JP2011197199A - Shrink label - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a shrink label having a printed layer which is hardly changed in color due to whitening or the like even after shrink processing and has a superior metal brilliance.SOLUTION: The shrink label has a printed layer comprising an urethane-type resin, a nonleafing-type aluminum pigment and an aluminum pigment prepared by a vapor-deposition method in which all the following conditions (1) to (3) are satisfied: (1) the total content of the nonleafing-type aluminum pigment and the aluminum pigment prepared according to the vapor-deposition method in the printed layer is 15 to 90 wt.%; (2) the proportion (wt.ratio) of the content of the nonleafing-type aluminum pigment to the content of the aluminum pigment prepared according to the vapor-deposition method in the printed layer is 5 to 50; and (3) the average particle size of the nonleafing type aluminum pigment in the printed layer is 6 to 20 μm.

Description

  The present invention relates to a shrink label. More specifically, the present invention relates to a shrink label having a printed layer that is small in color change such as whitening after shrink processing and can maintain an excellent metallic luster (high luminance feeling).

  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 printing layer are widely used (see, for example, Patent Documents 1 to 3).

  On the other hand, printing ink containing an aluminum pigment obtained by a wet ball mill method is known as a silver ink for forming a silver printing layer among printing layers provided on plastic labels (shrink labels and the like). Furthermore, in recent years, aluminum flake pigments obtained by a so-called vapor deposition method ("deposited aluminum pigments"), in which flakes are produced by pulverizing a deposited metal film as a printing ink for forming a printing layer having a particularly high-brightness metallic luster. High-intensity printing inks are known (for example, see Patent Documents 4 to 6).

JP 2008-201443 A JP 2008-170822 A JP 2006-160796 A JP 2007-224243 A JP 2003-96334 A JP 2002-20668 A

  However, the printing ink containing the above vapor-deposited aluminum pigment can form a printing layer having an excellent metallic luster for a normal plastic label, but when used for a shrink label, the shrink ink is used. (Shrinkage) During processing (especially during shrink processing with hot air), the printing layer may change in color, such as whitening, and the metallic luster (luminance) of the printing layer may be extremely reduced. all right. Accordingly, the present situation is that a shrink label having a printing layer capable of maintaining the color and excellent metallic luster (metallic luster) after shrink processing has not been obtained.

  That is, an object of the present invention is to provide a shrink label having a printed layer having a small metallic change due to whitening or the like and having an excellent metallic luster even after shrink processing.

  As a result of intensive studies to achieve the above object, the inventors of the present invention include a urethane-based resin, a non-leafing aluminum pigment and a vapor-deposited aluminum pigment on at least one side of the base material. By providing a printing layer in which the content ratio of leafing aluminum pigment and vapor-deposited aluminum pigment, and the average particle size of non-leafing aluminum pigment are controlled within a specific range, whitening and color change during shrink processing are suppressed, and after shrink processing In addition, the present inventors have found that a shrink label capable of maintaining the excellent metallic luster of the printed layer can be obtained, and the present invention has been completed.

  That is, the present invention includes a urethane-based resin, a non-leafing type aluminum pigment and an aluminum pigment produced by a vapor deposition method on at least one side of the substrate, and satisfies all the following conditions (1) to (3): A shrink label is provided having a printed layer that fills. (1) The total content of the non-leafing aluminum pigment and the aluminum pigment produced by the vapor deposition method in the printed layer is 15 to 90% by weight. (2) Ratio of content of non-leafing type aluminum pigment to content of aluminum pigment produced by vapor deposition method in said printing layer [(content of non-leafing type aluminum pigment) / (produced by vapor deposition method) Content of aluminum pigment)] (weight ratio) is 5-50. (3) The average particle diameter of the non-leafing aluminum pigment in the printed layer is 6 to 20 μm.

  Furthermore, the present invention provides the shrink label, wherein the print layer is a print layer containing a plasticizer, and the content of the plasticizer in the print layer is 3 to 45% by weight.

  The shrink label of the present invention uses a urethane-based resin, a non-leafing type aluminum pigment and a vapor deposition aluminum pigment for the printed layer. Furthermore, the total content of the non-leafing aluminum pigment and the vapor-deposited aluminum pigment in the printed layer, the content ratio of the non-leafing aluminum pigment and the vapor-deposited aluminum pigment, and the average particle size of the non-leafing aluminum pigment are controlled within a specific range. ing. For this reason, the printed layer has an excellent metallic luster. Further, even during shrink processing (particularly during shrink processing with hot air), the change in color due to whitening and the reduction in metallic luster are small. Even after processing, the color of the printed layer and excellent metallic luster are maintained.

The shrink label of the present invention includes a urethane resin, a non-leafing type aluminum pigment and an aluminum pigment produced by a vapor deposition method on at least one side of the base material, and all the following conditions (1) to (3): A printed layer satisfying The conditions (1) to (3) are as follows.
(1) The total content of the non-leafing aluminum pigment and the aluminum pigment produced by the vapor deposition method in the printed layer is 15 to 90% by weight.
(2) Ratio of content of non-leafing type aluminum pigment to content of aluminum pigment produced by vapor deposition method in said printing layer [(content of non-leafing type aluminum pigment) / (produced by vapor deposition method) Content of aluminum pigment)] (weight ratio) is 5-50.
(3) The average particle diameter of the non-leafing aluminum pigment in the printed layer is 6 to 20 μm.

  In the present specification, the printing layer, that is, the urethane resin, the non-leafing type aluminum pigment, and the aluminum pigment produced by the vapor deposition method, and all the above conditions (1) to (3) are satisfied. The printed layer that fills may be referred to as the “printed layer of the present invention”. In addition, an aluminum pigment produced by a vapor deposition method may be referred to as a “vapor deposition aluminum pigment”.

