JP2006315416A - Heat shrinkable laminated film, molded article, heat shrinkable label and container using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat shrinkable laminated film, a molded article, a heat shrinkable label and container which have an excellent breaking resistance, rigidity and shrinking finish, wherein free shrinking and interlaminar separation are suppressed. <P>SOLUTION: In a laminated film comprising a surface layer (S layer) containing a polyester resin as a main component, an intermediate layer (M layer) containing a styrene resin as a main component and an adhesive layer (AD layer) containing an adhesive resin as a main component, a heat shrinkage factor in at least one direction after immersing in a warm water at 70°C for 10 sec. is adjusted to 10% or more and less than 30%, and that of after immersing in a warm water at 80°C for 10 sec. is adjusted to 30% or more. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a heat-shrinkable laminated film, a molded product using the film, a heat-shrinkable label, and a container equipped with the molded product or the heat-shrinkable label. More specifically, the present invention is excellent in low-temperature shrinkage, rigidity, and shrink finish, and particularly suitable for applications such as shrink labels, molded articles using the film, heat-shrinkable labels, and The present invention relates to a container equipped with the molded product or the heat-shrinkable label.

  Conventionally, polyester-based and polystyrene-based heat-shrinkable films have been mainly used as heat-shrinkable films for shrink labels in plastic containers (mainly PET bottles). The polyester heat-shrinkable film has a low natural shrinkage ratio and good low-temperature shrinkage and rigidity, but has a problem in that uniform shrinkage cannot be obtained, resulting in shrinkage unevenness and shrinkage finish failure. Further, when the polyester heat-shrinkable film is used for labeling or the like, there is a problem in that the appearance shrinkage is caused because shrinkage occurs not only in the main shrinkage direction but also in the vertical direction.

On the other hand, as the polystyrene-based heat-shrinkable film, a polystyrene-based heat-shrinkable film having a styrene-butadiene block copolymer (SBS) as a main material has been conventionally used. The polystyrene-based heat-shrinkable film has good shrinkage finishing properties, but has a problem that the natural shrinkage rate increases when imparted with low-temperature shrinkage. In particular, recently, in heat-shrinkable films using SBS, the problem that the film itself deteriorates and breaks during printing and bag making due to the printing solvent has also become apparent. Furthermore, the polystyrene-based heat-shrinkable film mainly composed of SBS can improve the rupture resistance by increasing the content of butadiene which is a rubber component. However, in that case, since the rigidity of the film is lowered, there is a problem of compatibility between the rigidity of the film and the fracture resistance.

As means for solving the above problems, a two-layered three-layer film in which an outermost layer composed of a polyester resin is laminated on an intermediate layer composed of a polystyrene resin has been reported so far (for example, Patent Documents). 1). However, this two-layer / three-layer laminated film is inferior in transparency as compared with conventional polyethylene-based and polystyrene-based heat-shrinkable films, and when the film is contracted, it is between the outermost layer and the intermediate layer. There was a drawback of causing delamination. In order to solve this drawback, a two-layer / three-layer film using a polystyrene resin as an intermediate layer and a polyester resin containing 1,4-cyclohexanedimethanol as an outer layer has also been proposed (for example, Patent Document 2). And 3). However, the film described in Patent Document 2 has insufficient rupture resistance, and when a bag is made using a solvent as in a label application, the seal part peels off between layers, and sufficient solvent seal strength is It was not obtained. Furthermore, the film described in Patent Document 3 has insufficient fracture resistance, and further has insufficient shrink finish.
JP-A-61-41543 (Claims, page 8, upper left column, line 15 to page 8, upper right column, line 9) JP 7-137212 A (Claim 1, [0019] to [0029]) JP 2002-351332 A (Claim 1, [0020] to [0027])

  The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is a heat having excellent rupture resistance, rigidity and shrink finish, and having reduced natural shrinkage and delamination. The object is to provide a shrinkable laminated film.

  Another object of the present invention is to provide a molded article and a container having excellent rupture resistance, rigidity, shrink finish, and delamination strength using the heat shrinkable laminated film.

In order to solve the above-mentioned problems of the prior art, the present inventor has intensively studied a layer structure capable of obtaining desired fracture resistance, rigidity, and shrink finish when producing a stretched film. It came.
That is, the object of the present invention is achieved by the following heat-shrinkable laminated film, a molded article using the laminated film, a heat-shrinkable label, and a container equipped with the molded article or the heat-shrinkable label.

(1) A laminated film having a surface layer (S layer), an intermediate layer (M layer), and an adhesive layer (AD layer), wherein each layer is made of a resin having the following components as main components, and in 70 ° C. warm water The thermal shrinkage rate when immersed for 10 seconds is 10% or more and less than 30% in at least one, and the thermal shrinkage rate when immersed in warm water at 80 ° C. for 10 seconds is 30% or more and 70% or less in at least one. A heat-shrinkable laminated film characterized by
(S layer): Polyester resin (M layer): Styrene resin (AD layer): Adhesive resin (2) The adhesive resin of the adhesive layer (AD layer) consists of a surface layer (S layer) and an intermediate layer (M The heat-shrinkable laminated film according to (1), which is a mixture of resins contained in the layer.
(3) The adhesive resin of the adhesive layer (AD layer) has a polar group that has a high affinity or can react with soft styrene resins, modified styrene resins, and polyester resins, and is compatible with styrene resins. The heat-shrinkable laminated film according to (1), which is one resin selected from the group consisting of possible resins, or a mixture thereof.
(4) The polystyrene resin of the intermediate layer (M layer) is a styrene-butadiene block copolymer (SBS), a styrene-isoprene-butadiene block copolymer (SIBS), or a mixture thereof (1) to ( The heat-shrinkable laminated film according to any one of 3).
(5) The polyester-based resin of the surface layer (S layer) is composed of a dicarboxylic acid residue and a diol residue, and at least one of the dicarboxylic acid residue and the diol residue is composed of two or more residues. The total content of residues other than the most abundant residues among the two or more residues is the total amount of the dicarboxylic acid residues (100 mol%) and the total amount of the diol residues (100 mol%). The heat-shrinkable laminated film according to any one of (1) to (4), which is 10% to 40% by mole with respect to the total (200% by mole).
(6) The seal strength when peeled at a tensile rate of 200 mm / min in an environment of 23 ° C. and 50% RH is 3 N / 15 mm width or more and 20 N / 15 mm width or less according to any one of (1) to (5) Heat shrinkable laminated film.
(7) A molded product comprising the heat-shrinkable laminated film according to any one of (1) to (6) as a base material.
(8) A heat-shrinkable label comprising the heat-shrinkable laminated film according to any one of (1) to (6) as a base material.
(9) A container equipped with the molded article according to (7) or the heat-shrinkable label according to (8).

  The heat-shrinkable laminated film of the present invention (hereinafter referred to as “film of the present invention”) uses a styrene-based resin as the resin constituting the intermediate layer (M layer), and the surface layers (B) on both sides of the intermediate layer (M layer). A polyester resin is used as the resin constituting the S layer), and an adhesive layer (AD layer) mainly composed of an adhesive resin is interposed between the intermediate layer (M layer) and the surface layer (S layer). It is a film obtained by stretching the laminated sheet at least uniaxially. With this configuration, according to the present invention, it is possible to provide a heat-shrinkable film having excellent rupture resistance, rigidity, transparency, and shrink finish, and having reduced natural shrinkage and delamination.

  Moreover, since the molded product and container of the present invention are based on the film of the present invention, they have excellent rupture resistance, rigidity, transparency and shrink finish, and natural shrinkage and delamination are suppressed, It is possible to provide a molded product or a mounted container that has a beautiful appearance without abnormalities such as generation of wrinkles and avatars and insufficient shrinkage at a predetermined position regardless of the shape of the mounted object.

