JP5736572B2 - Shrink label - Google Patents

Description

  The present invention relates to a shrink label. In more detail, it is related with the shrink label excellent in the adhesiveness of a base material, especially a polyester film base material and a printing layer.

  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. These containers are often equipped with plastic labels for display, decoration, and functionality. These plastic labels have decorativeness, workability (followability to containers), wide display area, etc. In view of merits, shrink labels provided with a printed layer are widely used. As such a shrink label, a film based on a film made of a polyester resin, a polyolefin resin, a polystyrene resin, or the like is used according to required characteristics and applications.

  Especially, the film (polyester-type film) which consists of a polyester-type resin is inferior in the adhesiveness of ink, and it was difficult to obtain the shrink label excellent in the adhesiveness of a base material and a printing layer. For this reason, it has excellent adhesion to a printed layer having excellent adhesion to a polyester film, and further to a substrate made of various resins such as polyester resin, polyolefin resin and polystyrene resin. Therefore, a printing layer having excellent versatility has been demanded.

  As a printing ink that satisfies this requirement, for example, a printing ink containing a specific ratio of an acrylic resin and a cellulose resin and a specific solvent is known (see Patent Document 1). However, even with the printing ink, there is a problem that the adhesion is not sufficient particularly for a thin PET film having poor ink adhesion. Furthermore, a method for producing a printed matter for shrinkable labels is known in which a print layer containing a specific cellulose resin and an acrylic resin is provided on an anchor coat layer comprising an anchor coat agent containing nitrocellulose and a polyurethane resin. (See Patent Document 2). However, this production method has a problem in terms of safety and management because it uses a relatively large amount of flammable nitrocellulose.

  As described above, the present situation is that a shrink label having a printing layer excellent in adhesion to a polyester film having a wide range of thickness (various thicknesses) using a relatively safe acrylic resin has not been obtained. .

JP 2008-163215 A Japanese Patent No. 3895253

  That is, the object of the present invention is to provide a shrink label having a printed layer that exhibits excellent adhesion to many substrates that are generally used for shrink labels, and that is particularly excellent in adhesion to a wide range of polyester film. There is.

  As a result of intensive studies to achieve the above object, the present inventors have identified urethane acrylic resin and acrylic resin, or urethane acrylic resin, acrylic resin and cellulose resin on at least one side of the substrate. The present inventors have found that a shrink label having excellent adhesion between a substrate, particularly a polyester-based film substrate having a wide range of thickness, and the printed layer can be obtained by providing a printing layer containing at a ratio of 1 to 5%.

That is, the present invention comprises a printed layer containing a urethane acrylic resin and an acrylic resin, or containing a urethane acrylic resin, an acrylic resin and a cellulose resin on at least one side of the substrate, The urethane acrylic resin content is 4 to 40% by weight, the acrylic resin content is 40 to 96% by weight, and the cellulose resin based on the total amount of urethane acrylic resin, acrylic resin and cellulose resin in the printing layer. Content is 0 to 20% by weight , and the printing layer contains a solvent, a urethane acrylic resin, and an acrylic resin, or a solvent, a urethane acrylic resin, an acrylic resin, and a cellulose resin. the printing ink containing on the surface of the substrate, wherein the coating is a printing layer provided by drying Schullin To provide a label.
The printing layer may include titanium oxide, and the content of the titanium oxide may be 50 to 90% by weight with respect to the total amount of the printing layer.

  The shrink label of the present invention uses an acrylic resin as a resin component for forming the printed layer. For this reason, a hard printed layer can be formed relatively safely. Moreover, a specific amount of urethane acrylic resin is used as a resin component for forming the printing layer. For this reason, the adhesiveness of a base material and a printing layer improves especially also to a polyester-type film base material. Thereby, the peeling resistance of the shrink label, the scratch resistance, the rub resistance, and the ink cracking deterrence (ink cracking resistance) during shrink processing are improved. Furthermore, when a specific amount of cellulose resin is included, heat resistance, scratch resistance, and ink cracking resistance are improved.

  The shrink label of the present invention is a printing layer containing a urethane acrylic resin and an acrylic resin, or a printing layer containing a urethane acrylic resin, an acrylic resin and a cellulose resin on at least one side of the substrate. The urethane acrylic resin content is 4 to 40 wt% and the acrylic resin content is 40 to 96 based on the total amount (total weight) of the urethane acrylic resin, acrylic resin and cellulose resin in the printing layer. It has a printed layer with a content of 0 to 20% by weight of cellulose resin. The above print layer may be referred to as “print layer of the present invention”. The urethane acrylic resin, acrylic resin and cellulose resin in the printing layer of the present invention may be collectively referred to as “specific resin”. When the cellulose resin is not included in the printing layer of the present invention, the urethane acrylic resin and the acrylic resin are “specific resins”, and when the cellulose resin is included in the printing layer of the present invention. Urethane acrylic resin, acrylic resin and cellulose resin are “specific resins”.

[Print layer of the present invention]
The printed layer of the present invention is an essential printed layer in the shrink label of the present invention. The printing layer of the present invention contains a urethane acrylic resin and an acrylic resin as essential components. Moreover, it is preferable that the printing layer of this invention contains a cellulose resin. Furthermore, the printing layer of the present invention may contain pigments and other additives.

The acrylic resin is a main resin component that forms a printed layer. The acrylic resin is not particularly limited, and publicly known or commonly used acrylic resins for printing inks can be used, and examples thereof include acrylic resins configured with an acrylic monomer as an essential monomer component. It is done. Examples of the monomer component constituting the acrylic resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate. , Isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid alkyl ester having a linear or branched alkyl group such as isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate [preferably (meth) acrylic acid C _{1- 12} alkyl ester, etc.]; (meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid, mosquitoes, such as maleic acid Boxyl group-containing polymerizable unsaturated compound or its anhydride; 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6 -Hydroxyl-containing (meth) acrylic acid ester such as hydroxyhexyl (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate [preferably (meth) acrylic acid hydroxy C _1-8 alkyl ester, etc. ] Etc. are mentioned. “(Meth) acryl” means “acryl” and / or “methacryl”.

  In addition to the above, as required, (meth) acrylic acid cycloalkyl esters such as cyclohexyl (meth) acrylate; N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (Meth) acrylic acid amide derivatives such as (meth) acrylamide, N, N-diethyl (meth) acrylamide; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, dimethylamino (Meth) acrylic acid dialkylaminoalkyl esters such as propyl (meth) acrylate and dipropylaminopropyl (meth) acrylate; styrene compounds such as styrene, vinyltoluene and α-methylstyrene; vinyl acetate, Vinyl esters such as vinyl pionate; Vinyl halides such as vinyl chloride; Vinyl ethers such as methyl vinyl ether; Cyano group-containing vinyl compounds such as (meth) acrylonitrile; Polymerizability of olefins such as ethylene and propylene, and dienes Unsaturated compounds can also be used as monomer components.

