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WO2018180598A1 - Film thermorétractable - Google Patents

Film thermorétractable Download PDF

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Publication number
WO2018180598A1
WO2018180598A1 PCT/JP2018/010468 JP2018010468W WO2018180598A1 WO 2018180598 A1 WO2018180598 A1 WO 2018180598A1 JP 2018010468 W JP2018010468 W JP 2018010468W WO 2018180598 A1 WO2018180598 A1 WO 2018180598A1
Authority
WO
WIPO (PCT)
Prior art keywords
heat
shrinkage
film
shrinkable film
main
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/010468
Other languages
English (en)
Japanese (ja)
Inventor
裕一郎 勘坂
琢磨 金子
秀太 弓削
正浩 渡邉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CI Takiron Corp
Original Assignee
CI Takiron Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CI Takiron Corp filed Critical CI Takiron Corp
Priority to JP2019509287A priority Critical patent/JP6934936B2/ja
Publication of WO2018180598A1 publication Critical patent/WO2018180598A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
    • B29C61/06—Making preforms having internal stresses, e.g. plastic memory

Definitions

  • the present invention relates to a heat shrinkable film.
  • This application claims priority based on Japanese Patent Application No. 2017-064407 for which it applied to Japan on March 29, 2017, and uses the content here.
  • Heat-shrinkable films are widely used as shrink wrapping containers and shrink labels. Generally, the heat-shrinkable film is cut along perforations provided on the film in advance, and is discarded and recycled separately from the container.
  • the heat-shrinkable film has shrinkability, printability, environmentally friendly material, strong film, and excellent shrinkage finish (for example, less wrinkles and shrinkage spots), sewing machine Excellent eye-opening properties, excellent wearability (for example, label tearing is less likely to occur during mounting), low natural shrinkage, and excellent film stability during storage (for example, storage It is required that the film does not easily wrinkle or change in dimensions.
  • heat-shrinkable films used for container shrink-wrapping and shrinkage labels include polyvinyl chloride-based heat-shrinkable films, polyester-based heat-shrinkable films, and polystyrene-based heat-shrinkable films (Patent Documents 1 and 2).
  • Polyvinyl chloride heat-shrinkable films are excellent in shrink finish, perforation opening and wearability, and have a low natural shrinkage ratio, but have problems such as the generation of toxic chlorine-containing gas during incineration.
  • Polyester-based heat-shrinkable films are excellent in film stability during storage and waist strength, but have problems such as poor shrinkage, perforation opening, and wearability.
  • Polystyrene heat-shrinkable film is superior in shrink finish, perforation opening, and wearability compared to films using other materials described above, but has a high natural shrinkage rate and stability of the film during storage. Has a problem with sex.
  • the present invention has been made in view of the above circumstances, and has excellent shrinkage finish, perforation opening, and wearability, while compared with conventional polystyrene heat-shrinkable films.
  • An object of the present invention is to provide a polystyrene-based heat-shrinkable film having improved film stability.
  • a heat-shrinkable film containing a polystyrene-based resin which has a heat shrinkage rate of 15% or less when immersed in water at 70 ° C. for 10 seconds and is immersed in water at 98 ° C. for 10 seconds.
  • the thermal shrinkage rate in the main shrinkage direction is 60% or more
  • the Elmendorf tear strength in the main shrinkage direction is in the range of 3 to 10 N / mm
  • the Elmendorf tear strength in the direction orthogonal to the main shrinkage direction is 10
  • the shrinkage stress in the main shrinkage direction is 4.0 N / mm 2 or less when left at 85 ° C.
  • the heat-shrinkable film is formed by being stretched in the main shrinkage direction after extrusion, and the stretching has a preheating temperature of 100 ° C. or higher, a stretching temperature and a heat setting temperature of 90 ° C. or higher, and a stretching ratio of 4
