WO2008018528A1 - Emballage - Google Patents

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Publication number
WO2008018528A1
WO2008018528A1 PCT/JP2007/065586 JP2007065586W WO2008018528A1 WO 2008018528 A1 WO2008018528 A1 WO 2008018528A1 JP 2007065586 W JP2007065586 W JP 2007065586W WO 2008018528 A1 WO2008018528 A1 WO 2008018528A1
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WO
WIPO (PCT)
Prior art keywords
film
label
heat
less
shrinkage
Prior art date
Application number
PCT/JP2007/065586
Other languages
English (en)
Japanese (ja)
Inventor
Masayuki Haruta
Masakazu Iwasaki
Masatoshi Hashimoto
Katsuhiko Nose
Original Assignee
Toyo Boseki Kabushiki Kaisha
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
Priority claimed from JP2007206372A external-priority patent/JP2008273619A/ja
Application filed by Toyo Boseki Kabushiki Kaisha filed Critical Toyo Boseki Kabushiki Kaisha
Publication of WO2008018528A1 publication Critical patent/WO2008018528A1/fr

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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
    • 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
    • B29C61/003—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/744—Labels, badges, e.g. marker sleeves

Definitions

  • the present invention relates to a packaging body coated with a label formed of a heat-shrinkable film, and more particularly to a packaging body having a good tearing condition of a label made of a coated heat-shrinkable film. is there.
  • a film that is greatly shrunk in the width direction is widely used.
  • the film is stretched at a high magnification in the width direction in order to develop shrinkage characteristics in the width direction, but is orthogonal to the main shrinkage direction.
  • the longitudinal direction there are some that are only stretched at a low magnification and that are often not stretched.
  • a film that has been stretched at a low magnification in the longitudinal direction or a film that has been stretched only in the width direction has a drawback that the mechanical strength in the longitudinal direction is inferior.
  • a lapping method has been developed to hold the container in a closed state by covering the periphery of a single-open container made of synthetic resin with a belt-like film, and a film that shrinks in the longitudinal direction is suitable for such packaging applications. ing. Therefore, demand for films that shrink in the longitudinal direction is expected to increase dramatically in the future.
  • a non-stretched film that eliminates the mechanical strength defect in the direction orthogonal to the main shrinkage direction as described above and develops a function of shrinking in the longitudinal direction is referred to as the longitudinal direction (also referred to as the longitudinal direction).
  • Stretch in the longitudinal direction by stretching 2.0 to 5.0 times each in the width direction (also referred to as the transverse direction) and then re-stretching 1.1 times or more in the longitudinal direction.
  • a heat-shrinkable polyester film is known in which both the Young's modulus and the Young's modulus in the width direction are adjusted to a predetermined value or more (Patent Document 1).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 8-244114
  • FIG. 1 is an explanatory view showing the shape of a test piece in the measurement of right-angled tear strength (the unit of length of each part of the test piece in the figure is mm).
  • An object of the present invention is to solve the problems of the heat-shrinkable polyester film of Patent Document 1 described above, and in the width direction orthogonal to the main shrinkage direction in which the shrinkage in the longitudinal direction, which is the main shrinkage direction, is high.
  • a heat-shrinkable film that has high mechanical strength and does not cause winding and tightening in the roll film produced, and that has a good opening property that makes it difficult for paper rolls to enter the film roll. It is intended to provide a package in which a label made of an adhesive film is coated and the bow of the label is cracked well.
  • the invention described in claim 1 is a package formed by heat-shrinking at least a part of the outer periphery with a label having a heat-shrinkable film as a base material.
  • the Elmendorf ratio when measuring the Elmendorf tear load in the direction perpendicular to the main shrinkage direction of the coated label and the Elmendorf tear load in the main shrinkage direction is 0.5 or more and 2.0 or less. To do.
  • the heat-shrinkable film of the present invention examples include a heat-shrinkable polyester film, a heat-shrinkable polystyrene film, a heat-shrinkable polyolefin film, and a heat-shrinkable polychlorinated butyl film.
  • the perforation means that a plurality of slits are continuously provided in a linear shape or a curved shape, but includes one in which only one slit is provided.
  • the shape of the slit constituting the perforation is not particularly limited.
  • the notch refers to a notch provided at the edge of the label, and its shape is not particularly limited.
  • the Elmendorf tear load in the direction perpendicular to the main shrinkage direction of the coated label or in the main shrinkage direction is the direction perpendicular to the main shrinkage direction of the film substrate excluding the printed layer of the coated label or the main shrinkage direction.
  • the Elmendorf tear load in the direction of contraction is the direction perpendicular to the main shrinkage direction of the film substrate excluding the printed layer of the coated label or the main shrinkage direction.
  • the invention described in claim 2 is the invention described in claim 1, wherein the tensile fracture strength in the direction perpendicular to the main shrinkage direction of the coated label is not less than lOOMPa and not more than 300 MPa. It is characterized by. Note that the main shrinkage direction of the coated label
  • the tensile breaking strength in the intersecting direction refers to the tensile breaking strength in the direction orthogonal to the main shrinkage direction of the film substrate excluding the printed layer of the coated label.
  • the invention described in claim 3 is orthogonal to the main shrinkage direction of the film substrate excluding the printed layer of the coated label in the invention described in claim 1 or claim 2.
  • the refractive index in the direction is 1.570 or more and 1.600 or less.
  • the invention described in claim 4 is the invention described in any one of claims 1 to 3, wherein the right-angled tear strength in the direction perpendicular to the main shrinkage direction per unit thickness of the coated label. Is characterized by being 100 N / mm or more and 300 N / mm or less.
  • the right-angle tear strength in the direction perpendicular to the main shrinkage direction per unit thickness of the coated label is the perforation main shrinkage per unit thickness of the film substrate excluding the printed layer of the coated label. This is the right-angle tear strength in the direction perpendicular to the direction.
  • the invention described in claim 5 is the invention described in any one of claims 1 to 4, wherein a perforation or a pair of notches is provided along a direction orthogonal to the main contraction direction of the label. It is characterized by that.
  • the invention described in claim 6 is the invention described in any one of claims 1 to 5, wherein the unstretched film is held in the tenter in a state where both ends in the width direction are held by clips.