  The acrylic resin in the printing layer of the present invention does not include an acrylic resin having a urethane bond.

  Among the above, a monomer component selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, ethyl acrylate, butyl acrylate and methacrylic acid. An acrylic resin having a main component is particularly preferable.

  The weight average molecular weight of the acrylic resin is not particularly limited, but is preferably 10,000 to 150,000, more preferably from the viewpoint of improvement in shrinkage followability (followability of the printed layer with respect to shrinkage deformation during shrink processing) and prevention of blocking. It is 20000-80000, More preferably, it is 30000-60000.

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

  The urethane acrylic resin is a resin component that plays a role of improving the adhesion of the resin forming the printing layer to the substrate. The urethane acrylic resin is not particularly limited, and is a copolymer configured with a urethane component and an acrylic component as essential components.

Although the acrylic component in the said urethane acrylic resin is not specifically limited, An acrylic monomer is comprised as an essential monomer component. Examples of the monomer component constituting the acrylic component include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, Isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl ester having a linear or branched alkyl group such as isononyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate [preferably (meth) acrylic acid C _1-12 Alkyl esters, etc.]; (meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, etc. Xyl group-containing polymerizable unsaturated compound or anhydride thereof; 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6 -Hydroxyl-containing (meth) acrylic acid ester such as hydroxyhexyl (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate [preferably (meth) acrylic acid hydroxy C _1-8 alkyl ester, etc. ] Etc. are mentioned.

  In addition to the above, as required, (meth) acrylic acid cycloalkyl esters such as cyclohexyl (meth) acrylate; N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (Meth) acrylic acid amide derivatives such as (meth) acrylamide, N, N-diethyl (meth) acrylamide; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, dimethylamino (Meth) acrylic acid dialkylaminoalkyl esters such as propyl (meth) acrylate and dipropylaminopropyl (meth) acrylate; styrene compounds such as styrene, vinyltoluene and α-methylstyrene; vinyl acetate, Vinyl esters such as vinyl pionate; Vinyl halides such as vinyl chloride; Vinyl ethers such as methyl vinyl ether; Cyano group-containing vinyl compounds such as (meth) acrylonitrile; Polymerizability of olefins such as ethylene and propylene, and dienes Unsaturated compounds can also be used as monomer components.

Among the above, as the monomer component constituting the acrylic component, (meth) acrylic acid C _1-12 alkyl ester, carboxyl group-containing polymerizable unsaturated compound or its anhydride is preferable, methyl methacrylate, methacrylic acid n-butyl and acrylic acid are more preferable. More preferred are methyl methacrylate and n-butyl methacrylate.

  Although the urethane component in the said urethane acrylic resin is not specifically limited, For example, a polyisocyanate compound and a polyol compound are comprised as a raw material component.

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

  Examples of the polyol compound include ethylene glycol, diethylene glycol, 1,3-propanediol, propylene glycol (1,2-propanediol), butanediol (1,3-butanediol, 1,4-butanediol, etc.), 1, Low molecular weight glycols such as 6-hexanediol and cyclohexanedimethanol; polyether diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol-polycaprolactone copolymer; propylene glycol, butanediol, hexanediol Polyesters obtained from dibasic acids such as adipic acid, sebacic acid, azelaic acid, isophthalic acid, terephthalic acid and fumaric acid; Kutonjioru, polyvalerolactone diol, a known diols such as lactone diol, lactone block copolymer diols can be used. Moreover, said diols and trifunctional or more than polyol compounds (polyether polyol, polyester polyol, etc.) can also be mixed and used as needed. Of these, polyester diols and polyester polyols are preferable, and polyester diols having terephthalic acid, isophthalic acid, and adipic acid as acid components and methylene glycol, ethylene glycol, and neopentyl glycol as glycol components are more preferable. More preferred is a polyester diol having terephthalic acid and / or isophthalic acid as the acid component and ethylene glycol and / or neopentyl glycol as the glycol component.

  As the urethane acrylic resin, an acrylic component composed of methyl methacrylate and / or n-butyl methacrylate as an essential monomer component, terephthalic acid and / or isophthalic acid as an essential acid component, ethylene glycol In particular, a polymer composed of polyester diol having neopentyl glycol as an essential glycol component and urethane component having isophorone diisocyanate as an essential raw material component as essential components is particularly preferable. That is, the urethane acrylic resin comprises (i) a structural unit derived from methyl methacrylate (structural unit) and / or a structural unit derived from n-butyl methacrylate, (ii) a structural unit derived from terephthalic acid, and / or Or urethane acrylic resin containing at least a structural unit derived from isophthalic acid, (iii) a structural unit derived from ethylene glycol and / or a structural unit derived from neopentyl glycol, and (iv) a structural unit derived from isophorone diisocyanate. Is particularly preferred.

  Analysis and measurement of the content of monomer component (constituent unit) and the monomer component (constituent unit) constituting the urethane acrylic resin and the acrylic resin (ratio in the total monomer components) Although not particularly limited, it can be performed by, for example, nuclear magnetic resonance (NMR), gas chromatograph mass spectrometer (GCMS), or the like.

  The ratio of urethane component to acrylic component [urethane component: acrylic component] (weight ratio) in the urethane acrylic resin is preferably 1: 9 to 9: 1, more preferably 3: 7 to 7: 3. When [urethane component: acrylic component] is less than 1: 9, the adhesion between the printed layer and the substrate may be lowered. On the other hand, when the [urethane component: acrylic component] is less than 9: 1, the acrylic component is likely to be blocked, and the printability at the time of forming the printing layer may be reduced (plate fog is likely to occur).

  The glass transition temperature (Tg) of the urethane acrylic resin is preferably −30 to 100 ° C., more preferably 0 to 70 ° C. from the viewpoint of scratch resistance and ink crack resistance. The Tg can be measured, for example, by DSC (differential scanning calorimetry). 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.

  The weight average molecular weight of the urethane acrylic resin is not particularly limited. From the viewpoint of improving shrinkage followability, improving ink adhesion (improving adhesion between the printed layer and the substrate), and preventing blocking, 20000 to 100,000. Is more preferable, more preferably 25,000 to 80,000, still more preferably 30,000 to 60,000.