[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-based resin, a non-leafing type aluminum pigment and a vapor deposition aluminum pigment as essential components. The printing layer of the present invention preferably contains a plasticizer and a cellulose resin in addition to the above essential components (urethane resin, non-leafing aluminum pigment and vapor-deposited aluminum pigment). Furthermore, you may contain another additive as needed.

(Urethane resin)
The urethane-based resin in the printing layer of the present invention plays the role of the main binder resin (also referred to as “base resin”) in the printing layer. The printed layer of the present invention is improved in flexibility by including a urethane-based resin as a binder resin. This reduces the stress applied to the aluminum pigment (non-leafing type aluminum pigment and vapor-deposited aluminum pigment) in the printing layer during shrink processing, and suppresses disorder and deformation of the orientation of the aluminum pigment. Whitening, etc.) and reduction of metallic luster can be suppressed.

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

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

  Examples of the polyol compound include ethylene glycol, diethylene glycol, 1,3-propanediol, propylene glycol (1,2-propanediol), butanediol (1,3-butanediol, 1,4-butanediol, etc.), 1, Low molecular weight glycols such as 6-hexanediol and cyclohexanedimethanol; polyether diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol-polycaprolactone copolymer; propylene glycol, butanediol, hexanediol 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.

  Among the above, polyester diol-based polyurethane (polyurethane obtained by using polyester diol as a polyol compound) is preferable.

  The glass transition temperature (Tg) of the urethane resin is preferably −60 to 40 ° C., more preferably −50 to 30 ° C., from the viewpoint of flexibility. 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.

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

  Although content of the urethane type resin in the printing layer of this invention is not specifically limited, 5-50 weight% is preferable with respect to the total weight (100 weight%) of the printing layer of this invention, More preferably, 7- 40% by weight, more preferably 10 to 30% by weight. When the content of the urethane-based resin is less than 5% by weight, the adhesion between the printed layer of the present invention and the substrate may be lowered, and the printed layer may be easily peeled off from the substrate. On the other hand, if it exceeds 50% by weight, the content of the non-leafing aluminum pigment and the vapor-deposited aluminum pigment in the printing layer of the present invention may decrease, and an excellent metallic luster may not be obtained.

(Non-leafing type aluminum pigment)
The non-leafing type aluminum pigment in the printing layer of the present invention is a non-leafing type (non-leafing type) aluminum pigment generally used as a pigment for printing ink. The non-leafing aluminum pigment has a property of being uniformly dispersed and arranged in a coating film (film) of printing ink. The non-leafing aluminum pigment is preferably an aluminum pigment produced by ball milling (sometimes referred to as “ball mill method” or “wet ball mill method”). The non-leafing aluminum pigment may be coated with a resin.

  The average particle diameter (average particle diameter) of the non-leafing aluminum pigment in the printing layer of the present invention is 6 to 20 μm, preferably 8 to 18 μm. When the average particle size is less than 6 μm, the orientation of the pigment is easily changed during shrinkage (during shrink processing), so that the color of the printed layer is easily changed and the metallic luster is easily lowered. On the other hand, if the average particle size exceeds 20 μm, the printability is lowered and the area of the aluminum pigment in the printed layer is lowered, so that the metallic tone of the printed layer is weakened and the metallic luster is lowered. The said average particle diameter is an average particle diameter about all the non-leafing type | mold aluminum pigments contained in the printing layer of this invention.

  In addition, the said average particle diameter (average particle diameter) is a median diameter (D50) in volume reference distribution. The average particle diameter can be measured by a laser diffraction method. More specifically, it can be measured by, for example, “Microtrac (Microtrack) HRA9320-X100” manufactured by Honeywell, “Microtrac (Microtrack) MT3000” manufactured by Nikkiso Co., Ltd., or the like.

  In addition, the said non-leafing type aluminum pigment may use only 1 type, and may mix and use 2 or more types of non-leafing type aluminum pigments. Non-leafing aluminum pigments with a relatively small average particle size are excellent in hiding properties, and non-leafing aluminum pigments with a relatively large average particle size are highly effective in suppressing color changes such as whitening during shrink processing and reduction of metallic luster. Therefore, when two or more types of non-leafing aluminum pigments having different average particle diameters (average particle diameters before mixing) are used in combination, the concealability of the printed layer, whitening during shrink processing, color change and metallic luster The effect of suppressing the decrease can be improved in a balanced manner. For example, it is preferable to use a mixture of two types of non-leafing aluminum pigments having different average particle diameters of 13 to 20 μm (preferably 13 to 18 μm) and average particle diameters of 6 to 12 μm (preferably 8 to 12 μm).

  The thickness of the non-leafing aluminum pigment is not particularly limited, but is preferably 0.1 μm or more. Moreover, although the average thickness of the said non-leafing type aluminum pigment is not specifically limited, 0.1-2 micrometers is preferable, More preferably, it is 0.2-1 micrometers. If the said thickness and average thickness are less than 0.1 micrometer, a printing layer may become easy to whiten at the time of shrink processing. On the other hand, when the average thickness exceeds 2 μm, the metallic luster of the printed layer may be lowered. Said average thickness can be calculated | required by measuring the thickness of arbitrary 10 non-leafing type | mold aluminum pigments by scanning electron microscope (SEM) observation.

