Invention title: Heat-shrinkable multilayer film
Technical field
[0001]
The present invention relates to a heat-shrinkable multilayer film capable of producing a heat-shrinkable label having excellent perforation cutability in both the TD direction and the MD direction and also having excellent impact resistance and transparency.
Background technology
[0002]
In recent years, many containers such as plastic bottles and metal cans are equipped with shrink labels obtained by printing or the like on a base film made of a heat-shrinkable resin film.
Most shrink labels are made of polystyrene resin because of their excellent low temperature shrinkage. However, since polystyrene-based resin films have insufficient heat resistance, for example, when a PET bottle collapses during heating in a hot warmer in a convenience store or the like, it shrinks and the label is distorted or torn. There was a problem that it could be chilly. In addition, since polystyrene-based resin films have insufficient solvent resistance, there is also a problem that when they are used for packaging products containing oil, they may shrink or dissolve due to the adhesion of oil. It was.
[0003]
On the other hand, an attempt has been made to use a polyester-based film having excellent heat resistance and solvent resistance as a shrink label instead of the polystyrene-based resin film. However, the polyester-based film has a problem that it has poor low-temperature shrinkage and shrinks rapidly, so that wrinkles are likely to occur when it is attached to a container. In addition, the shrink film is often provided with perforations for peeling so that the shrink label can be easily peeled off from the used container in order to recycle the container. There is also a problem that the cuttability at the perforation is poor and the shrink label may not be easily peeled off from the container.
[0004]
On the other hand, Patent Document 1 discloses a hard multilayer shrinkable film in which an outer surface layer made of a polyester resin is laminated on an intermediate layer made of a polystyrene resin via an adhesive layer made of an olefin resin. ing. Further, in Patent Document 2, an outer surface layer made of a polyester resin made of a specific monomer is laminated on both sides of an intermediate layer made of a polystyrene resin, and the intermediate layer and the outer surface layer form an adhesive layer. A shrink label with a base film laminated without interposing is disclosed. The shrink label made of these multilayer films is excellent in low temperature shrinkage and cutability at perforations by the intermediate layer made of polystyrene resin, and the intermediate layer is covered with the outer surface layer made of polyester resin. It also has excellent solvent resistance and heat resistance.
Prior art literature
Patent documents
[0005]
Patent Document 1: Japanese Patent Application
Laid-Open No. 61-41543 Patent Document 2: Japanese Patent Application Laid-Open No. 2002-351332
Outline of the invention
Problems to be solved by the invention
[0006]
On the other hand, for example, in a supplement container or a chemical container, a shrink label is attached as a lid material so as to cover the entire container including the mouth of the container in order to guarantee the virginity of the product. In such a container, when using the product, it is common to remove the shrink label that covers the mouth, but from the viewpoint of design, the shrink label on the body of the bottle is not peeled off. is there. However, although the films described in Patent Documents 1 and 2 are excellent in perforation-cutting property for removing shrink labels, there is a problem that the label on the body is cut when the perforations are cut. It was. Further, there is a problem that the perforation cutability when removing the label along the perforation provided in the circumferential direction of the mouth portion is inferior, and a crevice other than the perforation is generated. Further, there is a problem that the label is torn when a strong tension is applied when printing the label or when a strong impact is applied due to a drop of the container after the label is attached.
[0007]
In view of the above situation, the present invention provides a heat-shrinkable multilayer film capable of producing a heat-shrinkable label having excellent perforation cutability in both the TD direction and the MD direction and also having excellent impact resistance and transparency. The purpose is to provide.
Means to solve problems
[0008]
The present invention is a heat-shrinkable multilayer film in which a front and back layer and an intermediate layer are laminated via an adhesive layer. The front and back layers contain a polyester resin, and the intermediate layer is a polystyrene resin. Is a heat-shrinkable multilayer film containing 80 to 99% by weight and 1 to 20% by weight of a polyester resin.
The present invention will be described in detail below.
[0009]
The present inventor uses a polyester resin as the resin constituting the front and back layers in a heat-shrinkable multilayer film in which the front and back layers and the intermediate layer are laminated via an adhesive layer, and the resin constituting the intermediate layer. It has been found that by using a mixed resin in which a polystyrene-based resin and a polyester-based resin are mixed at a predetermined ratio, it is possible to prevent unnecessary crevices from occurring when removing the label. Further, they have found that the label can be prevented from being torn even when an external force is applied during printing or after the label is attached, and have completed the present invention.
[0010]
The heat-shrinkable multilayer film of the present invention has a structure in which a front and back layer and an intermediate layer are laminated via an adhesive layer.
In the present specification, the front and back layers mean both the front surface layer and the back surface layer. Therefore, the heat-shrinkable multilayer film of the present invention has a structure in which the intermediate layer is sandwiched between the front surface layer and the back surface layer.
[0011]
(Front and back layers)
The front and back layers contain a polyester resin.
The polyester-based resin constituting the front and back layers can be obtained by polycondensing a dicarboxylic acid and a diol.
The dicarboxylic acid is not particularly limited, and for example, o-phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, octylsuccinic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, fumaric acid, etc. Examples thereof include maleic acid, itaconic acid, decamethylenecarboxylic acid, anhydrides thereof and lower alkyl esters.
The diol is not particularly limited, and for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, and triethylene. Glycol, tetraethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, neopentyl glycol (2,2-dimethylpropane-1,3-diol), 1,2-hexane Aliphatic diols such as diols, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol; 2, Alicyclic diols such as 2-bis (4-hydroxycyclohexyl) propane, alkylene oxide adducts of 2,2-bis (4-hydroxycyclohexyl) propane, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. And so on.
[0012]
Among the polyester resins, those containing a component derived from terephthalic acid as a dicarboxylic acid component and a component derived from ethylene glycol and 1,4-cyclohexanedimethanol as a diol component are preferable. is there. By using such a polyester-based resin, it is possible to impart particularly high heat resistance and solvent resistance to the obtained heat-shrinkable multilayer film of the present invention.
[0013]
In the polyester resin, the preferable lower limit of the content of the component derived from terephthalic acid is 70 mol%, the more preferable lower limit is 80 mol%, the preferable upper limit is 100 mol%, and the more preferable upper limit is 100 mol% of the dicarboxylic acid component. It is 95 mol%.
In the polyester resin, the preferable lower limit of the content of the component derived from isophthalic acid is 0 mol%, the more preferable lower limit is 5 mol%, the preferable upper limit is 30 mol%, and the more preferable upper limit is 100 mol% of the dicarboxylic acid component. It is 20 mol%.
