JP5049150B2 - Shrink film and shrink label - Google Patents

Description

  The present invention relates to a heterogeneous laminated shrink film that does not delaminate. Moreover, it is related with the shrink label which provided the printing layer in this shrink film.

  Currently, plastic bottles such as PET bottles (polyethylene terephthalate 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. In recent years, water vapor and hot air have been used because of their good trackability and increased display area. A heat-shrinkable plastic film (shrink film) that is made to follow and attach to a container by being shrunk by is widely used.

  In the field of shrink film, in order to achieve various properties such as rigidity, high shrinkage, shrink workability, beautiful finish, low density, etc., the film has printability, heat resistance, wear resistance and chemical resistance. For the purpose of imparting functions such as these, different types of laminated films in which different resin materials are laminated are widely used. For example, a shrink film in which a polyester resin and a polystyrene resin are laminated is known (see, for example, Patent Document 1).

  However, the laminated film composed of the above-mentioned polystyrene resin layer, polyester resin layer and adhesive layer exhibits sufficient sealing strength in the center sealing process, but when it is attached to the bottle by shrink processing (shrink processing), There has been a problem that the seal portion is delaminated. That is, in the present invention, a shrink film having a practically sufficient interlayer strength (adhesive strength between film layers) has not been obtained for different types of shrink films.

JP 2006-15745 A

  An object of the present invention is to provide a shrink film that does not delaminate in a laminated shrink film of different polymers of a polystyrene resin and a polyester resin. Another object of the present invention is to provide a shrink label using the shrink film.

  As a result of intensive studies to achieve the above object, the present inventors have found that a surface layer (A layer) containing an amorphous aromatic polyester resin and a plasticizer in a specific blending amount, and a styrene-conjugated diene copolymer. By making the center layer (B layer) whose main component is a polymer and / or its hydrogenated product into a shrink film having a laminated structure of at least three layers laminated in the order of A layer / B layer / A layer, The present inventors have found that a heterogeneous laminated film having excellent interlayer strength can be obtained, and the present invention has been completed.

  That is, the present invention is composed of a resin composition containing an amorphous aromatic polyester resin as a main component and 0.5 to 20 parts by weight of a plasticizer with respect to 100 parts by weight of an amorphous aromatic polyester resin. And a central layer (B layer) composed of a resin composition mainly composed of a styrene-conjugated diene copolymer and / or a hydrogenated product thereof is an A layer / B layer. A shrink film having at least a three-layer laminated structure in the order of / A layers is provided.

  Furthermore, the present invention provides the above shrink film having an adhesive resin layer (C layer) and having at least a five-layer laminated structure in which A layer / C layer / B layer / C layer / A layer are laminated in this order. To do.

  Furthermore, the present invention provides the shrink film, wherein the plasticizer is at least one selected from phthalic acid esters, adipic acid esters, and polyester plasticizers.

  Furthermore, this invention provides the said shrink film in which the said C layer is comprised from the styrene resin which has a polar group.

  Furthermore, this invention provides the shrink label which provided the printing layer in the at least one surface side of the said shrink film.

  The shrink film of the present invention reduces the shrinkage stress of the polyester-based resin layer, which is the surface layer, and reduces the difference in shrinkage stress from the center layer, so that troubles due to delamination do not occur even after shrink processing. For this reason, it is useful as a shrink label attached to a container such as a PET bottle.

  Below, the shrink film of this invention is demonstrated in detail.

  The shrink film of the present invention is a surface layer (hereinafter referred to as “A layer”) composed of a resin composition containing an amorphous aromatic polyester resin as a main component and further containing a plasticizer, styrene-conjugated. It has at least a central layer (hereinafter referred to as “B layer”) composed of a resin composition mainly composed of a diene copolymer and / or a hydrogenated product thereof. Furthermore, an adhesive resin layer (hereinafter referred to as “C layer”) may be included. The term “main component” as used in the present invention means that the content in each resin composition is 50% by weight or more based on the total weight of the resin composition unless otherwise specified. More preferably, it means 60% by weight or more.

  The shrink film of the present invention has at least a two-layer / three-layer structure in which the A and B layers are laminated in the order of A layer (surface layer) / B layer (center layer) / A layer (surface layer). ing. In addition, the A layer and the B layer may be laminated without interposing other layers, or may be laminated via a C layer (adhesive resin layer) or other layers. When the shrink film of this invention contains C layer, it is preferable that it is a 3 type | mold 5 layer laminated structure laminated | stacked in order of A layer / C layer / B layer / C layer / A layer. The A layer and the C layer provided on both sides of the B layer may be layers having the same resin composition, or layers having different compositions (for example, A1 layer and A2 layer). . If the shrink film of this invention is a layer which can be further provided in-line in the film forming process of the said laminated | multilayer film, you may have layers other than said AC layer. Examples of such a layer include coating layers such as an anchor coat layer, an easy adhesion layer, and an antistatic agent layer.

[Surface layer (A layer)]
The surface layer (A layer) in the shrink film of the present invention is a resin composition (hereinafter, referred to as “resin composition A”) containing an amorphous aromatic polyester resin as a main component and further containing at least a plasticizer. Are).

  The amorphous aromatic polyester-based resin (hereinafter, sometimes simply referred to as “amorphous polyester-based resin”) is not particularly limited as long as it is substantially amorphous. For example, a dicarboxylic acid component And various polyesters composed of diol components. In addition, since it is an aromatic polyester-based resin, 50 mol% or more (preferably 70 mol% or more) in the total dicarboxylic acid component is 50 mol% or more (preferably in the total diol component). 70 mol% or more) must be an aromatic diol.

  Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 5-t-butylisophthalic acid, 4,4′-biphenyldicarboxylic acid, trans-3,3′-stilbene dicarboxylic acid, and trans-4,4. '-Stilbene dicarboxylic acid, 4,4'-dibenzyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 2,2,6,6-tetramethylbiphenyl-4,4′-dicarboxylic acid, 1,1,3-trimethyl-3-phenylindene-4,5-dicarboxylic acid, 1,2- Aromatic dicals such as diphenoxyethane-4,4′-dicarboxylic acid, diphenyl ether dicarboxylic acid, and substituted products thereof Acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, Aliphatic dicarboxylic acids such as heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, icosanedioic acid, docosanedioic acid, 1,12-dodecanedioic acid, and their substitutions; 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and these And alicyclic dicarboxylic acids such as substitution products thereof. These dicarboxylic acid components can be used alone or in combination of two or more.

