WO2007013618A1 - Film de polyester thermorétractable et son procédé de fabrication - Google Patents

Film de polyester thermorétractable et son procédé de fabrication Download PDF

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Publication number
WO2007013618A1
WO2007013618A1 PCT/JP2006/315035 JP2006315035W WO2007013618A1 WO 2007013618 A1 WO2007013618 A1 WO 2007013618A1 JP 2006315035 W JP2006315035 W JP 2006315035W WO 2007013618 A1 WO2007013618 A1 WO 2007013618A1
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WO
WIPO (PCT)
Prior art keywords
film
polyester
heat
label
layer
Prior art date
Application number
PCT/JP2006/315035
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English (en)
Japanese (ja)
Inventor
Katsuya Ito
Norimi Tabota
Katsuhiko Nose
Original Assignee
Toyo Boseki Kabushiki Kaisha
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Filing date
Publication date
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Publication of WO2007013618A1 publication Critical patent/WO2007013618A1/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
    • B29C61/0608—Making preforms having internal stresses, e.g. plastic memory characterised by the configuration or structure of the preforms
    • 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
    • B32B27/08—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 synthetic resin
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/04—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps to be fastened or secured by the material of the label itself, e.g. by thermo-adhesion
    • 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
    • B29L2009/00—Layered products
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/58—Cuttability
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • 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 a heat-shrinkable polyester film, and more particularly to a heat-shrinkable polyester film suitable for labeling applications such as PET bottles (polyethylene terephthalate (PET) bottles).
  • PET polyethylene terephthalate
  • a heat-shrinkable film particularly a heat-shrinkable film for labeling the body of a bottle
  • a film having polyvinyl chloride, polystyrene or the like is mainly used.
  • the generation of chlorine-based gas has been a problem for incineration of discarded vinyl chloride products with respect to polyvinyl chloride, while the problem with polystyrene is that it is difficult to print on polystyrene film.
  • plastic labels such as polyvinyl chloride and polystyrene at the time of disposal. For this reason, polyester-based heat-shrinkable films that do not have these problems are attracting attention.
  • heat shrinkable polyester film used as a label for bottles is required to have perforation cut ability and strength of the adhesive portion when labeling is performed. ing.
  • the perforation cutability is required because a perforation for opening may be provided on a bottle label. If product bottles are beverage glass bottles, they are usually refrigerated. In this case, since label opening is performed at a low temperature, there is a problem that unsuccessful opening is likely to occur, and there is a high demand for perforation cutability.
  • Patent Document 1 in order to improve the perforation cutting property, the temperature conditions during stretching are optimized in the manufacturing process of the heat-shrinkable polyester film. Although the perforation cutting property of the heat-shrinkable polyester film obtained by this method is somewhat improved, it is still insufficient.
  • Patent Document 2 discloses a heat-shrinkable polyester film having a predetermined hot water shrinkage ratio and elongation at break. This heat-shrinkable polyester film can be used as a label on PET bottles. There was a problem that the strength of the adhesive part at the time of labeling was inferior, for example, when the plastic bottle dropped when attached, the adhesive part of the label was peeled off by impact.
  • the heat-shrinkable polyester film is required to have excellent perforation cutability and strength of the adhesive portion when labeling occurs.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2003-268131
  • Patent Document 2 JP-A-11-207818
  • FIG. 1 is a schematic view showing an example of a production line for a heat-shrinkable polyester film of the present invention.
  • FIG. 2 TEM photograph of film imported into image analysis software.
  • FIG. 3 is an image after the Fourier transform of FIG.
  • FIG. 5 is an image after clearing the shading of FIG.
  • the problem to be solved by the present invention is to provide a heat-shrinkable polyester film excellent in perforation cutting properties and strength of an adhesive portion at the time of labeling.
  • the heat-shrinkable polyester film of the present invention that has been able to solve the above-described problems is a heat shrinkable structure in which an X layer containing a polyester component M and a Y layer containing a polyester component N are alternately laminated.
  • a shrinkable polyester film which is coated with 1,3-dioxolan slightly inside from one edge of one end of the film, rolled up and overlapped to form a tubular film label, When a film label is coated on a 500 mL PET bottle, heated at 80 ° C for 2.5 seconds and then attached, and when 10 PET bottles are dropped even at a height of lm, all 10 PET bottles It is characterized in that the film label is not damaged due to peeling from the Y layer.
  • the heat-shrinkable polyester film of the present invention comprises polyester component M 1S polyester A 70 to 99% by mass and polyester Bl 30% by mass contained in the X layer, and polyester component N force polyester B 70 to 99% contained in the Y layer.
  • 0/0 and a is a preferred embodiment comprises a polyester a 1 to 30 wt%.
  • the X layer and the Y layer have a structure in which 500 layers or more are alternately laminated.