Commercially available products can be used as the non-leafing aluminum pigment. For example, “7130N”, “7160N”, “7790N”, “7620NS”, “7640NS”, “7675NS”, “7995N”, “5207N”, “5422NS”, “5620NS”, “5640NS” manufactured by Toyo Aluminum Co., Ltd. ”,“ 5660 NS ”,“ 5680 NS ”,“ TCR 3040 ”,“ TCR 3080 ”,“ TCR 3130 ”,“ TCR 2060 ”,“ TCR 2150 ”,“ 6315 NS ”,“ 6320 NS ”,“ 6340 NS ”,“ 6360 NS ”,“ 6370 NS ”, “6390 NS”, “4640 NS”, “4660 NS”, “4690 NS” and the above-mentioned resin coat types BP series, BPA series, etc .;
“FD-5060”, “FD-4070”, “FD-508H”, “GX-3108”, “GX-3109”, “GX-3100”, “GX-3110”, “GX” manufactured by Asahi Kasei Chemicals Corporation -3140 "," GX-3160 "," GX-3180 "," O-2100 "," O-2130 "," GX-2140 "," GX-2134 "," GX-2135 "," GX-180A " ”,“ GX-40A ”,“ GX-50A ”,“ BS-080 ”,“ BS-100 ”,“ BS-200 ”,“ BS-400 ”,“ BS-120 ”,“ BS-140 ”, “BS-150”, “BS-240”, “BS-440”, “AM-1501”, “MC-666”, “MH-8801”, “MH-9901” and the like are available on the market. Moreover, what was solvent-substituted can be used for the said commercial item as needed.

(Vapor deposited aluminum pigment)
The vapor-deposited aluminum pigment (aluminum pigment produced by the vapor deposition method) in the printed layer of the present invention is an aluminum flake produced by the vapor deposition method. With the above vapor deposition method, a metal (aluminum in the present invention) is vapor-deposited on a suitable support substrate (film or the like) to produce a vapor-deposited metal (aluminum) film, and then peeled off, pulverized, and if necessary This is a method for producing vapor-deposited metal film strips (vapor-deposited aluminum flakes) that are classified into flakes (see, for example, JP-A-2002-20668). According to said vapor deposition method, compared with the case where it manufactures by the conventional ball mill method etc., plate-shaped and thinner aluminum flakes can be obtained. For this reason, in the printed layer, the aluminum flakes, which are pigments, are easily oriented in the direction parallel to the surface of the shrink label, and the orientation is improved, and the incident light is easily regularly reflected. For this reason, the specular gloss of the printing layer is improved, and an excellent metallic gloss is exhibited.

  Although the thickness of the said vapor deposition aluminum pigment is not specifically limited, Less than 0.1 micrometer is preferable. Moreover, although the average thickness of the said vapor deposition aluminum pigment is not specifically limited, 0.01 micrometer or more and less than 0.1 micrometer are preferable, More preferably, it is 0.01-0.07 micrometer. If the average thickness is less than 0.01 μm, the production efficiency may be poor industrially. On the other hand, when the thickness and the average thickness are 0.1 μm or more, the orientation of the pigment in the printed layer is lowered, and the metallic luster may be lowered. Said average thickness can be calculated | required by measuring the thickness of arbitrary 10 vapor deposition aluminum pigments (aluminum flakes) by a scanning electron microscope (SEM) observation.

  Although the average particle diameter of the said vapor deposition aluminum pigment is not specifically limited, 1-30 micrometers is preferable, More preferably, it is 5-20 micrometers. When the average particle size is less than 1 μm, the specular gloss may be lowered. When the average particle size is more than 30 μm, blurring may occur when the printing ink is subjected to gravure printing. The average particle diameter can be measured in the same manner as the average particle diameter of the non-leafing aluminum pigment.

  A commercial item can also be used for the said vapor deposition aluminum pigment. For example, “Metacene 71-0010”, “Metacene 41-0010” manufactured by Ciba Japan Co., Ltd., “Metal Ar A41010AE” manufactured by Ecart Co., etc. are available on the market.

  In addition, the said vapor deposition aluminum pigment may use only 1 type, and may mix and use 2 or more types of different vapor deposition aluminum pigments.

  The total content of the non-leafing aluminum pigment and the vapor-deposited aluminum pigment in the printed layer of the present invention is 15 to 90% by weight with respect to the total weight (100% by weight) of the printed layer of the present invention. Preferably it is 20 to 85 weight%, More preferably, it is 30 to 80 weight%. If the total content is less than 15% by weight, the amount of aluminum pigment in the printed layer is small, so that the metallic tone is weakened and the metallic luster is lowered (luminance feeling is lowered). On the other hand, when the total content exceeds 90% by weight, the content of the binder resin is decreased, the adhesion between the printed layer and the substrate is decreased, and the printed layer is easily peeled off from the substrate. The above-mentioned “total content of non-leafing aluminum pigment and vapor-deposited aluminum pigment” means the content of non-leafing aluminum pigment (non-volatile content) and vapor-deposited aluminum pigment in the printing layer of the present invention. This is the total content (content of nonvolatile content).

  Ratio of content of non-leafing aluminum pigment to content of vapor-deposited aluminum pigment in the printing layer of the present invention [(content of non-leafing aluminum pigment) / (content of vapor-deposited aluminum pigment)] ( The weight ratio) is 5-50, preferably 10-40. That is, the content ratio [(content of non-leafing aluminum pigment) :( content of vapor-deposited aluminum pigment)] (weight ratio) of the non-leafing aluminum pigment and the vapor-deposited aluminum pigment in the printed layer of the present invention is: 5 to 50: 1, preferably 10 to 40: 1. When the ratio [(content of non-leafing aluminum pigment) / (content of vapor-deposited aluminum pigment)] is less than 5, the printed layer is whitened by shrink processing, and the metallic luster is lowered. On the other hand, when the said ratio exceeds 50, the metallic luster of the printing layer before shrink processing will become low.