  The printed layer of the present invention preferably contains a cellulose resin. The cellulose-based resin plays a role of adjusting the viscosity of a resin composition (sometimes referred to as “printing ink”) for forming a printing layer and a role of imparting hardness to the printing layer. In the case where the viscosity of the printing ink is low, it is preferable to increase the viscosity by adding a cellulose-based resin because the coating property (coating property) can be improved. Although the cellulose resin is not particularly limited, esterified cellulose resins such as nitrocellulose (nitrified cotton), cellulose acetate butyrate (CAB), cellulose acetate, and cellulose acetate propionate (CAP) are preferably exemplified. The Among these, cellulose acetate butyrate (CAB) and nitrocellulose are particularly preferable.

  Although the weight average molecular weight of the said cellulose resin is not specifically limited, 10,000-150,000 are preferable, More preferably, it is 20,000-100,000. If the weight average molecular weight is less than 10,000, the viscosity of the printing ink may not increase. On the other hand, if it exceeds 150,000, the solubility of the cellulose resin may deteriorate. Further, a stringing phenomenon may occur during gravure printing, which is not preferable.

  A commercial item can also be used for the said cellulose resin. For example, “CAB-381-20, CAB-381-0.5, CAB-551-0.1” manufactured by Eastman Chemical Co., “HIG Series”, “LIG Series” manufactured by Bergerac NC are available on the market. Is possible.

  The content of the specific resin (urethane acrylic resin, acrylic resin, cellulose resin) in the printing layer of the present invention (that is, the total content of urethane acrylic resin, acrylic resin, and cellulose resin) is as follows. , Preferably 10 wt% or more (10 to 100 wt%), more preferably 15 wt% or more (15 to 100 wt%) with respect to the total amount (total weight) (100 wt%) of the printing layer, More preferably, it is 20 to 99% by weight. When the content of the specific resin in the printing layer is less than 10% by weight, the adhesion may be lowered, and particularly, the scratch resistance and the rub resistance may be lowered.

In the printing layer of the present invention, the content of the urethane acrylic resin relative to the total amount of the specific resin [that is, the total amount of urethane acrylic resin, acrylic resin and cellulose resin (total amount)] (100 wt%) is: It is 4 to 40% by weight, preferably 6 to 30% by weight, and more preferably 8 to 20% by weight. Moreover, content of acrylic resin with respect to the total amount (100 weight%) of specific resin is 40 to 96 weight%, Preferably it is 55 to 94 weight%, More preferably, it is 70 to 91 weight%.
When the content of urethane acrylic resin is less than 4% by weight or when the content of acrylic resin exceeds 96% by weight, the adhesion between the printed layer and the substrate (particularly the polyester film substrate) is poor. The peel resistance is inferior before and after the shrink processing, and the print layer is likely to be peeled off during the manufacture, processing and distribution of the shrink label. In addition, the scratch resistance of the printing layer is reduced, and the surface of the shrink label is easily damaged. Furthermore, the printed layer becomes brittle, the resistance to padding is lowered, and the printed layer is easily cracked or peeled off during shrink processing or in the distribution process.
On the other hand, when the content of urethane acrylic resin exceeds 40% by weight, the printed layer becomes too soft, and the printed layer of the seal part is pulled during the shrinking process and easily breaks into vertical stripes. Decreases. Furthermore, printing ink is expensive and disadvantageous in terms of cost.

  In the printing layer of the present invention, the content of the cellulosic resin with respect to the total amount (100% by weight) of the specific resin is 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 3 to 10% by weight. %. When the content of the cellulose-based resin exceeds 20% by weight, the adhesion between the printed layer and the substrate is lowered, and particularly the peel resistance is deteriorated. Peeling tends to occur. In addition, the printing ink may have a too high viscosity and the coating property may deteriorate.

  The printing layer of the present invention may contain a pigment for the purpose of coloring or the like. The pigment may be a known or commonly used organic or inorganic coloring pigment used in printing ink depending on the application, and is not particularly limited. For example, white pigment such as titanium oxide (titanium dioxide), copper Indigo (blue) pigments such as phthalocyanine blue, red pigments such as condensed azo pigments, yellow pigments such as azo lake pigments, carbon black, aluminum flakes, mica (mica), and the like can be selected and used according to the application. In addition, extender pigments such as alumina, calcium carbonate, barium sulfate, silica, and acrylic beads can also be used as pigments for the purpose of adjusting gloss. Only 1 type may be used for the said pigment and it may use 2 or more types together.

  The average particle diameter of the pigment (in the case where an aggregate is formed, the particle diameter of the aggregate, so-called secondary particle diameter) is not particularly limited and varies depending on the pigment. -1.5 micrometers is preferable, More preferably, it is 0.1-0.8 micrometer. In particular, in the case of a white pigment, 0.01 to 1 μm is preferable, more preferably 0.1 to 0.5 μm, and still more preferably 0.2 to 0.5 μm. If the average particle size is less than 0.01 μm, the dispersion state of the pigment may be poor or the decorating property may be insufficient. If the average particle size exceeds 1.5 μm, so-called “plate fog” (image area of the plate) Printing failure due to defective ink scraping of other portions.

  The content of the pigment can be arbitrarily designed according to the type of pigment, the concentration of the target color, and the like, but is preferably 1 to 90% by weight, more preferably based on the total amount (100% by weight) of the printed layer. 5 to 85% by weight, more preferably 10 to 80% by weight. When two or more kinds of pigments are contained in the printing layer, the total content of all pigments preferably satisfies the above range.

  When using the printing layer of this invention as a white printing layer, it is preferable to use a titanium oxide as a pigment (white pigment). As the titanium oxide, any of rutile type (tetragonal high temperature type), anatase type (tetragonal low temperature type), and brookite type (orthorhombic crystal) may be used. For example, titanium oxide manufactured by TEIKA CORPORATION. "JR series" etc. are available. In addition, the content of titanium oxide in the white print layer is preferably 50 to 90% by weight, more preferably 55 to 85% by weight, based on the total amount of the print layer, from the viewpoint of concealability and coarse protrusion formation suppression. More preferably, it is 60 to 80% by weight.

  In addition to the specific resin and pigment described above, the printing layer of the present invention can be used as necessary with resins other than the specific resin (urethane acrylic resin, acrylic resin, cellulose resin) ("other resin"). Additives such as plasticizers, lubricants, anti-settling agents, dispersants, stabilizers, fillers, antioxidants, UV absorbers, antistatic agents, anti-coloring agents, fragrances, deodorants, etc. May be contained within a range not impairing the effects of the present invention. Examples of the lubricant include various waxes such as polyolefin wax such as polyethylene wax, fatty acid amide, fatty acid ester, paraffin wax, polytetrafluoroethylene (PTFE) wax, and carnauba wax.