  Examples of the diol component include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2 -Dimethyl-1,3-propanediol (neopentyl glycol), 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2,4-dimethyl-1,3-hexanediol, 1,10-decanediol, polyethylene glycol, polypropylene Aliphatic diols such as glycol; 1,2-cyclohexanedimethanol, 1,3-cyclohexane Cycloaliphatic diols such as sandimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol; 2,2-bis (4′-β-hydroxyethoxydiphenyl) Examples thereof include ethylene oxide adducts of bisphenol compounds such as propane and bis (4′-β-hydroxyethoxyphenyl) sulfone, and aromatic diols such as xylylene glycol. These diol components can be used alone or in combination of two or more.

  In addition to the above, the amorphous polyester-based resin may include oxycarboxylic acids such as p-oxybenzoic acid and p-oxyethoxybenzoic acid; monocarboxylic acids such as benzoic acid and benzoylbenzoic acid; A structural unit such as a monovalent alcohol such as a polyvalent carboxylic acid; a monohydric alcohol such as polyalkylene glycol monomethyl ether; a polyhydric alcohol such as glycerin, pentaerythritol, or trimethylolpropane may be included.

  As an amorphous polyester resin, among the above, in polyethylene terephthalate (PET) using terephthalic acid as the dicarboxylic acid component and ethylene glycol (EG) as the diol component, a part of the dicarboxylic acid component and / or diol component is used. Preferred examples include modified PET substituted with other dicarboxylic acid components and / or diol components. Examples of the dicarboxylic acid component used in the modified PET include cyclohexane dicarboxylic acid, adipic acid, and isophthalic acid. Examples of the diol component include 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), and diethylene glycol.

  Specifically, as the modified PET, terephthalic acid is used as the dicarboxylic acid component, EG as the diol component, and copolyester using CHDM as the copolymer component (hereinafter referred to as CHDM copolymerized PET or CHDM modified PET). And copolyesters using neopentyl glycol (NPG) as a copolymerization component (hereinafter referred to as NPG copolymerized PET or NPG-modified PET) are preferred from the viewpoints of cost, productivity, and the like. Furthermore, diethylene glycol may be copolymerized from the viewpoint of improving low-temperature shrinkage.

  In the modified PET, the copolymerization ratio of the copolymerization component used for modification (the ratio of the copolymerized dicarboxylic acid component to the total dicarboxylic acid component or the ratio of the copolymerized diolic acid component to the total diolic acid component) further increases the interlayer strength. From the viewpoint of improvement, 15 mol% or more (for example, 15 to 40 mol%) is preferable. Among them, for example, in the case of CHDM copolymerized PET, the proportion of CHDM copolymerization is 20 to 40 mol% (EG is 60 to 80 mol%) in the diol component (that is, with respect to 100 mol% of terephthalic acid). More preferably, it is 25-35 mol% (EG is 65-75 mol%). Moreover, in the case of NPG copolymerized PET, 15-40 mol% (EG is 60-85 mol%) in a diol component is preferable. Further, a part (preferably 10 mol% or less) of the EG component may be replaced with diethylene glycol.

  As described above, by modifying the polyester to be amorphous, the flow behavior at the melting temperature of the A layer and the B layer or the C layer can be made closer, so that the moldability and interlayer strength of the layer are improved.

  The degree of crystallinity of the amorphous polyester resin measured by the differential scanning calorimetry (DSC) method (measured at a heating rate of 10 ° C./min) is preferably 15% or less, more preferably 10% or less. is there. Further, the one that hardly shows the melting point (melting peak) by the DSC method (that is, the degree of crystallinity is 0%) is most preferable. The crystallinity can be calculated from the value of heat of crystal fusion obtained by DSC measurement using a sample with a clear crystallinity fixed by the X-ray method or the like as a standard. The heat of crystal melting is, for example, using a DSC (differential scanning calorimetry) device manufactured by Seiko Instruments Inc., performing a nitrogen seal at a sample amount of 10 mg and a heating rate of 10 ° C./min. The temperature can be determined from the area of the melting peak when the temperature is lowered to room temperature and then raised again. The crystallinity is preferably measured from a single resin, but when measured in a mixed state, the melting peak of the target polyester resin can be obtained by subtracting the melting peak of the resin to be mixed. That's fine.

  The weight average molecular weight of the amorphous polyester resin is preferably 50000 to 90000, more preferably 60000 to 80000, from the viewpoint of controlling the melting behavior within a preferable range. Furthermore, in the case of NPG copolymerized PET, it is preferably 50000 to 80000, more preferably 60000 to 70000.

  The IV value (intrinsic viscosity) of the amorphous polyester resin is preferably 0.70 (dl / g) or more, more preferably 0.7 to 0.9 (dl / g), from the viewpoint of interlayer strength. More preferably, it is 0.75-0.85 (dl / g). In addition, the glass transition temperature (Tg) of the amorphous polyester resin is preferably 70 to 100 ° C, more preferably 70 to 85 ° C, from the viewpoint of shrinkage suitability.

  As the amorphous polyester-based resin, existing products can be used. For example, “Easter Polymer”, “EMBRACE” (above, CHDM copolymerized PET) manufactured by Eastman Chemical; Bell Polyester Products Co., Ltd. “Bellepet” (NPG copolymerized PET, etc.) manufactured by the Company is available on the market.

  The content of the amorphous polyester resin relative to the total weight of the resin composition (resin composition A) constituting the A layer of the present invention is 50 to 99.5% by weight from the viewpoint of shrinkage and printability. Preferably, it is 80 to 99.5% by weight.

