WO2022191177A1 - 発泡フィルム、熱収縮性フィルム、及びラベル - Google Patents

発泡フィルム、熱収縮性フィルム、及びラベル Download PDF

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WO2022191177A1
WO2022191177A1 PCT/JP2022/009974 JP2022009974W WO2022191177A1 WO 2022191177 A1 WO2022191177 A1 WO 2022191177A1 JP 2022009974 W JP2022009974 W JP 2022009974W WO 2022191177 A1 WO2022191177 A1 WO 2022191177A1
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Prior art keywords
foamed
film
layer
resin composition
block copolymer
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PCT/JP2022/009974
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English (en)
French (fr)
Japanese (ja)
Inventor
瞳 橋本
正 澤里
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デンカ株式会社
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Priority to KR1020237033743A priority Critical patent/KR20230154922A/ko
Priority to JP2023505572A priority patent/JP7642057B2/ja
Publication of WO2022191177A1 publication Critical patent/WO2022191177A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0221—Vinyl resin
    • B32B2266/0228—Aromatic vinyl resin, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2519/00—Labels, badges

Definitions

  • the present invention relates to foamed films, heat-shrinkable films, and labels.
  • Patent Document 1 discloses a label using a foam film as a label that can be separated under water.
  • the present invention has been made in view of such problems, and provides a foamed film with excellent surface smoothness and low specific gravity.
  • the present invention also provides a heat-shrinkable film and a label that use the foamed film and have excellent surface smoothness even after being stretched.
  • a foamed film comprising a foamed layer and a non-foamed layer, wherein the first resin composition constituting the foamed layer is conjugated with a vinyl aromatic hydrocarbon monomer unit.
  • a second resin composition comprising at least one block copolymer having diene monomer units, having a melt mass flow rate of 5.0 to 15.0 g/10 min at 200° C. and a load of 5 kg, and constituting the non-foamed layer.
  • the product contains one or more block copolymers having vinyl aromatic hydrocarbon monomer units and conjugated diene monomer units, and has a melt mass flow rate of 2.0 to 7.0 g/10 min at 200°C and a load of 5 kg.
  • the foamed film has a specific gravity of 0.8 or more and less than 1.0.
  • the tilde symbol " ⁇ " is a symbol used to indicate a numerical range including the numerical values described before and after it. Specifically, the description "X to Y" (both X and Y are numerical values) indicates that "X or more and Y or less”.
  • FIG. 1A-1C are schematic diagrams of examples of laminated structures of foamed films;
  • FIG. FIG. 1A is an example of a foamed film in which non-foamed layers are provided on both sides of a foamed layer.
  • FIG. 1B is an example of a foamed film having a non-foamed layer on one side of the foamed layer.
  • FIG. 1C is an example of a foamed film in which a non-foamed layer is provided on a foamed layer via another layer.
  • a foamed film according to one embodiment of the present invention comprises a foamed layer and a non-foamed layer.
  • the foamed film may comprise multiple foamed and non-foamed layers.
  • the foamed film may include layers other than the foamed layer and the non-foamed layer. At least one non-foamed layer is preferably used as a surface layer.
  • FIG. 1A to 1C are schematic diagrams of examples of laminated structures of foamed films.
  • FIG. 1A is an example of a foamed film in which non-foamed layers are provided on both sides of a foamed layer.
  • FIG. 1B is an example of a foamed film having a non-foamed layer on one side of the foamed layer.
  • FIG. 1C is an example of a foamed film in which a non-foamed layer is provided on a foamed layer via another layer. A non-foamed layer may be provided directly on the foamed layer or via another layer.
  • the other layer can be an intermediate layer composed of one or more layers.
  • the other layer may be a subbing layer, such as an adhesive layer that allows the layers to adhere to each other.
  • the total thickness of the foamed film is preferably 30-200 ⁇ m, more preferably 50-150 ⁇ m.
  • the thickness of the foam layer in the foam film is preferably 20-190 ⁇ m, more preferably 30-140 ⁇ m.
  • a film with a low specific gravity can be easily obtained, and when it is 190 ⁇ m or less, wrinkles are less likely to occur during processing or when attached to a container as a label, and a film with good appearance can be obtained. Therefore, it is preferable.