[0014]
In the polyester resin, the preferable lower limit of the content of the component derived from ethylene glycol is 50 mol%, the more preferable lower limit is 60 mol%, the preferable upper limit is 80 mol%, and the more preferable upper limit is 70 in 100 mol% of the diol component. Mol%.
In the polyester resin, the preferable lower limit of the content of the component derived from 1,4-cyclohexanedimethanol is 10 mol%, the more preferable lower limit is 13 mol%, and the preferable upper limit is 40 mol% in 100 mol% of the diol component. A more preferred upper limit is 35 mol%.
In the polyester resin, the preferable lower limit of the content of the component derived from diethylene glycol is 0 mol%, the more preferable lower limit is 10 mol%, the preferable upper limit is 30 mol%, and the more preferable upper limit is 25 mol in 100 mol% of the diol component. %.
In the polyester resin, the preferable lower limit of the content of the component derived from 1,4-butanediol is 0 mol%, the more preferable lower limit is 5 mol%, the preferable upper limit is 40 mol%, and more, among 100 mol% of the diol components. The preferred upper limit is 35 mol%.
[0015]
The preferable lower limit of the glass transition temperature of the polyester resin is 30 ° C, the more preferable lower limit is 55 ° C, the preferable upper limit is 95 ° C, and the more preferable upper limit is 90 ° C.
The glass transition temperature can be measured with a differential scanning calorimeter (DSC).
[0016]
The preferable lower limit of the tensile elastic modulus of the polyester resin is 1000 MPa, the more preferable lower limit is 1500 MPa, the preferable upper limit is 4000 MPa, and the more preferable upper limit is 3700 MPa.
The tensile elastic modulus can be measured by a method based on ASTM-D992 (TestA).
[0017]
As the polyester-based resin constituting the front and back layers, the polyester-based resin having the above-mentioned composition may be used alone, or two or more kinds of polyester-based resins having the above-mentioned composition may be used in combination.
[0018]
The front and back layers are, if necessary, antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, lubricants, antistatic agents, antiblocking agents, flame retardants, antibacterial agents, fluorescent whitening agents, colorants, etc. May contain the additive of.
[0019]
(Intermediate layer)
The intermediate layer contains a polystyrene resin.
Examples of the polystyrene-based resin constituting the intermediate layer include aromatic vinyl hydrocarbon-conjugated diene copolymers. Since the aromatic vinyl hydrocarbon-conjugated diene copolymer is excellent in low temperature shrinkage, the obtained heat shrinkable multilayer film can be easily attached to the container without causing wrinkles or the like. In addition, the cuttability at the perforation in the MD direction is also excellent.
[0020]
In the present specification, the aromatic vinyl hydrocarbon-conjugated diene copolymer means a copolymer containing a component derived from an aromatic vinyl hydrocarbon and a component derived from a conjugated diene.
The aromatic vinyl hydrocarbon is not particularly limited, and examples thereof include styrene, o-methylstyrene, and p-methylstyrene. These may be used alone or in combination of two or more. The conjugated diene is not particularly limited, and is, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene. And so on. These may be used alone or in combination of two or more.
[0021]
The preferable lower limit of the styrene component content in the polystyrene resin constituting the intermediate layer is 60% by weight, the more preferable lower limit is 70% by weight, the preferable upper limit is 90% by weight, and the more preferable upper limit is 85% by weight.
When the polystyrene-based resin constituting the intermediate layer is a mixed resin in which a plurality of polystyrene-based resins are combined, the styrene component content in the polystyrene-based resin constituting the intermediate layer is determined by each polystyrene in the mixed resin. Calculated by multiplying the content of the polystyrene resin by the content of the styrene component in each polystyrene resin and dividing the total by 100.
[0022]
The preferable lower limit of the content of the conjugated diene component in the polystyrene resin constituting the intermediate layer is 10% by weight, the more preferable lower limit is 15% by weight, the preferable upper limit is 40% by weight, and the more preferable upper limit is 30% by weight.
When the polystyrene-based resin constituting the intermediate layer is a mixed resin in which a plurality of polystyrene-based resins are combined, the content of the conjugated diene component in the polystyrene-based resin constituting the intermediate layer is each of the mixed resins. It is calculated by multiplying the content of the polystyrene-based resin by the content of the conjugated diene component in each polystyrene-based resin and dividing by 100.
[0023]
The aromatic vinyl hydrocarbon-conjugated diene copolymer is particularly excellent in heat shrinkage, and therefore preferably contains a styrene-butadiene copolymer (SBS resin). Further, in the aromatic vinyl hydrocarbon-conjugated diene copolymer, 2-methyl-1,3-butadiene (isoprene) is used as the conjugated diene in order to prepare a heat-shrinkable multilayer film having less fish eyes. It is preferable to contain the styrene-isoprene copolymer (SIS resin), styrene-isoprene-butadiene copolymer (SIBS) and the like used.
The aromatic vinyl hydrocarbon-conjugated diene copolymer may contain any one of the SBS resin, the SIS resin and the SIBS resin alone, or may contain a plurality of them in combination. When a plurality of SBS resin, SIS resin and SIBS resin are used, each resin may be dry-blended, and a compound resin obtained by kneading and pelletizing each resin with a specific composition using an extruder is used. You may.
[0024]
The preferable lower limit of the Vicat softening temperature of the polystyrene resin is 60 ° C., and the preferable upper limit is 90 ° C.
When the Vicat softening temperature is 60 ° C. or higher, the low-temperature shrinkage of the heat-shrinkable multilayer film is improved, and wrinkles can be prevented when the film is attached to the container. When the Vicat softening temperature is 90 ° C. or lower, the low temperature shrinkage of the heat-shrinkable multilayer film can be sufficiently enhanced to prevent the generation of non-shrinkable portions when mounted on a container.
The more preferable lower limit of the Vicat softening temperature is 65 ° C., and the more preferable upper limit is 85 ° C.
The Vicat softening temperature can be measured by a method conforming to ISO 306.
[0025]
The preferable lower limit of MFR (melt flow rate) of the polystyrene resin at 200 ° C. is 2 g / 10 minutes, and the preferable upper limit is 15 g / 10 minutes.
When the MFR at 200 ° C. is 2 g / 10 minutes or more, the film-forming property of the film can be improved. When the MFR at 200 ° C. is 15 g / 10 minutes or less, the mechanical strength of the film can be sufficiently improved.
The more preferable lower limit of the MFR is 4 g / 10 minutes, and the more preferable upper limit is 12 g / 10 minutes.
The MFR can be measured by a method compliant with ISO1133.