  • 100 A process of heat treatment at a temperature not lower than 170 ° C and not higher than 170 ° C for a time not shorter than 1.0 second and not longer than 10.0 seconds, and then cooling until the surface temperature of the film reaches 30 ° C or higher and 70 ° C or lower
  • the clip gripping part at both edges in the width direction of the film is cut and removed, and stretched at a magnification of 2.0 times or more and 5.5 times or less in the longitudinal direction at a temperature of Tg + 50 ° C or more and Tg + 80 ° C or less After that, the film is cooled at a cooling rate
  • the invention described in claim 7 is the invention described in any one of claims 1 to 6, wherein the heat-shrinkable film is a heat-shrinkable polyester film. It is.
  • the heat-shrinkable film used as a label for the package of the present invention has high mechanical strength in the width direction perpendicular to the main shrinkage direction, which is highly shrinkable in the longitudinal direction, which is the main shrinkage direction.
  • the produced roll-shaped film does not cause winding tightness, and the film roll has good openability so that wrinkles can hardly enter. Therefore, the heat-shrinkable polyester film can be suitably used as a label for a container such as a bottle, and can be attached to a container such as a bottle very efficiently within a short time. When it is later heat-shrinked, it can produce a good finish with very little shrinkage due to heat shrinkage. In addition, the attached label will exhibit very good openability. Therefore, the package of the present invention has good tearing of the coated label, and when the perforated line is provided in the direction perpendicular to the main shrinkage direction with a suitable force, the coated label is perforated. I can tear it cleanly along my eyes.
  • the package of the present invention is formed by covering at least a part of the outer periphery with a label based on a heat-shrinkable polyester film, and subjecting the package to heat shrinkage.
  • a label based on a heat-shrinkable polyester film is coated on the packaging object by heat-shrinking, the label is heat-shrinked by about 2 to 15% and packaged. Adhere to the body.
  • the label to be coated on the packaging object may be printed or may have a perforation in a direction perpendicular to the main shrinkage direction of the label. Also good.
  • annular body is formed in advance so that the main shrinkage direction is the circumferential direction, and the annular body is covered with the packaging object and thermally contracted.
  • the force that can be adopted in the method When forming an annular body like this, in addition to the method of bonding the heat-shrinkable film using various adhesives, the heat-shrinkable film using a high-temperature heating element It is also possible to use a method of fusing (melting sealing method) or the like.
  • a predetermined automatic bag making machine for example, Kyoei Printing Machinery Materials Co., Ltd.—RP500
  • the label is wound around the packaged object by fusing and sealing the overlapped part, and then the heat shrinks after the label is placed around the packaged object. It is also possible to adopt the method of making them.
  • the heat-shrinkable film for forming a label various plastics such as a heat-shrinkable polyester film, a heat-shrinkable polystyrene film, a heat-shrinkable polyolefin film, and a heat-shrinkable polyvinyl chloride film are used.
  • the heat shrinkable film can be listed as S.
  • the use of heat-shrinkable polyester film increases the heat resistance of the label and makes the label excellent in solvent resistance. This is preferable because it can be easily incinerated. Therefore, in the following explanation, the explanation will focus on the heat-shrinkable polyester film.
  • the package of the present invention has an Elmendorf tear load in a direction orthogonal to a main shrinkage direction and an Elmendorf tear load in a main shrinkage direction of a coated label (film substrate excluding a printing layer),
  • the Elmendorf ratio measured by the following method must be 0.5 or more and 2.0 or less.
  • a test piece was prepared by cutting from the edge in the center of the longitudinal direction. , Shimadzu Corp. Autograph) and gripping both ends of the test piece, and performing a tensile test at a specified tensile speed, the Elmendorf tear load in the direction perpendicular to the main shrinkage direction of the label (Measured as Elmendorf tear load of the film base excluding the printed layer of the label) is measured.
  • a test piece is prepared by cutting the label into a rectangular shape that is long in the direction perpendicular to the main shrinkage direction, and then making a cut from the edge in the center of the longitudinal direction.
  • the Elmendorf tearing load in the main shrinkage direction of the label Measure the weight (converted as the Elmendorf tear load of the film base excluding the printed layer of the label). After that, the Elmendorf ratio is calculated using Equation 6 below.
  • the Elmendorf ratio of the label is less than 0.5, it is not preferable that there is a perforation in a direction perpendicular to the main contraction direction, because it is difficult to tear straight along the perforation.
  • the Elmendorf ratio of the label exceeds 2.0, it is not preferable because it is easy to tear at a position shifted from the perforation.
  • the lower limit value of the Elmendorf ratio of the label is preferably 0.6 or more, more preferably 0.7 or more, and particularly preferably 0.8 or more.
  • the upper limit of the Elmendorf ratio of the film substrate excluding the printed layer of the label is preferably 1.8 or less, more preferably 1.6 or less, and particularly preferably 1.5 or less. .
  • the package of the present invention when the tensile fracture strength in the direction orthogonal to the main shrinkage direction of the coated label (film substrate excluding the printing layer) is measured by the following method, The tensile fracture strength must be lOOMPa or more and 300MPa or less.
  • the label is sampled to a predetermined size according to JIS-K-7127 to obtain a test piece, and both ends of the test piece (main shrinkage direction) using a universal tensile tester (for example, Autograph manufactured by Shimadzu Corporation) And tensile test at a tensile speed of 200 mm / min, and the stress value at break (converted as the stress value of the film substrate excluding the printed layer of the label) calculate.
  • a universal tensile tester for example, Autograph manufactured by Shimadzu Corporation
  • tensile test at a tensile speed of 200 mm / min
  • the tensile fracture strength in the direction perpendicular to the main shrinkage direction of the label is less than lOOMPa, when the label is torn along the perforation in the direction perpendicular to the main shrinkage direction, On the contrary, if the tensile fracture strength in the direction perpendicular to the main shrinkage direction of the label exceeds 300 MPa, the initial cut W will be poor when tearing. It is not preferable.
  • the lower limit of the tensile fracture strength is preferably 120 MPa or more, more preferably 140 MPa or more, and even more preferably 160 MPa or more.
  • the upper limit value of the tensile fracture strength is preferably 280 MPa or less, more preferably 260 MPa or less, and particularly preferably 240 MPa or less.