  • the layer ratio (ratio of thickness of each layer) of the multilayer film it is preferable that the non-foamed layer accounts for 75% or less of the total thickness in order to obtain a foamed film with a low specific gravity. A content of 5% or more is preferable in order to obtain good surface smoothness.
  • the foamed film in FIG. 1A is a foamed film having a three-layer structure in which a non-foamed layer 3 and a non-foamed layer 4 are provided on both sides of a foamed layer 1, respectively.
  • a non-foamed layer 3 when the thickness of the non-foamed layer 3 is d 1 , the thickness of the foamed layer 1 is d 2 , and the thickness of the non-foamed layer 4 is d 3 , their ratio [d 1 /d 2 /d 3 ] is, for example, [1/38/1] to [1/1/1], preferably [1/5/1] to [1/1/1].
  • the foamed film has a specific gravity of 0.8 or more and less than 1.0, preferably 0.82 to 0.95.
  • a foamed film having excellent surface smoothness and low specific gravity can be provided by adjusting the content to such a range. When it is 0.8 or more, a film having good surface smoothness can be obtained, and when it is less than 1.0, it is possible to separate the specific gravity from 1.0 or more with water, which is preferable.
  • the foam layer is a layer composed of the first resin composition.
  • the first resin composition contains at least one block copolymer having a vinyl aromatic hydrocarbon monomer unit and a conjugated diene monomer unit.
  • the first resin composition has a melt mass flow rate (first MFR) at 200° C. and a load of 5 kg of 5.0 to 15.0 g/10 min, preferably 8.0 to 14.0 g/10 min, and more It is preferably 10.0 to 14.0 g/10 min.
  • first MFR melt mass flow rate
  • the first MFR is, for example, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0 g/10 min, and may be in the range between any two of the values exemplified here.
  • the content of the conjugated diene monomer unit is preferably is 10 to 40% by mass, more preferably 15 to 30% by mass.
  • the non-foamed layer is a layer composed of the second resin composition.
  • the second resin composition contains at least one block copolymer having a vinyl aromatic hydrocarbon monomer unit and a conjugated diene monomer unit.
  • the second resin composition has a melt mass flow rate (second MFR) at 200° C. and a load of 5 kg of 2.0 to 7.0 g/10 min, preferably 4.0 to 6.0 g/10 min.
  • second MFR melt mass flow rate
  • the second MFR is, for example, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0 g/10 min, and may be in the range between any two of the values exemplified here.
  • the second resin composition preferably has a conjugated diene monomer unit content when the total of the vinyl aromatic hydrocarbon monomer units and the conjugated diene monomer units in the composition is 100% by mass. is 10 to 40% by mass, more preferably 15 to 30% by mass.
  • the block copolymer contained in the first resin composition or the second resin composition is a block copolymer having vinyl aromatic hydrocarbon monomer units and conjugated diene monomer units.
  • a block copolymer is a copolymer synthesized by block-copolymerizing a vinyl aromatic hydrocarbon monomer and a conjugated diene monomer.
  • a block copolymer is a copolymer having one or more block chains composed of vinyl aromatic hydrocarbon monomer units and/or conjugated diene monomer units.
  • a vinyl aromatic hydrocarbon monomer unit is a structural unit of a copolymer derived from a vinyl aromatic hydrocarbon monomer used for block copolymerization.
  • vinyl aromatic hydrocarbon monomers include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene and ⁇ -methylstyrene. , vinylnaphthalene, vinylanthracene, and the like.
  • the vinyl aromatic hydrocarbon monomer is preferably styrene. These monomers may be used alone or in combination of two or more.
  • a conjugated diene monomer unit is a structural unit of a copolymer derived from a conjugated diene monomer used for block copolymerization.
  • Conjugated diene monomers include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3 - hexadiene and the like.
  • the conjugated diene monomer is preferably 1,3-butadiene or isoprene. These monomers may be used alone or in combination of two or more.
  • the overall structure of the block copolymer and the structure of the polymer blocks that constitute the block copolymer are not particularly limited.
  • the structure of the polymer block includes polymer blocks mainly composed of vinyl aromatic hydrocarbon monomer units (eg styrene units), polymer blocks mainly composed of conjugated diene monomer units (eg 1,3-butadiene units).