[0026]
The polystyrene-based resin constituting the intermediate layer is a polystyrene-based resin having a Vicat softening temperature of 80 ° C. or higher (hereinafter, also referred to as “high-softening temperature polystyrene-based resin”) and a polystyrene-based resin having a Vicat softening temperature of less than 80 ° C. It is preferably a mixed resin with (hereinafter, also referred to as “low softening temperature polystyrene resin”).
[0027]
Regarding the content of the high softening temperature polystyrene resin in the polystyrene resin constituting the intermediate layer, the preferable lower limit is 1% by weight, the more preferable lower limit is 5% by weight, the preferable upper limit is 50% by weight, and the more preferable upper limit is 45. By weight%.
Regarding the content of the low softening temperature polystyrene resin in the polystyrene resin constituting the intermediate layer, the preferable lower limit is 50% by weight, the more preferable lower limit is 55% by weight, the preferable upper limit is 99% by weight, and the more preferable upper limit is 95. By weight%.
[0028]
The difference in the Vicat softening temperature between the high softening temperature polystyrene resin and the low softening temperature polystyrene resin is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and more preferably 30 ° C. or lower. It is preferably 20 ° C. or lower, more preferably 20 ° C. or lower.
[0029]
When the polystyrene resin constituting the intermediate layer is a mixed resin of the high softening temperature polystyrene resin and the low softening temperature polystyrene resin, the apparent bicut softening temperature of the mixed resin has a preferable lower limit. 71.1 ° C., a more preferable lower limit is 71.5 ° C., a preferred upper limit is 76.0 ° C., and a more preferable lower limit is 75.5 ° C.
The apparent vicut softening temperature is the sum of the contents of the high softening temperature polystyrene resin and the low softening temperature polystyrene resin in the polystyrene resin constituting the intermediate layer multiplied by the bicut softening temperature of each resin. It can be calculated by dividing by 100.
[0030]
Examples of commercially available polystyrene-based resins constituting the intermediate layer include "Clearene" (manufactured by Denki Kagaku Kogyo Co., Ltd.), "Asaflex" (manufactured by Asahi Kasei Chemicals Co., Ltd.), "Styrolux" (manufactured by BASF), and "PSJ". -Polystyrene "(manufactured by PS Japan Corporation) and the like.
[0031]
The lower limit of the content of the polystyrene resin in the intermediate layer is 80% by weight, and the upper limit is 99% by weight.
When the content of the polystyrene-based resin is not less than the above lower limit and not more than the above upper limit, the perforation cut property in both the MD direction and the TD direction can be excellent.
Regarding the content of the polystyrene resin in the intermediate layer, a preferable lower limit is 85% by weight, a further preferable lower limit is 87% by weight, a preferable upper limit is 97% by weight, and a further preferable upper limit is 95% by weight.
[0032]
The intermediate layer further contains a polyester resin.
Examples of the polyester-based resin that can be used for the intermediate layer include those similar to those that can be used for the front and back layers.
As the polyester-based resin, the same ones as those constituting the front and back layers may be used, or different ones may be used.
[0033]
The lower limit of the content of the polyester resin in the intermediate layer is 1% by weight, and the upper limit is 20% by weight.
When the content of the polyester resin is not less than the above lower limit and not more than the above upper limit, the perforation cut property in both the MD direction and the TD direction can be excellent.
Regarding the content of the polyester resin in the intermediate layer, a preferable lower limit is 3% by weight, a further preferable lower limit is 5% by weight, a preferable upper limit is 15% by weight, and a further preferable upper limit is 13% by weight.
[0034]
The intermediate layer may further contain a polyester-based elastomer.
As the polyester-based elastomer, the same ones that can be used for the adhesive layer described later can be used.
[0035]
The content of the polyester-based elastomer in the intermediate layer is such that the preferable lower limit is 0% by weight, the more preferable lower limit is 0.1% by weight, the preferable upper limit is 1.0% by weight, and the more preferable upper limit is 0.7% by weight. ..
[0036]
The intermediate layer may further contain a styrene-based elastomer.
As the styrene-based elastomer, the same ones that can be used for the adhesive layer described later can be used.
[0037]
The content of the styrene-based elastomer in the intermediate layer is such that the preferable lower limit is 0% by weight, the more preferable lower limit is 2% by weight, the preferable upper limit is 10% by weight, and the more preferable upper limit is 7% by weight.
[0038]
The intermediate layer preferably has a sea-island structure in which a polyester resin as a dispersed phase is dispersed in a polystyrene resin as a continuous phase.
By having the sea-island structure, a dispersed phase extending in the TD direction is formed in the heat-shrinkable multilayer film stretched in the TD direction, and the cuttability at the perforation in the TD direction can be improved.
[0039]
The average dispersion diameter of the dispersed phase has a preferable lower limit of 50 nm, a more preferable lower limit of 70 nm, a preferable upper limit of 2000 nm, and a more preferable upper limit of 1800 nm.
The average dispersion diameter can be obtained by photographing the intermediate layer portion of the heat-shrinkable multilayer film with an electron microscope and calculating the average diameter of the dispersed phases in the obtained image.
[0040]
The intermediate layer may contain additives such as antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, lubricants, antistatic agents, flame retardants, antibacterial agents, fluorescent whitening agents, and colorants, if necessary. It may be contained.
[0041]
(Adhesive Layer)
The heat-shrinkable multilayer film of the present invention has a structure in which a front and back layer and an intermediate layer are laminated via an adhesive layer.
By having the adhesive layer, the adhesive strength between each layer of the heat-shrinkable multilayer film can be increased.
[0042]
The adhesive layer preferably contains a polystyrene-based resin, a polyester-based resin, a styrene-based elastomer, or a polyester-based elastomer.
[0043]
The polystyrene-based resin constituting the adhesive layer preferably contains an aromatic vinyl hydrocarbon-conjugated diene copolymer because of its excellent adhesiveness, and in particular, a styrene-butadiene copolymer (SBS resin). Is preferably contained. Further, in order to produce a heat-shrinkable multilayer film having more excellent adhesiveness, 2-methyl-1,3-butadiene (isoprene) was used as the conjugated diene of the aromatic vinyl hydrocarbon-conjugated diene copolymer. It preferably contains a styrene-isoprene copolymer (SIS resin), a styrene-isoprene-butadiene copolymer (SIBS resin), and the like.
As the polystyrene resin, any one of the SBS resin, the SIS resin and the SIBS resin may be used alone, or a plurality of the polystyrene resins may be used in combination. When a plurality of SBS resin, SIS resin and SIBS resin are used in combination, each resin may be dry-blended, and a compound resin obtained by kneading and pelletizing each resin with a specific composition using an extruder is used. You may.