(Plasticizer)
The printing layer of the present invention preferably contains a plasticizer. By containing a plasticizer, the flexibility of the printed layer is improved, and the disorder (arrangement) and deformation of the non-leafing aluminum pigment and vapor deposited aluminum pigment during shrink processing are suppressed, and the printed layer is whitened by shrink processing. The effect of suppressing the color change and the metallic luster deterioration due to the above is further improved. As the plasticizer, known or conventional plasticizers can be used, and are not particularly limited. For example, diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate (DCHP: melting point 66 ° C.), dihydro phthalate Phthalic acid ester compounds such as ethyl and dimethyl isophthalate; Citric acid ester compounds such as tributyl acetyl citrate (ATBC: melting point -80 ° C.); Trimethylol ethane tribenzoate, trimethylol propane tribenzoate (melting point 88 ° C. ), Benzoic acid ester compounds such as tribenzoic acid glyceride (melting point 73 ° C.), tetrabenzoic acid pentaerythritol; sucrose octaacetate, tricyclohexyl ketenoate, triethylene glycol bis [3- (3-t-butyl-4 -Hydroxy-5-methylphenyl) propylone )] (Melting point 77 ° C.), fatty acid ester compounds such as 1,6-hexanediol bis [3- (2,5-di-t-butyl-4-hydroxyphenyl) propionate] (melting point 103 ° C.); N— It can be selected from sulfonic acid ester compounds such as cyclohexyl-p-toluenesulfonic acid amide; phosphate ester compounds, hindered phenol compounds, triazole compounds, hydroquinone compounds, and the like. Among these, dicyclohexyl phthalate (DCHP) and tributyl acetylcitrate (ATBC) are preferable, and ATBC is particularly preferable.

  A commercial item can also be used for the plasticizer. For example, “ATBC” manufactured by Asahi Kasei Finechem Co., Ltd. and “DCHP” manufactured by Wako Pure Chemical Industries, Ltd. are available on the market.

  The content of the plasticizer in the printing layer of the present invention is preferably 3 to 45% by weight, more preferably 5 to 40% by weight, based on the total weight (100% by weight) of the printing layer of the present invention. . If the content of the plasticizer is less than 3% by weight, the effect of softening the printed layer is insufficient, and at the time of shrink processing, particularly the specular gloss of the printed layer is lowered and the metallic luster is lowered (the brightness feeling is reduced). May decrease). On the other hand, if it exceeds 45% by weight, the printed layer becomes too flexible, and the printed layer may be easily peeled off, may be easily blocked, or scratch resistance may be reduced.

(Cellulosic resin)
The printed layer of the present invention preferably contains a cellulose resin. Cellulosic resin plays a role of adjusting the viscosity of a resin composition (sometimes referred to as “printing ink”) for forming a printing layer. Since the viscosity of the printing ink for forming the printing layer of the present invention tends to be relatively low, it is preferable to increase the viscosity by adding a cellulose-based resin in order to improve applicability (coating property). 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.

  Although content of the said cellulose resin in the printing layer of this invention is not specifically limited, 0.5 to 45 weight% is preferable with respect to the total weight (100 weight%) of the printing layer of this invention, More preferably Is 1 to 35% by weight. When the content of the cellulose resin is less than 0.5% by weight, the effect of adjusting the viscosity of the printing ink is insufficient, and the applicability of the printing ink may be lowered. On the other hand, if it exceeds 45% by weight, the printing ink may have too high a viscosity and the applicability may deteriorate or the performance of the printing layer may deteriorate. In addition, an excellent metallic luster may not be obtained after shrink processing.

(Other pigments)
The printing layer of the present invention may contain a pigment (other pigment) other than the non-leafing aluminum pigment and the vapor-deposited aluminum pigment. When the printed layer contains other pigments, the printed layer is colored according to the type of pigment in addition to having a metallic luster. For this reason, a color metallic print layer is obtained. As other pigments, known or commonly used organic and inorganic color pigments used in printing inks can be used depending on applications and the like, and are not particularly limited. For example, white pigments such as titanium oxide (titanium dioxide), Indigo (blue) pigments such as copper phthalocyanine blue, red pigments such as condensed azo pigments, yellow pigments such as azo lake pigments, and carbon black.

  Commercially available products may be used as the other pigments. For example, “Red CABR-T-7172”, “Yellow CABR-T-7703”, “Blue CABR-T-6461”, “Black CABR-T-7094” manufactured by Resino Color Industry Co., Ltd. are available on the market. is there.

  When the printing layer of the present invention contains the other pigments described above, the content of the other pigments is not particularly limited, but is 0.1 to 0.1% based on the total weight (100% by weight) of the printing layer of the present invention. 20 weight% is preferable, More preferably, it is 0.5 to 15 weight%. If the content of other pigments is less than 0.1% by weight, the coloring effect may not be obtained, and if it exceeds 20% by weight, the metallic luster may be lowered. In addition, when 2 or more types of other pigments are contained in the printing layer of this invention, it is preferable that the total amount (total content) of content of all the other pigments satisfy | fill said range.

(Other additives)
In addition to the above essential components (urethane resin, non-leafing type aluminum pigment and vapor-deposited aluminum pigment), plasticizer, cellulosic resin, and other pigments, the printing layer of the present invention may contain other resin components, if necessary. Other additives such as lubricants, anti-settling agents, dispersants, stabilizers, fillers, antioxidants, UV absorbers, antistatic agents, anti-coloring agents, fragrances, deodorants, etc. You may contain within the range which does not impair.

  In order to obtain an excellent metallic luster, the printed layer of the present invention preferably has a thin printed layer. Although the thickness of the printing layer of this invention is not specifically limited, 0.05-3 micrometers is preferable, More preferably, it is 0.1-2 micrometers. If the thickness of the printing layer is less than 0.05 μm, the amount of aluminum pigment per unit area is small, so that the metallic tone is weakened and the metallic luster may be lowered. On the other hand, if the thickness exceeds 3 μm, the thickness of the printing ink coating layer when forming the printing layer or the printing layer becomes thick, so that the aluminum pigment is less likely to be oriented in the printing layer or the printing ink coating layer, resulting in a specular gloss. In some cases, the metallic luster is lowered due to a decrease in the degree of metal. Moreover, the usage-amount of printing ink increases, and it may be unpreferable in terms of cost or an environment. Furthermore, it may be difficult to apply uniformly, or the printed layer may become brittle and easily peel off.