  • Coalescing block a polymer block having a random structure in which vinyl aromatic hydrocarbon monomer units (e.g., styrene units) and conjugated diene monomer units (e.g., 1,3-butadiene units) are randomly arranged, vinyl aromatic A polymer block with a tapered structure in which a group hydrocarbon monomer unit (e.g., styrene unit) and a conjugated diene monomer unit (e.g., 1,3-butadiene unit) are arranged in a tapered shape with a gradient in distribution density. It's okay.
  • the overall structure of the block copolymer has a structure having at least two types of polymer blocks.
  • the polymer blocks may be connected linearly, branched or star-shaped.
  • a polymer block having a random structure having styrene units and 1,3-butadiene units can be obtained by simultaneously and continuously adding styrene and 1,3-butadiene little by little to polymerization active terminals and polymerizing them.
  • a polymer block having a tapered structure having styrene units and 1,3-butadiene units can be obtained by simultaneously adding excess amounts of styrene and 1,3-butadiene to the polymerization active terminal and polymerizing them.
  • the overall structure of the block copolymer can be made branched or star-shaped.
  • the number average molecular weight of the block copolymer is preferably 40,000 to 500,000, more preferably 80,000 to 300,000. When it is 40,000 or more, sufficient rigidity and impact resistance of the block copolymer composition can be obtained, and when it is 500,000 or less, the block copolymer composition has good workability, which is preferable.
  • the number average molecular weight of the block copolymer can be measured using gel permeation chromatography (hereinafter abbreviated as GPC).
  • the melt mass flow rate of the first resin composition at 200°C and a load of 5 kg is greater than the melt mass flow rate of the second resin composition at 200°C and a load of 5 kg. That is, it is preferable to satisfy the relationship "first MFR>second MFR".
  • the method for producing a block copolymer according to one embodiment of the present invention is not particularly limited. is a method of polymerizing
  • organic solvents examples include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, and isooctane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene are included.
  • aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, and isooctane
  • alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane
  • An organolithium compound is a compound in which one or more lithium atoms are bound in the molecule.
  • organic lithium compounds include monofunctional organic lithium compounds such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium and tert-butyllithium, hexamethylenedilithium, butadienyl Polyfunctional organic lithium compounds such as dilithium and isoprenyldilithium can be used.
  • the molecular weight of the polymer is controlled by the amount of the organolithium compound added, and by adjusting the amount added, a polymer that satisfies the desired melt mass flow rate can be obtained.
  • a mixture that satisfies the desired melt mass flow rate may be obtained by melt-blending a plurality of resins.
  • a randomizer may also be added to control the state of polymerization.
  • Tetrahydrofuran THF is mainly used as a randomizing agent, but other ethers, amines, thioethers, phosphoramides, alkylbenzenesulfonates, potassium or sodium alkoxides, etc. can also be used.
  • Suitable ethers include THF as well as dimethyl ether, diethyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and the like.
  • amines tertiary amines such as trimethylamine, triethylamine, tetramethylethylenediamine, and cyclic amines can be used.
  • triphenylphosphine, hexamethylphosphoramide, potassium or sodium alkylbenzenesulfonate, potassium or sodium butoxide, etc. can also be used as randomizing agents.
  • the amount of the randomizing agent to be added may be, for example, 0.001 to 10 parts by mass with respect to 100 parts by mass of all charged monomers.
  • the timing of addition may be before the initiation of the polymerization reaction or before polymerization of the copolymer chain. Moreover, additional addition can also be carried out as needed.
  • the block copolymer thus obtained is deactivated by adding a polymerization terminator such as water, alcohol, or carbon dioxide in an amount sufficient to deactivate the active terminals.
  • a polymerization terminator such as water, alcohol, or carbon dioxide in an amount sufficient to deactivate the active terminals.
  • Methods for recovering the copolymer from the resulting block copolymer solution include (A) a method of precipitating with a poor solvent such as methanol; method), (C) a method of concentrating the solution with a concentrator and then removing the solvent with a vented extruder, (D) dispersing the solution in water and blowing steam to remove the solvent by heating to recover the copolymer Arbitrary methods, such as the method of carrying out (steam stripping method), can be employ
  • the first resin composition or the second resin composition is obtained by mixing at least one type of block copolymer obtained by the above-described manufacturing method, etc., and other additives as necessary.