  Hereinafter, the film, molded product, heat-shrinkable film, and container equipped with the molded product or heat-shrinkable film of the present invention will be described in detail.

  It should be noted that the upper and lower limits of the numerical range in the present invention are those of the present invention as long as they have the same operational effects as those in the numerical range even if they are slightly outside the numerical range specified by the present invention. Include within the equivalent range. Further, in the present specification, “main component” is intended to allow other components to be included within a range that does not hinder the action and effect of the resin constituting each layer. Although this term does not restrict | limit a specific content rate, it is a component which occupies 50 mass% or more of the whole component of each layer, Preferably it is 70 mass% or more, More preferably, it is 80 mass% or more. In addition, the upper and lower limits of the numerical range in the present invention, even if slightly deviating from the numerical range specified by the present invention, as long as the same effect as in the numerical range is provided. Include within the equivalent range.

[Heat-shrinkable laminated film]
The film of the present invention has a surface layer (S layer) whose main component is a polyester-based resin, and an intermediate layer (M layer) whose main component is a styrene-based resin, and further has a surface layer (S layer) and an intermediate layer. It is a heat-shrinkable laminated film in which an adhesive layer (AD layer) is interposed between the layer (M layer).

  By using a polyester-based resin for the surface layer (S layer) of the film, it is possible to give the film rigidity and rupture resistance, impart low-temperature shrinkage, and suppress natural shrinkage. However, as described above, uniform shrinkage cannot be obtained only with a polyester-based resin, and there are problems such as shrinkage unevenness such as shrinkage unevenness and appearance defects due to shrinkage in the main shrinkage direction and the vertical direction in label applications. There is.

Therefore, the film of the present invention is formed by interposing an intermediate layer (M layer) mainly composed of a polystyrene resin between surface layers (S layer) composed mainly of a polyester resin. The problem can be solved. That is, the film of the present invention is obtained by interposing an intermediate layer (M layer) mainly composed of a styrene resin between a surface layer (S layer) composed mainly of a polyester resin. It has both good shrinkage finish that could not be solved with a film composed solely of polyester resin, and the strength of waist that could not be resolved with a film composed solely of styrenic resin. A film capable of suppressing shrinkage in the direction perpendicular to the shrinkage direction is obtained. As a result, according to the film of the present invention, it is possible to provide a heat-shrinkable laminated film having rigidity, rupture resistance, and low natural shrinkage and having improved shrink finish.

  A laminated film consisting of a polyester-based resin layer and a styrene-based resin layer is constructed by laminating layers containing different types of resin, so when making a bag like a label application, in the sealing part of the bag-making There is a possibility that delamination occurs and the seal strength is reduced. Therefore, the film of the present invention has an adhesive layer (AD layer) interposed between the polyester-based resin layer (S layer) and the styrene-based resin layer (M layer) in order to eliminate such drawbacks. Improve seal strength).

  Further, when a mixture of the polyester resin used in the surface layer (S layer) and the styrene resin used in the intermediate layer (M layer) is used as the adhesive layer (AD layer), the surface layer (S layer) and the intermediate layer are used. In addition to suppressing delamination with the (M layer) and maintaining good transparency of the film, the tail portion of the film of the present invention, which becomes waste in the film forming process, is reused as a raw material for the adhesive layer. Can do. Thereby, the film of the present invention can minimize the delamination of the laminated film and the decrease in transparency, and the film can be recycled.

Next, each layer which comprises the film of this invention is demonstrated.
<Intermediate layer (M layer)>
In the present invention, a styrenic resin is used as the resin constituting the main component of the intermediate layer (M layer) of the film. As the styrene resin, block copolymerization of a styrene hydrocarbon and a conjugated diene hydrocarbon is preferably used. Examples of the styrenic hydrocarbon include polystyrene, poly (p-, m- or o-methylstyrene), poly (2,4-, 2,5-, 3,4- or 3,5-dimethylstyrene), Polyalkylstyrenes such as poly (pt-butylstyrene); poly (o-, m- or p-chlorostyrene), poly (o-, m- or p-bromostyrene), poly (o-, m- Or p-fluorostyrene), poly (halogenated styrene) such as poly (o-methyl-p-fluorostyrene); polyhalogenated substituted alkylstyrene such as poly (o-, m- or p-chloromethylstyrene); poly ( p-, m-, or o-methoxystyrene), poly (o-, m-, or p-ethoxystyrene) and other polyalkoxystyrenes; poly (o-, m-, or p-carboxymethylstyrene), etc. Li carboxyalkyl styrene, poly (p- trimethylsilylstyrene) polyalkyl silyl styrene such as; poly (p- vinylbenzyl ether) and poly alkyl ether styrene more polyvinyl benzyl dimethoxyphosphinyl sulfide and the like. The styrenic hydrocarbon block may contain a homopolymer, a copolymer and / or a copolymerizable monomer other than the styrenic hydrocarbon in the block.

  Examples of conjugated diene hydrocarbons include butadiene, isoprene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. It is done. The conjugated diene hydrocarbon block may contain a copolymerizable monomer other than these homopolymers, copolymers and / or conjugated diene hydrocarbons in the block.

As one of the block copolymers of styrene hydrocarbons and conjugated diene hydrocarbons preferably used in the intermediate layer (M layer), the styrene hydrocarbon is styrene and the conjugated diene hydrocarbon is butadiene. And styrene-butadiene block copolymer (SBS). SBS preferably has a styrene / butadiene mass% ratio of about (95-60) / (5-40), more preferably (93-60) / (7-40), (90- More preferably, it is about 60) / (10-40). Furthermore, the melt flow rate (MFR) measurement value of SBS (measurement conditions: temperature 200 ° C., load 49 N) is 2 g /
It is 10 minutes or more, preferably 3 g / 10 minutes or more, and 15 g / 10 minutes or less, preferably 10 g / 10 minutes or less, more preferably 8 g / 10 minutes or less.

  Another example of the styrene hydrocarbon and conjugated diene hydrocarbon block copolymer preferably used in the present invention is a styrene-isoprene-butadiene block copolymer (SIBS). In SIBS, the mass% ratio of styrene / isoprene / butadiene is preferably (60-90) / (5-40) / (5-30), (60-85) / (10-30) / ( 5 to 25) is more preferable, and (60 to 80) / (10 to 25) / (5 to 20) is more preferable. Further, the melt flow rate (MFR) measurement value (measurement conditions: temperature 200 ° C., load 49 N) of SIBS is 2 g / 10 min or more, preferably 3 g / 10 min or more, and 15 g / 10 min or less, preferably It is desirable that it is 10 g / 10 min or less, more preferably 8 g / 10 min or less. If the butadiene content is high and the isoprene content is low, the butadiene heated inside the extruder or the like may cause a cross-linking reaction to increase the gel-like material. On the other hand, if the butadiene content is low and the isoprene content is high, the raw material unit price may increase and the production cost may increase.

  The styrenic resin is not limited to a simple substance, and may be a mixture of two or more. For example, when the styrenic resin is a mixture of SBS and SIBS, the mass% ratio of SBS / SIBS is preferably about (90 to 10) / (10 to 90), and (80 to 20) / ( More preferably, it is about 20-80), more preferably about (70-30) / (30-70).

  The content of the styrenic resin contained in the intermediate layer (M layer) is 50% by mass or more, preferably 65% by mass or more, and preferably 80% by mass or more of the total amount of the resin constituting the intermediate layer (M layer). More preferably. However, when GPPS is contained, the TPS (peak temperature of loss elastic modulus E ″) of GPPS is as high as about 100 ° C., so the content of GPPS to be mixed is a resin constituting the intermediate layer (M layer) The total amount is 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less.