[Base material]
The base material in the shrink label of the present invention serves as a carrier (support) for the printing layer, and plays a role of label strength, rigidity, and shrinkage characteristics. 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. 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, polyethylene terephthalate (PET) resin, poly (ethylene-2,6-naphthalenedicarboxylate) (PEN), polylactic acid (PLA), and the like can be used. PET) resin. 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.

  Examples of the polystyrene resin include styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, p-ethyl styrene, p-isobutyl styrene, pt-butyl styrene, chloromethyl styrene as constituent monomers. Examples thereof include resins containing one or more styrene monomers. 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.

  Examples of the polyolefin resin include polyethylene resins such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and metallocene catalyst LLDPE (mLLDPE), polypropylene such as polypropylene and propylene-α-olefin copolymer. Resin, ethylene vinyl acetate copolymer, cyclic olefin resin and the like. 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 may have a single layer configuration or a stacked 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 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. 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, for example, about 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 75%. Preferably, it is 20 to 70%, more preferably 30 to 70%. 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 (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 2.0%. Is less than. 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.

  Commercially available products may be used as the shrink film. For example, “Space Clean S7042” manufactured by Toyobo Co., Ltd., “LX-10S”, “LX-61S” manufactured by Mitsubishi Plastics, Inc. ); CI Kasei Co., Ltd. “Bonset”, Gunze Co., Ltd. “GMLS” (polystyrene film); Gunze Co., Ltd. “FL” (polyolefin film); Mitsubishi Plastics Co., Ltd. “Ecology” (Polylactic acid-based film); Mitsubishi resin "DL", Gunze "HGS" (a laminated film having a surface layer of polyester resin and a center layer of polystyrene resin).

  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.

[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 does not necessarily have to be provided on the entire surface of the label, and can be provided only on a part of the base material on which a metallic luster is desired. Moreover, the above-mentioned printing layer of the present invention may be provided on the substrate via an anchor coat layer as necessary.

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. Examples of the other print layers include design print layers (color print layers, etc.) such as drawings and designs, protective print layers (transparent medium protective print layers and white protective prints) that provide wear resistance and / or slipperiness. Layer, etc.). Although the said design printing layer is not specifically limited, It is preferable to be provided in the front side (front side of a label) rather than the printing layer of this invention. Moreover, although the said protective printing layer is not specifically limited, It is preferable to be provided so that the printing layer of this invention provided on the base material may be covered.
Note that the shrink label provided so that the protective print layer covers the print layer of the present invention generally tends to cause a decrease in metallic luster and a color change particularly during shrink processing. Even in the case of such a laminated structure, the printed layer is preferable because it can suppress a decrease in metallic luster and a change in color during shrink processing.

Although the lamination 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),
A two-layer structure comprising a substrate / printed layer of the present invention;
Base material (transparent film) / anchor coat layer (transparent) / printed layer of the present invention,
Base material (transparent film) / anchor coat layer (transparent) / printing layer of the present invention / protective printing layer (transparent medium or white),
Substrate (transparent film) / design printing layer (color printing layer) / printing layer of the present invention,
Base material (transparent film) / design printing layer (color printing layer) / printing layer of the present invention / protective printing layer (transparent medium or white),
Base material (transparent film) / printing layer of the present invention / protective printing layer (transparent medium or white),
Protective printing layer (transparent medium) / printing layer of the present invention / substrate (transparent film or opaque film),
Examples of the multilayer laminated structure include a protective printing layer (transparent medium) / design printing layer (color printing layer) / printing layer of the present invention / base material (transparent film or opaque film).

  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 75%). ), Preferably 20 to 70%, more preferably 30 to 70%. 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. Even when the printing layer of the present invention is highly shrunk in shrink processing (for example, when shrunk by 30% or more), it can maintain color and excellent metallic luster. For this reason, in the case of a highly shrinkable shrink label, the effect of the present invention is particularly remarkable, which is preferable. 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.

  The mirror glossiness of the printed layer portion of the present invention on the front side of the shrink label [before shrink processing (before heat shrinking) of the present invention is preferably 220 or more, more preferably 230 or more. If the specular gloss is less than 220, the printed layer has insufficient metallic luster (luminance). The upper limit of the specular gloss is not particularly limited, but is preferably 600 or less.

  The mirror gloss of the printed layer portion of the present invention on the front side of the shrink label of the present invention [after shrink processing (after heat shrinkage, for example, after 30% heat shrinkage in the main orientation direction)] is preferably 165 or more, More preferably, it is 175 or more. When the specular gloss is less than 165, the metallic luster (luminance) of the printed layer after shrink processing becomes insufficient. The upper limit of the specular gloss is not particularly limited, but is preferably 600 or less.

  The specular glossiness can be measured under conditions of 60 ° (incident angle) / 60 ° (reflection angle) in accordance with JIS K 5600-4-7. As a measuring instrument, for example, a gloss meter “micro-TRI-gloss” manufactured by BYK-Gardner, a gloss meter “UGV-5” manufactured by Suga Test Instruments Co., Ltd. can be used. . The specular gloss can be measured by measuring the printed layer portion of the present invention from the front side of the label. For example, when there is a print layer on the front side, the exposed print layer surface of the present invention may be measured as a measurement surface. Further, when there is a printing layer on the front side and a transparent printing layer (for example, a transparent medium protective printing layer) is provided on the printing layer of the present invention, the label surface on the transparent printing layer side is measured. It may be measured as a surface. Further, when a printed layer is provided on the back side and the printed layer is viewed from the front side through the substrate, the label surface on the substrate side may be measured as the measurement surface.