  As the plasticizer, those usually used for polyester resins can be used, and are not particularly limited. Examples thereof include phthalic acid esters, acetylated monoglycerides, adipic acid esters, and polyester plasticizers. Among these, from the viewpoints of flexibility and compatibility, phthalic acid esters and adipic acid esters are preferable. Examples of the phthalic acid ester include dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and dibutyl phthalate (DBP). Examples of adipic acid esters include dioctyl adipate (DOA) and diisononyl adipate (DINA). Examples of the polyester plasticizer include polyester composed of an adipic acid component and an aliphatic diol component.

  The aromatic polyester resin used for the A layer generally has a larger shrinkage stress than the polystyrene resin such as the styrene-conjugated diene copolymer forming the B layer or the C layer, and shrinkage is caused thereby. During processing, a difference in shrinkage stress occurs between the A layer and the B layer or the C layer, and the interlayer strength tends to decrease. By adding the plasticizer to the A layer, flexibility can be imparted to the resin forming the A layer and the shrinkage stress can be reduced, so that the interlayer strength is improved.

  The content of the plasticizer in the A layer is 0.5 to 20 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the amorphous aromatic polyester resin used in the A layer. More preferably, it is 12-18 weight part. When the content is less than 0.5 parts by weight, the effect of improving the interlayer strength is small, and when it exceeds 20 parts by weight, the plasticizer bleeds to the film surface, leading to blocking and printability deterioration.

  For layer A, if necessary, other additives such as lubricants, fillers, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, colorants, pinning agents (alkaline earth metals) ) And the like.

[Center layer (B layer)]
The central layer (B layer) in the shrink film of the present invention may be referred to as a resin composition (hereinafter referred to as “resin composition B”) containing a styrene-conjugated diene copolymer and / or a hydrogenated product thereof as a main component. ).

  The styrene-conjugated diene copolymer is a copolymer composed of a styrene monomer and a conjugated diene as essential monomer components.

  Although it does not specifically limit as said styrene-type monomer, For example, styrene, alpha-methyl styrene, m-methyl styrene, p-methyl styrene, p-ethyl styrene, p-isobutyl styrene, pt-butyl styrene, Examples include chloromethylstyrene. Among these, styrene is particularly preferable from the viewpoint of physical properties such as strength and moldability. In addition, these styrenic monomers may be used independently and may use 2 or more types together.

  The conjugated diene is not particularly limited. For example, 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, Examples include 1,3-hexadiene and chloroprene. Among these, 1,3-butadiene and isoprene are particularly preferable from the viewpoints of improving brittleness and imparting flexibility. In addition, these conjugated dienes may be used independently and may use 2 or more types together.

  In the styrene-conjugated diene copolymer, the content of the styrene monomer is preferably 60 to 95% by weight, more preferably 70 to 85% by weight, based on the total weight of the monomer components. . On the other hand, the content of the conjugated diene is preferably 5 to 40% by weight or more, more preferably 15 to 30% by weight, based on the total weight of the monomer components. When the content of the styrenic monomer is less than 60% by weight (or when the content of the conjugated diene exceeds 40% by weight), the film may lose its elasticity or natural shrinkage may increase. When the content of the conjugated diene is less than 5% by weight (or when the content of the styrene monomer exceeds 95% by weight), it may become brittle or the elongation may be lowered.

  The styrene-conjugated diene copolymer may contain monomer components other than the styrene monomer and conjugated diene as long as the effects of the present invention are not impaired. Examples of such monomer components include vinyl monomers and polymerizable unsaturated carboxylic acid ester copolymers.

  The B layer in the shrink film of the present invention contains a hydrogenated product obtained by hydrogenating the styrene-conjugated diene copolymer together with the styrene-conjugated diene copolymer or in place of the styrene-conjugated diene copolymer. It may be used.

  The form of copolymerization of the styrene-conjugated diene copolymer is not particularly limited, such as a random copolymer, a block copolymer, and an alternating copolymer, but a block copolymer is preferable, and a styrene block (S)- Examples include conjugated diene block (D) type, SDS type, DSD type, SSD type, and the like. Further, it may be a hydrogenated product of the copolymer.

  Specific examples of the styrene-conjugated diene copolymer or the hydrogenated product thereof include, for example, a styrene-butadiene block copolymer (SBS), a styrene-isoprene block copolymer (SIS), and a styrene-butadiene-isoprene. Examples thereof include a block copolymer (SBIS), a styrene-ethylene / butadiene block copolymer (SEBS), and a styrene-ethylene / propylene copolymer (SEPS). Of these, SBS and SBIS are most preferable.

  The melt flow rate (MFR) (JIS K 7210: temperature 200 ° C./load 49 N) of the styrene-conjugated diene copolymer or its hydrogenated product is preferably 1 to 20 g / 10 minutes, more preferably 3 to 10 g / 10 minutes.

  As the styrene-conjugated diene copolymer or hydrogenated product thereof, commercially available products may be used. For example, “Asaflex”, “Tuftec” manufactured by Asahi Kasei Co., Ltd .; “Clearene” manufactured by Denki Kagaku Kogyo Co., Ltd. ; “Kuraray Co., Ltd.” “Septon” and the like.

  The content of the styrene-conjugated diene copolymer and / or hydrogenated product thereof with respect to the total weight of the resin composition (resin composition B) constituting the B layer of the present invention is preferably 50% by weight or more, Is 70 to 100% by weight. In addition, when using 2 or more types of styrene-conjugated diene copolymers and / or its hydrogenated material, those total amounts should just satisfy said relationship.

  The resin composition B may contain a tackifier (tackifier) such as petroleum resin in order to improve the high shrinkage, the strength of the waist and the prevention of natural shrinkage. Examples of the tackifier include rosin resins (rosin, polymerized rosin, hydrogenated rosin and derivatives thereof, resin acid dimers, etc.), terpene resins (terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, Terpene-phenol resins, etc.), petroleum resins (aliphatic, aromatic, alicyclic) and the like. Among these, petroleum resin is preferable. A tackifier can be used individually or in combination of 2 or more types. The addition amount in the case of adding a tackifier is preferably 5 to 30% by weight, more preferably 10 to 25% by weight, based on the total weight of the resin composition B. If the amount added exceeds 30% by weight, the shrink film may become brittle. Moreover, if it is less than 5 weight%, the effect of addition may be small.