  If the styrene-based resin contained in the intermediate layer (M layer) is contained in an amount of 50% by mass or more of the total amount of the resin constituting the intermediate layer (M layer) as described above, other resins can be mixed. Examples of such resins include polyester resins, polyolefin resins, acrylic resins, polycarbonate resins, and the like, among which polyester resins are preferable.

When the styrene resin contained in the intermediate layer (M layer) is a block copolymer of a styrene hydrocarbon and a conjugated diene hydrocarbon, the refractive index measured according to JIS K7142 of the block copolymer ( n ₁ ) is desirably within a range of ± 0.02, preferably ± 0.015, of the refractive index (n ₂ ) of the polyester resin contained in the surface layer (S layer). Thus, by adjusting the difference between the refractive index of the intermediate layer (M layer) and the refractive index of the surface layer (S layer) within a predetermined range, a cut piece of the film generated in the film manufacturing process can be obtained. Even when the film is kneaded into an adhesive layer (AD layer) described later, a film having good transparency can be obtained.

The styrene-based hydrocarbon and conjugated diene-based hydrocarbon block copolymer has a refractive index (n ₁ ) substantially equal to a desired value by appropriately adjusting the composition ratio of the styrene-based hydrocarbon and the conjugated diene-based hydrocarbon. Can be adjusted. Therefore, by adjusting the composition ratio of the styrene hydrocarbon and the conjugated diene hydrocarbon corresponding to the refractive index (n ₂ ) of the polyester resin used in the surface layer (S layer), n ₂ ± 0.02 A refractive index (n ₁ ) within the range is obtained. This predetermined refractive index may be adjusted with a styrene-based hydrocarbon and a conjugated diene-based hydrocarbon block copolymer alone or may be adjusted by mixing two or more resins.

In the present invention, the storage elastic modulus (E ′) at 0 ° C. of the styrene resin contained in the intermediate layer (M layer) is preferably 1.00 × 10 ⁹ Pa or more, and 1.50 × 10 ⁹ Pa or more. More preferably. The storage elastic modulus (E ′) at 0 ° C. represents the rigidity of the film, that is, the strength of the film. By having a storage elastic modulus (E ′) of 1.00 × 10 ⁹ Pa or more, a film having rigidity in addition to transparency can be obtained. This storage elastic modulus (E ′) is a block copolymer of the above-mentioned styrenic hydrocarbon and conjugated diene hydrocarbon, a mixture of two or more of these copolymers, or a range that does not impair transparency. It can be obtained by mixing with other resins.

  When using a mixed system of a block copolymer of a styrene hydrocarbon and a conjugated diene hydrocarbon or a mixed system of the copolymer and another resin as a main component of the intermediate layer (M layer), fracture resistance Good results can be obtained by appropriately selecting a copolymer or resin that bears the properties and a copolymer or resin that bears the rigidity. That is, by combining a styrene hydrocarbon-conjugated diene hydrocarbon block copolymer having high fracture resistance with a styrene hydrocarbon-conjugated diene hydrocarbon block copolymer having high rigidity, or high By mixing a styrenic hydrocarbon-conjugated diene hydrocarbon block copolymer having rupture resistance and other types of resins having high rigidity, these styrenic hydrocarbon-conjugated diene hydrocarbons are mixed. The total composition, or a mixture of these and other types of resins, can be adjusted to meet the desired refractive index (n1) and storage modulus (E ') at 0 ° C.

Preferred as the styrene-based hydrocarbon-conjugated diene-based hydrocarbon block copolymer capable of imparting fracture resistance are pure block SBS and random block SBS. Among them, the storage elastic modulus (E ′) at 0 ° C. is 1.00 × 10 ⁸ Pa or more and 1.00 × 10 ⁹ Pa or less, and at least one peak temperature of the loss elastic modulus (E ″) is − Those having viscoelastic properties at 20 ° C. or lower are particularly preferred. If the storage elastic modulus at 0 ° C. is 1.0 × 10 ⁸ Pa or more, waist strength can be imparted by increasing the blend amount of the resin responsible for rigidity. On the other hand, at the peak temperature of the loss elastic modulus (E ″), the temperature on the low temperature side mainly shows fracture resistance. Although the characteristics vary depending on the stretching conditions, it is difficult to impart sufficient film breakability to the laminated film when the peak temperature of the loss modulus (E ″) is not below −20 ° C. before stretching. It may become.

Further, as a resin capable of imparting rigidity, a copolymer composed of a styrene hydrocarbon having a storage elastic modulus (E ′) at 0 ° C. of 2.00 × 10 ⁹ Pa or more, for example, a styrene resin having a controlled block structure Examples thereof include block copolymers of hydrocarbons and conjugated diene hydrocarbons, polystyrene, styrene hydrocarbons and aliphatic unsaturated carboxylic acid ester copolymers.

As the styrene hydrocarbon-conjugated diene hydrocarbon block copolymer having a controlled block structure, the storage elastic modulus (E ′) at 0 ° C. is 2.00 × 10 ⁹ as a characteristic of the styrene-butadiene block copolymer. SBS that is Pa or higher is exemplified. The composition ratio of styrene-butadiene of SBS satisfying this is preferably adjusted to about styrene / butadiene = (95-80) / (5-20).

  The structure of the block copolymer and the structure of each block part are preferably a random block and a tapered block. More preferably, in order to control the shrinkage characteristic, the peak temperature of the loss modulus (E ″) is 40 ° C. or more, and more preferably, the clear loss modulus (E ″) is 40 ° C. or less. There is no peak temperature. When the peak temperature of the loss elastic modulus (E ″) does not exist up to 40 ° C., the storage elastic modulus characteristic is almost the same as that of polystyrene, so that the rigidity of the film can be imparted. Further, the peak temperature of the loss modulus (E ″) exists in the range of 40 ° C. or higher, preferably 40 ° C. or higher and 90 ° C. or lower. This peak temperature is a factor that mainly affects the shrinkage rate. If this temperature is in the range of 40 ° C. or more and 90 ° C. or less, the natural shrinkage and the low temperature shrinkage rate are not extremely lowered.

A polymerization method of a styrene-based hydrocarbon-conjugated diene-based hydrocarbon copolymer that satisfies the above viscoelastic properties is shown below. Usually, after a part of styrene or butadiene is charged to complete the polymerization, a mixture of styrene monomer and butadiene monomer is charged and the polymerization reaction is continued. This preferentially polymerizes butadiene having a higher polymerization activity, and finally a block composed of a single monomer of styrene is generated. For example, when styrene is homopolymerized first, and after the polymerization is completed, a mixture of styrene monomer and butadiene monomer is added and polymerization is continued, so that the styrene / butadiene monomer ratio gradually changes between the styrene block and the butadiene block. A styrene-butadiene block copolymer having a copolymer site is obtained. By providing such a site, a polymer having the above viscoelastic properties can be obtained. In this case, the two peaks due to the butadiene block and the styrene block as described above cannot be clearly confirmed, and it appears that only one peak exists. That is, in a block structure such as SBS of a random block in which a pure block and a butadiene block are clearly present, Tg due to the butadiene block is mainly present at 0 ° C. or less, and therefore, storage modulus at 0 ° C. ( It becomes difficult for E ′) to be not less than a predetermined value. Further, regarding the molecular weight, the melt flow rate (MFR) measurement value (measurement conditions: temperature 200 ° C., load 49 N) is adjusted in the range of 2 g / 10 min to 15 g / 10 min. The mixing amount of the styrene-butadiene block copolymer imparting this rigidity is appropriately adjusted according to the characteristics of the heat-shrinkable laminated film, and is 20% by mass or more and 80% by mass of the total amount of the resin constituting the intermediate layer (M layer). % Or less, preferably 40% by mass or more and 70% by mass or less. If it is 80 mass% or less of resin total amount, the rigidity of a film can be improved significantly and it can suppress that fracture resistance falls. On the other hand, if it is 20 mass% or more of the total resin amount, sufficient rigidity can be imparted to the film.