[0044]
Regarding the content of the styrene component in the polystyrene-based resin constituting the adhesive layer, the preferable lower limit is 50% by weight, the more preferable lower limit is 60% by weight, the preferable upper limit is 90% by weight, and the more preferable upper limit is 85% by weight.
[0045]
Regarding the content of the conjugated diene component in the polystyrene resin constituting the adhesive layer, the preferable lower limit is 10% by weight, the more preferable lower limit is 15% by weight, the preferable upper limit is 50% by weight, and the more preferable upper limit is 40% by weight.
[0046]
The styrene component content in the polystyrene resin constituting the adhesive layer is preferably smaller than the styrene component content in the polystyrene resin constituting the intermediate layer.
[0047]
The polystyrene-based resin constituting the adhesive layer has a preferred lower limit of 55 ° C. and a preferred upper limit of 85 ° C.
When the Vicat softening temperature is 55 ° C. or higher, it is possible to prevent peeling between the layers due to heating when the heat-shrinkable label using the heat-shrinkable multilayer film as the base film is attached to the container. When the Vicat softening temperature is 85 ° C. or lower, the interlayer adhesion strength of the heat-shrinkable multilayer film can be sufficiently improved.
The more preferable lower limit of the Vicat softening temperature is 60 ° C, the more preferable lower limit is 65 ° C, and the more preferable upper limit is 80 ° C.
The Vicat softening temperature can be measured by a method conforming to ISO 306.
[0048]
The vicut softening temperature of the polystyrene resin constituting the adhesive layer is preferably higher than the vicut softening temperature of the polystyrene resin constituting the intermediate layer.
When the polystyrene-based resin constituting the intermediate layer is a mixed resin in which a plurality of polystyrene-based resins are combined, the bicut softening temperature of the polystyrene-based resin constituting the intermediate layer is the polystyrene-based resin constituting the intermediate layer. It means the apparent Vicat softening temperature calculated based on the content of each polystyrene-based resin in the above and the Vicat softening temperature of each resin.
[0049]
The preferred lower limit of MFR (melt flow rate) of the polystyrene resin constituting the adhesive layer at 200 ° C. is 2 g / 10 minutes, and the preferred upper limit is 15 g / 10 minutes.
When the MFR at 200 ° C. is 2 g / 10 minutes or more, the resin is less likely to stay in the extruder, and the generation of foreign substances such as gel can be prevented. When the MFR at 200 ° C. is 15 g / 10 minutes or less, the pressure in the film forming process can be made uniform and the thickness can be made uniform.
The more preferable lower limit of the MFR is 4 g / 10 minutes, and the more preferable upper limit is 12 g / 10 minutes.
The MFR can be measured by a method compliant with ISO1133.
[0050]
As the polystyrene-based resin, the same one as that constituting the intermediate layer may be used, or a different one may be used.
[0051]
The content of the polystyrene resin in the adhesive layer is such that the preferable lower limit is 10% by weight, the more preferable lower limit is 20% by weight, the preferable upper limit is 95% by weight, and the more preferable upper limit is 80% by weight.
[0052]
As the polyester resin constituting the adhesive layer, a resin obtained by polycondensing a dicarboxylic acid and a diol can be used.
The dicarboxylic acid is not particularly limited, and for example, o-phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, octylsuccinic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, fumaric acid, etc. Examples thereof include maleic acid, itaconic acid, decamethylenecarboxylic acid, anhydrides thereof and lower alkyl esters.
The diol is not particularly limited, and for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, and triethylene. Glycol, tetraethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, neopentyl glycol (2,2-dimethylpropane-1,3-diol), 1,2-hexane Aliphatic diols such as diols, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol; 2, Alicyclic diols such as 2-bis (4-hydroxycyclohexyl) propane, alkylene oxide adducts of 2,2-bis (4-hydroxycyclohexyl) propane, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. And so on.
[0053]
Among the polyester resins, those containing a component derived from terephthalic acid as a dicarboxylic acid component and a component derived from ethylene glycol and 1,4-cyclohexanedimethanol as a diol component are preferable. Can be used.
Further, as the polyester resin, a resin containing a component derived from terephthalic acid as a dicarboxylic acid component and a component derived from 1,4-butanediol as a diol component can also be preferably used.
[0054]
The preferable lower limit of the glass transition temperature of the polyester resin is 30 ° C, the more preferable lower limit is 55 ° C, the preferable upper limit is 95 ° C, and the more preferable upper limit is 90 ° C.
The glass transition temperature can be measured with a differential scanning calorimeter (DSC).
[0055]
The preferable lower limit of the tensile elastic modulus of the polyester resin is 1000 MPa, the more preferable lower limit is 1500 MPa, the preferable upper limit is 4000 MPa, and the more preferable upper limit is 3700 MPa.
The tensile elastic modulus can be measured by a method based on ASTM-D992 (TestA).
[0056]
As the polyester-based resin, the same ones as those constituting the front and back layers may be used, or different ones may be used.
[0057]
The styrene-based elastomer constituting the adhesive layer includes a resin composed of polystyrene as a hard segment and polybutadiene or polyisoprene as a soft segment, or a copolymer of polybutadiene and polyisoprene, and hydrogenated products thereof. And so on. The hydrogenated product may be a part of polybutadiene, polyisoprene or the like hydrogenated, or may be entirely hydrogenated.
[0058]
The styrene-based elastomer may be a modified product.
Examples of the modified product of the styrene-based elastomer include those modified by a functional group such as a carboxylic acid group, an acid anhydride group, an amino group, an epoxy group and a hydroxyl group.
[0059]
The preferable lower limit of the content of the functional group in the modified product of the styrene-based elastomer is 0.05% by weight, and the preferable upper limit is 5.0% by weight.
When the content of the functional group is 0.05% by weight or more, the interlayer strength of the heat-shrinkable multilayer film can be sufficiently increased. When the content of the functional group is 5.0% by weight or less, the generation of gel or the like due to thermal deterioration of the styrene-based elastomer can be suppressed.
The more preferable lower limit of the content of the functional group is 0.1% by weight, and the more preferable upper limit is 3.0% by weight.
[0060]
Examples of commercially available products of the styrene-based elastomer or a modified product of the styrene-based elastomer include Tough Tech, Tough Plen (all manufactured by Asahi Kasei Chemicals Co., Ltd.), Clayton (manufactured by Clayton Polymer Japan Co., Ltd.), Dynalon, JSR TR, etc. Examples thereof include JSR SIS (manufactured by JSR) and Septon (manufactured by Kuraray).
[0061]
The polyester-based elastomer is composed of a polyester which is a hard segment and a polyether or polyester which is a soft segment rich in rubber elasticity. Specifically, for example, an aromatic polyester as a hard segment. , A block copolymer composed of an aliphatic polyether or an aliphatic polyester as a soft segment, and the like, preferably a saturated polyester-based elastomer, and particularly saturated containing a polyalkylene ether glycol segment as a soft segment. It is preferably a polyester-based elastomer.