[Adhesive resin layer (C layer)]
In the shrink label of the present invention, the adhesive resin layer (C layer) used as necessary is preferably composed of a polystyrene-based resin having a polar group.

  The polar group is preferably a functional group that reacts with or interacts with the ester bond portion of the polyester (such as a hydrogen bond), and is not particularly limited. For example, a carboxyl group (including a carboxylic acid anhydride), a hydroxyl group, and an oxazoline Group, isocyanate group, epoxy group and the like. Among these, from the viewpoint of improving the interlayer strength, a dicarboxylic anhydride group (dicarboxylic anhydride modified) and an epoxy group (epoxy modified) are preferable, and a maleic anhydride group (maleic anhydride modified) is particularly preferable. The polar group may be grafted to the main chain of the polystyrene-based polymer, or may be introduced into the polymer main chain by copolymerization. The term “modified” includes both “reactive functional groups introduced by grafting into the polymer main chain” and “introduced by copolymerization”.

  The polystyrene resin constituting the main chain skeleton of the polymer of the polystyrene resin having the polar group is not particularly limited, and general polystyrene (GPPS) which is a homopolymer of styrene, styrene monomer alone or in combination. Examples thereof include a polymer, a styrene-conjugated diene copolymer, a styrene-polymerizable unsaturated carboxylic acid ester copolymer, and a styrene-conjugated diene-polymerizable unsaturated carboxylic acid ester copolymer.

  Among these, a modified product obtained by modifying a styrene-based thermoplastic elastomer composed of styrene-based monomer and conjugated diene as essential monomer components or a hydrogenated product thereof and introducing the above polar group is preferable. Although it does not specifically limit as said styrene-type monomer, For example, styrene, alpha-methyl styrene, m-methyl styrene, p-methyl styrene, p-ethyl styrene, p-isobutyl styrene, pt-butyl styrene, Examples include chloromethylstyrene. Among these, styrene is particularly preferable from the viewpoint of physical properties such as strength and moldability. The conjugated diene is not particularly limited. For example, 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, Examples include 1,3-hexadiene and chloroprene. Among these, 1,3-butadiene and isoprene are particularly preferable from the viewpoint of imparting elasticity and imparting polarity. Furthermore, other copolymer components such as vinyl monomers and polymerizable unsaturated carboxylic acid ester copolymers may be included. In addition, these monomer components, such as a styrene-type monomer and a conjugated diene, may be used independently and may use 2 or more types together. Further, the form of copolymerization of the styrene-based thermoplastic elastomer is not particularly limited, such as a random copolymer, a block copolymer, and an alternating copolymer, but a block copolymer is preferable. Specific examples of the styrenic thermoplastic elastomer include, for example, a styrene-butadiene block copolymer (SBS), a styrene-isoprene block copolymer (SIS), and a styrene-butadiene-isoprene block copolymer (SBIS). Examples of the hydrogenated styrene-based thermoplastic elastomer include styrene-ethylene / butadiene block copolymer (SEBS) and styrene-ethylene / propylene copolymer (SEPS).

  In the styrenic thermoplastic elastomer, the content of the styrenic monomer is 10 to 60% by weight, preferably 20 to 50% by weight, more preferably 20%, based on the total weight of the monomer components. ~ 45 wt%. On the other hand, content of the said conjugated diene is 40 to 90 weight% with respect to the total weight of a monomer component, Preferably it is 50 to 80 weight%, More preferably, it is 55 to 80 weight%.

  The weight-average molecular weight of the polystyrene-based resin having a polar group is preferably 100,000 to 500,000, more preferably 200,000 to 400,000, from the viewpoint of fluidity during layer formation.

  Specific examples of the polystyrene resin having a polar group include maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, epoxy-modified SEBS, and epoxy-modified SEPS. Commercially available products may be used, and examples thereof include “Tuftec M” manufactured by Asahi Kasei Corporation, “Clayton FG” manufactured by Clayton Co., Ltd., and the like.

  Content of the polystyrene-type resin which has the said polar group with respect to the total weight of the resin composition (resin composition C) which comprises C layer of this invention is 5 to 100 weight%, and is a viewpoint of adhesiveness (interlayer strength). Therefore, it is preferably 20 to 100% by weight. When the content is less than 5% by weight, the adhesive strength is insufficient and delamination (delamination) may occur.

  The resin composition C may contain a tackifier such as petroleum resin in order to improve heat resistance. Examples of the tackifier include rosin resins (rosin, polymerized rosin, hydrogenated rosin and derivatives thereof, resin acid dimers, etc.), terpene resins (terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, Terpene-phenol resins, etc.), petroleum resins (aliphatic, aromatic, alicyclic) and the like. Among these, petroleum resin is preferable. A tackifier can be used individually or in combination of 2 or more types. The addition amount in the case of adding a tackifier is preferably 5 to 30% by weight, more preferably 10 to 25% by weight, based on the total weight of the resin composition C.

[Shrink film]
As described above, the shrink film of the present invention includes at least a two-layer / three-layer structure in which the A layer and the B layer are stacked in the order of A layer (surface layer) / B layer (center layer) / A layer. It is a laminated structure. Preferably, it is a laminated structure of 3 types and 5 layers of A layer / C layer (adhesive resin layer) / B layer / C layer / A layer.

  The laminated structure is formed by coextrusion. The above general method of coextrusion (explained by taking the case of three layers of five layers of A layer / C layer / B layer / C layer / A layer as an example) is applied to a plurality of extruders each set at a predetermined temperature. In this method, resin compositions A to C are respectively charged and coextruded from a T die, a circular die or the like. At this time, it is preferable to use a manifold or a merging block to form a predetermined laminated structure. Further, if necessary, the supply amount may be adjusted using a gear pump, and it is preferable to remove foreign substances using a filter because film tearing can be reduced. The extrusion temperature varies depending on the types of the resin compositions A to C to be used, and is not particularly limited. However, it is preferable that the molding temperature regions of the resin compositions are close to each other. Specifically, the extrusion temperature of the resin composition A (A layer) is preferably 210 to 250 ° C, the resin composition B (B layer) is 180 to 220 ° C, and the resin composition C (C layer) is 190 to 220 ° C. ° C is preferred. An unstretched laminated film (sheet) can be obtained by quenching the coextruded polymer using a cooling drum or the like.