[Base material]
The base material in the shrink label of the present invention serves as a support for the printed layer, and has a major influence on the strength, rigidity and shrinkage characteristics of the label. If the said base material is a shrink film (heat-shrinkable film), it will not specifically limit, The shrink film used as a 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 be used alone or in combination of two or more. Furthermore, the same kind or different kinds of resins may be laminated to be used as a laminated film. Of these, polyester resins, polyolefin resins, and polystyrene resins are preferable. That is, the shrink film includes a polyester film made of a polyester resin, a polystyrene film made of a polystyrene resin, a polyolefin film made of a polyolefin resin, a polyester resin as an outer layer, and a polyolefin resin or a polystyrene resin as an inner layer. The heterogeneous laminated film is preferred. Among the above, a polyester film is particularly preferable from the viewpoint of transparency. Moreover, the printing layer of this invention exhibits the outstanding adhesiveness also with respect to the base material of the polyester-type film which adhesiveness tends to fall with a general printing ink and a printing layer. 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.

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

  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, and propylene-α-olefin. Examples include polypropylene resins such as copolymers, ethylene-vinyl acetate copolymers, and 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).

  The substrate in the present invention may have a single layer configuration or may have a laminated configuration. 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 used as the substrate is preferably a uniaxially, biaxially or multiaxially oriented film from the viewpoint of exhibiting shrinkage characteristics. When the shrink film is a laminated film, it is preferable that at least one film layer in the laminated film is oriented. When all the film layers are non-oriented, sufficient shrink characteristics may not be exhibited. As the shrink film, a uniaxial or biaxially oriented film is often used, and among them, a film that is strongly oriented in the uniaxial direction of the film (substantially uniaxially stretched film) is generally used. It is done. A film uniaxially stretched in the width direction is particularly preferable.

  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. Biaxial stretching in the longitudinal direction (the film production line direction; also referred to as the longitudinal direction or MD direction) and the width direction (the direction perpendicular to the longitudinal direction; also referred to as the transverse direction or TD direction) is used as a method for orienting the shrink film. Further, uniaxial stretching or the like in the longitudinal direction or the width direction can be used. As the stretching method, any method such as a roll method, a tenter method, and a tube method may be used. For example, the stretching treatment of the film substantially uniaxially stretched in the width direction is, for example, 1.01 to 1.5 times, preferably 1.05 in the longitudinal direction at a temperature of about 70 to 100 ° C., if necessary. After stretching to about 1.3 times, it can be carried out by stretching 3 to 6 times, preferably about 4 to 5.5 times in the width direction.

  The shrinkage rate of the shrink film in the main orientation direction at 90 ° C. for 10 seconds (sometimes referred to as “thermal shrinkage rate (90 ° C., 10 seconds)”) is not particularly limited, but is 15 to 90%. Preferably, it is 20 to 85%. The thermal contraction rate (90 ° C., 10 seconds) in the direction orthogonal to the main alignment direction is not particularly limited, but is preferably −3 to 15%. The above-mentioned “main orientation direction” is a direction mainly subjected to a stretching process (a direction having the largest thermal shrinkage), and is generally a longitudinal direction or a width direction, for example, substantially in the width direction. In the case of a uniaxially stretched film, it is the width direction.

  When the shrink film is a transparent film, the haze value (%) of the shrink film (based on JIS K 7105) is preferably less than 10%, more preferably less than 5.0%, and still more preferably less than 2.0%. . When the haze value is 10% or more, when printing is shown through the shrink film, the printing may become cloudy and the decorativeness may be deteriorated.

  Although the thickness of the said base material is not specifically limited, 10-100 micrometers is preferable, More preferably, it is 12-80 micrometers, More preferably, it is 15-60 micrometers. When the substrate thickness is thin (for example, about 10 to 45 μm), details are unknown, but generally, the crystallinity of the substrate is increased during film formation, and thus the adhesion between the printed layer and the substrate is low. Although it tends to decrease, the printed layer of the present invention is preferable because it can exhibit excellent adhesion even to such a thin substrate, that is, a so-called thin substrate (particularly a thin polyester film).

  A commercial item can also be used for the shrink film used as the substrate. For example, “Space Clean S7042” and “SV-808” manufactured by Toyobo Co., Ltd. “LX-10S” and “LX-61S” manufactured by Mitsubishi Plastics Co., Ltd. (hereinafter polyester film); CI Kasei Co., Ltd. “Bonset” manufactured by Gunze Co., Ltd. “GMLS” manufactured by Gunze (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. (a laminated film having a polyester resin as a surface layer and a polystyrene resin as a central layer).

[Shrink label]
As described above, the shrink label of the present invention has the printed layer of the present invention on at least one side of the substrate. The printed layer of the present invention is not necessarily provided on the entire surface of the label, and can be provided only on a part of the substrate. Even if the printed layer of the present invention is directly provided on the base material without any other layer such as an anchor coat layer, sufficient adhesion can be exhibited. For this reason, it is advantageous in terms of productivity and cost. In addition, the printing layer of this invention may be provided on the base material through the anchor coat layer as needed. The print layer of the present invention is, for example, a design print layer (color print layer or the like) such as a figure or a design, a protective print layer (transparent medium protective print layer, white protective print layer or the like) that imparts abrasion resistance and / or slipperiness. ).

  Furthermore, in addition to the base material and the printing layer of the present invention, the shrink label of the present invention includes an adhesive layer, an ultraviolet protection layer, an anchor coating layer, a primer coating layer, and a printing layer other than the printing layer of the present invention (“ A layer such as a nonwoven fabric or paper may be provided as necessary.

In the shrink label of the present invention, the printed layer of the present invention may be provided so as to be inside the label, or may be provided so as to be outside the label.
The laminated structure of the shrink label of the present invention is not particularly limited. For example, from the front side (the front side of the label), the substrate / the printed layer of the present invention, and the two-layer laminated structure of the printed layer / substrate of the present invention; Examples of the multi-layer structure include a printing layer of the invention / a substrate / a printing layer of the invention.

  In the present specification, the “front side” of the shrink label means the side viewing the design of the label (the side of the surface on which the design looks correct), and the “back side” of the shrink label means the above “front side”. Means the other side. The “outside” of the shrink label means the side that does not contact the container (the side opposite to the container) when the shrink label is attached to the container, and the “inside” of the shrink label contacts the container. Means side (container side).