As the saturated polyester-based elastomer containing the polyalkylene ether glycol segment, for example, a block copolymer composed of an aromatic polyester as a hard segment and a polyalkylene ether glycol as a soft segment is preferable.
[0062]
When a block copolymer composed of aromatic polyester and polyalkylene ether glycol is used as the polyester-based elastomer, the ratio of the segment composed of polyalkylene ether glycol is preferably 5% by weight in the lower limit and 90% by weight in the upper limit. is there.
When the proportion of the segment composed of the polyalkylene ether glycol is 5% by weight or more, the adhesiveness with the intermediate layer can be sufficiently enhanced, and when it is 90% by weight or less, the adhesiveness with the front and back layers is sufficiently enhanced. Can be enhanced.
The proportion of the segment made of the polyalkylene ether glycol has a more preferable lower limit of 30% by weight, a further preferable lower limit of 55% by weight, and a more preferable upper limit of 80% by weight.
[0063]
Examples of the polyalkylene ether glycol include polyethylene glycol, poly (propylene ether) glycol, poly (tetramethylene ether) glycol, poly (hexanemethylene ether) glycol and the like.
[0064]
The number average molecular weight of the polyalkylene ether glycol has a preferable lower limit of 400, a more preferable lower limit of 600, a further preferable lower limit of 1000, a preferable upper limit of 6000, a more preferable upper limit of 4000, and a further preferable upper limit of 3000.
When the number average molecular weight is within the above preferable range, the interlayer strength can be further improved.
The number average molecular weight can be measured by gel permeation chromatography (GPC).
[0065]
The method for producing the polyester-based elastomer is not particularly limited, and for example, (i) an aliphatic and / or alicyclic diol having 2 to 12 carbon atoms and (ii) an aromatic dicarboxylic acid and / or an alicyclic diol are produced. Using a dicarboxylic acid or an ester thereof and a (iii) polyalkylene ether glycol having a number average molecular weight of 400 to 6000 as a raw material, an oligomer is obtained by an esterification reaction or an ester exchange reaction, and then the oligomer is further polycondensed. Can be produced by
[0066]
Examples of the aliphatic and / or alicyclic diol having 2 to 12 carbon atoms include those commonly used as a raw material for polyester, particularly as a raw material for polyester-based thermoplastic elastomer. Specific examples thereof include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. Of these, ethylene glycol and 1,4-butanediol are preferable, and 1,4-butanediol is more preferable.
These may be used alone or in combination of two or more.
[0067]
Examples of the aromatic dicarboxylic acid and / or alicyclic dicarboxylic acid include those commonly used as a raw material for polyesters, particularly as a raw material for polyester-based thermoplastic elastomers. Specific examples thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid and the like. Of these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable, and terephthalic acid is more preferable.
These may be used alone or in combination of two or more.
[0068]
Examples of commercially available polyester-based elastomers include "Primaloy" (manufactured by Mitsubishi Chemical Corporation), "Perprene" (manufactured by Toyobo Co., Ltd.), and "Hytrel" (manufactured by Toray DuPont).
[0069]
The melting point of the polyester-based elastomer has a preferable lower limit of 120 ° C. and a preferred upper limit of 200 ° C.
When the melting point is 120 ° C. or higher, the heat resistance can be sufficiently enhanced and peeling from the solvent-sealed portion can be prevented when the container is coated as a heat-shrinkable label. When the melting point is 200 ° C. or lower, the adhesive strength can be sufficiently increased.
The melting point has a more preferable lower limit of 130 ° C. and a more preferable upper limit of 190 ° C.
The melting point can be measured using a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation) or the like under the condition of a heating rate of 10 ° C./min.
[0070]
The melting point of the polyester-based elastomer is due to the copolymerization ratio and structure of the polyester which is a hard segment and the polyether or polyester which is a soft segment.
Generally, the melting point of a polyester-based elastomer tends to depend on the copolymerization amount of a polyether or polyester which is a soft segment. When the copolymerization amount of the polyether or polyester is large, the melting point is low, and when the copolymerization amount is small, the melting point is high.
Further, the melting point of polyester, which is a hard segment constituting the polyester-based elastomer, can be adjusted by changing the copolymerization component to prepare the melting point of the entire polyester-based elastomer.
Further, when the molecular weight of the soft segment of the polyether or polyester is reduced, the blocking property of the obtained polyester-based elastomer is lowered, so that the melting point is likely to be lowered.
[0071]
The preferable lower limit of the durometer hardness of the polyester-based elastomer is 10, and the preferred upper limit is 80.
When the durometer hardness is 10 or more, the mechanical strength of the adhesive layer can be improved. When the durometer hardness is 80 or less, the flexibility and impact resistance of the adhesive layer can be improved.
The more preferable lower limit of the durometer hardness is 15, the more preferable lower limit is 20, the more preferable upper limit is 70, and the further preferable upper limit is 60.
The durometer hardness can be measured by using the durometer type D by a method conforming to ISO18517.
[0072]
The specific gravity of the polyester-based elastomer has a preferable lower limit of 0.95 and a preferable upper limit of 1.20.
When the specific gravity is 0.95 or more, the heat resistance can be sufficiently enhanced and peeling from the solvent-sealed portion can be prevented when the container is coated as a heat-shrinkable label. When the specific gravity is 1.20 or less, the adhesive strength can be sufficiently increased.
The more preferable lower limit of the specific gravity is 0.98, and the more preferable upper limit is 1.18.
The specific gravity can be measured by an underwater substitution method in a method conforming to ISO 1183.
[0073]
The adhesive layer may contain polystyrene-based resin, polyester-based resin, styrene-based elastomer, or polyester-based elastomer, respectively, or may contain two or more of these.
[0074]
When the adhesive layer contains a mixed resin of the polystyrene resin and the polyester elastomer, the content of the polystyrene resin in the adhesive layer has a preferable lower limit of 20% by weight and a more preferable lower limit of 25% by weight. The preferred upper limit is 80% by weight, and the more preferable upper limit is 75% by weight.
The content of the polyester-based elastomer in the adhesive layer is such that the preferable lower limit is 20% by weight, the more preferable lower limit is 25% by weight, the preferable upper limit is 80% by weight, and the more preferable upper limit is 75% by weight.
[0075]
When the adhesive layer contains a mixed resin of the polystyrene resin and the polyester resin, the content of the polystyrene resin in the adhesive layer has a preferable lower limit of 20% by weight and a more preferable lower limit of 25% by weight. The preferred upper limit is 80% by weight, and the more preferable upper limit is 75% by weight.