  The molecular weight of the styrenic resin contained in the intermediate layer (M layer) has a weight (mass) average molecular weight (Mw) of 100,000 or more, preferably 150,000 or more and 500,000 or less, preferably 400,000. 000 or less, more preferably 300,000 or less. If the weight (mass) average molecular weight (Mw) of a styrene resin is 100,000 or more, it is preferable without a defect which causes deterioration of a film. Furthermore, if the molecular weight of the styrene resin is 500,000 or less, there is no need to adjust the flow characteristics and there are no defects such as a decrease in extrudability, which is preferable.

  When a copolymer of a styrene hydrocarbon and an aliphatic unsaturated carboxylic acid ester is used as the styrene resin, the aliphatic unsaturated carboxylic acid ester copolymerized with the styrene hydrocarbon includes methyl (meth) acrylate, butyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate may be mentioned. Preferably, it is a copolymer of styrene and butyl (meth) acrylate, more preferably styrene is in the range of 70% by mass to 90% by mass, and Tg (peak temperature of loss elastic modulus E ″). The melt flow rate (MFR) measured value (measurement conditions: temperature 200 ° C., load 49 N) is 2 g / 10 min or more and 15 g / 10 min or less. In addition, the said (meth) acrylate shows an acrylate and / or a methacrylate.

  Content in the intermediate | middle layer (M layer) of the copolymer of a styrene-type hydrocarbon and aliphatic unsaturated carboxylic acid ester is suitably determined according to the composition ratio. Typically, it is adjusted in the range of 20% by mass or more and 70% by mass or less with respect to the total amount of resin constituting the intermediate layer (M layer). If mixed at 70% by mass or less, the rigidity of the film can be greatly improved and good fracture resistance can be maintained. Moreover, if it mixes by 20 mass% or more, sufficient rigidity can be provided to a film.

<Surface layer (S layer)>
The polyester resin constituting the main component of the surface layer (S layer) of the film of the present invention can suppress spontaneous shrinkage while imparting rigidity, rupture resistance and low-temperature shrinkage to the film. A polyester resin suitable for the present invention is a polyester resin derived from a dicarboxylic acid residue and a diol residue. Examples of dicarboxylic acid residues include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid , Orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-di Aromatic dicarboxylic acids such as phenoxyethanedicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1, Aliphatic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid or It includes residues derived from these ester derivatives. These dicarboxylic acid residues may contain one kind alone or two or more kinds. As the polyester resin, a polyester resin composed of terephthalic acid and ethylene glycol is preferably used.

  In the present invention, it is more preferable that at least one of a dicarboxylic acid residue and a diol residue is a mixture composed of two or more types of residues. In the present specification, among the two or more types of residues, a main residue, that is, a residue having the largest mass (mol%) is defined as a first residue, and a smaller amount than the first residue is defined as a second residue. The following residues (namely, second residue, third residue,...) Are assumed. By making the dicarboxylic acid residue and the diol residue into such a mixture system, the crystallinity of the resulting polyester resin can be lowered. Therefore, when used as an intermediate layer (M layer), the intermediate layer (M layer) This is preferable because the progress of crystallization can be suppressed.

  Preferred diol residue mixtures include, for example, the ethylene glycol residue as the first residue, 1,4-butanediol, neopentyl glycol, diethylene glycol, polytetramethylene glycol, and 1,4-cyclohexane as the second residue. Examples thereof include a residue derived from at least one selected from the group consisting of dimethanol, preferably 1,4-cyclohexanedimethanol residue.

  The preferred dicarboxylic acid residue mixture is, for example, selected from the group consisting of terephthalic acid residue as the first residue and isophthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid and adipic acid as the second residue. Examples thereof include a residue derived from at least one kind, preferably an isophthalic acid residue.

  The total content of dicarboxylic acid residues and diol residues below the second residue is the sum of the total amount of dicarboxylic acid residues (100 mol%) and the total amount of diol residues (100 mol%) ( 200 mol%) or more, preferably 20 mol% or more, and 40 mol% or less, preferably 35 mol% or less. If the content rate of the said 2 or less residue is 10 mol% or more, the crystallinity degree of polyester obtained can be restrained low. On the other hand, when the content of the residues of 2 residues or less is 40 mol% or less, the advantages of the first residue can be utilized.

  For example, when the dicarboxylic acid residue is a terephthalic acid residue, the first residue of the diol residue is an ethylene glycol residue, and the second residue is a 1,4-cyclohexanedimethanol residue, the second residue The content of 1,4-cyclohexanedimethanol residues is the total amount of terephthalic acid residues that are dicarboxylic acid residues (100 mol%), ethylene glycol residues, and 1,4-cyclohexanedimethanol residues. 10 mol% or more, preferably 15 mol% or more, more preferably 25 mol% or more, and 40 mol% or less, preferably 38 mol%, based on the total (200 mol%) of the total amount (100 mol%) Hereinafter, it is more preferably in the range of 35 mol% or less. By using an ethylene glycol residue and a 1,4-cyclohexanedimethanol residue as the diol residue within this range, the crystallinity of the obtained polyester is almost lost, and the fracture resistance can be improved.

  Furthermore, in the above example, when the dicarboxylic acid residue is a terephthalic acid residue as the first residue and an isophthalic acid residue as the second residue, the dicarboxylic acid residue is an isophthalic acid residue and a diol residue. The content of 1,4-cyclohexanedimethanol residue is the total amount of terephthalic acid residue and isophthalic acid residue (100 mol%) and the total amount of ethylene glycol residue and 1,4-cyclohexanedimethanol residue. 10 mol% or more, preferably 15 mol% or more, more preferably 25 mol% or more, and 40 mol% or less, preferably 38% mol or less, with respect to the total (200 mol%) of (100 mol%), More preferably, it is the range of 35 mol% or less.

The refractive index (n ₂ ) of the polyester resin is 1. 56 or more 1. 58 or less, preferably about 1. 57. In this case, the refractive index (n ₁ ) of the styrene hydrocarbon-conjugated diene hydrocarbon block copolymer contained in the intermediate layer (M layer) is 1. 54 or more and 1.60 or less, preferably 1. 55 or more 1. 59 or less, more preferably 1. 555 or more 1. 585 or less.

  The intrinsic viscosity (IV) of the polyester resin is 0.5 dl / g or more, preferably 0.6 dl / g or more, more preferably 0.7 dl / g or more, and 1.5 dl / g or less, preferably It is 1.2 dl / g or less, More preferably, it is 1.0 dl / g or less. If intrinsic viscosity (IV) is 0.5 dl / g or more, it can suppress that a film strength characteristic and heat resistance fall. On the other hand, if the intrinsic viscosity is 1.5 dl / g or less, it is possible to prevent breakage associated with an increase in stretching tension.

  Examples of the above-mentioned commercially available polyester-based resins include “PETG copyester 6663” (manufactured by Eastman Chemical Co.), “PETG SKYGREEN S2008” (manufactured by SK Chemical Co., Ltd.), and the like.