  • the heat-shrinkable film according to [1] which is stretched to be 9 or more.
  • the heat-shrinkable film of the present invention has an excellent shrink finish, perforation opening, and wearability, while improving the stability of the film during storage compared to conventional polystyrene heat-shrinkable films. Yes.
  • the heat-shrinkable film of the present invention (hereinafter also referred to as “this film”) contains a polystyrene resin.
  • the polystyrene resin may be any known one used for the production of heat-shrinkable films, such as styrene-butadiene copolymer, styrene-butadiene-styrene copolymer, styrene-ethylene-butadiene-styrene copolymer, Polystyrene thermoplastic elastomers such as styrene-vinyl / polyisoprene-styrene copolymer; styrene-methacrylic acid copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate Examples thereof include impact-resistant styrene resins such as copolymers and styrene-phenyl methacrylate copolymers. Among these
  • This film may contain a resin other than the polystyrene-based resin as another resin as long as the effects of the present invention are not impaired.
  • a resin other than the polystyrene-based resin as another resin as long as the effects of the present invention are not impaired.
  • other resin the well-known thing used for the use of manufacture of a heat-shrinkable film may be sufficient.
  • other resins include olefin resins (such as propylene resins), polyester resins, and acrylic resins.
  • One of these other resin components may be used alone, or two or more thereof may be used.
  • the content of the polystyrene resin is preferably 50 to 100% by mass, and more preferably 80 to 100% by mass.
  • heat shrinkable film When this film is immersed in water at 70 ° C. for 10 seconds, the heat shrinkage rate in the main shrinkage direction (hereinafter also referred to as “heat shrinkage rate 1”) is 15% or less, and 5 to 15%. Is more preferable, and 7 to 12% is more preferable. If the thermal shrinkage rate 1 is 15% or less, the film shrinks normally by a normal steam tunnel, and wrinkles, shrinkage spots, etc. are prevented, and the shrinkage finish is good.
  • the heat shrinkage rate in the main shrinkage direction (hereinafter also referred to as “heat shrinkage rate 2”) is 60% or more and 60 to 80%. Is more preferable, and 65 to 75% is more preferable.
  • the heat shrinkage ratio 2 is 60% or more, the shrinkage is excellent, and it is possible to mount on various containers, and it is possible to prevent mounting trouble due to insufficient shrinkage.
  • the heat shrinkage rate in the main shrinkage direction (hereinafter also referred to as “heat shrinkage rate 3”) is 60% or more, and 60 to 80%. Is more preferable, and 65 to 75% is more preferable.
  • the shrinkage ratio 3 is 60% or more, the shrinkage is excellent, and it is possible to mount on various containers, and it is possible to prevent mounting trouble due to insufficient shrinkage.
  • the difference ( ⁇ 23 ) between the heat shrinkage rate 2 and the heat shrinkage rate 3 is preferably within ⁇ 1%. If delta 23 is within 1% ⁇ , it is possible to mount to various containers, a mounting trouble due to shrinkage shortage can be further prevented.
  • thermal shrinkage is a value measured at 70 ⁇ 0.5 ° C., 98 ⁇ 0.5 ° C., and 100 ⁇ 0.5 ° C. according to JIS Z1709.
  • the Elmendorf tear strength of the main shrinkage direction (hereinafter also referred to as “TD direction”) of the film is in the range of 3 to 10 N / mm, preferably in the range of 3 to 8 N / mm. / Mm is more preferable. If the Elmendorf tear strength in the MD direction is in the range of 3 to 10 N / mm, the perforation is excellent.
  • excellent perforation opening means, for example, when a label using this film is separated by a perforation provided along a direction perpendicular to the main shrinkage direction of the label. It means that the label can be easily peeled off from the container without tearing the label.