  The L value (brightness, based on HUNTER Lab) of the shrink label [before shrink processing (before heat shrink)] of the present invention is preferably 31.5 or less, more preferably 30.5 or less. When the L value exceeds 31.5, the whiteness of the printed layer becomes strong and the expression of metallic tone becomes weak. The lower limit of the L value is not particularly limited, but is preferably 20.0 or more from the viewpoint of preventing the darkness from becoming strong and the metallic tone from becoming weak.

  The L value (in accordance with HUNTER Lab) of the shrink label [after shrink processing (after heat shrinkage, for example, after heat shrinkage in the main orientation direction)] of the present invention is preferably 39.0 or less, more Preferably it is 37.5 or less. When the L value exceeds 39.0, the printed layer is whitened (changes in color) due to the shrink processing, and the metallic luster (luminance) after the shrink processing is insufficient. The lower limit of the L value is not particularly limited, but is preferably 20.0 or more from the viewpoint of preventing the darkness from becoming strong and the metallic tone from becoming weak.

  As the measuring device for the L value, for example, a color difference meter “X-Rite 938” or “X-Rite 939” manufactured by Nippon Flat Plate Equipment Co., Ltd. can be used. The L value can be measured by measuring the printed layer portion of the present invention from the front side of the label, similarly to the above-described specular gloss.

The shrink label of the present invention uses a non-leafing type aluminum pigment and a vapor-deposited aluminum pigment in combination as a pigment for developing a metallic luster in the printed layer.
The vapor-deposited aluminum pigment has a small thickness, is easily oriented (arranged) in parallel with the surface of the printing layer, and can exhibit excellent gloss (high specular gloss) even at a relatively low content. However, since the vapor-deposited aluminum pigment is thin, when shrinking (especially shrinking with high shrinkage or shrinking with hot air with severe processing conditions because heat is not easily applied and local shrinkage is likely to occur) In addition, due to shrinkage deformation of the printed layer during shrink processing, the pigment is likely to be bent and the orientation is easily disturbed. For this reason, there has been a problem that irregular reflection increases and whitening occurs to change the color of the printed layer, and a problem that the glossiness of the mirror is lowered and the metallic luster is greatly lost (luminance feeling is lowered).
On the other hand, in this invention, the non-leafing type aluminum pigment which exhibits the effect which strengthens the metallic tone of a printing layer especially with the vapor deposition aluminum pigment from which the outstanding glossiness is obtained is used together by specific ratio. When the vapor-deposited aluminum pigment and the non-leafing type aluminum pigment are used in combination, even if the content of the vapor-deposited aluminum pigment in the printed layer is very small, the printed layer exhibits a good metallic tone and has an excellent metallic luster. In addition, since the vapor-deposited aluminum pigment is such a small amount, deformation and orientation disorder are less likely to occur during shrink processing. Furthermore, since the non-leafing type aluminum pigment has a relatively thick pigment and a relatively large pigment, there is little deformation or disorder in the shrink processing. As a result, the printed layer of the present invention has excellent metallic luster, and even when subjected to shrink processing, the color change due to whitening and the decrease in specular gloss are small, and the color and excellent metallic luster are maintained. It became possible.

  In the present invention, the base resin of the printing layer is made of a relatively flexible urethane resin, so that the stress applied to the aluminum pigment due to shrinkage deformation during shrink processing is reduced, and deformation and orientation disturbance are reduced. This further suppresses changes in color and a decrease in specular gloss due to whitening during shrink processing. This effect can be further improved by adding a plasticizer to the printed layer of the present invention to make the printed layer more flexible.

  The shrink label of the present invention is not particularly limited, such as a cylindrical label, a wound label, etc., but from the viewpoint of exhibiting the features of the present invention that can maintain the color and excellent metallic luster even if the shrinkage deformation amount in shrink processing is large. A cylindrical shrink label (cylindrical shrink label) 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 includes the urethane resin, non-leafing aluminum pigment, vapor-deposited aluminum pigment, solvent, and, if necessary, a plasticizer, a cellulose resin, It is manufactured by mixing other pigments and other additives. Mixing can be performed by a known and common mixing method, and is not particularly limited. For example, a mixer such as a paint shaker, butterfly mixer, planetary mixer, pony mixer, dissolver, tank mixer, homomixer, homodisper, or roll mill , 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 each component such as urethane-based resin, non-leafing type aluminum pigment, vapor-deposited aluminum pigment in the printing layer of the present invention, the content of each component in the non-volatile content of the printing ink is The printing ink may be prepared so as to have a desired content in the printing 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 print layer of the shrink film. That is, the total content (nonvolatile content) of the non-leafing aluminum pigment and the vapor deposited aluminum pigment in the total nonvolatile content (100 wt%) of the printing ink is 15 to 90 wt% (preferably 20 to 85 wt%, more preferably 30 to 80% by weight), [(content of non-leafing aluminum pigment) / (content of vapor-deposited aluminum pigment)] (weight ratio of non-volatile content) is 5 to 50 (preferably 10 to 40) A printing ink may be prepared.

  As said solvent, the organic solvent (organic solvent) 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 Alcohols such as isopropyl alcohol, 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; cyclohexane and methylcyclohexane Alicyclic hydrocarbons; glycols such as ethylene glycol and propylene glycol; glycol ethers such as propylene glycol monomethyl ether and propylene glycol monobutyl ether; propylene glycol monomethyl Such as glycol ether esters such as ether acetate can be exemplified. Among these, acetates and alcohols are preferable from the viewpoints of solubility and safety. An organic solvent can be used individually or in mixture of 2 or more types. The organic 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 of urethane resin, the blending amount (content) of each component, the thickener, the thickener, and the like. In particular, the printing ink in the present invention tends to have a low viscosity. In this case, since it becomes easy to control a viscosity to an appropriate range by adding a cellulose resin so that it may become above-mentioned content, it is preferable. In the present specification, “viscosity” is JIS Z unless otherwise specified, using an E-type viscometer (conical plate-type rotational viscometer) under the conditions of 23 ± 2 ° C. and cylinder rotation speed of 50 rotations. The value measured according to 8803 is meant.