  • additives include, for example, various stabilizers, lubricants, processing aids, antiblocking agents (antiblocking agents), antistatic agents, antifogging agents, light resistance improvers, softeners, plasticizers, pigments, and the like. mentioned.
  • Each additive may be added to the block copolymer solution, or may be blended with the recovered copolymer and melt-mixed.
  • Stabilizers include, for example, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2-hydroxy-3, 5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 2,6- Phenolic antioxidants such as di-tert-butyl-4-methylphenol, phosphorus antioxidants such as trisnonylphenyl phosphite, and the like.
  • antiblocking agents examples include fatty acid amides, ethylenebisstearamide, sorbitan monostearate, saturated fatty acid esters of fatty alcohols, and pentaerythritol fatty acid esters. These additives are preferably used in an amount of 5 mass % or less based on the block copolymer.
  • the first resin composition or the second resin composition may contain two or more block copolymers, and a known method can be adopted as a method for mixing these block copolymers. For example, they may be dry-blended using a Henschel mixer, a ribbon blender, a super mixer, a V-blender, or the like, or may be melted and pelletized using an extruder. In one aspect, melt mixing is preferred. A method of removing the solvent after mixing the polymer solutions can also be used.
  • the method for producing the foamed film is not particularly limited, but for example, a method of forming a foamed layer and a non-foamed layer by co-extrusion using the first resin composition and the second resin composition can be used. At this time, it may be extruded together with the resin composition constituting other layers.
  • the foamed film may also be produced by extruding each layer one by one or several layers together and then laminating.
  • the method of forming the foam layer is not limited, and a commonly used method, that is, a chemical foaming method in which the resin is foamed with gas generated by thermal decomposition of the chemical foaming agent when the resin and the chemical foaming agent are melt-kneaded.
  • a foaming method, a physical foaming method in which gas is injected into a resin melted in an extruder to foam, and the like can be used.
  • chemical foaming agents used in the chemical foaming method include sodium bicarbonate, organic acids such as citric acid, azodicarbonamide, azobisisobutyronitrile, diazoaminobenzene, N,N'-dinitrosopentamethylenetetramine. , N,N'-dimethyl-N,N'-dinitroterephthalamide, benzenesulfonylhydrazide, p,p'-oxybisbenzenesulfonylhydrazide, carbonates, etc., and two or more of these may be used in combination.
  • the method of adding the chemical foaming agent is not particularly limited, but it can be dry blended with resin pellets, added using a fixed amount feeder in the hopper of an extruder, or based on the same resin as the main raw material. Any method of preparing and adding a masterbatch (foaming agent masterbatch) may be used. The amount of the chemical foaming agent added is appropriately adjusted according to the desired expansion ratio and the amount of gas generated by the foaming agent.
  • physical foaming agents used in the physical foaming method include carbon dioxide, propane, butane, n-pentane, dichlorodifluoromethane, dichloromonofluoromethane, trichloromonofluoromethane, methanol, ethanol, water, and the like.
  • carbon dioxide gas is preferably used in terms of safety.
  • the method of adding the physical foaming agent include a method of supplying it to the central zone of the extruder or, when a tandem extruder is used, the central zone of the first stage extruder.
  • resin pellets impregnated with a foaming gas may be charged into an extruder to obtain a foamed film. The amount of the physical foaming agent to be added is appropriately adjusted depending on the desired foaming ratio.
  • a heat-shrinkable film according to one embodiment of the present invention is a film using the foamed film.
  • the heat-shrinkable film is the stretched foamed film (heat-shrinkable foamed film).
  • the specific gravity of the foamed film hardly changes even if it is stretched.
  • the stress distribution during stretching is not always uniform, so the smoothness of the original foam film tends to decrease.
  • a heat-shrinkable film according to one embodiment of the present invention is a heat-shrinkable film that maintains surface smoothness suitable for printing even after being stretched.
  • each layer may be stretched and then laminated to produce a heat-shrinkable film.