  The polyester resin contained in the surface layer (S layer) is 20% by mass or more, preferably 40% by mass or more, and more preferably 60% by mass or more with respect to the total resin amount of the surface layer (S layer). A resin other than the polyester resin may be contained. Examples of such resins include polyolefin resins, polystyrene resins, polycarbonate resins, and acrylic resins, among which polystyrene resins are preferable.

  As the polyester resin used in the surface layer (S layer) of the film of the present invention, in addition to the polyester resin derived from the dicarboxylic acid residue and the diol residue, a carboxylic acid residue and an alcohol residue are used. It is also possible to use a polyester resin obtained by polymerizing a monomer having in a molecule. In particular, polylactic acid obtained by condensation polymerization of lactic acid can be suitably used because it imparts rigidity, low-temperature shrinkage, and low natural shrinkage.

<Adhesive layer (AD layer)>
In the film of the present invention, an adhesive layer (AD layer) is formed between the intermediate layer (M layer) and the surface layer (S layer). As the resin constituting the main component of the adhesive layer (AD layer), it is preferable to use a mixture of a polyester resin contained in the surface layer (S layer) and a styrene resin contained in the intermediate layer (M layer). . By using such a mixture as the main component resin of the adhesive layer, the affinity between the polyester resin contained in the surface layer (S layer) and the polyester resin component contained in the adhesive layer (AD layer) is increased, and the intermediate layer The affinity between the polystyrene resin contained in (M layer) and the styrene resin component contained in the adhesive layer (AD layer) can be increased, and as a result, the adhesive strength between both layers can be improved. The mixing ratio of the polyester resin and the styrene resin contained in the adhesive layer (AD layer) is (20 to 80) / (80 to 80%) from the viewpoint of improving the adhesive effect between the adjacent layers. 20), preferably (30 to 70) / (70 to 30), more preferably (40 to 60) / (60 to 40). When both resins are contained in the adhesive layer (AD layer) in an amount of 20% by mass or more, a good adhesive effect with the corresponding layer can be obtained.

  In addition to the above mixed resin, the resin constituting the adhesive layer (AD layer) has a polar group that has high affinity or can react with soft styrene resins, modified styrene resins, and polyester resins. A compatible resin (hereinafter also referred to as “specific adhesive resin”) or a mixture thereof can be used.

  The soft styrene resin means a resin comprising an elastomer component and a styrene copolymer of 10% by mass to 50% by mass, preferably 10% by mass to 40% by mass. Examples of the resin suitably used as the elastomer component include butadiene, isoprene, 1,3-pentadiene, and the like.

Specific examples of soft styrene resins include styrene-butyl acrylate copolymer, styrene-butadiene block copolymer (SBS), styrene-isoprene block copolymer (SIS), and styrene-ethylene-propylene copolymer. And an elastomer obtained by modifying a styrene-ethylene-butylene copolymer with a modifier having a polar group. Moreover, a block copolymer contains a pure block, a random block, a tapered block, etc., and the form of copolymerization is not specifically limited. In addition, the block unit may overlap with any number of repeating units. Specifically, in the case of a styrene-butadiene block copolymer, there are several block units such as a styrene-butadiene copolymer, a styrene-butadiene-styrene block copolymer, and a styrene-butadiene-styrene-butadiene block copolymer. It may be repeated.

  Further, as the soft styrene resin, a hydrogenated styrene-butadiene block copolymer (SEBS) or a hydrogenated styrene-isoprene block copolymer (SEPS) which is a resin obtained by adding hydrogen to SBS or SIS can be used. . For example, “Tuftec H Series” (Asahi Kasei Chemicals) and the like are suitably used as specific products of elastomers to which hydrogen is added.

  As the modified styrene resin, a modified styrene elastomer containing a large amount of an elastomer component is preferably used, and among these, modified products of SEBS and SEPS are preferably used. Specific examples include maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, epoxy-modified SEBS, and epoxy-modified SEPS. The modified styrene (based elastomer) may be used alone or in combination of two or more. Specific products of modified styrenic resins include polymers modified with hydrogenated styrene thermoplastic elastomers with highly reactive functional groups such as “Tuftec M1943” (Asahi Kasei Chemicals), “Septon” (Kuraray), “JSR SIS”. (JSR).

  The specific adhesive resin has a polar group having high affinity with the polyester resin contained in the surface layer (S layer) or a polar group capable of reacting with the polyester resin, and is contained in the intermediate layer (M layer). It refers to a styrene block copolymer or graft copolymer having a portion compatible with the styrene resin. Specific examples of the polar group having high affinity with the polyester resin or the functional group capable of reacting include, for example, an acid anhydride group, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid chloride group, a carboxylic acid amide group, Examples include carboxylic acid groups, sulfonic acid groups, sulfonic acid ester groups, sulfonic acid chloride groups, sulfonic acid amide groups, sulfonic acid groups, epoxy groups, amino groups, imide groups, or oxazoline groups. An anhydride group, carboxylic acid group or carboxylic acid ester group is preferred.

  Moreover, the site | part which can be compatible with a styrene resin means having a chain | strand with affinity with a styrene resin. More specifically, a random copolymer having a styrene chain, a styrene copolymer segment or the like as a main chain, a block chain or a graft chain, or having a styrene monomer unit may be used.

  Specific products of the specific adhesive resin include, for example, “Tuftec M1943” (Asahi Kasei Chemicals), “Polar group-modified Dynalon” (JSR), epoxidized thermoplastic elastomer “Epofriend” (Daicel Chemical), “RESEDA”. (Toagosei Co., Ltd.).

  The resin used in the adhesive layer (AD layer) is not limited to the above-mentioned soft styrene resin, modified styrene resin, and specific adhesive resin, and may be used by mixing more than one kind. In that case, the mixing amount can be appropriately determined according to the characteristics of the resin used.

  In addition to the components described above, the film of the present invention has a plasticizer and a plasticizer in each layer for the purpose of improving and adjusting the molding processability, productivity, and various properties of the heat-shrinkable film, as long as the effects of the present invention are not significantly impaired. The tackifier resin is 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and 10% by mass or less, preferably 8% by mass or less, based on the total amount of resin constituting each layer. More preferably, it can be contained in the range of 5% by mass or less. When the content of the plasticizer and / or tackifying resin is 10% by mass or less with respect to the total amount of the resin, the decrease in melt viscosity and the decrease in heat-resistant fusing property are small, and natural shrinkage hardly occurs. In addition to the plasticizer and tackifier resin, the film of the present invention may have various additives depending on the purpose, such as an ultraviolet absorber, a light stabilizer, an antioxidant, a stabilizer, a colorant, an antistatic agent, Lubricants, inorganic fillers, and the like can be appropriately added depending on each application.

<Layer structure of film>
The film structure of the present invention is not particularly limited as long as it has at least a three-layer structure having an adhesive layer (AD layer) between the surface layer (S layer) and the intermediate layer (M layer). Here, the surface layer (S layer) may have the same layer as the intermediate layer (M layer) in addition to the surface layer (S layer) constituting the outermost layer.

  A preferred laminated structure in the present invention is a five-layer structure comprising a surface layer (S layer) / adhesive layer (AD layer) / intermediate layer (M layer) / adhesive layer (AD layer) / surface layer (S layer). . By adopting this layer structure, it is suitable for applications such as shrink wrapping, shrink tying wrapping, shrink labels, etc., which are excellent in film rigidity, shrink finish, rupture resistance, and delamination is suppressed. A heat-shrinkable laminated film can be obtained with good productivity and economy.

  Next, a surface layer (S layer), an intermediate layer (M layer), and an adhesive layer (AD layer), which is one of the preferred embodiments of the present invention (S layer) / (AD layer) / (M layer) ) / (AD layer) / (S layer) will be described.