  The shrink film of the present invention is a film oriented uniaxially or biaxially from the viewpoint of shrinkage characteristics. In the case where the shrink film has a two-kind three-layer structure composed of an A layer and a B layer, both of the A layer and the B layer, and in the case of a three-kind five-layer structure composed of A to C layers, A to All layers (5 layers) of C need to be oriented. When all the layers are not oriented, good shrinkage cannot be obtained. The orientation is not particularly limited, such as uniaxial orientation or biaxial orientation, but substantially uniaxial orientation in the width direction, which is strongly oriented in the film width direction (direction that becomes the circumferential direction when the label is formed into a cylinder) is preferable. Further, it may be a substantially uniaxially oriented film in the longitudinal direction that is strongly oriented in the longitudinal direction (direction perpendicular to the width direction) of the film.

  An oriented film such as the uniaxial orientation or the biaxial orientation can be produced by stretching an unstretched laminated film. Stretching can be selected according to the desired orientation, and may be biaxial stretching in the longitudinal direction (longitudinal direction; MD direction) and width direction (transverse direction; TD direction), or uniaxial stretching in the longitudinal direction or width direction. But you can. The stretching method may be any of a roll method, a tenter method, and a tube method. The stretching conditions vary depending on the types of resin compositions A to C used, and are not particularly limited, but are generally in the range of 70 to 110 ° C. and about 1.01 to 8 times in the longitudinal and width directions. It is preferable to carry out at a magnification. For example, the film is stretched about 1.01 to 1.5 times (preferably 1.05 to 1.3 times) in the longitudinal direction and then stretched about 2 to 8 times (preferably 3 to 6 times) in the width direction. Is preferred.

  In the shrink film of the present invention, the thickness of the A layer (one layer) is not particularly limited, but is preferably 2 to 10 μm, more preferably 3 to 5 μm. When the thickness of the A layer exceeds 10 μm, the shrinkage stress of the A layer increases, and the delamination may easily occur. When the thickness is less than 2 μm, the solvent resistance may decrease.

  In the shrink film of the present invention, the thickness of B layer (one layer) is not particularly limited, but is preferably 10 to 40 μm, more preferably 20 to 30 μm. If the thickness of the B layer exceeds 40 μm, it may be difficult to follow the shrinkage of the A layer. If the thickness is less than 10 μm, the shrinkage stress between the B layer and the A layer may be extremely different, and thus delamination may be likely.

  In the shrink film of the present invention, the thickness (one layer) of the C layer when the C layer is provided is not particularly limited, but is preferably 2 to 10 μm, more preferably 3 to 5 μm. If the thickness of the C layer exceeds 10 μm, the shrinkage may be nonuniform, and if it is less than 2 μm, the adhesion function may not be exhibited.

  Although the thickness of the shrink film of this invention is not specifically limited, 20-60 micrometers is preferable, More preferably, it is 35-55 micrometers, More preferably, it is 30-50 micrometers.

  In the shrink film of the present invention, when the total thickness is 100%, the thickness ratio of the A layer (total of all A layers) is 5 to 40%, and the thickness ratio of the B layer (total of all B layers) is 50 to 90. %, C layer thickness ratio (total of all C layers) is preferably 5 to 40%. Controlling the thickness of each layer within the above range is preferable because the balance between the shrinkage and shrinkage stress of each layer can be adjusted and delamination can be prevented.

  In the shrink film of the present invention, the surface layer (A layer) has a polyester resin as a main component, and therefore has high shrinkability, and can impart wear resistance and chemical resistance to the surface. On the other hand, the styrene-conjugated diene copolymer or hydrogenated product used for the central layer (B layer) can suppress the rapid shrinkage of the label and can moderate the shrinkage behavior. Moreover, the adhesive resin layer (C layer) provided as needed has high adhesiveness with both the A layer and the B layer and plays a role of further improving the interlayer strength.

  However, in the laminated film in which different kinds of materials are laminated as described above, it is possible to exert a sufficient interlayer strength in the shrink film manufacturing process, the center seal process, etc. by providing an adhesive layer, etc. After being attached to the bottle by processing (shrink processing), there was a problem that delamination occurred at the center seal portion. The above problem is that when a polyester resin layer and a polystyrene resin such as a styrene-conjugated diene copolymer have different shrinkage stress when heated, the shrinkage stress between each film layer when shrink processing (heating) is applied. It is estimated that delamination occurs, thereby causing delamination. In particular, in the center seal portion, since one surface side of the film is fixed by the seal, it is estimated that the difference in shrinkage stress between the film layers appears remarkably.

  On the other hand, in the shrink film of the present invention, by adding a specific amount of plasticizer to the polyester resin of the A layer having a larger shrinkage stress than the resin of the B layer or the C layer, the shrinkage stress of the A layer is obtained. Is reduced, the shrinkage stress difference generated between the layers is reduced, and the occurrence of delamination is suppressed. Further, by laminating each layer by coextrusion, the adhesion between the film layers is improved to increase the interlayer strength. Furthermore, by controlling the thickness and thickness ratio of each layer within the above ranges, the shrinkage stress difference can be further reduced and delamination can be suppressed. Although the shrinkage stress difference can be reduced by lowering the stretch orientation, in that case, the shrinkage characteristics (shrinkage rate, etc.) are also lowered, which is not preferable.