  • the Elmendorf tear strength of the film in the direction orthogonal to the main shrinkage direction (hereinafter also referred to as “MD direction”) is in the range of 10 to 20 N / mm, and preferably in the range of 10 to 17 N / mm. More preferably, it is in the range of 10 to 14 N / mm. If the Elmendorf tear strength in the TD direction is in the range of 10 to 20 N / mm, the perforation is excellent.
  • “Elmendorf tear strength” is a value obtained by dividing a value measured in the MD direction and the TD direction by the thickness of the film according to JIS K7128-2.
  • This film when left at 85 ° C. 5 min, main shrinkage direction of the shrinkage stress is at 4.0 N / mm 2 or less, preferably 3.5 N / mm 2 or less, 3.0 N / mm More preferably, it is 2 or less. If the shrinkage stress in the main shrinkage direction is 4.0 N / mm 2 or less, the label can be prevented from breaking from the perforation when the label using this film is attached to a container or the like. Excellent.
  • shrinkage stress refers to a sample piece having a length in the main shrinkage direction of 80 mm and a width of 25 mm in an oven at 85 ° C. in a state where the sample piece is held on a chuck equipped with a load cell at a distance of 50 mm between chucks. It is the maximum stress per unit cross-sectional area measured when it is put in and left for 5 minutes.
  • the shrinkage in the main shrinkage direction (hereinafter also referred to as “natural shrinkage”) is 1.5% or less and 1.2% or less. Preferably, it is 1.0% or less. If the natural shrinkage is 1.5% or less, shrinkage during storage can be reduced, and the film during storage is less likely to wrinkle or change in dimensions, and the stability of the film during storage is excellent.
  • the natural shrinkage rate is a shrinkage rate in the main shrinkage direction when a sample having a length of 500 mm in the main shrinkage direction is left at 40 ° C. for 7 days, and is a value calculated by the following formula (I).
  • Natural shrinkage [%] ⁇ [(500) ⁇ (length after standing [mm])] / (500) ⁇ ⁇ 100 (I)
  • the present film may be a single layer film made of polystyrene resin, or may be a multilayer film having an outermost layer made of polystyrene resin and another layer made of polystyrene resin and another resin.
  • the film may be a transparent film or an opaque film or a colored film such as white from the viewpoint of printability.
  • the heat-shrinkable film may contain additives such as a filler, a stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, and a lubricant.
  • the thickness of the film is preferably 20 to 80 ⁇ m, more preferably 40 to 60 ⁇ m.
  • the thickness of the outermost layer of this film is preferably 2 to 8 ⁇ m, more preferably 4 to 6 ⁇ m, and the total thickness of other layers is preferably 18 to 78 ⁇ m, more preferably 16 to 54 ⁇ m. .
  • the heat-shrinkable film is not particularly limited, but is mainly used as a label for a bottle container.
  • the heat shrinkable film may be printed.
  • the heat-shrinkable film is cut into a predetermined length, and the ends of the cut film are joined to form a cylindrical body.
  • An example is a method in which a bottle container is inserted into a cylindrical body and then heated to shrink.
  • This film can be obtained by a known method (T-die method, inflation method or the like, in the case of a multilayer film, a coextrusion method thereof).
  • T-die method inflation method or the like
  • the material is extruded in a flat shape or a tube shape from a die heated to 160 to 240 ° C.
  • the resulting unstretched product has a main shrinkage direction (TD direction) and Biaxial stretching is preferably performed in an orthogonal direction (MD direction).
  • TD direction main shrinkage direction
  • MD direction main shrinkage direction
  • MD direction orthogonal direction
  • sequential biaxial stretching in the MD direction and TD direction may be used, or simultaneous biaxial stretching may be used.
  • the film of this embodiment is stretched at a preheating temperature of 100 ° C. or higher, a stretching temperature and a heat setting temperature of 90 ° C. or higher, and a draw ratio of 4.9 or higher in the step of performing the stretching process in the TD direction of the production. It is preferable to do so.