  The shrinkage rate of the shrink label of the present invention in the main orientation direction at 90 ° C. for 10 seconds (thermal shrinkage rate (90 ° C., 10 seconds)) is not particularly limited, but is 15% or more (for example, 15 to 90%). ) Is preferable, and more preferably 20 to 85%. When the heat shrinkage (90 ° C., 10 seconds) is less than 15%, the followability with respect to the shape of a container or the like to which the label is attached is insufficient during shrink processing, and a beautiful finish may not be obtained. The thermal contraction rate (90 ° C., 10 seconds) in the direction orthogonal to the main alignment direction is not particularly limited, but is preferably −3 to 15%. The “main orientation direction” is a direction mainly subjected to a stretching process (a direction having the largest thermal shrinkage rate), and is generally a circumferential direction when the shrink label is a cylindrical shrink label.

In the shrink label of the present invention, an acrylic resin is used as a main resin component for forming the printed layer of the present invention. For this reason, it is relatively safe. Furthermore, since the printing layer of the present invention contains a specific amount of urethane acrylic resin, the printed layer has high adhesion to the substrate and further has appropriate flexibility. Therefore, the shrink label of the present invention is difficult to peel off the printed layer, and is excellent in the resistance to scratching and scratch of the printed layer. Therefore, it can be used for a polyester film, particularly a thin (thin) polyester film, which is safe and whose adhesion to a general printing layer tends to be lowered. In addition, the printed layer of the present invention can be provided on various types of substrates such as polyester, polystyrene, and polyolefin, and various thicknesses. In other words, the shrink label of the present invention is based on The type and thickness of the material can be widely changed, and it has excellent versatility.
In addition, the toughness of the printing layer increases due to the effect of the printing layer becoming flexible, so there is no problem of cracking the printing layer and blowing powder on the guide in the label manufacturing and processing processes, and productivity is improved. To do.

  Although the shrink label of this invention is not specifically limited, such as a cylindrical label and a winding label, it is a cylindrical shrink label (cylindrical shrink label) from a viewpoint which is excellent in design property (decorative property) and followability with respect to a container shape. In particular, a cylindrical shrink label having the printed layer of the present invention inside is preferable.

  In general, the shrink label of the present invention is mounted on a container by being placed so that the front side is opposite to the container and thermally contracted, and used as a labeled container. Such containers include, for example, soft drink bottles such as PET bottles, milk containers for home delivery, food containers such as seasonings, alcohol beverage bottles, pharmaceutical containers, containers for chemical products such as detergents and sprays, cups, etc. This includes noodle containers. Also, the material of the container includes plastic such as PET, glass, metal and the like. In addition, the shrink label of this invention may be used for adherends other than a container.

[Shrink label manufacturing method and processing method]
Examples of the shrink label manufacturing method and processing method (cylindrical shrink label processing method) of the present invention are shown below.
The resin composition (printing ink) for forming the printing layer of the present invention is produced by mixing the specific resin, a solvent, and, if necessary, a pigment, other resins and other additives. The Mixing can be performed by a known and common mixing method, and is not particularly limited. , Sand mills, ball mills, bead mills, line mills, kneaders and the like are used. The mixing time (retention time) during mixing is not particularly limited, but is preferably 10 to 120 minutes.

  In order to control the content of components such as urethane acrylic resin, acrylic resin, and cellulose resin in the printing layer of the present invention, the content of each component in the non-volatile content of the printing ink is printed. What is necessary is just to prepare printing ink so that it may become desired content in a layer. In general, the content (% by weight) of each component (nonvolatile content) in the total nonvolatile content of the printing ink is equal to the content (% by weight) of each component in the printing layer of the present invention of the shrink label. Become.

  As said solvent, the organic solvent etc. which are normally used for printing inks, such as gravure printing and flexographic printing, etc. can be used, for example, acetates, such as ethyl acetate, propyl acetate, butyl acetate; methanol, ethanol, isopropyl alcohol, Alcohols such as propanol and butanol; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene; Aliphatic hydrocarbons such as hexane and octane; Alicyclic carbonization such as cyclohexane and methylcyclohexane Hydrogens; glycols such as ethylene glycol and propylene glycol; glycol ethers such as ethylene glycol monopropyl ether, propylene glycol monomethyl ether and propylene glycol monobutyl ether; B propylene glycol monomethyl ether glycol ether esters such as acetate, etc. are exemplified. Among these, acetates and alcohols are preferable from the viewpoints of solubility and safety. The said solvent can be used individually or in mixture of 2 or more types. The solvent can be removed by drying after applying the printing ink to the substrate.

  The viscosity (23 ± 2 ° C.) of the printing ink is not particularly limited. For example, in the case of coating by gravure printing, 10 to 1000 mPa · s is preferable, and 20 to 500 mPa · s is more preferable. When the viscosity exceeds 1000 mPa · s, for example, the gravure printability is lowered, and “blur”, “plate fog”, etc. may occur, and printing may not be performed as desired. In addition, when the viscosity is less than 10 mPa · s, the storage stability is lowered, for example, pigments and additives are likely to settle, or “crossing” occurs, resulting in uneven printing, and printing according to the desired design. May not be possible. The viscosity of the printing ink can be controlled by the type and blending amount (content) of a specific resin and other components, a thickener, a thinning agent, and the like. In particular, it is preferable to add a cellulose-based resin because the viscosity can be easily controlled in an appropriate range. In the present specification, “viscosity” is JIS Z 8803 under the conditions of 23 ± 2 ° C. and cylinder rotation speed of 50 rpm using an E-type viscometer (conical flat plate rotational viscometer) unless otherwise specified. The value measured according to.

  Next, the printing ink is coated on the surface of the substrate (shrink film) and dried to provide a printing layer, whereby the shrink label of the present invention can be produced. The application and drying steps described above may be performed during the shrink film manufacturing process (in-line coating) or after film formation (off-line coating), from the viewpoint of productivity and workability, An off-line coat is preferred. Moreover, you may provide layers other than the printing layer of this invention as needed.

  As a method for applying the printing ink, gravure printing, flexographic printing, and letterpress printing are preferable from the viewpoints of cost, productivity, printing decoration, and the like, and gravure printing is particularly preferable. Moreover, when drying the applied printing ink layer (application layer) by heating or the like, a general heating device capable of heating on the printing device can be preferably used. From the viewpoint of safety, a hot air heater or the like can be preferably used.