  The shrinkage stress (85 ° C., main orientation direction) of the A layer (single layer) in the shrink film of the present invention is preferably 3 to 10 MPa, more preferably 4 to 6 MPa. When the shrinkage stress of the A layer exceeds 10 MPa, the difference in shrinkage stress between the B layer and the C layer becomes large and delamination tends to occur. If it is less than 3 MPa, label shrinkage (during shrink processing) may not be able to follow the container shape. The shrinkage stress (85 ° C., main orientation direction) of the B layer (single layer) is preferably 2 to 10 MPa, more preferably 3 to 5 MPa. When the shrinkage stress of the B layer exceeds 10 MPa, the shrinkage difference from the C layer becomes large and the film is easily peeled off. If it is less than 2 MPa, the difference in shrinkage stress with the A layer becomes large and delamination tends to occur. The shrinkage stress (85 ° C., main orientation direction) of the C layer (single layer) is preferably 2 to 8 MPa, more preferably 3 to 4 MPa. When the shrinkage stress of the B layer exceeds 8 MPa, the adhesive properties are deteriorated. If it is less than 2 MPa, the difference in shrinkage stress with the A layer becomes large and delamination tends to occur. The “main orientation direction” means “a direction in which a stretching process is mainly performed”. In the case of a uniaxially stretched film, it refers to the stretched direction, and in the case of a biaxially stretched film, it refers to a stretched direction having a larger orientation. In the case of a shrink film for a cylindrical shrink label, generally, the direction (the width direction of the film) that becomes the circumferential direction of the container when mounted is often the main orientation direction.

  The shrinkage stress of each layer (single layer) was prepared by preparing a test piece made of each layer resin and having a width of 15 mm and a length of 100 mm in the TD direction, and immersed in a 85 ° C. hot water bath for 10 seconds at 50 mm between chucks. It is obtained by measuring the stress. The shrinkage stress is a value representing the shrinkage stress of each layer before shrink processing.

  The shrinkage stress difference between the A layer and the B layer (absolute value), the shrinkage stress difference between the B layer and the C layer (absolute value), and the shrinkage stress difference between the C layer and the A layer (absolute value) are as follows. The pressure is preferably less than 3 MPa, more preferably less than 2 MPa.

  The shrinkage stress (85 ° C.) of the shrink film of the present invention is preferably 2 to 13 MPa, more preferably 2 to 8 MPa, and still more preferably 2 to 5 MPa. When the shrinkage stress is less than 2 MPa, the shrinkage followability of the printed layer is lowered, and the finish may be lowered. If it exceeds 13 MPa, the container may be deformed or the contents may overflow when opened.

  The shrink film of the present invention has excellent interlayer strength. The interlayer strength (the interlayer strength of the shrink film after stretch orientation (before shrink processing)) is preferably 1 N / 15 mm or more, more preferably 2 N / 15 mm or more. The interlayer strength (the interlayer strength of the shrink film after stretch orientation (after shrink processing)) is preferably 1 N / 15 mm or more, more preferably 2 N / 15 mm or more. If the interlaminar strength is less than the above range, the film layers may be peeled off after processing or commercialization, resulting in reduced productivity or quality problems.

  The shrinkage ratio in the main orientation direction (mainly in the direction subjected to the stretching treatment) at 90 ° C. for 10 seconds (warm water treatment) of the shrink film (before shrink processing) of the present invention is preferably 15% or more, more preferably 25 to 25%. 80%, more preferably 30 to 70%. When the heat shrinkage rate is less than 15%, the shrinkage is not sufficient in the process of closely attaching the label to the container with heat, making it difficult to follow the shape of the container, and the finish is particularly poor for a complex shaped container. Sometimes.

  In addition, as for the thermal contraction rate of the direction orthogonal to the said main orientation direction in 90 degreeC 10 second (warm water process) of the shrink film (before shrink process) of this invention, -5-15% is preferable.

  The compressive strength (thickness 40 μm: JIS P 8126) of the shrink film (before shrink processing) of the present invention is preferably 2N or more, more preferably 3.5N or more, and further preferably 5N or more. In addition, when the compressive strength is less than 2N, the waist of the label becomes weak, and the label tends to be bent in the process of mounting the cylindrical shrink label on the container.

  The transparency (transparency) (haze value: JIS K 7105, converted to 40 μm thickness) (unit:%) of the shrink film of the present invention is preferably less than 10, more preferably less than 5.0, and still more preferably less than 2.0. It is. When the haze value is 10 or more, the inside of the shrink film (the side that becomes the container side when the label is attached to the container) is printed, and in the case of a shrink label that shows printing through the film, Printing may be cloudy and decorative properties may be reduced. However, even if the haze is 10 or more, it can be sufficiently used in applications other than the above-mentioned applications that show printing through a film.

[Shrink label]
By using the shrink film of the present invention as a base material and providing a printing layer on at least one side thereof, it can be preferably used as a shrink label. In addition to the printed layer, the shrink label may be provided with a protective layer, an anchor coat layer, a primer coat layer, a resin layer such as an adhesive layer (pressure sensitive, heat sensitive, etc.), a coating layer, Furthermore, you may provide layers, such as a nonwoven fabric and paper. Specific examples of the shrink label of the present invention include, for example, printing layer / A / B / A, printing layer / A / B / A / printing layer, printing layer / A / C / B / C / A, and printing layer. A layer structure such as / A / C / B / C / A / print layer is preferably exemplified. In addition, the shrink film of this invention can also be used for shrink label use by itself, even when a printing layer is not provided.

  The shrink label of the present invention has a printed layer (for example, a layer displaying a product name, an illustration, handling precautions, etc.) on at least one surface. The printing layer is formed by applying printing ink. From the viewpoint of productivity, workability, and the like, the coating method is preferably provided by off-line coating in which coating is performed using a known and commonly used printing method after film formation. As a printing method, a conventional method can be used, but gravure printing or flexographic printing is most preferable. The printing ink used for forming the printing layer is made of, for example, a pigment, a binder resin, a solvent, and other additives. Although it does not specifically limit as said binder resin, For example, resin, such as an acrylic type, a urethane type, a polyamide type, a vinyl chloride-vinyl acetate copolymer type, a cellulose type, a nitrocellulose type, can be used individually or in combination. As the pigment, white pigments such as titanium oxide (titanium dioxide), indigo pigments such as copper phthalocyanine blue, carbon black, aluminum flakes, mica (mica), and other colored pigments can be selected and used in accordance with 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. Examples of the solvent include organic solvents such as toluene, xylene, methyl ethyl ketone, ethyl acetate, methyl alcohol, ethyl alcohol, and isopropyl alcohol, and commonly used solvents such as water.