In the film of the present invention, the thickness ratio between the surface layer (S layer) and the intermediate layer (M layer) is such that when the surface layer (S layer) is 1, the intermediate layer (M layer) is 2 or more, preferably It is 3 or more, more preferably 4 or more, and 12 or less, preferably 10 or less, more preferably 8 or less. The thickness of the adhesive layer (AD layer) is 10% or more, preferably 15% or more, 150% or less, preferably 100% or less, more preferably 80% of the thickness of the surface layer (S layer). The following thickness is desirable. When the thickness of the adhesive layer (AD layer) is 10% or more of the thickness of the surface layer (S layer), a good adhesive effect is obtained, and 150% or less, that is, 1. of the surface layer (S layer).
If the thickness is 5 times or less, the transparency is not significantly lowered.

  Although the total thickness of the film of the present invention is not particularly limited, it is preferably thinner from the viewpoint of suppressing raw material costs as much as possible. Specifically, the thickness after stretching is preferably 60 μm or less, and is 55 μm or less. Is more preferably 50 μm or less, and most preferably 45 μm or less.

<Physical properties>
The film of the present invention has a thermal shrinkage rate of 10% or more and less than 30%, preferably 10% or more and 25% or less, more preferably 10% or more and 20% in at least one direction when immersed in warm water at 70 ° C. for 10 seconds. The range is as follows. The film of the present invention has a thermal shrinkage rate of 30% or more, preferably 35% or more, more preferably 40% or more, and 70% or less in at least one direction when immersed in warm water at 80 ° C. for 10 seconds. , Preferably 60% or less, more preferably 50% or less.
In this specification, “at least one direction” means either or both of the main contraction direction and the direction orthogonal to the main contraction direction, and usually refers to the main contraction direction. Here, the “main contraction direction” means a direction in which the stretching direction is larger between the longitudinal direction and the lateral direction, and is, for example, a direction corresponding to the outer peripheral direction when being attached to a bottle.

  If the thermal contraction rate in at least one direction when immersed in warm water at 70 ° C. and 80 ° C. for 10 seconds is within the above range, the heat is such that the laminated film is temporarily fixed to a container in a low temperature region near 70 ° C., for example. It has shrinkability, and suddenly shrinks in a high temperature range exceeding 70 ° C. and near 80 ° C. As a result, at a predetermined position, not only the trunk of the container but also the trunk is very thin. No abnormalities such as wrinkles and avatars occur on the neck and top surface, and uniform shrinkage is obtained, resulting in a beautiful shrinkage finish.

  When the heat shrinkage rate in the main shrinkage direction near 70 ° C. is less than 10%, the heat shrinkage force is small. For example, when the laminated film is used as the container label, it cannot be temporarily fixed to the container. Then, the film may be shifted up in the direction of the top surface. On the other hand, if the thermal contraction rate in the main contraction direction is higher than 30% at around 70 ° C., the thermal contraction may occur suddenly in a low temperature region, so that the thermal contraction may not be performed at a predetermined position. On the other hand, if the thermal shrinkage rate in the main shrinkage direction near 80 ° C. is less than 30%, the thermal shrinkage rate in the main shrinkage direction near 80 ° C. It is 30% or more, preferably 40% or more, more preferably 50% or more.

  When the film of the present invention is used as a PET container label, the thermal shrinkage in the orthogonal direction when immersed in warm water at 80 ° C. for 10 seconds is preferably 10% or less, more preferably 5% or less. Preferably, it is 3% or less. Further, the thermal contraction rate in the orthogonal direction when immersed in warm water at 70 ° C. for 10 seconds is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less. When the shrinkage rate in the orthogonal direction exceeds 10%, the shrinkage in the vertical direction becomes remarkable after shrinkage in label applications, which may cause a dimensional deviation or an appearance defect.

  The natural shrinkage ratio of the film of the present invention is preferably 1.5% or less after 30 days in a 30 ° C. environment, more preferably 1.0% or less, and 0.8% or less. Further preferred. If the natural shrinkage is 1.5% or less under the above conditions, the produced film can be stably attached to a container or the like even when stored for a long period of time.

  The transparency of the film of the present invention is evaluated by a haze value measured according to JIS K7105. The haze value is preferably 10% or less, more preferably 7% or less, and further preferably 5% or less. preferable. If the haze value is 10% or less, good transparency can be obtained, and beautiful printing or the like becomes possible.

  Further, the film of the present invention is preferably 40% by mass or less, preferably 40% by mass or less, based on the total amount of the film of the present invention, recycled to the surface layer (S layer) and the intermediate layer (M layer), preferably the intermediate layer (M layer). Is 35% by mass or less, more preferably 30% by mass or less, even when re-added, the haze value measured according to JIS K7105 of a film having a thickness of 50 μm is 10% or less, preferably 7% or less, more preferably 5% or less. If the haze value after re-adding the recycled product is 10% or less, good transparency in the recycled film can be maintained.

  The rupture resistance of the film of the present invention is evaluated by tensile elongation at break, and in a tensile test under an environment of 0 ° C., particularly in the label application, the elongation is 100% or more in the film take-off (flow) direction (MD), preferably It is 200% or more, more preferably 300% or more.

In the film of the present invention, it is important that the tensile elastic modulus in the direction orthogonal to the film main shrinkage direction is 1,200 MPa or more, more preferably 1,300 MPa, from the viewpoint of waist strength (rigidity at normal temperature). More preferably, it is 1,400 MPa or more. Moreover, the upper limit value of the tensile elastic modulus of the heat-shrinkable film that is usually used is about 3,000 MPa, preferably about 2,900 MPa, and more preferably about 2,800 MPa. If the tensile modulus of elasticity in the direction perpendicular to the main shrinkage direction of the film is 1,200 MPa or more, the waist as a whole film (rigidity at room temperature) can be increased, especially when the thickness of the film is reduced, When a film made in a container such as a plastic bottle is covered with a labeling machine or the like, it is preferable that problems such as covering at an angle or a decrease in yield due to folding of the film or the like are unlikely to occur. The said tensile elasticity modulus can be measured on 23 degreeC conditions according to JISK7127. Further, the tensile elastic modulus in the film main shrinkage direction is not particularly limited as long as the film has low stiffness, but it is 1,500 MPa or more, preferably 2,000 MPa or more, more preferably 2,500 MPa or more, and the upper limit is 6 1,000 MPa or less, preferably 4,500 MPa or less, more preferably 3,500 MPa or less. It is preferable to set the tensile elastic modulus in the film main contraction direction within the above range because the strength of the waist of the film can be increased in both directions.

  The delamination strength of the film of the present invention is expressed as seal strength and is described in the examples described later (in the environment of 23 ° C. and 50% RH, the test speed is 200 mm / min in the TD direction by the T-type peeling method). 3N / 15mm width or more, preferably 4N / 15mm width or more, more preferably 5N / 15mm width or more and 20N / 15mm width or less. Since the film of the present invention has a delamination strength of 3 N / 15 mm or more, troubles such as peeling of the seal portion during use do not occur.

(Method for producing heat-shrinkable laminated film)
The film of the present invention includes an intermediate layer (M layer) mainly composed of a styrene resin, and a surface layer (S layer) mainly composed of a polyester resin disposed on both sides of the intermediate layer (M layer). ) And the adhesive layer (AD layer) formed between the surface layer (S layer) and the intermediate layer (M layer) are laminated simultaneously or sequentially to produce a laminated film, and then the laminated film is heated. And obtained by stretching in at least one axial direction.

  The laminated film is coextruded by an existing method such as a T-die method or a tubular method using an extruder equipped with a T-die, so that an intermediate layer (M layer), a surface layer (S layer) and an adhesive layer ( AD layer) can be manufactured at the same time. In addition, the laminated film can be sequentially produced by separately forming the resin constituting each layer and then laminating them using a press method or a roll nip method.