  The shrink label may be processed into a cylindrical label. For example, the shrink label is formed in a cylindrical shape so that the main orientation direction is the circumferential direction. Specifically, a shrink label having a predetermined width in the main orientation direction is formed into a cylindrical shape by overlapping both ends in the main orientation direction so that the outer surface (outside) of the shrink label is on the front side, and one side of the label Apply a solvent or adhesive such as tetrahydrofuran (THF) or an adhesive (hereinafter referred to as an adhesive) on the inner surface at a width of about 2 to 4 mm on the edge, and apply the adhesive or the like to the outer surface of the other side edge. To obtain a cylindrical shrink label. In addition, it is preferable that the printing layer is not provided in the part which apply | coats said adhesive agent etc., and the part to adhere | attach.

  In addition, when providing the perforation for label cutting to a cylindrical shrink label, the perforation of predetermined length and a pitch is formed in the direction orthogonal to the circumferential direction. The perforation can be applied by 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, or the like). The process stage for perforating can be appropriately selected after the printing process and before and after the cylindrical processing process.

  The cylindrical shrink label can be attached to a container to form a labeled container. For example, after a cylindrical shrink label is externally fitted to a predetermined container, the label is thermally contracted by heat treatment, and a container with a label is manufactured by closely contacting the container. Examples of the heat treatment include treatment with steam at 80 to 100 ° C. (passing through a heating tunnel filled with steam and steam). In addition, in the above, it is preferable that the shrink label is attached to the container so that the printed layer is on the inner side.

EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
In Table 1, the composition (mixing amount) of the printing ink used in Examples and Comparative Examples, the resin content in the printing layer, the urethane acrylic resin, acrylic resin, and cellulose resin relative to the total amount of the specific resin. The content of the urethane resin and the evaluation result of the obtained shrink label are shown.
The blending composition of the above printing ink is indicated by the blending amount (parts by weight) based on the weight of the product used. The resin content in the printing layer (equal to the resin content in the non-volatile content of the printing ink) is the urethane acrylic resin, urethane resin, acrylic resin in the printing layer (in the total non-volatile content of the printing ink). And the total content of cellulose resin (nonvolatile content) (% by weight). Furthermore, the content of urethane acrylic resin, acrylic resin, cellulose resin, and urethane resin with respect to the total amount of the specific resin is indicated by the content as resin (nonvolatile content) (% by weight).
Table 2 shows details of products (resins, pigments, etc.) used for printing ink.
Further, Table 3 shows the urethane acrylic resin solution (trade name “Acryt 8UA-140” manufactured by Taisei Fine Chemical Co., Ltd.) used as the urethane acrylic resin (A), and the urethane acrylic resin (C). In the urethane acrylic resin solution used, the type and structure of the resin contained in each solution [monomer component constituting the resin (the compound from which the structural unit constituting the resin is derived) and the weight percentage of each monomer component ( The ratio among all monomer components)], acid value and weight average molecular weight. Moreover, the solvent composition (type and content ratio of the solvent) and nonvolatile content concentration of each solution are shown. In addition, the structure of said resin was measured by < ¹ > H-NMR analysis and thermal decomposition analysis. ¹ H-NMR analysis was performed under the following conditions using NMR (500 MHz) [manufactured by JEOL Ltd., “JNM-LA500”]. In addition, pyrolysis analysis was performed by gas chromatograph mass spectrometer [manufactured by Shimadzu Corporation, “GCMS-QP2010”], medium polarity column [manufactured by Restek, “Rtx-200”], and micropolar column [manufactured by Frontier Lab. , “UltraALLOY-5”] and a portable pyrolyzer [manufactured by Japan Analytical Industries, Ltd., “JCI-22”].
^<1 H-NMR analysis conditions>
EXMOD (measurement method): non (measure in a state in which the influence of hydrogen nuclei remains)
OBNUC (observation nucleus): ¹ H
IRNUC (irradiation nucleus): ¹ H
CTEMP (set temperature): 22.9 ° C
SLVNT (measurement solvent): CDCl ₃ (deuterated chloroform)

Example 1
(Printing ink)
As urethane acrylic resin (A), urethane acrylic resin solution (manufactured by Taisei Fine Chemical Co., Ltd., trade name “Acryt 8UA-140”, nonvolatile content concentration: 40% by weight) 2 parts by weight (as urethane acrylic resin, 0 .8 parts by weight) was used. As shown in Table 3, the urethane acrylic resin solution (Acryt 8UA-140) was neopentyl glycol 8.1% by weight, ethylene glycol 3.3% by weight, terephthalic acid 12.9% by weight, isophthalic acid 12 9.9% by weight, isophorone diisocyanate 17.2% by weight, n-butyl methacrylate 30.9% by weight, methyl methacrylate 14.7% by weight as a monomer component (compound derived from the structural unit), A polyester diol urethane acrylic resin solution having a weight average molecular weight of 40,000 and an acid value of 2.5 mgKOH / g (solvent: mixed solvent of 99% by weight of ethyl acetate and 1% by weight of isopropyl alcohol, non-volatile content: 40% by weight) is there.
As the acrylic resin (A), 10 parts by weight of an acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name “Dianar BR-113”, nonvolatile concentration: 100% by weight) was used.
As the acrylic resin (C), 2 parts by weight of an acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name “Dianar BR-105”, nonvolatile content concentration: 100% by weight) was used.
As the cellulose resin (A), 0.5 part by weight of CAB resin (manufactured by Eastman Chemical Co., Ltd., trade name “CAB-381-20”, nonvolatile content concentration: 100% by weight) was used.
To the above urethane acrylic resin (A), acrylic resin (A), acrylic resin (C), and cellulose resin (A), titanium oxide (A) (trade name “JR-707” manufactured by Teika Co., Ltd.) 37 parts by weight of non-volatile content: 100% by weight, 0.5 part by weight of an anti-settling agent (manufactured by Ito Oil Co., Ltd., trade name “ASA-TS-021”, non-volatile content: 20% by weight), wax (A) (trade name “SPRAY105”, manufactured by Sasol, nonvolatile concentration: 100% by weight) 2 parts by weight, ethyl acetate 9 parts by weight, n-propyl acetate 13 parts by weight, propyl cellosolve 5 parts by weight and isopropyl alcohol (IPA ) 19 parts by weight were added to make a printing ink (100 parts by weight).
The content of the urethane acrylic resin is 6.0% by weight and the content of the acrylic resin with respect to the total amount (100% by weight) of the specific resin (urethane acrylic resin, acrylic resin and cellulose resin) in the printing ink. Was 90.2% by weight, and the content of the cellulose resin was 3.8% by weight. In addition, the ratio of content of each resin in said printing ink is equal to the ratio of content of each resin in the printing layer of a shrink label.