Although the said printing layer is not specifically limited, Active energy ray-curable resin layers, such as visible light, an ultraviolet-ray, and an electron beam, may be sufficient. This is effective for preventing deformation of the film due to excessive heat. For example, in the case of curing by ultraviolet rays, an ultraviolet (UV) lamp, such as using an ultraviolet LED or an ultraviolet laser, ultraviolet ray having a wavelength 300～460Nm (or near UV), irradiation intensity 150~1000mJ / cm ^2, irradiation time 0.1 It can be performed under about 3 seconds. In the case of an active energy ray-curable printing layer, it is preferable to add a photopolymerization initiator such as a photoradical polymerization initiator and a photocationic polymerization initiator to the printing ink in addition to the above. Examples of the photo radical polymerization initiator include benzophenone, thioxanthone, acetophenone, and acylphosphine polymerization initiators. Examples of the photo cationic polymerization initiator include diazonium salts, diaryl iodonium salts, and triaryls. Examples include sulfonium salts, silanol / aluminum complexes, sulfonate esters, and imide sulfonates. Although content of these photoinitiators is not specifically limited, 0.5-7 weight% is preferable with respect to the whole printing ink, More preferably, it is 1-5 weight%. Furthermore, you may add a sensitizer to printing ink as needed from a viewpoint of improving production efficiency. In this case, the sensitizer is, for example, an amine-based sensitizer such as an aliphatic, aromatic amine, piperidine, or other amine containing a nitrogen in the ring; an allyl-based or o-tolylthiourea-based urea-based sensitizer; sodium diethyl Sulfur compound sensitizers such as dithiophosphate; Anthracene sensitizers; Nitrile sensitizers such as N, N-disubstituted p-aminobenzonitrile compounds; Phosphorus compound systems such as tri-n-butylphosphine Sensitizers; nitrogen compound sensitizers such as N-nitrosohydroxylamine derivatives and oxazolidine compounds; chlorine compound sensitizers such as carbon tetrachloride. Although it does not specifically limit as content of a sensitizer, 0.1 to 5 weight% is preferable with respect to the whole printing ink, Most preferably, it is 0.3 to 3 weight%.

  Although the thickness of the said printing layer is not specifically limited, For example, it is about 0.1-10 micrometers. If the thickness is less than 0.1 μm, it may be difficult to provide a uniform printing layer, and partial “blur” may occur, resulting in a loss of decorativeness or printing as designed. May be difficult. In addition, when the thickness exceeds 10 μm, a large amount of printing ink is consumed, which increases the cost, makes it difficult to apply uniformly, makes the printed layer brittle and easily peels off. . Moreover, the rigidity of a printing layer becomes high and it may become difficult to follow the shrinkage | contraction of a film at the time of shrink processing.

[processing]
The shrink label of the present invention is, for example, a cylindrical label of a type in which both ends of the label are sealed with a solvent or an adhesive and attached to the container, or one end of the label is attached to the container and the label is wound The other end can be suitably used as a winding-type label that overlaps with one end to form a cylinder. Especially, it is preferably used as a cylindrical shrink label. The center seal strength of this cylindrical label is preferably 2 N / 15 mm or more. When the seal strength is less than 2N / 15 mm, the seal portion may be peeled off after processing or product production, which may reduce the productivity or cause the label to drop off.

  Although the manufacturing method of the said cylindrical label is not specifically limited, For example, it is as follows. After the shrink label of the present invention is printed on a long shrink film, it is slit into a predetermined width, wound into a roll, and after the roll is formed into a plurality of continuous labels in the long direction, Used for processing. While feeding one of these rolls, the film is formed into a cylindrical shape so that the main stretching direction (for example, the width direction) of the film is in the circumferential direction. Specifically, a long shrink label is formed into a cylindrical shape, and a solvent or adhesive (such as tetrahydrofuran (THF)) having a width of about 2 to 4 mm in the longitudinal direction on one side edge of the label. (Solvent, etc.) is applied to the inner surface, rounded into a cylindrical shape, and the coated portion of the solvent, etc. is superposed at a position of 5 to 10 mm from the other side edge and bonded to the outer surface of the other side edge (center seal) ) To obtain a long cylindrical label continuous body (long cylindrical shrink label). In the case where a perforation for label excision is provided, a perforation having a predetermined length and pitch is formed in the longitudinal 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 shrink label of the present invention is attached to a container and used as a labeled container. Such containers include, for example, soft drink bottles such as PET bottles, milk bottles for home delivery, food containers such as seasonings, alcoholic beverage bottles, pharmaceutical containers, containers for chemical products such as detergents and sprays, cups, etc. This includes noodle containers. The shape of the container includes various shapes such as a cylindrical shape, a square bottle, and a cup type. Further, the material of the container includes plastic such as PET, glass, metal and the like.

  The above-mentioned container with a label can be produced by cutting a long cylindrical shrink label, mounting it on a predetermined container, shrinking the label by heat treatment, and closely contacting the container. Specifically, the above-described long cylindrical shrink label in a roll shape is supplied to an automatic label mounting device (shrink labeler), cut into a required length, and formed into a cylindrical shrink label. A shrink label is externally fitted to a container filled with the contents, and is passed through a hot air tunnel or steam tunnel at a predetermined temperature, or is heat-shrinked by radiant heat such as infrared rays, and is brought into close contact with the container to obtain a labeled 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).