  The laminated film is cooled with a cooling roll, air, water, etc., and then reheated by an appropriate method such as hot air, hot water, infrared rays, etc., roll stretching method, tenter stretching method, tubular stretching method, long interval stretching method, etc. Uniaxially or biaxially stretched simultaneously or sequentially. In biaxial stretching, stretching in the MD and TD directions may be performed at the same time, but sequential biaxial stretching in which one of them is performed first is effective, and the order of either MD or TD may be first. The stretching temperature needs to be changed depending on the softening temperature of the resin constituting the film and the use required for the heat-shrinkable laminated film, but is generally 60 ° C., preferably 70 ° C. or more, and 130 ° C. or less, preferably 120 It is controlled in the range of ℃ or less. The draw ratio in the main shrink direction (TD) is 2 times or more, preferably 3 times or more, more preferably 4 times or more, and 7 times depending on the film constituents, stretching means, stretching temperature, and target product form. Hereinafter, it is suitably determined within a range of preferably 6 times or less. Whether to use uniaxial stretching or biaxial stretching is determined by the application of the target product.

  Even in the case of an application that requires shrinkage characteristics in almost one direction, such as a PET container label, it is effective to stretch the film in a range that does not impair the shrinkage characteristics in the vertical direction. The stretching temperature depends on components other than PET, but typically ranges from 60 ° C. to 90 ° C. Furthermore, with respect to the draw ratio, as the size is increased, the fracture resistance is improved, but the heat shrinkage rate is increased accordingly, and it is difficult to obtain a good shrinkage finish. It is particularly preferred that

  Moreover, the film of this invention can provide and hold | maintain shrinkage | contraction property by cooling this film rapidly within the time when the molecular orientation of a stretched film is not relieved after extending | stretching.

[Molded products, heat-shrinkable labels and containers]
The film of the present invention can be used as various molded products such as coating films for containers, binding bands, exterior films, etc. by forming or forming a printing layer, vapor deposition layer and other functional layers as necessary. it can. In particular, when the film of the present invention is used as a heat-shrinkable label for food containers (for example, PET bottles, glass bottles, preferably PET bottles for soft drinks or foods), a complicated shape (for example, a cylinder with a constricted center, Even a square column, pentagonal column, hexagonal column or the like having a square shape can be adhered to the shape, and a container with a beautiful label without wrinkles or avatars can be obtained.

  Since the film of the present invention has excellent low-temperature shrinkage and shrinkage finish properties, in addition to the heat-shrinkable label material of a plastic molded product that is deformed when heated to a high temperature, the coefficient of thermal expansion, water absorption, etc. Material very different from this film, for example, polyolefin resin such as metal, porcelain, glass, paper, polyethylene, polypropylene, polybutene, polyester resin such as polymethacrylate resin, polycarbonate resin, polyethylene terephthalate, polybutylene terephthalate In addition, it can be suitably used as a heat-shrinkable label material for a package (container) using at least one selected from polyamide-based resins as a constituent material.

  As a material constituting the plastic package in which the film of the present invention can be used, in addition to the above resin, polystyrene, rubber-modified impact-resistant polystyrene (HIPS), styrene-butyl acrylate copolymer, styrene-acrylonitrile copolymer, Styrene-maleic anhydride copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), (meth) acrylic acid-butadiene-styrene copolymer (MBS), polyvinyl chloride resin, phenol resin, urea resin, melamine Examples thereof include resins, epoxy resins, unsaturated polyester resins, and silicone resins. These plastic packages may be a mixture of two or more resins or a laminate.

Examples of the film of the present invention, heat-shrinkable labels, and containers equipped with the labels are shown below, but the present invention is not limited by these examples.
In addition, the measured value and evaluation which are shown to an Example were performed as follows. In the examples, the take-up (flow) direction of the laminated film is described as “MD”, and the direction orthogonal thereto is described as “TD”.

<Measurement method>
(1) Heat Shrinkage The film of the present invention was cut into a size of MD 100 mm and TD 100 mm, and the amount of TD shrinkage was immersed in a hot water bath at 70 ° C. or 80 ° C. for 10 seconds and measured. The thermal shrinkage rate was expressed as a percentage of the shrinkage amount relative to the original size before shrinkage.
(2) Natural shrinkage ratio After the film was manufactured, it was allowed to stand at 23 ° C. and 50% RH for 5 hours, then cut into a size of MD 50 mm and TD 1000 mm, and left in a constant temperature bath at 30 ° C. for 30 days, and then the shrinkage ratio of TD was measured. The results are shown in Table 1.
(3) Tensile elongation at break MD50mm, TD15mm cut out the test piece, the test piece is set to a tensile tester with a thermostatic bath with a chuck interval of 40mm, this is pulled at a test speed of 0 ℃, 100mm / min, the following The tensile elongation at break was determined from the calculation formula.
Tensile elongation at break (%) = {(length between chucks when fractured−40 (mm)) /
40 (mm)} × 100
(4) Transparency (all haze)
The haze value of a film having a thickness of 50 μm was measured according to JIS K7105.
(5) Tensile elasticity modulus About MD, the tensile test was done at 23 mm50% RH, the film test piece of 3 mm in width | variety with the chuck | zipper space | interval of 80 mm, and the tensile speed of 5 mm / min. As for TD, a tensile test was performed at a tensile rate of 5 mm / min with a film test piece of 23 ° C. and 50% RH and a width of 5 mm set to 300 mm between chucks. Using the first linear part of the tensile stress-strain curve in MD and TD, the calculation was performed according to the following formula.
E = σ / ε
In the above equation, E represents the tensile modulus, and σ represents the difference in stress per unit area (average cross-sectional area of the sample before the tensile test) between two points on the straight line.
(6) Delamination strength The delamination strength was measured as the seal strength. At a position 10 mm from both ends of the TD of the film, it was adhered using a mixed solvent composed of 90% by mass of THF and 10% by mass of n-hexane to produce a cylindrical label. The seal portion was cut to a width of 5 mm in a direction perpendicular to the circumference, and a peel test was performed using a tensile tester with a thermostatic bath (“201X” manufactured by Intesco Corporation). The sealing strength between the front and back layers and the intermediate layer was evaluated by the following numerical values.
A: Seal strength is 4 N / 15 mm width or more. ○: Seal strength is 2 N / 15 mm width or more and less than 4 N / 15 mm width. X: Seal strength is less than 2 N / 15 mm width. (7) Shrinkage finish. Was cut into a size of MD 100 mm and TD 298 mm, and both ends of TD were overlapped by 10 mm and adhered with a solvent to form a cylinder. This cylindrical film was attached to a 500 mL capacity plastic bottle and passed through the steam heating type 3.2 m (3 zones) shrink tunnel for about 4 seconds without rotating. The atmospheric temperature in the tunnel in each zone was set to a range of 80 to 90 ° C. by adjusting the amount of steam with a steam valve. The film was visually evaluated according to the following criteria.
A: Shrinkage is sufficient, and there is no wrinkle, avatar or lattice distortion, and adhesion is good.
○: Shrinkage is sufficient, but there are slight wrinkles, avatars, lattice distortions, or a slight shrinkage in the vertical direction, but there is no practical problem.
X: Insufficient shrinkage of TD or shrinkage of MD is conspicuous and causes a practical problem.
(8) Viscoelasticity measurement (storage modulus, loss modulus)
Using a viscoelastic spectrometer DVA-200 (made by IT Measurement Control Co., Ltd.), the vibration frequency was 10 Hz, the temperature rising rate was 3 ° C./min, and the measurement temperature was −120 ° C. to 130 ° C. The peak temperature of the loss modulus was obtained as the temperature at which the slope of the temperature dependence curve of the loss modulus was zero (the first derivative was zero). In addition, the measurement film produced the resin which comprises in the thickness range of about 0.2-1.0 mm, and measured the non-orientation direction.
(9) Haze value of film after return After the obtained heat-shrinkable laminated film was pulverized using a pulverizer and regenerated into pellets, an intermediate layer (M Returning to layer), a regenerated additive film was obtained in the same manner as in each Example. Using the obtained film having a thickness of 50 μm, the haze value was measured according to JIS K7105. The results of evaluation based on the following criteria are also shown.
◎: Haze value is less than 7% ○: Haze value is 7% or more and less than 10% ×: Haze value is 10% or more