  • a general method such as a method using an adhesive or a method using heat can be used.
  • the lamination temperature is not particularly limited, the preferred temperature range is less than 70°C.
  • a heat-shrinkable film may be produced by stretching a foamed film that is a multilayer film after coextrusion or lamination.
  • sheet and film are not used to distinguish between the terms “sheet” and “film” when it comes to differences in thickness. ”.
  • the stretching may be uniaxial, biaxial or multiaxial.
  • uniaxial stretching include a method of stretching an extruded foam sheet with a tenter in a direction perpendicular to the extrusion direction (TD direction), a method of stretching an extruded tubular foam film in the circumferential direction, and a method of stretching an extruded foamed film.
  • MD direction perpendicular to the extrusion direction
  • MD direction stretching a sheet in the extrusion direction
  • biaxial stretching examples include a method of stretching an extruded foam sheet with rolls in the direction of extrusion (MD direction) and then stretching in a direction perpendicular to the direction of extrusion (TD direction) with a tenter or the like; A method of stretching the foamed film in the extrusion direction and the circumferential direction simultaneously or separately may be used.
  • the stretching temperature is preferably 60 to 120°C, for example.
  • the temperature is 60° C. or higher, the film is less likely to break during stretching, and when the temperature is 120° C. or lower, a film having good shrinkage properties can be obtained, which is preferable.
  • Particularly preferred is a range of Tg+5° C. to Tg+20° C. with respect to the glass transition temperature (Tg) of the composition constituting the film.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) can be obtained from, for example, the peak temperature of the loss elastic modulus.
  • the draw ratio is not particularly limited, but is preferably 1.5 to 8 times.
  • a stretching ratio of 1.5 times or more is preferable because a film having good shrinkage properties can be obtained, and a stretching ratio of 8 times or less enables easy production of a stretched film.
  • the heat-shrinkable film preferably has a heat-shrinkage rate of 65% or more at 100° C. for 10 seconds.
  • the heat-shrinkage rate is preferably 10% or more at 70°C for 10 seconds.
  • the heat shrinkage is 10% or more, the temperature does not have to be high during shrinkage, so the effect on the covered article can be suppressed.
  • a preferable heat shrinkage rate is 15% or more at the same temperature. In one aspect, it is preferably 65% or more at 100° C. for 10 seconds.
  • the natural shrinkage rate is preferably 2.5% or less at 40° C. for 7 days.
  • the total thickness of the heat-shrinkable film is preferably 30-200 ⁇ m, more preferably 50-150 ⁇ m.
  • a heat-shrinkable label using a heat-shrinkable film as a label can be produced by a known method. For example, it can be produced by printing a stretched film, setting the stretched direction to the circumferential direction, and sealing with a solvent. can. It can also be produced by pasting a printed heat-shrinkable label on a non-stretched foamed film, and then performing solvent sealing with the direction of large shrinkage being the circumferential direction.
  • Labels are not particularly limited, but cans made of tinplate, TFS, aluminum and other metal can containers (3-piece cans and 2-piece cans, bottle cans with lids, etc.), glass containers or polyethylene terephthalate (PET and It can be used as a label for containers made of resin such as polyethylene, etc.
  • foamed films and heat-shrinkable films, especially heat-shrinkable labels have a specific gravity of less than 1, when used as a PET bottle label, they can be separated from the container under water, which has the advantage of being excellent in recyclability.
  • Solvent Tetrahydrofuran Concentration: 2% by mass Calibration curve: Created using standard polystyrene (manufactured by VARIAN).
  • a block copolymer of P-3 was obtained in the same manner as P-2, except that 670 mL of a 10% by mass cyclohexane solution of n-butyllithium was added as a polymerization initiator solution.
  • a block copolymer of P-4 was obtained in the same manner as P-1 except that 1340 mL of a 10% by mass cyclohexane solution of n-butyllithium was added as a polymerization initiator solution.
  • a block copolymer of P-5 was obtained in the same manner as P-1, except that 540 mL of a 10% by mass cyclohexane solution of n-butyllithium was added as a polymerization initiator solution.
  • melt mass flow rate (MFR) of the obtained compositions SBC-A to SBC-I was measured according to JIS K7210.