The content of the polyester resin in the adhesive layer is such that the preferable lower limit is 20% by weight, the more preferable lower limit is 25% by weight, the preferable upper limit is 80% by weight, and the more preferable upper limit is 75% by weight.
[0076]
When the adhesive layer contains a mixed resin of the polyester resin and the styrene elastomer, the content of the polyester resin in the adhesive layer has a preferable lower limit of 20% by weight and a more preferable lower limit of 25% by weight. The preferred upper limit is 80% by weight, and the more preferable upper limit is 75% by weight.
The content of the styrene-based elastomer in the adhesive layer is such that the preferable lower limit is 20% by weight, the more preferable lower limit is 25% by weight, the preferable upper limit is 80% by weight, and the more preferable upper limit is 75% by weight.
[0077]
When the adhesive layer contains the polystyrene-based resin, the polyester-based resin, and the styrene-based elastomer or a mixed resin containing the polyester-based elastomer, the content of the polystyrene-based resin in the adhesive layer is a preferable lower limit. Is 10% by weight, the more preferable lower limit is 20% by weight, the preferred upper limit is 80% by weight, and the more preferable upper limit is 75% by weight.
The content of the polyester resin in the adhesive layer is such that the preferable lower limit is 10% by weight, the more preferable lower limit is 20% by weight, the preferable upper limit is 80% by weight, and the more preferable upper limit is 75% by weight.
Regarding the content of the styrene-based elastomer or the polyester-based elastomer in the adhesive layer, the preferable lower limit is 2% by weight, the more preferable lower limit is 4% by weight, the preferable upper limit is 10% by weight, and the more preferable upper limit is 8% by weight.
[0078]
If necessary, the adhesive layer may contain additives such as antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, lubricants, antistatic agents, flame retardants, antibacterial agents, fluorescent whitening agents, and colorants. It may be contained.
[0079]
(Characteristics
of Heat-Shrinkable Multilayer Film) Regarding the thickness of the entire heat-shrinkable multilayer film of the present invention, a preferable lower limit is 10 μm, a more preferable lower limit is 15 μm, a further preferable lower limit is 20 μm, a preferable upper limit is 100 μm, and a more preferable upper limit is 80 μm. A more preferable upper limit is 70 μm.
When the thickness of the entire heat-shrinkable multilayer film is within the above range, excellent heat-shrinkability, excellent converting property such as printing or center sealing, and excellent wearability can be obtained.
Further, in the heat-shrinkable multilayer film of the present invention, the thickness of the front and back layers is preferably 7%, a more preferable lower limit is 8%, and a preferable upper limit is 18% with respect to the thickness of the entire heat-shrinkable multilayer film. The preferred upper limit is 16%.
The thickness of the front and back layers means the thickness of the front layer or the back layer, and does not mean the total thickness of the front and back layers.
In the heat-shrinkable multilayer film of the present invention, the thickness of the intermediate layer has a preferable lower limit of 60%, a more preferable lower limit of 65%, a preferable upper limit of 84%, and a more preferable upper limit with respect to the thickness of the entire heat-shrinkable multilayer film. Is 82%.
[0080]
In the heat-shrinkable multilayer film of the present invention, the preferable lower limit of the thickness of the adhesive layer is 0.3 μm, and the preferable upper limit is 3.0 μm.
When the thickness of the adhesive layer is 0.3 μm or more, sufficient adhesiveness can be exhibited. When the thickness of the adhesive layer is 3.0 μm or less, sufficient heat shrinkage characteristics and optical characteristics can be imparted to the heat shrinkable multilayer film.
The more preferable lower limit of the thickness of the adhesive layer is 0.5 μm, and the more preferable upper limit is 2.0 μm.
By subtracting the thickness of the adhesive layer to prepare the thickness of the front and back layers and the intermediate layer, the thickness of the entire heat-shrinkable multilayer film can be prepared.
[0081]
The heat-shrinkable multilayer film of the present invention has a heat-shrinkage rate in the main shrinkage direction (TD direction) when immersed in warm water at 70 ° C. for 10 seconds (hereinafter, "TD heat-shrinkage rate (70 ° C. x 10 seconds)". The preferred lower limit is 15%, and the preferred upper limit is 50%.
When the TD heat shrinkage rate (70 ° C. × 10 seconds) is 15% or more, the shrinkage finish can be improved. When the TD heat shrinkage rate (70 ° C. × 10 seconds) is 50% or less, natural shrinkage can be suppressed.
The TD heat shrinkage rate (70 ° C. × 10 seconds) has a more preferable lower limit of 20%, a further preferable lower limit of 25%, a particularly preferable lower limit of 30%, a more preferable upper limit of 47%, and a further preferable upper limit of 45%. ..
The heat shrinkage rate can be calculated from the length after heat shrinkage at a predetermined temperature and time and the ratio with the length before heat shrinkage.
[0082]
The heat-shrinkable multilayer film of the present invention has a heat-shrinkage rate in the main shrinkage direction (TD direction) when immersed in warm water at 80 ° C. for 10 seconds (hereinafter, "TD heat-shrinkage rate (80 ° C. x 10 seconds)". The preferred lower limit is 50%, and the preferred upper limit is 70%.
When the TD heat shrinkage rate (80 ° C. × 10 seconds) is 50% or more, it is possible to prevent the occurrence of wrinkles and the like when shrinking. When the TD heat shrinkage rate (80 ° C. × 10 seconds) is 70% or less, it is possible to prevent appearance defects such as label misalignment when shrinking.
Regarding the TD heat shrinkage rate (80 ° C. × 10 seconds), a more preferable lower limit is 55%, a further preferable lower limit is 58%, a particularly preferable lower limit is 60%, a more preferable upper limit is 69%, and a further preferable upper limit is 68%, particularly. The preferred upper limit is 67%.
[0083]
The heat-shrinkable multilayer film of the present invention has a heat-shrinkage rate in the main shrinkage direction (TD direction) when immersed in warm water at 100 ° C. for 10 seconds (hereinafter, "TD heat-shrinkage rate (100 ° C. x 10 seconds)". The preferred lower limit is 65%, and the preferred upper limit is 85%.
When the TD heat shrinkage rate (100 ° C. × 10 seconds) is 65% or more, it is possible to prevent the occurrence of wrinkles and the like when shrinking. When the TD heat shrinkage rate (100 ° C. × 10 seconds) is 85% or less, it is possible to prevent appearance defects such as label misalignment when shrinking.
