) of the background printing layer) was visually observed and judged according to 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) Scratch resistance (scratch test)
From the shrink labels obtained in Examples and Comparative Examples, a measurement sample of 100 mm (main shrinkage direction) × 100 mm (perpendicular to the main shrinkage direction) was collected. A test in which a measurement sample is placed on a smooth table, and the surface on which the printed layer is provided is rubbed 10 times at the back of the nail of the hand (a section 20 mm perpendicular to the main contraction direction) ( The surface was observed after performing a test (forced test) that rubbed the nail 10 times (section 20 mm perpendicular to the main contraction direction) after the nail was raised. Evaluated by criteria. In this evaluation, the print layer refers to a protective print layer, and in the case of Comparative Example 5, it refers to a background print layer.
Good scratch resistance (○): No peeling on the printed layer after the forced test Level where the scratch resistance can be used (△): The printed layer after the normal test is not peeled off, but the printed layer after the forced test is peeled off Scratch resistance is poor (×): Print layer after normal test is peeled off

(3) Scratch resistance (scratch test)
From the shrink labels obtained in Examples and Comparative Examples, a measurement sample of 100 mm (main shrinkage direction) × 100 mm (perpendicular to the main shrinkage direction) was collected. Hold both ends of the sample for measurement with both hands, and even 10 times. The printed layer on the surface of the measurement sample was visually observed, and the resistance to rubble was evaluated according to the following criteria. In this evaluation, the print layer refers to a protective print layer, and in the case of Comparative Example 5, it refers to a background print layer.
Good resistance to cracking (○): No peeling Level of resistance to scratching (△): There is peeling along the ridges Poor resistance to resistance (x): There is also peeling around the ridges

(4) Resistance to chemical components (content resistance test)
100 μL of the trade name “Kao Attack Neo” (manufactured by Kao Corporation) was dropped onto the surface on the side provided with the printed layer of the shrink label obtained in the Examples and Comparative Examples, and allowed to stand at 40 ° C. for 24 hours. Then, the state of the shrink label after rinsing the surface on which the shrink label was dropped with tap water was observed, and the resistance to chemical components was judged according to the following criteria. In this evaluation, the print layer refers to a protective print layer, and in the case of Comparative Example 5, it refers to a background print layer.
Stable and good resistance to chemical components (○): No change before and after dropping Dropping level of stability to chemical components (△): Whitening or discoloration No resistance to stable chemical components (× : There is peeling of the printed layer

(5) Resistance to chemical components (rubbing test)
After the surface of the side provided with the printed layer of the shrink label obtained in Examples and Comparative Examples was rubbed with a cotton swab soaked in ethyl acetate, the state of the surface of the shrink label was visually observed, and the resistance to chemical components was as follows. Evaluation based on the criteria.
Good resistance to chemical components (○): The level of resistance to chemical components in which the background printed layer does not peel off even when rubbed 6 times (△): against chemical components where the background printed layer begins to rub 4-6 times Poor resistance (x): Rub 1 to 3 times and background print layer begins to peel off

(6) Haze value of protective printing layer (non-shrinkage)
The shrink labels obtained in Examples and Comparative Examples without the background printing layer were prepared, and a label piece having a size of 150 mm (main shrinkage direction) × 100 mm (perpendicular to the main shrinkage direction) was cut out. A sample for measurement was obtained.
Using the “Haze-Guard II” manufactured by Toyo Seiki Seisakusho Co., Ltd., the haze value of the above measurement sample was measured in accordance with JIS K 7136. The haze value of the protective printing layer was calculated by subtracting the haze value of the shrink film from the haze value of the measurement sample measured above. In addition, the said haze value made the number of tests (n number) 5 (n = 5), and made the average value the evaluation result.

(7) Haze value of protective printing layer (30% shrinkage)
The shrink labels obtained in Examples and Comparative Examples without a background printing layer were prepared, and a label piece having a size of 150 mm (main shrinkage direction) × 100 mm (perpendicular to the main shrinkage direction) was cut. I came out. The 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 intervals of 70 mm (fixed at a position of 25 mm from both ends of the label piece in the main contraction direction, and 100 mm therebetween) The length portion of each is 70 mm apart, and is in a sagging state before the heat shrink treatment). The label piece fixed on 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 30% compared to before the heat-shrinking treatment ( 30% heat shrinkage in the main shrinkage direction). In this way, a measurement sample was obtained which was thermally contracted by 30% in the main contraction direction.
Using the “Haze-Guard II” manufactured by Toyo Seiki Seisakusho Co., Ltd., the haze value of the above measurement sample was measured in accordance with JIS K 7136. The haze value of the protective printing layer was calculated by subtracting the haze value of the shrink film after 30% shrinkage from the haze value of the measurement sample measured above. In addition, the said haze value made the number of tests (n number) 5 (n = 5), and made the average value the evaluation result.

As can be seen from the evaluation results, the shrink label (Example) of the present invention was stable and excellent in resistance to chemical components, and even after 30% contraction, the increase in haze value was extremely small and it was difficult to shrink whitening.
On the other hand, when the protective printing layer is the active energy ray-curable resin composition layer of the present invention itself and is not cured by the active energy rays (Comparative Examples 1 and 2), the shrink label corresponds to a stable chemical component. It was not resistant. In addition, when the protective printing layer is not a printing layer obtained by curing the active energy ray-curable resin composition layer of the present invention with active energy rays (Comparative Examples 3 and 4), the chemicals with a stable shrink label are used. It did not have resistance to the components, and the haze value increased greatly before and after 30% shrinkage from before heat shrinkage (non-shrinkage), resulting in shrinkage whitening. When the active energy ray-curable resin composition layer of the present invention does not have a printed layer obtained by curing with an active energy ray (Comparative Example 5), the shrink label has resistance to a stable chemical component. I did not.

DESCRIPTION OF SYMBOLS 1 Cylindrical shrink label of this invention 11 Seal part 21 Shrink film 22 Design printing layer 23 Background printing layer 24 Solvent or adhesive agent 25,26 Protective printing layer

Claims (4)

A shrink label having a printed layer on at least one surface of the shrink film,
An active energy ray-curable resin composition layer containing the polymer compound (X) in which the printing layer has an acrylic resin as a main chain and a urethane oligomer having an active energy ray polymerizable group as a side chain is an active energy. A shrink label, which is a printed layer obtained by curing with a wire.   The shrink label according to claim 1, wherein the polymer compound (X) has a weight average molecular weight of 5,000 to 200,000 of the acrylic resin and a weight average molecular weight of the urethane oligomer of 200 to 10,000. .   The content ratio [acrylic resin: urethane oligomer] (weight ratio) of the acrylic resin and the urethane oligomer in the polymer compound (X) is 10: 1 to 2: 1. 2. The shrink label according to 2.   An active energy ray-curable resin composition comprising a polymer compound (X) having an acrylic resin as a main chain and a urethane oligomer having an active energy ray polymerizable group as a side chain on at least one surface of a shrink film. The laminated body for shrink labels which has a layer.

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