  • the package of the present invention preferably has a refractive index of 1.570 or more and 1.600 or less in the direction orthogonal to the main shrinkage direction of the coated label. If the refractive index in the direction perpendicular to the main shrinkage direction exceeds 1.600, the solvent adhesion deteriorates, which is not preferable. On the other hand, if it is less than 1.570, the cutting property is deteriorated, which is not preferable.
  • the upper limit of the refractive index in the direction perpendicular to the main contraction direction is preferably 1.595 or less, more preferably 1.590 or less.
  • the lower limit of the refractive index in the direction orthogonal to the main shrinkage direction is preferably 1.573 or more, and more preferably 1.575 or more.
  • the perpendicular tear strength in the direction perpendicular to the main shrinkage direction per unit thickness of the coated label (film substrate excluding the printing layer) was measured by the following method.
  • the right-angle tear strength must be 100N / mm or more and 300N / mm or less.
  • the label is sampled as a test piece of a predetermined size according to JIS-K-7128. After that, grip both ends of the test piece with a universal tensile tester (for example, Autograph manufactured by Shimadzu Corporation), and in a direction perpendicular to the main shrinkage direction of the label at a pulling speed of 200 mm / min. Measure the strength at tensile failure. Then, calculate the right-angle tear strength per unit thickness using Equation 2 below.
  • a universal tensile tester for example, Autograph manufactured by Shimadzu Corporation
  • a right-angled bow in the direction perpendicular to the main shrinkage direction of the label I If the crack strength is less than 1 OON / mm, there is a possibility that it may be easily broken by an impact such as a drop during transportation. On the other hand, if the right-angle tear strength in the direction perpendicular to the main shrinkage direction of the label exceeds 300 N / mm, it is not preferable because the cutting property (easy to tear) at the initial stage of tearing becomes poor.
  • the lower limit of the right angle tear strength is preferably 120 N / mm or more, more preferably 140 N / mm or more, and even more preferably 160 N / mm or more.
  • the upper limit of the right-angled tear strength is preferably 280 N / mm or less, more preferably 260 N / mm or less, and more preferably 240 N / mm or less.
  • the dicarboxylic acid component constituting the polyester used in the present invention includes terephthalol.
  • aromatic dicarboxylic acids such as acid, isophthalic acid, naphthalenedicarboxylic acid and orthophthalic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid, and alicyclic dicarboxylic acids.
  • an aliphatic dicarboxylic acid for example, adipic acid, sebacic acid, decanedicarboxylic acid, etc.
  • the content is preferably less than 3 mol%.
  • a heat-shrinkable polyester film obtained by using a polyester containing 3 mol% or more of these aliphatic dicarboxylic acids has insufficient film stiffness at high speed.
  • Examples of the diol component constituting the polyester used in the present invention include aliphatic diols such as ethylene glycol, 13 propanediol, 14 butanediol, neopentino glycol, hexanediol, Examples include alicyclic diols such as 4-cyclohexanedimethanol, and aromatic diols such as bisphenol A.
  • the polyester used in the heat-shrinkable polyester film used as the label of the package of the present invention is a cyclic diol such as 1,4-cyclohexanedimethanol or a diol having 3 to 6 carbon atoms (for example, a polyester containing one or more of 13 propanediol, 14 butanediol, neopentyldaricol, hexanediol, etc.) and having a glass transition point (Tg) adjusted to 60 to 80 ° C Is preferred.
  • Tg glass transition point
  • the polyester used for the heat-shrinkable polyester film has a total of 10 mol% or more of one or more monomer components that can be an amorphous component in 100 mol% of the polyhydric alcohol component in all the polyester resins. It is preferably 15 mol% or more, more preferably 17 mol% or more.
  • monomers that can be an amorphous component include neopentyl glycol, 1,4-cyclohexanediol, and isophthalanolic acid.
  • a diol having 8 or more carbon atoms such as octanediol
  • a polyhydric alcohol having 3 or more valences for example, For example, trimethylolpropane, trimethylolethane, glycerin, diglycerin, etc.
  • a heat-shrinkable polyester film obtained by using a polyester containing these diols or polyhydric alcohols can achieve the necessary high shrinkage.
  • the polyester used for the heat-shrinkable polyester film preferably contains as little diethylene glycol, triethylene glycol, or polyethylene glycol as possible.
  • diethylene glycol is easily present because it is a by-product component during polyester polymerization, it is preferred that the polyester used in the present invention has a diethylene glycol content of less than 4 mol%! /.
  • a heat-shrinkable polyester-based film is a film length calculated by the following formula 1 from the length before and after shrinkage when treated for 10 seconds in 90 ° C warm water under no load.
  • the direction of heat shrinkage (that is, hot water heat shrinkage at 90 ° C) must be 40% or more and 80% or less.
  • Heat shrinkage rate ⁇ (length before shrinkage, length after shrinkage) / length before shrinkage ⁇ X 100 (%) ⁇ Equation 1
  • Longitudinal hot water thermal shrinkage at 90 ° C 40% If the temperature is below, the shrinkage amount is small, and the thermal shrinkage of the label after heat shrinkage will occur. Therefore, the hot water heat shrinkage in the longitudinal direction at 90 ° C is 80% or more. If it is used as a label, it is not preferable because the shrinkage tends to occur at the time of heat shrinkage, or so-called "jumping" occurs.
  • the lower limit value of the hot water thermal contraction rate in the longitudinal direction at 90 ° C is particularly preferably 45% or more, more preferably 50% or more, and more preferably 55% or more.
  • the upper limit value of the hot water heat shrinkage in the longitudinal direction at 90 ° C is particularly preferably 75% or less, preferably 70% or less, and more preferably 65% or less.
  • the heat-shrinkable polyester film is a film thickness calculated by the above equation 1 from the length before and after shrinkage when treated in 90 ° C warm water for 10 seconds under no load.
  • the hot water thermal contraction rate in the width direction must be 0% or more and 15% or less.
  • the hot water thermal shrinkage in the width direction at 90 ° C is less than 0%, a good shrinkage appearance cannot be obtained when used as a bottle label. If the hot-water heat shrinkage in the width direction exceeds 15%, it can be used as a label! / It is not preferred because sometimes the shrinkage tends to be distorted.
  • the lower limit value of the hot-water heat shrinkage in the width direction at 90 ° C. is particularly preferably 3% or more, more preferably 4% or more when 2% or more.