  • the natural shrinkage rate of the film can be set to an appropriate value.
  • the heat-shrinkable film of the present invention satisfies the above-mentioned physical property values, so that it has an excellent shrink finish, perforation opening, and wearability, while having a conventional polystyrene heat-shrinkability. Compared to the film, the stability of the film during storage is improved.
  • Heat shrinkage According to JIS Z1709, 70 ⁇ 0.5 ° C. (measurement temperature of “heat shrinkage rate 1”), 98 ⁇ 0.5 ° C. (measurement temperature of “heat shrinkage rate 2”) and 100 ⁇ 0.5 ° C. (“ The heat shrinkage rate of the heat-shrinkable film at a measurement temperature of 3 ”was measured.
  • shrinkage stress For a sample piece having a length in the main shrinkage direction of 80 mm and a width of 25 mm, the maximum value of stress measured when left for 5 minutes at 85 ° C. was defined as shrinkage stress.
  • Perforation opening A label of the above-described cylindrical body in which perforations were previously provided in a direction perpendicular to the main contraction direction was attached to the bottle container. However, the perforations were formed by putting holes having a length of 1 mm at intervals of 4 mm, and two perforations were provided in the direction of the perforation (MD direction) over a width of 20 mm and a length of 200 mm. Thereafter, the perforation of the label was torn with a fingertip, and it was determined whether the label was torn along the perforation provided in the MD direction. ⁇ : The label was torn along the perforation. X: The label was not torn along the perforation, or the label was torn in a direction other than the TD direction.
  • Example 1 (Raw material for polystyrene heat-shrinkable film)
  • the polystyrene-based heat-shrinkable film of the examples described below has a three-layer structure composed of the following components.
  • a mixture of SBC (A) and SBC (B), which is a styrene-butadiene copolymer was used as a raw material.
  • a mixture of a styrene-butadiene copolymer (SBC (A)) and an impact-resistant polystyrene resin (referred to as “HiPS” in Table 1) was used as a raw material.
  • Table 1 shows the Vicat softening point and melt mass flow rate (referred to as “MFR” in Table 1) of each component, and the component ratio of each layer.
  • the polyester-based heat-shrinkable film of Comparative Example 2 described below has a single-layer structure and is a polyester-based resin (referred to as “polyester (A)” in Table 1) that is P-SF manufactured by SK Chemical Company.
  • a mixture of silica gel master batches (referred to as “silica gel MB” in Table 1) which is EPM7E-325 manufactured by Sumika Color was used as a raw material.
  • Table 1 shows the glass transition point (referred to as “Tg” in Table 1) and intrinsic viscosity (referred to as “IV” in Table 1) and the component ratio of the components constituting the film of the polyester A used.
  • polyester heat-shrinkable film Manufacture of polyester heat-shrinkable film
  • the raw materials of the polyester heat-shrinkable film were mixed in the blending amounts shown in Table 1, and extruded from a die kept at 260 ° C., to obtain a polyester film original fabric having a single-layer structure having a thickness of 200 ⁇ m.
  • a polyester heat-shrinkable film was obtained in the same manner as in Example 1 except that this single-layer structure film was used and the stretching conditions were changed as shown in Table 2.
  • Table 3 shows the results of evaluation based on the above criteria for each evaluation item.
  • the polystyrene heat-shrinkable film of Example 1 is more stable during storage than the polystyrene heat-shrinkable film of Comparative Example 1 in which the natural shrinkage rate exceeds 1.5%. Improved.
  • the polyester heat-shrinkable film of Comparative Example 2 using the polyester-based resin was inferior to the heat-shrinkable film of Example 1 in shrink finish, wearability, and perforation opening.