The TD heat shrinkage rate (100 ° C. × 10 seconds) has a more preferable lower limit of 70%, a further preferable lower limit of 75%, a more preferable upper limit of 83%, and a further preferable upper limit of 82%.
[0084]
The heat-shrinkable multilayer film of the present invention has a preferable lower limit of 3.5 MPa and a preferable upper limit of 11 MPa when immersed in warm water at 80 ° C. for 30 seconds.
When the maximum shrinkage stress is 3.5 MPa or more, the shrinkage finish when mounted on a container can be sufficiently enhanced. When the maximum shrinkage stress is 11 MPa or less, the displacement between layers at the center seal portion of the label can be suppressed. In addition, it is possible to prevent the container from being deformed when it is attached to the container.
The more preferable lower limit of the maximum shrinkage stress is 4.5 MPa, and the more preferable upper limit is 10 MPa.
The maximum shrinkage stress refers to the maximum value of the shrinkage stress when the heat-shrinkable multilayer film is immersed in warm water at 80 ° C. for 30 seconds and the shrinkage stress is measured.
[0085]
In the heat-shrinkable multilayer film of the present invention, the preferable lower limit of the interlayer strength (adhesive strength) in the direction orthogonal to the main shrinkage direction (MD direction) is 0.8 N / 10 mm, and the preferable upper limit is 2 N / 10 mm.
When the interlayer strength is within the above range, delamination can be prevented when the heat-shrinkable label is attached to the container.
The more preferable lower limit of the interlayer strength is 0.9 N / 10 mm, and the more preferable lower limit is 1 N / 10 mm.
Further, in the heat-shrinkable multilayer film of the present invention, the preferable lower limit of the interlayer strength in the main shrinkage direction (TD direction) is 0.5 N / 10 mm, and the preferable upper limit is 2 N / 10 mm.
When the interlayer strength is within the above range, it is possible to prevent delamination due to wear when the label is attached to the container and transported.
The more preferable lower limit of the interlayer strength is 0.65 N / 10 mm, and the more preferable lower limit is 0.8 N / 10 mm.
[0086]
In the heat-shrinkable multilayer film of the present invention, the preferable upper limit of the tear strength in the main shrinkage direction (TD direction) is 200 mN.
In the heat-shrinkable multilayer film of the present invention, the preferable lower limit of the tear strength in the direction orthogonal to the main shrinkage direction (MD direction) is 1000 mN, and the preferable upper limit is 3000 mN.
The tear strength can be measured by a method conforming to ISO 6383-2.
[0087]
The heat-shrinkable multilayer film of the present invention has a preferable lower limit of impact drilling strength of 0.3 J.
The impact drilling strength can be measured by a method based on ISO 3036: 1975.
[0088]
The method for producing the heat-shrinkable multilayer film of the present invention is not particularly limited, but a method in which each layer is simultaneously molded by a coextrusion method is preferable. When the coextrusion method is coextrusion with a T-die, the laminating method may be a feed block method, a multi-manifold method, or a method in which these are used in combination.
[0089]
Specifically, as a method for producing the heat-shrinkable multilayer film of the present invention, for example, the raw materials constituting the front and back layers, the intermediate layer and the adhesive layer are put into an extruder, and a sheet is formed by using a multilayer die. There is a method of extruding the film, cooling and solidifying it with a take-up roll, and then stretching it in one or two axes.
As the stretching method, for example, a roll stretching method, a tenter stretching method, or a combination thereof can be used. The stretching temperature varies depending on the softening temperature of the resin constituting the film, the shrinkage characteristics required for the heat-shrinkable multilayer film, etc., but the preferable lower limit is 65 ° C, the more preferable lower limit is 70 ° C, and the preferable upper limit is 120 ° C. A more preferable upper limit is 115 ° C. The stretching ratio in the main shrinkage direction varies depending on the resin constituting the film, the stretching means, the stretching temperature, etc., but is preferably 3 times or more, more preferably 4 times or more, preferably 7 times or less, and more. It is preferably 6 times or less. By setting the stretching temperature and stretching ratio as such, excellent thickness accuracy can be achieved, and when the perforations are torn, delamination occurs and only the front and back layers on the inner surface side remain in the container. It is possible to prevent it from being stored.
[0090]
The use of the heat-shrinkable multilayer film of the present invention is not particularly limited, but the heat-shrinkable multilayer film of the present invention has high interlayer strength, and when the overlapped portion is scratched or the perforations are torn after mounting the container. Since it suppresses delamination and has excellent transparency, it is suitably used as a base film for heat-shrinkable labels attached to containers such as PET bottles and metal cans. A heat-shrinkable label made of the heat-shrinkable multilayer film of the present invention is also one of the present inventions.
Effect of the invention
[0091]
According to the present invention, it is possible to provide a heat-shrinkable multilayer film capable of producing a heat-shrinkable label having excellent perforation cutability in both the TD direction and the MD direction and also having excellent impact resistance and transparency. Can be done.
Mode for carrying out the invention
[0092]
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[0093]
In the examples and comparative examples, the following raw materials were used.
(Polyester-based resin)
-Polyester-based resin A: Dicarboxylic acid component (component derived from terephthalic acid: 100 mol%) and diol component (component derived from ethylene glycol: 65 mol%, component derived from diethylene glycol: 20 mol%) , 1,4-Cyclohexanedimethanol-derived component: 15 mol%) polyester resin (glass transition temperature: 69 ° C)
( polyester resin)
, polystyrene resin A: styrene-butadiene copolymer (containing styrene) Amount: 81.3% by weight, butadiene content: 18.7% by weight, Vicat softening temperature: 81 ° C.)
・ Polyester resin B: Polyester-butadiene copolymer (styrene content: 77.7% by weight, containing butadiene) Amount: 22.3% by weight, Vicat softening temperature: 71 ° C.)
・ Polyester resin C: styrene-butadiene copolymer (styrene content: 72% by weight, butadiene content: 28% by weight, Vicat softening temperature: 76 ° C.) )
(polyester-based elastomer)
elastomer a: a polyester as a hard segment composed of a polyether as a soft segment unmodified polyester-polyether block copolymer (durometer hardness: 55, glass transition temperature: 45 ℃, Vicat softening temperature: 126 ℃, melting point: 191 ℃, specific gravity: 1.17)
[0094]
(Example 1) As
the resin constituting the front and back layers, 100% by weight of polyester resin A was used.
As the resin constituting the adhesive layer, a mixed resin containing 30% by weight of the elastomer A and 70% by weight of the polystyrene resin C was used.
As the resin constituting the intermediate layer, a mixed resin containing 15% by weight of the polyester resin A, 25% by weight of the polystyrene resin A and 60% by weight of the polystyrene resin B was used.