  • the upper limit value of the hot water thermal contraction rate in the width direction at 90 ° C is particularly preferably 13% or less, more preferably 11% or less, preferably 14% or less.
  • the heat shrinkable polyester film may have a natural shrinkage ratio of 0.05% or more and 1.5% or less after aging for 700 hours or more in an atmosphere of 40 ° C and 65% RH. is necessary.
  • the natural shrinkage rate can be calculated using the following equation 4.
  • Natural shrinkage rate ⁇ (length before aging) / length before aging ⁇ X 100 (%) ⁇ Formula 4
  • the natural shrinkage rate is 1.5% or less, when a product wound in a roll shape is stored, winding tightening occurs and the film roll is easily wrinkled, which is not preferable.
  • 0.05% is considered to be the lower limit.
  • the natural shrinkage rate is preferably 1.3% or less, more preferably 1.1% or less, and particularly preferably 1.0% or less.
  • the maximum heat shrinkage stress force in the longitudinal direction of the film is preferably not less than MPa and not more than 25 MPa.
  • Maximum heat shrinkage stress value in the longitudinal direction of the film ⁇ ⁇ If it is less than a, when the label is attached to a container such as a PET bottle and thermally contracted, the label is attached together with the cap when the PET bottle cap is opened. This is not preferable because it may cause a situation where the cap opens and deteriorates the opening of the cap.
  • the maximum heat shrinkage stress value in the longitudinal direction of the film exceeds 25 MPa, the sealed part may be removed or the appearance may deteriorate when the film is attached to a container such as a PET bottle as heat-condensed.
  • the lower limit of the maximum heat contraction stress value in the longitudinal direction of the film is more preferably 6 MPa or more, particularly preferably 7 MPa or more.
  • the upper limit of the maximum heat shrinkage stress value in the longitudinal direction of the film is more preferably 23 MPa or less, and particularly preferably 21 MPa or less.
  • the fusing seal strength of the film is preferably 8 N / 15 mm or more. If the fusing seal strength of the film is less than 8N / 15mm, It is not preferable because the fusing seal part is removed when it is heat-shrinked after being attached to a container such as a PET bottle, or when the container after heat-shrinking is dropped, the fusing seal part is removed. It should be noted that the higher the fusing seal strength of the film, the higher the preferred breaking strength of the film. Further, the fusing seal strength of the film is more preferably 10 N / 15 mm or more, further preferably 12 N / 15 mm or more, and particularly preferably 14 N / 15 mm or more.
  • the heat-shrinkable polyester film preferably has a solvent adhesive strength of 4 (N / 15mm) or more. If the solvent adhesive strength is less than 4 (N / l 5 mm), it is preferable because the label is easily peeled off from the solvent-adhered portion after heat shrinkage.
  • the solvent adhesive strength is more preferably 4.5 (N / l 5 mm) or more, particularly preferably 5 (N / l 5 mm) or more.
  • the heat-shrinkable polyester film preferably has a thickness unevenness of 10% or less in the longitudinal direction. If the thickness unevenness in the longitudinal direction is more than 10%, it is not preferable because printed spots are likely to occur during printing at the time of label production or shrinkage spots after heat shrinkage are likely to occur.
  • the longitudinal thickness unevenness is more preferably 8% or less, and more preferably 6% or less.
  • the heat-shrinkable polyester film does not detect the endothermic curve peak during the melting point measurement in differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the thickness of the heat-shrinkable polyester film is not particularly limited.
  • 00 ⁇ m force ⁇ preferably, 20 ⁇ ; more preferably 100 ⁇ m force.
  • the heat-shrinkable polyester film is obtained by using the above-described polyester raw material by an extruder.
  • the film can be obtained by melt extrusion to form an unstretched film, and then subjecting the unstretched film to a two-wheel drive and heat treatment by the method described below.
  • the polyester raw material is preferably dried using a dryer such as a hopper dryer or a pad dryer, or a vacuum dryer. After drying the polyester raw material in this way, it is melted at a temperature of 200 to 300 ° C and extruded into a film using an extruder.
  • a dryer such as a hopper dryer or a pad dryer, or a vacuum dryer.
  • any existing method such as T-die method or tubular method can be used.
  • an unstretched film by rapidly cooling the extruded sheet-like molten resin.
  • a method of rapidly cooling the molten resin a method of obtaining a substantially unoriented resin sheet by casting the molten resin on a rotating drum from a die and rapidly solidifying it can be suitably employed.
  • the obtained unstretched film was stretched in the width direction under predetermined conditions, and then heat-treated, and then stretched in the longitudinal direction under predetermined conditions, and then longitudinally stretched.
  • the preferred biaxial stretching / heat treatment method for obtaining the heat-shrinkable polyester film used in the package of the present invention is different from the conventional biaxial stretching of the heat-shrinkable polyester film. This will be described in detail in consideration of the above.
  • a normal heat-shrinkable polyester film is produced by stretching an unstretched film in the direction in which it is desired to shrink.
  • production is not possible because a wide film cannot be produced by simply stretching an unstretched film in the longitudinal direction.
  • the film cannot be produced with good thickness and unevenness.
  • a method of stretching in the longitudinal direction after previously stretching in the width direction is adopted, the amount of contraction in the longitudinal direction becomes insufficient, or the width direction shrinks unnecessarily.
  • 8-244114 discloses a method of stretching an unstretched film in the order of length, width, and length under predetermined conditions in order to improve the mechanical properties in the longitudinal direction.
  • Power S the inventors' pilot According to a follow-up test on a sheet machine, such a method cannot provide a film having sufficient shrinkage in the longitudinal direction, which is the main shrinkage direction, and the produced film roll is likely to be crushed in the width direction. Turned out to be.
  • increasing the draw ratio in the machine direction (the first draw ratio or the second draw ratio) in order to increase the shrinkability in the longitudinal direction will eventually increase the film when stretched in the longitudinal direction. It was also found that it was difficult to carry out continuous and stable production due to frequent fractures.
  • the film obtained by the above-described test had a longitudinal crease on a film roll produced with a high natural shrinkage rate, and the unsealing property was also poor.
  • the present inventors perform biaxial stretching in the longitudinal direction and width direction as in JP-A-8-244114, and then stretch in the longitudinal direction.
  • the method is disadvantageous and we thought that it would be advantageous to simply stretch in the width direction and then stretch in the longitudinal direction.