(Shrink label)
Polyester (PET) shrink film (trade name “SV808”, manufactured by Toyobo Co., Ltd., thickness: 30 μm, heat shrinkage ratio in main orientation direction (width direction) (90 ° C., 10 seconds): 50%) on one side using a gravure plate with an engraving of 70 lines / inch and a plate depth of 30 μm. And got a shrink label. The thickness of the printed layer after drying was about 3 μm.
The base material was a polyester (PET) shrink film (Mitsubishi Resin Co., Ltd., trade name “LX-61S”, thickness: 45 μm, heat shrinkage in the main orientation direction (width direction) (90 ° C., 10 seconds). ): 81%) A shrink label was obtained in the same manner as above except that the content was changed to 81%). The thickness of the printed layer after drying was about 3 μm.

Example 2 and Comparative Example 2
As shown in Table 1, printing inks and shrink labels were produced in the same manner as in Example 1 by changing the blending amount of the urethane acrylic resin.

Comparative Example 1
As shown in Table 1, printing ink and shrink labels were produced in the same manner as in Example 1 without using urethane acrylic resin.

Comparative Example 3
As shown in Table 1, printing inks and shrink labels were produced in the same manner as in Example 1 except that the amount of urethane acrylic resin was changed without using acrylic resin.

Comparative Examples 4 and 5
As shown in Table 1, printing inks and shrink labels were produced in the same manner as in Example 1 using urethane resins instead of urethane acrylic resins.
In Comparative Examples 4 and 5 in Table 1, the content of each resin relative to the total amount of the specific resin is calculated with the total content of the acrylic resin, the cellulose resin and the urethane resin as the total amount of the specific resin. .

Example 3
As shown in Table 1, printing inks and shrink labels were produced in the same manner as in Example 1 except that the type of urethane acrylic resin was changed.

Examples 4-6
As shown in Table 1, printing inks and shrink labels were produced in the same manner as in Example 1 by changing the type and blending amount of the acrylic resin.

Example 7
As a base material, instead of polyester (PET) -based shrink films (“SV808” and “LX-61S”), polystyrene-based shrink films (trade name “BS55S”, manufactured by CI Kasei Co., Ltd.), thickness: 50 μm, main orientation A printing ink and a shrink label were produced in the same manner as in Example 1 except that the heat shrinkage rate in the direction (width direction) (90 ° C., 10 seconds): 63%) was used.

Examples 8 and 9
In Example 8, instead of polyester (PET) -based shrink films (“SV808” and “LX-61S”) as a base material, polyolefin-based shrink films (manufactured by Gunze Co., Ltd., trade name “FL-2”), A printing ink and a shrink label were prepared in the same manner as in Example 1 except that the thickness: 50 μm and the thermal shrinkage rate (90 ° C., 10 seconds): 50% in the main orientation direction (width direction) were used.
In Example 9, as shown in Table 1, printing inks and shrink labels were produced in the same manner as in Example 8 by changing the blending amount of the urethane acrylic resin and the like.

Comparative Example 6
As shown in Table 1, printing was performed in the same manner as in Example 1 using acrylic resin (D), cellulose resin (B), titanium oxide (B), wax (B), ethyl acetate, and isopropyl alcohol. Ink and shrink labels were made.

Example 10
As shown in Table 1, printing inks and shrink labels were produced in the same manner as in Example 1 except that the type of urethane acrylic resin was changed.
In addition, as shown in Table 3, as urethane acrylic resin (C), neopentyl glycol, terephthalic acid, isophthalic acid, isophorone diisocyanate, and n-butyl methacrylate are used as monomer components (compounds derived from structural units). An ethyl acetate solution (nonvolatile content concentration: 41.5 wt%) of a polyesterdiol urethane acrylic resin having a weight average molecular weight of 42000 and an acid value of 3.0 mgKOH / g was used.

Examples 11 and 12
As shown in Table 1, printing inks and shrink labels were produced in the same manner as in Example 1 except that the type of urethane acrylic resin was changed.
In addition, the kind of monomer component (structural unit) which comprises urethane acrylic resin in urethane acrylic resin (D) and urethane acrylic resin (E) is the same as urethane acrylic resin (C). The ratio of urethane component to acrylic component [urethane component: acrylic component] is as shown in Table 2.

(Evaluation)
For the shrink labels obtained in the examples and comparative examples, the peel resistance (tape peel test), scratch resistance (scratch test), flaw resistance (fir test), shrink suitability (ink crack test), main orientation direction The thermal shrinkage rate (90 ° C., 10 seconds) was evaluated and tested by the following method.
In addition, about Examples 1-6, 10-12, and a comparative example, Toyobo Co., Ltd. make in a tape peeling test (peeling resistance), a scratch test (scratch resistance), and a fir tree test (fir resistance). Using a shrink label based on the trade name “SV808” (thin type PET film) as a base material, the ink cracking test (shrink suitability) is made by Mitsubishi Plastics Co., Ltd., trade name “LX-61S” (high shrinkage). A shrink label based on a PET film of the type) was used.
Moreover, the tape peeling test (peeling resistance), the scratch test (scratch resistance), and the fouling test (fir resistance) were tested on shrink labels immediately after production.

(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 “Cello Tape (registered trademark))” is pasted on the surface of the printed layer of the shrink label obtained in Examples and Comparative Examples. Peeled in the direction.
In the area of 5 mm (longitudinal direction; orthogonal direction to the main orientation direction) × 5 mm (width direction; main orientation direction) in the surface of the printed layer with the adhesive tape attached, the remaining area (ratio) of the print layer was visually observed. And judged according to the following criteria.
The remaining area of the printed layer is 90% or more. : Good peel resistance (○)
The remaining area of the printed layer is 80% or more and less than 90%. : Peeling resistance is slightly poor but usable (△)
The remaining area of the printed layer is less than 80%. : Poor peel resistance (×)

(2) Scratch resistance (scratch test)
Samples for measurement measuring 100 mm (longitudinal direction; orthogonal direction to the main orientation direction) × 100 mm (width direction; main orientation direction) were collected from the shrink labels obtained in the examples and comparative examples. Place the sample for measurement on a smooth table, observe the surface after rubbing the surface on the side where the printed layer was provided 10 times in the back of the nail of the hand (20 mm in the longitudinal direction). Judged by criteria.
The printed layer is not peeled at all. : Good scratch resistance (○)
Partial peeling is observed on the printed layer. : Scratch resistance is slightly poor but usable level (△)
The printed layer is peeled off significantly. : Scratch resistance failure (×)