These resins were put into an extruder having a barrel temperature of 160 to 250 ° C., extruded into a sheet having a five-layer structure from a multilayer die at 250 ° C., and cooled and solidified by a take-up roll at 30 ° C. Next, after stretching at a stretching ratio of 6 times in a tenter stretching machine at a preheating zone of 105 ° C., a stretching zone of 90 ° C., and a heat fixing zone of 85 ° C., the film is wound by a winding machine so that the direction orthogonal to the main contraction direction is MD. , A heat-shrinkable multilayer film having a main shrinkage direction of TD was obtained.
The obtained heat-shrinkable multilayer film has a total thickness of 40 μm, and has a surface layer (5.7 μm) / adhesive layer (0.7 μm) / intermediate layer (27.2 μm) / adhesive layer (0.7 μm) / back surface. It had a five-layer structure of layers (5.7 μm).
[0095]
(Example 2) As
the resin constituting the front and back layers, 100% by weight of polyester resin A was used.
As the resin constituting the adhesive layer, a mixed resin containing 65% by weight of the elastomer A and 35% by weight of the polystyrene resin C was used.
As the resin constituting the intermediate layer, a mixed resin containing 15% by weight of the polyester resin A, 25% by weight of the polystyrene resin A and 60% by weight of the polystyrene resin B was used.
These resins were put into an extruder having a barrel temperature of 160 to 250 ° C., extruded into a sheet having a five-layer structure from a multilayer die at 250 ° C., and cooled and solidified by a take-up roll at 30 ° C. Next, after stretching at a stretching ratio of 6 times in a tenter stretching machine at a preheating zone of 105 ° C., a stretching zone of 90 ° C., and a heat fixing zone of 85 ° C., the film is wound by a winding machine so that the direction orthogonal to the main contraction direction is MD. , A heat-shrinkable multilayer film having a main shrinkage direction of TD was obtained.
The obtained heat-shrinkable multilayer film has a total thickness of 50 μm and has a five-layer structure of a surface layer (7 μm) / adhesive layer (1 μm) / intermediate layer (34 μm) / adhesive layer (1 μm) / back layer (7 μm). Met.
[0096]
(Example 3) The same
as in Example 1 except that a mixed resin containing 5% by weight of polyester resin A, 28% by weight of polystyrene resin A and 67% by weight of polystyrene resin B was used as the resin constituting the intermediate layer. A heat-shrinkable multilayer film was obtained.
[0097]
(Example 4) The same
as in Example 1 except that a mixed resin containing 10% by weight of polyester resin A, 27% by weight of polystyrene resin A and 63% by weight of polystyrene resin B was used as the resin constituting the intermediate layer. A heat-shrinkable multilayer film was obtained.
[0098]
(Comparative Example 1) As
the resin constituting the front and back layers, 100% by weight of polyester resin A was used.
As the resin constituting the adhesive layer, a mixed resin containing 30% by weight of the elastomer A and 70% by weight of the polystyrene resin C was used.
As the resin constituting the intermediate layer, a mixed resin containing 30% by weight of the polystyrene-based resin A and 70% by weight of the polystyrene-based resin B was used.
These resins were put into an extruder having a barrel temperature of 160 to 250 ° C., extruded into a sheet having a five-layer structure from a multilayer die at 250 ° C., and cooled and solidified by a take-up roll at 30 ° C. Next, after stretching at a stretching ratio of 6 times in a tenter stretching machine at a preheating zone of 105 ° C., a stretching zone of 90 ° C., and a heat fixing zone of 85 ° C., the film is wound by a winding machine so that the direction orthogonal to the main contraction direction is MD. , A heat-shrinkable multilayer film having a main shrinkage direction of TD was obtained.
The obtained heat-shrinkable multilayer film has a total thickness of 40 μm, and has a surface layer (5.7 μm) / adhesive layer (0.7 μm) / intermediate layer (27.2 μm) / adhesive layer (0.7 μm) / back surface. It had a five-layer structure of layers (5.7 μm).
[0099]
(Evaluation) The
heat-shrinkable multilayer films produced in Examples and Comparative Examples were evaluated by the following methods.
The results are shown in Table 1.
[0100]
(1) Tear strength
in MD direction and TD direction Tear strength in MD direction and TD direction was measured using HEIDONTYPE: 17 manufactured by Shinto Kagaku Co., Ltd. in accordance with ISO 6383-2.
[0101]
(2) Impact drilling strength The
impact drilling strength was measured using a film impact tester manufactured by Toyo Seiki Seisakusho in accordance with ISO 3036: 1975.
[0102]
(3)
Cutability at perforations Thirty PET bottles (those that could be attached without delamination or wrinkles) equipped with shrink labels were manually torn from the perforations to remove the shrink labels. The state at this time was observed, and the heat resistance was evaluated according to the following criteria.
◯: The perforations in the MD direction and the TD direction were easily broken, and the shrink label could be removed.
X: It was difficult to remove because it could not be cut along the perforation.
[0103]
(4) Haze
was measured using NDH5000 manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with ISO 14782.
[0104]
[table 1]

Industrial applicability
[0105]
According to the present invention, it is possible to provide a heat-shrinkable multilayer film capable of producing a heat-shrinkable label having excellent perforation cutability in both the TD direction and the MD direction and also having excellent impact resistance and transparency. Can be done.
The scope of the claims
[Claim 1]
The front and back layers and the intermediate layer are heat-shrinkable multilayer films laminated via an adhesive layer. The
front and back layers contain a polyester resin, and the
intermediate layer contains 80 to 99 polystyrene resins.
A heat-shrinkable multilayer film containing 1 to 20% by weight of a polyester resin .
[Claim 2]
The heat-shrinkable multilayer film according to claim 1, wherein the adhesive layer contains a polystyrene-based resin, a polyester-based resin, a styrene-based elastomer, or a polyester-based elastomer.
[Claim 3]
The intermediate layer is characterized by containing 50 to 99% by weight of a polystyrene resin having a Vicat softening temperature of less than 80 ° C. and 1 to 50% by weight of a polystyrene resin having a Vicat softening temperature of 80 ° C. or higher. The heat-shrinkable multilayer film according to 1 or 2.
[Claim 4]
The heat-shrinkable multilayer film according to claim 1, 2 or 3, wherein the intermediate layer further contains a styrene-based elastomer or a polyester-based elastomer.
[Claim 5]
The heat-shrinkable multilayer film according to claim 1, 2, 3 or 4, wherein the polyester-based resin constituting the intermediate layer has a glass transition temperature of 30 to 95 ° C.
[Claim 6]
A heat-shrinkable label comprising the heat-shrinkable multilayer film according to claim 1, 2, 3, 4 or 5.