  • a transverse and longitudinal stretching method In such a method of stretching in the longitudinal direction after stretching in the width direction (hereinafter, simply referred to as a transverse and longitudinal stretching method), the hot water temperature shrinkage rate, the natural shrinkage rate in the longitudinal direction of the film, depending on the conditions in each stretching step, We studied earnestly how the openability changes.
  • the film used as a label of the package of the present invention is produced by the transverse and longitudinal stretching method.
  • the unstretched film is stretched in the width direction, it is heat-treated at a temperature of 100 ° C or higher and lower than 170 ° C for a time of 1.0 second or more and 10.0 seconds or less (hereinafter referred to as intermediate heat treatment).
  • intermediate heat treatment a temperature of 100 ° C or higher and lower than 170 ° C for a time of 1.0 second or more and 10.0 seconds or less.
  • the lower limit of the temperature of the heat treatment is preferably 110 ° C or higher, more preferably 115 ° C or higher.
  • the upper limit of the heat treatment temperature is preferably 165 ° C. or less, more preferably 160 ° C. or less.
  • the heat treatment time needs to be appropriately adjusted according to the raw material composition within a range of 1.0 second to 10.0 seconds.
  • the unstretched film is stretched in the width direction at a temperature of Tg + 5 ° C or higher and Tg + 40 ° C or lower with a clip held at both ends in the width direction in the tenter. It is necessary to make the magnification between 2 times and 6.0 times. If the stretching temperature is lower than Tg + 5 ° C, breakage is likely to occur during stretching. On the other hand, if it exceeds Tg + 40 ° C, thickness unevenness in the width direction is deteriorated.
  • the lower limit of the transverse stretching temperature is preferably Tg + 10 ° C. or more, more preferably Tg + 15 ° C. or more. Further, the upper limit of the transverse stretching temperature is preferably Tg + 35 ° C.
  • the lower limit of the transverse stretching ratio is preferably 3.0 times or more, more preferably 3.5 times or more.
  • the upper limit of the transverse stretching ratio is preferably 5.5 times or less, more preferably 5.0 times or less.
  • the laterally stretched film is led to the intermediate zone to be applied and allowed to pass through the intermediate zone over a predetermined time. If the time for passing through the intermediate zone is less than 0.5 seconds, the hot air in the transverse stretching zone flows into the heat setting zone due to the accompanying flow of the passing film, making it difficult to control the temperature of the intermediate heat treatment in the heat setting zone. I don't like it.
  • the time required to pass through the intermediate zone is sufficient if it is 3.0 seconds, and setting it longer than that is not preferable because it wastes equipment.
  • the lower limit of the time for passing through the intermediate zone is preferably 0.7 seconds or more, more preferably 0.9 seconds or more.
  • the upper limit of the time for passing through the intermediate zone is preferably 2.5 seconds or less, and more preferably 2.0 seconds or less.
  • the film subjected to the intermediate heat treatment is not sufficiently stretched at the edge of the film before stretching in the longitudinal direction.
  • trim the thick part mainly the clip gripping part during transverse stretching. More specifically, the thickness of the central part located at the edges of the left and right edges of the film is about 1.;! It is preferable to cut the thick portion and remove the thick portion, while stretching only the remaining portion in the longitudinal direction.
  • trimming of the film edge can be done using a normal cutter.
  • a round blade with a circumferential edge is used, the edge of the edge does not become dull locally, and the film edge can continue to be cut sharply over a long period of time. Since the situation which induces the fracture
  • the intermediate heat treatment is performed after the transverse stretching as described above, and then the film is stretched in the longitudinal direction, and then 30 ° C / second or more and 70 °
  • the film is preferably cooled at a cooling rate of C / sec or less until the surface temperature is 45 ° C or higher and 75 ° C or lower.
  • the natural shrinkage rate can be reduced only by cooling the film at an appropriate speed. If the cooling rate is lower than 30 ° C / sec or the surface temperature after cooling is higher than 75 ° C, a low natural shrinkage rate cannot be obtained.
  • the cooling rate is so rapid that the cooling rate exceeds 70 ° C / second, since the degree of shrinkage in the width direction of the film (so-called neck-in) increases and the film surface is easily damaged. Absent.
  • Tables 1 and 2 show the properties, compositions, examples, and film production conditions (stretching and heat treatment conditions, etc.) of the raw materials used in the examples and comparative examples, respectively.
  • the film evaluation method is as follows.
  • the film was sampled into a long roll of 30 m length x 40 mm width and measured at a speed of 5 (m / min) using a continuous contact thickness gauge manufactured by Micron Measuring Instruments Co., Ltd.
  • the length direction of the film sample was set as the main shrinkage direction of the film.
  • the maximum thickness at the time of measurement was Tmax.
  • the minimum thickness was Tmin.
  • the average thickness was Tave.
  • Thickness unevenness ⁇ (13 ⁇ 4 &. 13 ⁇ 4.) / Ding & 6. ⁇ 100 (%) ⁇ Formula 5
  • the stretched film was sealed by applying 1,3 dioxolan and pasting the two together. After that, the seal part is cut to a width of 15mm in the direction perpendicular to the main shrinkage direction of the film (hereinafter referred to as the orthogonal direction), and then set in the universal tension tester STM-50 manufactured by Baldwin Co., Ltd. A 180 ° peel test was performed at 200 mm / min. And the tensile strength at that time was made into solvent adhesive strength.
  • the cut film was set and the stress value was measured when held for 10 seconds.
  • each sample film was left in an atmosphere of 23 ° C. and 65% RH for 2 hours or more, and measurement was performed.
  • the method for evaluating the coated label is as follows.
  • the label attached to the PET bottle is peeled off, and the label is tested in accordance with JIS-K-7127 in a rectangular shape with a length of 50mm perpendicular to the main shrinkage direction and a length of 20mm in the main shrinkage direction.
  • JIS-K-7127 JIS-K-7127
  • a universal tensile tester manufactured by Shimadzu Corp., Auto Draft
  • the stress value at break was calculated as the tensile fracture strength.
  • a test piece was prepared by peeling off the label attached to the PET bottle and sampling the label into the shape shown in Fig. 1 in accordance with JIS-K-7128. Is the perforation direction of the label). After a while Using a universal tensile tester (Autograph made by Shimadzu Corp.), hold both ends of the test piece and bow in a direction perpendicular to the main shrinkage direction of the label at a pulling speed of 200 mm / min. I measured the strength at the time of tensile fracture, and calculated the right-angled tear strength per unit thickness using Equation 2 above.