Landscapes

  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Wrappers (AREA)

Abstract

L'invention fournit un film thermorétractable à base de polystyrène qui est doté d'excellentes propriétés de finition de rétraction, de facilité d'ouverture de perforations et d'ajustement, et qui simultanément présente une amélioration de sa stabilité lors d'un stockage par rapport aux films thermorétractables à base de polystyrène de l'art antérieur. Plus précisément, l'invention concerne un film thermorétractable qui comprend une résine à base de polystyrène. Lorsque le taux de thermorétraction dans une direction de rétraction principale est inférieur ou égal à 15% après immersion de 10 secondes dans une eau à 70°C, et lorsque le taux de thermorétraction dans la direction de rétraction principale est supérieur ou égal à 60% après immersion de 10 secondes dans une eau à 98°C, la résistance au déchirement d'Elmendorff dans la direction de rétraction principale est comprise dans une plage de ３ à １０Ｎ／ｍｍ, et la résistance au déchirement d'Elmendorff dans une direction perpendiculaire à la direction de rétraction principale est comprise dans une plage de １０ à ２０Ｎ／ｍｍ. La contrainte de contraction dans la direction de rétraction principale après repos de 5 minutes à 85°C, est inférieure ou égale à ４,０Ｎ／ｍｍ２. Le taux de rétraction dans la direction de rétraction principale après repos de 7 jours à 40°C, est inférieur ou égal à 1,5%.
PCT/JP2018/010468 2017-03-29 2018-03-16 Film thermorétractable Ceased WO2018180598A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019509287A JP6934936B2 (ja) 2017-03-29 2018-03-16 熱収縮性フィルム

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-064407 2017-03-29
JP2017064407 2017-03-29

Publications (1)

Publication Number Publication Date
WO2018180598A1 true WO2018180598A1 (fr) 2018-10-04

Family

ID=63675563

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Application Number Title Priority Date Filing Date
PCT/JP2018/010468 Ceased WO2018180598A1 (fr) 2017-03-29 2018-03-16 Film thermorétractable

Country Status (5)

Country Link
JP (1) JP6934936B2 (fr)
AR (1) AR111191A1 (fr)
TW (1) TWI756389B (fr)
UY (1) UY37663A (fr)
WO (1) WO2018180598A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000211072A (ja) * 1999-01-28 2000-08-02 C I Kasei Co Ltd 艶消し多層ポリスチレン系熱収縮フイルム
JP2002285020A (ja) * 2001-03-23 2002-10-03 Gunze Ltd 熱収縮性ラベル用白色フィルム、該フィルムから作製された熱収縮性ラベル、及び、該ラベルを熱収縮装着した容器
JP2003340987A (ja) * 2002-05-31 2003-12-02 C I Kasei Co Ltd 多層ポリスチレン系熱収縮フィルム
WO2008075707A1 (fr) * 2006-12-20 2008-06-26 Toyo Boseki Kabushiki Kaisha Film de polystyrène thermorétractable et son procédé de fabrication
JP3189169U (ja) * 2013-12-13 2014-02-27 日本ポリエチレン株式会社 易開封性袋並びに易引裂性フィルム及び易引裂性テープ
JP2016068567A (ja) * 2014-09-29 2016-05-09 積水フィルム株式会社 多層熱収縮フィルム及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000211072A (ja) * 1999-01-28 2000-08-02 C I Kasei Co Ltd 艶消し多層ポリスチレン系熱収縮フイルム
JP2002285020A (ja) * 2001-03-23 2002-10-03 Gunze Ltd 熱収縮性ラベル用白色フィルム、該フィルムから作製された熱収縮性ラベル、及び、該ラベルを熱収縮装着した容器
JP2003340987A (ja) * 2002-05-31 2003-12-02 C I Kasei Co Ltd 多層ポリスチレン系熱収縮フィルム
WO2008075707A1 (fr) * 2006-12-20 2008-06-26 Toyo Boseki Kabushiki Kaisha Film de polystyrène thermorétractable et son procédé de fabrication
JP3189169U (ja) * 2013-12-13 2014-02-27 日本ポリエチレン株式会社 易開封性袋並びに易引裂性フィルム及び易引裂性テープ
JP2016068567A (ja) * 2014-09-29 2016-05-09 積水フィルム株式会社 多層熱収縮フィルム及びその製造方法

Also Published As

Publication number Publication date
TW201843221A (zh) 2018-12-16
JPWO2018180598A1 (ja) 2020-02-06
AR111191A1 (es) 2019-06-12
JP6934936B2 (ja) 2021-09-15
UY37663A (es) 2018-07-31
TWI756389B (zh) 2022-03-01

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