  Next, the printing ink (the printing layer of the present invention) is provided by applying and drying the printing ink on the surface of the base material (shrink film) to produce the shrink label of the present invention. 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 printing layers other than the printing layer of this invention as needed.

  As a method for applying the printing ink, a gravure printing method, a flexographic printing method, and a letterpress printing method are preferable from the viewpoints of cost, productivity, printing decoration, and the like, and a gravure printing method 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 hot air at 100 to 200 ° C., treatment with steam at 80 to 100 ° C. (passing through a heating tunnel filled with steam and steam), and the like. 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 total content of non-leafing type aluminum pigment and vapor-deposited aluminum pigment in the printing layer (silver printing layer), urethane type The evaluation results of the content of resin, plasticizer and cellulose resin, [(content of non-leafing aluminum pigment) / (content of vapor-deposited aluminum pigment)] and the obtained shrink label were 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 content of each component in the printing layer (equal to the content of each component in the non-volatile content of the printing ink) is indicated by the content (content in terms of non-volatile content) (wt%) as each component. It was.
Table 2 shows details of each component (resin, pigment, etc.) used in the printing ink.

Example 1
(Printing ink)
As a vapor-deposited aluminum pigment, a mixed solvent of a vapor-deposited aluminum pigment (mixed solvent of ethyl acetate and isopropyl acetate) dispersion (manufactured by Ciba Japan Co., Ltd., trade name “Metacene 71-0010”, nonvolatile content: 10 wt%) 6 wt. Parts (0.6 parts by weight as a vapor deposition aluminum pigment) were used.
18 parts by weight of non-leafing type aluminum pigment paste produced by a wet ball mill method (trade name “6320NS”, average particle size 14 μm, nonvolatile content: 70% by weight) manufactured by a wet ball mill method as a non-leafing type aluminum pigment (12.6 parts by weight as a non-leafing aluminum pigment) was used.
As binder resin (base resin), 6.5 parts by weight of urethane resin in ethyl acetate solution (product name “FS-8809”, nonvolatile content: 37% by weight, manufactured by Nippon Kako Paint Co., Ltd.) (as urethane resin, 2.4 parts by weight) was used.
As a plasticizer, 2 parts by weight of tributyl acetylcitrate (manufactured by Asahi Kasei Finechem Co., Ltd., trade name “ATBC”) was used.
As the cellulose resin, 1.5 parts by weight of CAB resin (manufactured by Eastman Chemical Co., Ltd., trade name “CAB-381-20”) was used.
Furthermore, 33 parts by weight of ethyl acetate and 33 parts by weight of n-propyl acetate were added to prepare a printing ink (100 parts by weight).
The total content of vapor-deposited aluminum pigment and non-leafing type aluminum pigment in the total nonvolatile content (100% by weight) of the printing ink is 69.1% by weight, [(content of non-leafing type aluminum pigment) / (vapor deposited aluminum Pigment content)] (weight ratio) was 21. Moreover, in the total non-volatile content (100% by weight) of the printing ink, the content of urethane resin is 12.6% by weight, the content of plasticizer (ATBC) is 10.5% by weight, the content of cellulose resin Was 7.8% by weight. In addition, content of each component in the non volatile matter of said printing ink is equal to content of each component in the printing layer of a shrink label.

(Shrink label)
Polyester (PET) shrink film (trade name “S7042”, manufactured by Toyobo Co., Ltd., thickness: 45 μm, main orientation direction (width direction) thermal shrinkage (90 ° C., 10 seconds): 60%) on one side using a table-top gravure printing machine (manufactured by Nissho Gravure Co., Ltd., trade name “GRAVO PROOF MINI”) and a gravure plate (engraving 70 lines, angle 0) Dried to form a silver print layer.
Next, gravure ink for back printing (manufactured by DIC Corporation, trade name “GR backing varnish”) is applied on the printing layer (silver printing layer) formed above, and the same desktop gravure printing machine and gravure plate as above are used. It was used and applied and dried by full gravure printing to form a protective printing layer (transparent medium).
As described above, a shrink label having a laminated structure of shrink film (layer thickness 45 μm) / silver print layer (layer thickness 1 μm) / protective print layer (layer thickness 1 μm) was obtained from the front side.

Examples 2 to 4, 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 types and blending amounts of the non-leafing aluminum pigment and the vapor deposition aluminum pigment were changed.
In Comparative Example 3, a non-leafing aluminum pigment having an average particle size exceeding 20 μm was used.

Example 5
As shown in Table 1, printing inks and shrink labels were produced in the same manner as in Example 1 except that the blending amounts of urethane resin and plasticizer were changed.

Example 6
As shown in Table 1, printing inks and shrink labels were prepared in the same manner as in Example 1 by using two types of non-leafing aluminum pigments and further changing the blending amount of urethane resin and plasticizer. .

Comparative Examples 1 and 4
As shown in Table 1, printing inks and shrink labels were produced in the same manner as in Example 1, except that the non-leafing aluminum pigment was not used and the blending amount of the vapor deposition aluminum pigment was changed.
In Comparative Example 4, a leafing type aluminum pigment was used instead of a non-leafing type aluminum pigment.

Comparative Example 2
As shown in Table 1, printing inks and shrink labels were produced in the same manner as in Example 1, except that the vapor-deposited aluminum pigment was not used and the blending amount of the non-leafing aluminum pigment was changed.

Comparative Example 5
As shown in Table 1, printing inks and shrink labels were prepared in the same manner as in Example 1 using acrylic resins instead of urethane resins.