  • the label attached to the PET bottle is peeled off, and the label is cut to a size of 37.5 mm X 31.5 mm in the main shrinkage direction X in the direction perpendicular to the main shrinkage direction according to JIS-K-7128.
  • a test piece was prepared by making a 10 mm slit (cut) perpendicular to the edge from the center of the edge along the shrinkage direction. Then, using a universal tensile tester (Autograph manufactured by Shimadzu Corporation), both ends of the prepared test piece are grasped and a tensile test is performed at a tension speed of 200 mm / min. The Elmendorf tear load in the orthogonal direction was measured.
  • test pieces were produced by switching the direction perpendicular to the main shrinkage direction and the main shrinkage direction of the film, and the Elmendorf tear load in the direction perpendicular to the main shrinkage direction was measured. Then, the Elmendorf ratio was calculated using the above formula 6 from the obtained main contraction direction and the Elmendorf bow I crack load in the direction perpendicular to the main contraction direction.
  • the label attached to the PET bottle is peeled off, the printing on the surface of the label is removed with a solvent (ethyl acetate, methyl ethyl ketone, etc.), and the label is left in an atmosphere of 65% RH for 2 hours or more. Later, measurement was performed using an “Abbe refractometer 4T type” manufactured by Atago Co., Ltd. The refractive index was measured by the method described above.
  • the finished condition of the label attached around the PET bottle was visually evaluated according to the following criteria. ⁇ : No wrinkles, jumps, or insufficient shrinkage occurred, and no color spots were observed. ⁇ : No wrinkles, jumps, or insufficient shrinkage could be confirmed, but some color spots were observed. : Neither jumping up nor insufficient shrinkage has occurred, but spots on the neck are seen X: Wrinkles, jumping up, insufficient shrinkage occurred
  • Polyesters used in Examples and Comparative Examples are as follows.
  • Polyester 1 Ethylene glycol 70 mol 0/0, polyester consisting of neopentyl glycol 30 mol 0/0 and terephthalic acid (IV 0. 72dl / g)
  • Polyester 2 Polyethylene terephthalate (IV 0.775dl / g)
  • Polyester 3 terephthalic acid units as dicarboxylic acid component 82.5 mole 0/0, consists isophthalic acid unit 17.5 mole 0/0, consisting of ethylene glycol as the diol component.
  • the above polyester 1 and polyester 2 were mixed at a weight ratio of 90:10 and charged into an extruder. Thereafter, the mixed resin is melted at 280 ° C, extruded from a T-die, wound around a rotating metal roll cooled to a surface temperature of 30 ° C, and rapidly cooled to form an unstretched film having a thickness of 360 m. Obtained. At this time, the take-up speed of the unstretched film (rotation speed of the metal roll) was about 20 m / min. The Tg of the unstretched film was 67 ° C. Thereafter, the unstretched film was led to a tenter (first tenter) in which a transverse stretching zone, an intermediate zone, and an intermediate heat treatment zone were continuously provided.
  • first tenter first tenter
  • the length of the intermediate zone located between the transverse stretching zone and the intermediate heat treatment zone is set to about 40 cm.
  • the hot air from the stretching zone and the hot air from the heat treatment zone are blown so that the piece of paper hangs almost completely in the vertical direction. Blocked.
  • the edge of the lateral uniaxially stretched film center The portion of the film having a thickness of about 1 to 2 times the thickness of the film was cut, and the ends of the finolem located outside the cutting site were continuously removed.
  • the film with the end trimmed as described above was guided to a longitudinal stretching machine in which a plurality of roll groups were continuously arranged, and preheated on the preheating roll until the film temperature reached 70 ° C. Later, the film was stretched 3 times between stretching rolls set at a surface temperature of 95 ° C. Thereafter, the longitudinally stretched film was forcibly cooled by a cooling roll set at a surface temperature of 25 ° C.
  • the surface temperature of the film before cooling was about 70 ° C
  • the surface temperature of the film after cooling was about 25 ° C.
  • the time required for cooling from 70 ° C to 25 ° C was about 1.0 seconds, and the film cooling rate was 45 ° C / second.
  • the cooled film is guided to a tenter (second tenter), heat-treated in an atmosphere of 95 ° C for 2.0 seconds in the second tenter, cooled, and both edges are cut.
  • a biaxially stretched film of about 30 m was continuously formed over a predetermined length to obtain a film roll made of a heat-shrinkable polyester film.
  • the film roll obtained as described above is slit to a width of about 200 mm, and is then rolled into a predetermined length to create a small slit roll.
  • Label printing three-color printing was repeatedly performed using the grass “gold” white ink of Co., Ltd.
  • the longitudinal direction of the film roll and In the orthogonal direction two perforations (a perforation in which circles of about 1 mm diameter are continuous at intervals of about 4 mm) across the entire width of the film were formed in parallel at intervals of about 22 mm.
  • one end of the roll-shaped film on which printing for labeling was applied was applied to a part of the outer periphery of a 500 ml PET bottle (month diameter 62 mm, minimum neck diameter 25 mm).
  • the roll film was pulled out by a predetermined length and wound around the outer periphery of the PET bottle.
  • the outer periphery of the PET bottle was covered with a label by covering the outer periphery of the PET bottle by fusing and sealing with a fusing seal blade adjusted to about 240 ° C.
  • the PET bottle covered with the label was allowed to pass under the conditions of a passage time of 2.5 seconds and a zone temperature of 80 ° C.
  • Label attachment was completed by heat-shrinking the label around the outer periphery of the PET bottle, and the neck part was adjusted so that the 40 mm diameter part would be one end of the label.
  • the characteristics of the heat-shrinkable film, label (before and after mounting), and package (the PET bottle with the label) obtained as described above were evaluated by the method described above. Shown in
  • a heat-shrinkable film was continuously produced in the same manner as in Example 1 except that polyester 1 and polyester 2 were mixed at a weight ratio of 70:30 and charged into an extruder. Further, a label was produced by the same method as in Example 1, and the label was attached to the outer periphery of the PET bottle by the same method as in Example 1. Then, the characteristics of the obtained film, the label before and after mounting, and the package were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 3 and 4.