Example 1
As shown in Table 1, 50% by mass of styrene resin A (styrene / butadiene = 90/10 (% by mass), storage elastic modulus E ′: 3.15 × 109 Pa, loss elastic modulus E ″ peak temperature: 55 ° C., hereinafter referred to as “SBS-A”) and 50% by mass of styrene resin B (styrene / butadiene / isoprene = 71/14/15 (% by mass), storage elastic modulus E ′ (0 ° C.): 4.03 × 108 Pa, peak temperature of loss elastic modulus E ″: −32 ° C., hereinafter referred to as “SBS-B”) As an intermediate layer (M layer), a polyester resin (dicarboxylic acid component is 100 mol of terephthalic acid) %, A copolymer polyester comprising a glycol component of 70 mol% of ethylene glycol and 30 mol% of 1,4-cyclohexanedimethanol, trade name PETG6763, manufactured by Eastman Chemical Co., Ltd. “PETG”) as a surface layer (S layer), and a mixed resin of 50% by mass of a surface layer (S layer) resin and 50% by mass of an intermediate layer (M layer) resin as an adhesive layer (AD layer) The intermediate layer (M layer): adhesive layer (AD layer): surface layer (S layer) = 3: 1: 1 is melted with an extruder set in the range of 210 ° C. to 230 ° C. It was made to merge, it extruded by 3 types 5 layers (extrusion amount ratio = 1: 1: 6: 1: 1), it cooled with the cast roll, and the 300-micrometer-thick unstretched film was obtained. The unstretched film was stretched 1.3 times at 80 ° C. in the flow direction (MD) and then stretched 4.05 times at 94 ° C. in the perpendicular direction (TD) to produce a heat-shrinkable laminated film having a thickness of 50 μm. . The evaluation results of the obtained film are shown in Table 2.

(Example 2)
As shown in Table 1, styrene resin C (styrene / butadiene = 76/24 (mass%), storage elastic modulus E ′ (0 ° C.): 6.89 × 108 Pa, loss elastic modulus as the intermediate layer (M layer) E ″ peak temperature: −74 ° C., MFR: 6.8, trade name DK-11, manufactured by Chevron Phillips, hereinafter referred to as “SBS-C”), and an unstretched film is 75 in the flow direction (MD). A laminated film was produced in the same manner as in Example 1, except that the film was stretched 1.3 times at 0 ° C. and then stretched 4.0 times at 92 ° C. in the perpendicular direction (TD). The evaluation results of the obtained film are shown in Table 2.

(Example 3)
As shown in Table 1, a modified styrenic thermoplastic elastomer resin (trade name Toughtech M1943, Asahi Kasei Chemicals, hereinafter referred to as “AD”) is used as an adhesive layer (AD layer), and an unstretched film is made in the flow direction (MD). A laminated film was produced in the same manner as in Example 1 except that the film was stretched 1.3 times at 75 ° C. and then stretched 4.0 times at 92 ° C. in the perpendicular direction (TD). The evaluation results of the obtained film are shown in Table 2.

(Comparative Example 1)
As shown in Table 1, a mixed resin of 50% by mass SBS-A and 50% by mass SBS-B is an intermediate layer (M layer), PETG is a surface layer (S layer), and the amount of extrusion is an intermediate layer. : Surface layer = 3: 1, melted in an extruder set in a range of 210 to 230 ° C., merged with a die, and extruded in two types and three layers (extrusion amount ratio = 1: 6: 1), An unstretched film having a thickness of 300 μm was obtained by cooling with a cast roll. This unstretched film was stretched 1.3 times in the flow direction (MD) at 80 ° C., and then stretched 4.4 times in the perpendicular direction (TD) at 97 ° C. to produce a laminated film having a thickness of 50 μm. The evaluation results of the obtained film are shown in Table 2.

  From Tables 1 and 2, the films of the present invention (Examples 1 to 3) have a large tensile elongation at break at 0 ° C. and a seal strength as compared with a heat-shrinkable film (Comparative Example 1) having no adhesive layer. large. Moreover, the tensile elasticity modulus, shrinkage finish, and transparency of the film of the present invention (Examples 1 to 3) are equivalent to those of the conventional film (Comparative Example 1). Thus, the film of the present invention is a heat-shrinkable film that exhibits low-temperature shrinkage and delamination strength superior to those of conventional films, and has the same rigidity, shrink finish, and transparency as conventional films. I understand.

  Since the film of the present invention has excellent rupture resistance, rigidity, shrinkage finish, and seal strength, it can be suitably used for molded products that require heat shrinkage, particularly shrink labels.

Claims (9)

A laminated film having a surface layer (S layer), an intermediate layer (M layer), and an adhesive layer (AD layer), wherein each layer is made of a resin having the following components as main components and immersed in 70 ° C. warm water for 10 seconds. The thermal shrinkage rate at least when it is 10% or more and less than 30% and when immersed in 80 ° C. warm water for 10 seconds is at least 30% or more and 70% or less. Heat shrinkable laminated film.
(S layer): Polyester resin (M layer): Styrene resin (AD layer): Adhesive resin   The heat-shrinkable laminated film according to claim 1, wherein the adhesive resin of the adhesive layer (AD layer) is a mixture of resins contained in the surface layer (S layer) and the intermediate layer (M layer). The adhesive resin of the adhesive layer (AD layer) has a polar group that has high affinity or can react with soft styrene resins, modified styrene resins, and polyester resins, and is compatible with styrene resins. The heat-shrinkable laminated film according to claim 1, which is one kind of resin selected from the group consisting of:   The styrene resin of the intermediate layer (M layer) is a styrene-butadiene block copolymer (SBS), a styrene-isoprene-butadiene block copolymer (SIBS), or a mixture thereof. The heat-shrinkable laminated film described in 1. The polyester resin of the surface layer (S layer) is composed of a dicarboxylic acid residue and a diol residue, and at least one of the dicarboxylic acid residue and the diol residue is composed of two or more residues, and the 2 The total content of residues other than the most abundant residues among the species or more is the sum of the total amount of the dicarboxylic acid residues (100 mol%) and the total amount of the diol residues (100 mol%). The heat-shrinkable laminated film according to any one of claims 1 to 4, wherein the heat-shrinkable laminated film is 10% or more and 40% by mol or less with respect to (200 mol%).   The heat-shrinkable laminated film according to any one of claims 1 to 5, wherein a seal strength when peeled at a tensile rate of 200 mm / min in an environment of 23 ° C and 50% RH is 3 N / 15 mm width or more and 20 N / 15 mm width or less. .   A molded article comprising the heat-shrinkable laminated film according to claim 1 as a base material.   The heat-shrinkable label which uses the heat-shrinkable laminated film in any one of Claims 1 thru | or 6 as a base material.   A container equipped with the molded product according to claim 7 or the heat-shrinkable label according to claim 8.