[Methods for measuring physical properties and methods for evaluating effects]
(1) Interlaminar strength (before shrink processing)
Evaluation is performed using a shrink film.
A strip-shaped sample (200 mm (shrink film width direction) × 15 mm (shrink film length direction)) having a width of 15 mm in the length direction (shrink film forming direction) and long in the width direction (direction perpendicular to the length direction) is collected. did. Hereinafter, the sample width direction refers to the longitudinal direction of the shrink film.
Using the long side direction of the sample (the width direction of the shrink film) as the measurement direction, a T-type peel test (based on JIS K 6854-3) is performed under the following conditions to measure the peeling load between layers.
The average value of the peeling load is defined as the interlayer strength (N / 15 mm), and evaluated according to the following criteria.
1N / 15mm or more: ○ (good interlayer strength)
Less than 1 N / 15 mm: × (interlayer strength is inferior)
(Measurement condition)
Measuring device: Autograph manufactured by Shimadzu Corporation (AG-IS: load cell type 500N)
Temperature and humidity: Temperature 23 ± 2 ° C, humidity 50 ± 5% RH (JIS K 7000 standard temperature state 2nd grade)
Initial chuck interval: 40 mm
Sample width: 15mm
Number of tests: 3 times Tensile speed: 200 mm / min First half deleted range: 50 mm
Sensitivity: 1
The interlayer strength is evaluated for the interlayer having the weakest interlayer strength in the laminated structure.

(2) Interlaminar strength (after shrink processing)
The obtained shrink film is used for evaluation after shrinking the film by 30% at 85 ° C. using a jig.
Using the sample, the interlayer strength is measured by the same evaluation method as the evaluation of (1) above, and evaluated by the same standard.

(3) Thermal shrinkage (90 ° C for 10 seconds)
From the shrink film (before shrink processing), a rectangular sample piece having a length of 120 mm in the measurement direction (main orientation direction: longitudinal direction or width direction of the base film) and a sample width of 5 mm is prepared.
The sample piece is heat-treated in warm water at 90 ° C. for 10 seconds (under no load), the difference between the marked lines before and after the heat treatment is read, and the thermal contraction rate is calculated by the following formula.
Shrinkage rate (%) = (L ₀ −L ₁ ) / L ₀ × 100
L ₀ : Size of sample before heat treatment (main orientation direction: longitudinal direction or width direction)
L ₁ : Sample dimensions after heat treatment (same direction as L ₀ )

(4) Compressive strength (ring crush method)
Evaluation is performed using a shrink film (before shrink processing).
In accordance with JIS P 8126, the compressive strength of the shrink label is measured under the following conditions. The measurement direction is the longitudinal direction.
Measuring device: Shimadzu Corporation autograph (AGS-50G: load cell type 500N)
Sample size: 15 mm (longitudinal direction) x 152.4 mm (width direction)
Number of tests: 5

(5) Transparency (haze value)
Measurement is performed according to JIS K 7105 using a shrink film (thickness 40 μm). In the case of films having different thicknesses, the thickness may be converted to 40 μm.

  EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
As the resin composition A, a mixed resin of 100 parts by weight of an amorphous aromatic polyester resin (manufactured by Eastman Chemical, trade name “Embrac”) and 20 parts by weight of dioctyl phthalate (DOP) as a plasticizer was used.
As resin composition B, 60 parts by weight of SBS (manufactured by Asahi Kasei Co., Ltd., trade name “Asaflex 830”) and 40 parts by weight of SBIS (manufactured by Asahi Kasei Co., Ltd., trade name “Asaflex i-100”) The mixed resin was used.
Further, 100 parts by weight of maleic anhydride-modified hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Co., Ltd., trade name “Tuftec M”) was used as the resin composition C.
The resin composition A was charged in the extruder a heated to 210 ° C., the resin composition B in the extruder b heated to 210 ° C., and the resin composition C in the extruder c heated to 210 ° C. Melt extrusion was performed using the above three extruders. The resin extruded from the extruder b is the center layer, the resin extruded from the extruder c is on both sides of the center layer, and the resin extruded from the extruder a is further joined on both sides using a merge block. After extruding from a T-die (slit interval 0.7 mm), it was rapidly cooled on a casting drum cooled to 25 ° C. to obtain a three-kind five-layer laminated unstretched film.
Next, the unstretched film whose thickness was adjusted was stretched 5.6 times at 90 ° C. in the width direction to obtain a biaxially stretched film that contracts mainly in the uniaxial direction. By adjusting the film forming speed, a shrink film having a total thickness of 50 μm (layer thickness ratio: (2/1/8/1/2)) was obtained.
Moreover, Dainippon Ink Industries Co., Ltd. "fine wrap NTV" was gravure-printed on the obtained shrink film, the printing layer was formed in thickness of 5 micrometers, and the shrink label was obtained.
The obtained shrink film and shrink label were immersed in hot water at 90 ° C. for 10 seconds and thermally contracted to confirm the presence or absence of delamination. Both the film and the label were excellent in interlayer adhesion without delamination.

Example 2
A shrink film and a shrink label were obtained in exactly the same manner as in Example 1 except that the plasticizer used for the A layer was changed to dioctyl adipate (DOA).
The obtained shrink film and shrink label were immersed in hot water at 90 ° C. for 10 seconds and thermally contracted to confirm the presence or absence of delamination. Both the film and the label were excellent in interlayer adhesion without delamination.

Comparative Example 1
A shrink film and a shrink label were obtained in the same manner as in Example 1 except that no plasticizer was used for the A layer.
The obtained shrink film and shrink label were immersed in hot water at 90 ° C. for 10 seconds and thermally contracted to confirm the presence or absence of delamination. Both the film and the label had delamination and poor interlayer adhesion.

Claims (5)

  A surface layer composed of a resin composition containing an amorphous aromatic polyester-based resin as a main component and containing 0.5 to 20 parts by weight of a plasticizer with respect to 100 parts by weight of the amorphous aromatic polyester-based resin (A Layer) and a central layer (B layer) composed of a resin composition mainly composed of a styrene-conjugated diene copolymer and / or a hydrogenated product thereof, is laminated in the order of A layer / B layer / A layer. A shrink film having a laminated structure of at least three layers.   Furthermore, the shrink film of Claim 1 which has an adhesive resin layer (C layer) and has at least 5 layer laminated structure laminated | stacked in order of A layer / C layer / B layer / C layer / A layer.   The shrink film according to claim 1, wherein the plasticizer is at least one selected from a phthalate ester, an adipate ester, and a polyester plasticizer.   The shrink film according to any one of claims 1 to 3, wherein the C layer is composed of a styrene resin having a polar group.   The shrink label which provided the printing layer in the at least one surface side of the shrink film in any one of Claims 1-4.