  • a heat-shrinkable film was continuously produced in the same manner as in Example 1 except that the transverse stretch ratio in the tenter (first tenter) was changed to 5.0 times.
  • the biaxially stretched heat-shrinkable polyester film had a thickness of about 24 m.
  • a label was produced by the same method as in Example 1, and the label was attached to the outer periphery of the pet bottle by the same method as in Example 1. And the obtained film, the label before and after mounting, and the package The characteristics were evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 3 and 4.
  • a heat-shrinkable film was continuously produced in the same manner as in Example 1 except that the temperature of the intermediate heat treatment in the tenter (first tenter) was changed to 140 ° C.
  • the biaxially stretched heat-shrinkable polyester film had a thickness of about 24 m.
  • a label was produced by the same method as in Example 1, and the label was attached to the outer periphery of the pet bottle by the same method as in Example 1. The characteristics of the obtained film, the label before and after mounting, and the package were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 3 and 4.
  • a heat-shrinkable film was continuously produced in the same manner as in Example 1 except that the temperature of the stretching roll in the longitudinal stretching machine was changed to 92 ° C and the stretching ratio in the longitudinal direction was changed to 5.0 times. .
  • the biaxially stretched heat-shrinkable polyester film had a thickness of about 18 m.
  • a label was produced by the same method as in Example 1, and the label was attached to the outer periphery of the PET bottle by the same method as in Example 1. The characteristics of the obtained film, the label before and after mounting, and the package were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 3 and 4.
  • a heat-shrinkable film was continuously produced in the same manner as in Example 1 except that the temperature of the stretching roll in the longitudinal stretching machine was changed to 92 ° C and the stretching ratio in the longitudinal direction was changed to 7.0 times. .
  • the biaxially stretched heat-shrinkable polyester film had a thickness of about 13 m.
  • a label was produced by the same method as in Example 1, and the label was attached to the outer periphery of the PET bottle by the same method as in Example 1. The characteristics of the obtained film, the label before and after mounting, and the package were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 3 and 4.
  • the above polyester 3 is put into an extruder, melted at 265 ° C, extruded from a T-die, wound around a rotating metal roll cooled to a surface temperature of 30 ° C, and rapidly cooled to give a thickness of 360 m.
  • An unstretched film was obtained.
  • the undrawn film take-off speed is Same as Example 1.
  • the unstretched film is led to a longitudinal stretching machine (first longitudinal stretching machine) in which a plurality of roll groups are continuously arranged, preheated on a preheating roll, and then set to a surface temperature of 88 ° C.
  • the drawn rolls were stretched 2.7 times.
  • the film stretched in the longitudinal direction is led to a tenter (first tenter) in which a transverse stretching zone and a heat treatment zone are continuously provided, and the transverse stretching zone is 97 ° C at a stretching temperature of 97 ° C. After being stretched by 3.5 times, it was heat treated at 125 ° C in a heat treatment zone. Thereafter, the heat-treated film was led to a longitudinal stretching machine (second longitudinal stretching machine) in which a plurality of roll groups were continuously arranged, preheated on a preheating roll, and then set to a surface temperature of 98 ° C. It was stretched again 1.5 times between the stretching rolls.
  • first tenter first tenter
  • second longitudinal stretching machine in which a plurality of roll groups were continuously arranged, preheated on a preheating roll, and then set to a surface temperature of 98 ° C. It was stretched again 1.5 times between the stretching rolls.
  • the film stretched again in the longitudinal direction is guided to a tenter (second tenter), heat-treated at 85 ° C, cooled, and both edges are cut and removed, so that about 35 111 biaxially stretched films are obtained.
  • a film was continuously formed over the length to obtain a heat-shrinkable polyester film roll.
  • a label was produced by the same method as in Example 1, and the label was attached to the outer periphery of the PET bottle by the same method as in Example 1. Then, the characteristics of the obtained film, the label before and after mounting, and the package were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 3 and 4.
  • a heat-shrinkable film was continuously produced in the same manner as in Example 1 except that the temperature of the intermediate heat treatment in the tenter (first tenter) was changed to 70 ° C. Further, a label was produced by the same method as in Example 1, and the label was attached to the outer periphery of the PET bottle by the same method as in Example 1. The characteristics of the obtained film, the label before and after mounting, and the package were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 3 and 4.
  • a transversely uniaxially stretched film of about 45 Hm was continuously formed over a predetermined length to obtain a heat-shrinkable polyester film roll.
  • a label was produced by the same method as in Example 1, and the label was attached to the outer periphery of the PET bottle by the same method as in Example 1.
  • the characteristics of the obtained film, the label before and after mounting, and the package were evaluated by the same method as in Example 1.
  • the evaluation results are shown in Tables 3 and 4.
  • the width direction is the main shrinkage direction
  • the longitudinal direction is the direction orthogonal to the main shrinkage direction.
  • a heat-shrinkable film was continuously produced in the same manner as in Comparative Example 1 except that the draw ratio at the time of longitudinal stretching again with the second longitudinal stretching machine was 3.0 times. Further, a label was produced by the same method as in Example 1, and the label was attached to the outer periphery of the pet bottle by the same method as in Example 1. The characteristics of the obtained film, the label before and after mounting, and the package were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 3 and 4.
  • the films obtained in Example 16 were all not shrinkable in the width direction perpendicular to the main shrinkage direction, which is highly shrinkable in the longitudinal direction, which is the main shrinkage direction. It was always low. In addition, the films obtained in Example 16 all had high solvent adhesive strength, small thickness spots in the longitudinal direction, good label adhesion, and good shrink finish with no shrink spots. . In addition, the heat-shrinkable polyester film of Example 16 has a good perforation opening property, and has a film roll manufactured with a small natural shrinkage rate. None occurred.
  • the packaging body in which the label made of the heat-shrinkable polyester film obtained in each example is packaged has a good perforation-opening property of the label, and the label has a proper force along the perforation. It was possible to tear it cleanly.
  • the heat-shrinkable film obtained in Comparative Example 1 had an insufficient heat-shrinkage, poor label adhesion, and shrinkage spots.
  • the heat-shrinkable film obtained in Comparative Example 2 had shrinkage spots due to poor label adhesion with a high heat shrinkage rate in the film width direction.