(3) Scratch resistance (scratch test)
Samples for measurement measuring 100 mm (longitudinal direction; orthogonal direction to the main orientation direction) × 100 mm (width direction; main orientation direction) were collected from the shrink labels obtained in the examples and comparative examples. Hold both ends of the sample for measurement with both hands, and even 10 times. The remaining area (ratio) of the printed layer on the surface provided with the printed layer was visually observed and evaluated according to the following criteria.
The remaining area of the printed layer is 90% or more. : Good resistance to cracking (○)
The remaining area of the printed layer is 80% or more and less than 90%. : Slightly poor resistance to wear, but usable level (△)
The remaining area of the printed layer is less than 80%. : Poor resistance to cracking (×)

(4) Shrinkability (ink cracking test)
From the shrink labels obtained in Examples and Comparative Examples, a measurement sample of 110 mm (longitudinal direction; direction orthogonal to the main orientation direction) × 210 mm (width direction; main orientation direction) was collected. After making the measurement sample into a cylindrical shape so that the main orientation direction of the measurement sample (the main orientation direction of the shrink film) is the circumferential direction, and the surface on the side where the printing layer is provided is inside, the both ends are overlapped The overlapping portions were joined by heat welding to obtain a cylindrical shrink label (peripheral length: 200 mm).
A cylindrical glass bottle having a diameter of 62 mm (circumferential length of 194 mm) and a height of 108 mm was prepared. Furthermore, a strip of shrink film of 110 mm (longitudinal direction; perpendicular direction to the main orientation direction) × 10 mm (width direction; main orientation direction) was prepared. In addition, as a shrink film of the said strip, about Examples 1-6, 10-12 and a comparative example, brand name "LX-61S" (Mitsubishi Resin Co., Ltd. product, thickness: 45 micrometers), Example 7 The name “BS55S” (CI Kasei Co., Ltd., thickness: 50 μm), and for Examples 8 and 9, the trade name “FL-2” (Gunze Co., Ltd., thickness: 50 μm) was used.
The strips were aligned so that the width direction (main orientation direction) was the circumferential direction of the cylindrical glass bottle, and the upper and lower ends of the strip and the upper and lower ends of the cylindrical glass bottle were fixed with cellophane adhesive tape (upper and lower ends). The strip and the cylindrical glass bottle are not bonded at the center of the strip, except for). Next, the cylindrical shrink label is placed over the cylindrical glass bottle (with strips) so that the printed layer faces the strip, and immersed in hot water at 90 ° C. for 20 seconds to heat the shrink label. Shrinkage (the strip also thermally shrinks in the width direction at this time) to obtain a labeled container.
Observe the appearance (outside) of the label of the container with the label, peel off the cylindrical shrink label, observe the inside of the label, and crack the ink along the strip (stripe ink in the height direction of the container) It was visually observed whether or not peeling occurred. Evaluation was made according to the following criteria.
No ink cracks are seen from the outside or from the inside after peeling off the label. : Good shrinkability (○)
Even when observed from the outside, no ink cracks are seen, but when the label is peeled off, ink cracks are seen inside the label. : Shrinkability is slightly poor but usable level (△)
Ink cracks are seen from the outside. : Shrinkability failure (×)
Note that Comparative Examples 4 and 5 were not evaluated.

(5) Thermal shrinkage in main orientation direction (90 ° C., 10 seconds)
From the shrink labels obtained in the examples and comparative examples, rectangular measurement samples having a length of 200 mm (mark interval 150 mm) and a width of 10 mm in the measurement direction (main alignment direction) were cut out.
The measurement sample is heat-treated for 10 seconds (under no load) in hot water at 90 ° C., the difference between the marked lines before and after the heat treatment is read, and the heat shrinkage rate is calculated by the following formula.
Thermal shrinkage (%) = (L ₀ −L ₁ ) / L ₀ × 100
L ₀ : Marking interval before heat treatment L ₁ : Marking interval after heat treatment In the examples and comparative examples, the main orientation direction is the width direction of the shrink label.
Further, the thermal contraction rate (90 ° C., 10 seconds) in the direction orthogonal to the main alignment direction can be measured in the same manner as described above by changing the measurement direction to the direction orthogonal to the main alignment direction.

As can be seen from the evaluation results, the shrink labels (Examples) of the present invention have excellent adhesion between the printed layer and the substrate, while using an acrylic resin as the main resin component for forming the printed layer, Excellent resistance to scratching and excellent scratch resistance. Furthermore, it was the shrink label which has the outstanding characteristic which is hard to produce the ink crack at the time of shrink processing.
On the other hand, when the urethane acrylic resin is not added to the printing layer (Comparative Examples 1, 4 to 6) or when the content is small (Comparative Example 2), the adhesion between the printing layer and the substrate is lowered, and peeling resistance Sex was inferior. Further, when urethane acrylic resin was used as the main resin component without using acrylic resin (Comparative Example 3), the printed layer became too soft, and ink cracking occurred during shrink processing.
In addition, the thermal contraction rate (90 degreeC, 10 second) of the main orientation direction of the shrink label (a base material is SV808 thing) obtained in Examples 1-6, 10-12, and a comparative example is 50%, and it shrinks. The thermal contraction rate (90 ° C., 10 seconds) in the main orientation direction of the label (base material: LX-61S) was 81%. Further, the shrinkage rate (90 ° C., 10 seconds) in the main orientation direction of the shrink label (base material BS55S) obtained in Example 7 is 63%, and the shrinkage obtained in Examples 8 and 9 is used. The thermal contraction rate (90 ° C., 10 seconds) in the main orientation direction of the label (with the base material of FL-2) was 50%.

Claims (2)

At least one side of the substrate has a printed layer containing a urethane acrylic resin and an acrylic resin, or a urethane acrylic resin, an acrylic resin and a cellulose resin, and the urethane acrylic in the printed layer The content of urethane acrylic resin is 4 to 40% by weight, the content of acrylic resin is 40 to 96% by weight, and the content of cellulosic resin is 0 to 0% based on the total amount of acrylic resin, acrylic resin and cellulose resin. 20% by weight , and the printing layer contains a solvent, a urethane acrylic resin, and an acrylic resin, or a printing ink containing a solvent, a urethane acrylic resin, an acrylic resin, and a cellulose resin. A shrink label, which is a printed layer provided by applying and drying on a surface of a substrate . The shrink label according to claim 1, wherein the printed layer contains titanium oxide, and the content of the titanium oxide is 50 to 90% by weight based on the total amount of the printed layer.