  • the second resin composition of the non-foaming layer also contains an antiblocking agent, and its melt mass flow rate is 100 for each of the compositions SBC-A, SBC-C, SBC-D, SBC-E, and SBC-F. It is a value measured using a sample prepared by melting and kneading the mass parts and the anti-blocking material at the predetermined ratios shown in Tables 3 and 4.
  • Example 1 A method for producing the heat-shrinkable film (heat-shrinkable foamed film) of Example 1 is described below.
  • the heat-shrinkable foamed film of Example 1 was produced by the method described below.
  • the second layer of the heat shrinkable film according to the present embodiment is referred to as the front and back layers (surface layer or back layer when representing one)
  • the first layer is referred to as the inner layer
  • the heat shrinkable foam film The manufacturing process is divided into (1) extrusion of the front and back layers, (2) extrusion of the inner layer, and (3) sheet (film) stretching.
  • Inner layer sheet extrusion A block copolymer of SBC-D (first resin composition) and a foaming agent masterbatch (foaming agent MB), product name "Polythrene ES405" (manufactured by Eiwa Kasei Kogyo Co., Ltd.) were extruded at 0.00%. Using 6 parts by mass, the inner layer was co-extruded simultaneously with the extrusion of the front and back layers described in (1). Polystyrene ES405 contained sodium bicarbonate, and the amount corresponding to sodium bicarbonate in 0.6 parts by mass was 0.24 parts by mass.
  • the extruder for the inner layer resin was a single screw extruder with a diameter of 65 mm, and the set temperature was 200°C.
  • the front and back layers described in (1) and the inner layer described in (2) are discharged from the multilayer T die as a laminated sheet of two types and three layers that are in close contact with each other. was done.
  • the SBC-D block copolymer 91 parts by mass of P-2 block copolymer pellets and 9 parts by mass of P-3 block copolymer pellets are dry-blended at the entrance of the extruder. Both pellets are melt mixed in the extruder and fed to a multi-layer die.
  • the set temperature of the multilayer T die was set to 190°C.
  • the mass ratio of SBC-A (second resin composition) and SBC-D (first resin composition) supplied to the surface layer/inner layer/back layer was 1/2/1.
  • the resulting laminated sheet (foamed film) had a thickness of 0.30 mm, and since foaming occurred in the inner layer, the thickness ratio of surface layer/inner layer/back layer was 1/3/1.
  • Examples 2 to 9 and Comparative Examples 1 to 5 were formed in the same manner as in Example 1 under the conditions shown in Tables 3 and 4.
  • the specific gravity of the heat-shrinkable foamed film was measured by cutting out a test piece from the foamed film and using the test piece according to JIS Z8807:2012 "Submerged Weighing Method" using the device shown below.
  • ⁇ Heat shrinkage rate The heat shrinkage rate at 100°C was calculated from the following formula after immersing a stretched film (heat-shrinkable foamed film) in hot water adjusted to 100°C for 10 seconds.
  • Thermal shrinkage rate (%) (L1-L2) / L1 x 100
  • the calculated thermal shrinkage rate was evaluated according to the following criteria. If the evaluation of the heat shrinkage rate was "excellent” or "good", it was determined that the heat shrinkage rate, which is a basic characteristic of a heat shrinkable film, is provided and that there is no practical problem. Excellent: 70% ⁇ heat shrinkage rate Good: 60% ⁇ heat shrinkage rate ⁇ 70% Impossible: Heat shrinkage ⁇ 60%
  • Film formability was evaluated according to the following criteria. If the film formability is evaluated as “excellent” or “good”, it is possible to manufacture a heat-shrinkable foamed film. Excellent: Film formation is good Good: Film formation is possible, but the following defects (*1) to (*3) may occur in film formation *1: Foaming is difficult to stabilize * 2: FE (fish eye: generation of foreign matter due to poor kneading, etc.) tends to increase *3: Breakage may occur.
  • Examples 2 to 9 and Comparative Examples 1 to 5 In the same manner as in Example 1, heat-shrinkable foamed films of Examples 2 to 9 and Comparative Examples 1 to 5 were prepared according to Tables 3 and 4. Tables 3 and 4 show the physical properties and evaluation of the heat-shrinkable foamed films.

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