(Evaluation)
Specular glossiness (before heat shrinkage, after heat shrinkage), L value (before heat shrinkage, after heat shrinkage), heat shrinkage rate in main orientation direction (90 ° C., 10 ° C.) of shrink labels obtained in Examples and Comparative Examples Second) was evaluated by the following method. In addition, in an Example and a comparative example, the main orientation direction of a shrink label is a main orientation direction of the shrink film which is a base material.

(1) Specular gloss (before heat shrink)
The shrink labels obtained in the examples and comparative examples were used as measurement samples.
By using a gloss meter “micro-TRI-gloss” manufactured by BYK-Gardner, in accordance with JIS K 5600-4-7, the above-mentioned conditions under the conditions of an incident angle of 60 ° / reflection angle of 60 ° The specular gloss (before heat shrinkage) of the printed layer portion of the measurement sample was measured. The surface on the shrink film side was measured as a measurement surface.
The specular gloss was evaluated according to the following criteria.
Specular gloss is 230 or more: Good (○)
Specular gloss is 220 or more and less than 230: Usable (△)
Specular gloss is less than 220: Poor (x)

(2) Specular gloss (after heat shrink)
From the shrink labels obtained in Examples and Comparative Examples, a label piece having a size of 10 cm (longitudinal direction; perpendicular direction to the main orientation direction) × 15 cm (width direction; main orientation direction) was cut out. The label piece was fixed to a jig capable of fixing a portion having a length of 100 mm in the main orientation direction (width direction) of the label piece at an interval of 70 mm. It is in a state of sagging before the heat shrink treatment). The label piece fixed to the jig was heat-treated by blowing hot air at 150 ° C. using a jetter, and the label piece was heat-shrinked to a length of 70% compared to before the heat-shrinking treatment. (30% thermal shrinkage in the main orientation direction (width direction)). In this way, a measurement sample was obtained that was heat shrunk by 30% in the main orientation direction (width direction).
By using a gloss meter “micro-TRI-gloss” manufactured by BYK-Gardner, in accordance with JIS K 5600-4-7, the above-mentioned conditions under the conditions of an incident angle of 60 ° / reflection angle of 60 ° The specular gloss (after heat shrinkage) of the printed layer portion of the measurement sample was measured. The surface on the shrink film side was measured as a measurement surface.
The specular gloss was evaluated according to the following criteria.
Specular gloss is 175 or more: Good (○)
Specular gloss is 165 or more and less than 175: Usable (△)
Specular gloss is less than 165: Poor (x)

(3) L value (lightness) (before heat shrink)
The shrink labels obtained in the examples and comparative examples were used as measurement samples.
Using a color difference meter “X-Rite 938” manufactured by Nippon Flat Plate Equipment Co., Ltd., the L value (before heat shrinkage) was measured from the shrink film side of the measurement sample according to HUNTER Lab.
The L value was evaluated according to the following criteria.
L value is 30.5 or less: Good (◯)
L value exceeds 30.5 and is 31.5 or less: Usable (△)
L value exceeds 31.5: Defect (x)

(4) L value (lightness) (after heat shrinkage)
In the same manner as in the evaluation of (2) above, a measurement sample that was heat-shrinked by 30% in the main orientation direction (width direction) was obtained.
Using a color difference meter “X-Rite 938” manufactured by Nippon Flat Plate Equipment Co., Ltd., the L value (after heat shrinkage) was measured from the shrink film side of the measurement sample according to HUNTER Lab.
The L value was evaluated according to the following criteria.
L value is 37.5 or less: Good (◯)
L value exceeds 37.5 and is 39.0 or less: Usable (△)
L value exceeds 39.0: Bad (x)

(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 label (Example) of the present invention has a relatively low L value, a high specular gloss, and an excellent metallic luster. In addition, even after a high shrinkage (30%) shrink (shrinkage) process, the specular gloss is hardly lowered, and an excellent metallic luster can be maintained. Furthermore, even after shrink processing, the L value does not become too high, whitening (change in color) is suppressed, and color is maintained.
On the other hand, the shrink label (Comparative Example 1) using only the deposited aluminum pigment as the aluminum pigment is used as a shrink label having a laminated structure in which the aluminum pigment is easily deformed at the time of shrink processing having a protective printing layer, and when shrink processing is performed with hot air , Whitening occurred and the color changed. The shrink label (Comparative Example 2) that did not use the vapor-deposited aluminum pigment and the shrink label (Comparative Example 3) that used the non-leafing aluminum pigment having a large average particle diameter could not exhibit excellent metallic luster. The shrink label using the leafing type aluminum pigment (Comparative Example 4) had a high L value and was whitish and inferior in metallic tone. The shrink label (Comparative Example 5) using an acrylic resin as the base resin of the printed layer could not exhibit an excellent metallic luster. Moreover, whitening occurred by shrink processing and the color changed.
In addition, the thermal contraction rate (90 degreeC, 10 second) of the main orientation direction of the shrink label obtained by the Example and the comparative example was 60%.

Claims (2)

At least one side of the substrate has a printed layer containing a urethane resin, a non-leafing aluminum pigment and an aluminum pigment produced by a vapor deposition method, and satisfying all the following conditions (1) to (3) Shrink label characterized by
(1) The total content of the non-leafing aluminum pigment and the aluminum pigment produced by the vapor deposition method in the printing layer is 15 to 90% by weight (2) produced by the vapor deposition method in the printing layer Ratio of content of non-leafing aluminum pigment to content of aluminum pigment [(content of non-leafing aluminum pigment) / (content of aluminum pigment produced by vapor deposition)] (weight ratio) is 5 to 5 (3) The average particle size of the non-leafing aluminum pigment in the printing layer is 6 to 20 μm.   The shrink label according to claim 1, wherein the print layer is a print layer containing a plasticizer, and the content of the plasticizer in the print layer is 3 to 45% by weight.