  • the film obtained in Comparative Example 4 (the main shrinkage direction is the width direction) is produced with shrinkage spots having a large thermal shrinkage rate in the direction orthogonal to the main shrinkage direction and a large natural shrinkage rate. The film roll was wrinkled.
  • the package that wraps the label made of heat-shrinkable polyester film obtained in each comparative example has poor perforation of the label, so that the label can be cleaned with an appropriate force along the perforation. The percentage of those that could not be torn was high.
  • the package of the present invention has excellent characteristics as described above, it can be suitably used for packaging use for various articles.

Abstract

Emballage recouvert d'une étiquette constituée à partir d'un film thermorétractable et qui peut être déchiré de façon satisfaisante. Le film en polyester thermorétractable destiné à constituer l'étiquette se rétracte principalement dans le sens de la machine. Elle a été réglée de manière à avoir les propriétés suivantes dans des plages données respectives : le degré de rétraction thermique dans le sens de la machine au cours d'une immersion de 10 secondes dans une eau à 90°C; résistance à l'arrachement selon un angle à direction transversal après retrait en sens machine de 10% après une immersion dans une eau à 80°C; ratio d'Elmemdorf déterminé par la mesure du taux de déchirement d'Elmendorf après rétraction de 10% dans le sens de la machine dans une eau à 80°C; et degré de rétraction naturelle après 700 heures ou plus dans une atmosphère à 40°C et avec un taux d'humidité de 65%.
PCT/JP2007/065586 2006-08-09 2007-08-09 Emballage WO2008018528A1 (fr)

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JP2006-217386 2006-08-09
JP2006217386 2006-08-09
JP2007-099028 2007-04-05
JP2007099028 2007-04-05
JP2007206372A JP2008273619A (ja) 2006-08-09 2007-08-08 包装体
JP2007-206372 2007-08-08

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009107591A1 (fr) * 2008-02-27 2009-09-03 東洋紡績株式会社 Film de polyester blanc thermorétractable, procédé pour produire un film de polyester blanc thermorétractable, étiquette et emballage
JP2009226935A (ja) * 2008-02-27 2009-10-08 Toyobo Co Ltd 白色熱収縮性ポリエステル系フィルムの製造方法、白色熱収縮性ポリエステル系フィルム及び包装体
JP2009226934A (ja) * 2008-02-27 2009-10-08 Toyobo Co Ltd 白色熱収縮性ポリエステル系フィルムの製造方法、白色熱収縮性ポリエステル系フィルム及び包装体
JP2009230120A (ja) * 2008-02-27 2009-10-08 Toyobo Co Ltd ラベル
JP2009227337A (ja) * 2008-02-29 2009-10-08 Toyobo Co Ltd ラベル
JP2009237561A (ja) * 2008-03-03 2009-10-15 Toyobo Co Ltd ラベル
US8673414B2 (en) 2006-08-30 2014-03-18 Toyo Boseki Kabushiki Kaisha Heat-shrinkable polyester film, process for production thereof, and package
US8685305B2 (en) 2007-09-25 2014-04-01 Toyo Boseki Kabushiki Kaisha Process for production of heat-shrinkable polyester film, heat-shrinkable polyester film and packages

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JP2005194466A (ja) * 2004-01-09 2005-07-21 Toyobo Co Ltd 熱収縮性ポリエステル系フィルムおよび熱収縮性ラベル
JP2005232435A (ja) * 2004-01-20 2005-09-02 Mitsubishi Plastics Ind Ltd 熱収縮性フィルム
JP2006045317A (ja) * 2004-08-03 2006-02-16 Mitsubishi Plastics Ind Ltd 熱収縮性ポリエステル系フィルム及び該フィルムを用いた成形品、容器

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Publication number Priority date Publication date Assignee Title
JPS51114475A (en) * 1975-04-02 1976-10-08 Asahi Chemical Ind Method of manufacturing polyamide film
JPH08244114A (ja) * 1995-03-08 1996-09-24 Toray Ind Inc ポリエステル系収縮フィルム
JP2005194466A (ja) * 2004-01-09 2005-07-21 Toyobo Co Ltd 熱収縮性ポリエステル系フィルムおよび熱収縮性ラベル
JP2005232435A (ja) * 2004-01-20 2005-09-02 Mitsubishi Plastics Ind Ltd 熱収縮性フィルム
JP2006045317A (ja) * 2004-08-03 2006-02-16 Mitsubishi Plastics Ind Ltd 熱収縮性ポリエステル系フィルム及び該フィルムを用いた成形品、容器

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8673414B2 (en) 2006-08-30 2014-03-18 Toyo Boseki Kabushiki Kaisha Heat-shrinkable polyester film, process for production thereof, and package
US8685305B2 (en) 2007-09-25 2014-04-01 Toyo Boseki Kabushiki Kaisha Process for production of heat-shrinkable polyester film, heat-shrinkable polyester film and packages
WO2009107591A1 (fr) * 2008-02-27 2009-09-03 東洋紡績株式会社 Film de polyester blanc thermorétractable, procédé pour produire un film de polyester blanc thermorétractable, étiquette et emballage
JP2009226935A (ja) * 2008-02-27 2009-10-08 Toyobo Co Ltd 白色熱収縮性ポリエステル系フィルムの製造方法、白色熱収縮性ポリエステル系フィルム及び包装体
JP2009226934A (ja) * 2008-02-27 2009-10-08 Toyobo Co Ltd 白色熱収縮性ポリエステル系フィルムの製造方法、白色熱収縮性ポリエステル系フィルム及び包装体
JP2009230120A (ja) * 2008-02-27 2009-10-08 Toyobo Co Ltd ラベル
US8728594B2 (en) 2008-02-27 2014-05-20 Toyo Boseki Kabushiki Kaisha Heat-shrinkable white polyester film, process for producing heat-shrinkable white polyester film, label, and package
KR101491876B1 (ko) * 2008-02-27 2015-02-09 도요보 가부시키가이샤 백색 열수축성 폴리에스테르계 필름, 백색 열수축성 폴리에스테르계 필름의 제조방법, 라벨, 및 포장체
JP2009227337A (ja) * 2008-02-29 2009-10-08 Toyobo Co Ltd ラベル
JP2009237561A (ja) * 2008-03-03 2009-10-15 Toyobo Co Ltd ラベル

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