  • the heat-shrinkable polyester film of the present invention has a heat shrinkage ratio of 50% or more in the main shrinkage direction after being immersed in warm water of 95 ° C ⁇ 0.5 ° C for 10 seconds, and has a solvent adhesive strength of 2.0 N. / 15 mm or more, tear propagation strength is 2. ON or less, and the thickness after breaking into hot water at 60 ° C ⁇ 1 ° C for 30 minutes is 20 MPa or more. Thickness is 5 to: L00 ⁇ m It is also expressed as a heat-shrinkable polyester film.
  • the heat-shrinkable polyester film of the present invention is suitable for a bottle label, and a bottle label using the heat-shrinkable polyester film of the present invention is also included in the present invention.
  • the heat-shrinkable polyester film of the present invention comprises a polyester component M containing 70 to 99% by weight of polyester A and 30 to 30% by weight of polyester Bl, and a polyester component containing 70 to 99% by weight of polyester B and 30 to 30% by weight of polyester Al.
  • N is fed into separate extruders E and F, respectively, and melted.
  • Polyester components M and N in a molten state are fed into a laminating apparatus to obtain a laminated body of polyester components X and Y.
  • the laminated body is guided from the laminating apparatus to a slit die so that it takes 45 seconds to 10 minutes until the force is discharged from the laminating apparatus and the force comes into close contact with the cooling roll.
  • the unstretched sheet can be produced by a method characterized by stretching at least uniaxially, and this method is also included in the present invention.
  • a heat-shrinkable polyester-based film having general characteristics of heat-shrinkable polyester film such as heat-shrinkability and tensile strength, and having excellent perforation cutability and strength of an adhesive portion at the time of labeling.
  • a film is provided.
  • the film of the present invention is a full-bottle label, it is easy to peel off the label even at low temperatures, causing a problem of label breakage when a beverage product in a PET bottle falls to the outlet with a vending machine. It can be used favorably as a label for bottles with a long gap.
  • the present invention relates to a heat-shrinkable polyester film having a structure in which an X layer containing a polyester component M and a Y layer containing a polyester component N are laminated in a force alternating fashion, on one side of the film. Apply 1,3-dioxolan slightly inward from the edge, roll the film and overlap the edges to form a tube-shaped film label, and cover the film label on a 500 mL PET bottle at 80 ° C. 2. If the PET bottle is heated and attached for 5 seconds and dropped from the height of lm, the film label will be damaged due to the peeling between the X layer and the Y layer for all 10 PET bottles.
  • This is a heat-shrinkable polyester film characterized by the absence of the heat-shrinkable polyester film.
  • the heat-shrinkable polyester film of the present invention has a structure in which X layers and Y layers are alternately laminated, and the X layers and Y layers are composed of different polyester components (polyester components M and N).
  • polyester components M and N can be selected to meet the object of the present invention in any combination as long as they have different thermal characteristics. It is preferable that the difference between the glass transition temperatures of the polyester components M and N is 3 ° C. or more and 100 ° C. or less and the difference in crystal heat of fusion is 5 jZg or more and 100 J Zg or less.
  • Polyester component M is a crystalline polyester component having a glass transition temperature measured by DSC of ⁇ 50 ° C or more and less than 60 ° C and a heat of crystal melting of 5jZg or more and lOOjZg or less
  • polyester component N is More preferably, it is a substantially amorphous polyester component having a glass transition temperature of 60 ° C.
  • the starting polyester components M and N may be either homopolymers or copolymers, and may be a polyester composition containing two or more arbitrary polyesters.
  • polyester component M and N wherein the polyester component M power Po Riesuteru A70 ⁇ 99 mass 0/0 and polyester Bl ⁇ 30 mass 0/0, the polyester component N is polyester B70 ⁇ 99 wt% And polyester Al to 30% by mass is preferable. Also includes B3 ⁇ 27 wt% polyester component M force polyester A73 ⁇ 97 mass 0/0 and polyester, and more preferably contains B73 ⁇ 97 wt% polyester component N force polyester Oyobi polyester A3 ⁇ 27 wt%. In addition, police Include ether components M force polyester A75 ⁇ 94 wt% and the polyester B6 ⁇ 25 mass 0/0, most preferred to contain B75 ⁇ 94 wt% polyester component N force polyesters and polyester A6 to 25 wt%.
  • the polyester components M and N are preferably used in a mass ratio (polyester component MZN) of 97Z3 to 3Z97. If the mass ratio is outside this range, it becomes difficult to form a layer structure, and it becomes difficult to simultaneously achieve a heat shrinkage ratio of 60% or more at 95 ° C and a tear strength of 2. ON or less. There is a fear.
  • polyester components M and N are used in a mass ratio (polyester component MZN) of 90/10 to 10/90, more preferably force S, and used in 85/15 to 60/40 or 40/60 to 15 Z85. Most preferably.
  • polyester A examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polypentamethylene terephthalate, polyhexamethylene terephthalate, polyethylene 2, 6 naphthalate.
  • Crystalline polyester such as (PEN) can be used.
  • an acid component and Z or glycol component described later may be copolymerized with 10 mol% or less in 100 mol% of the acid component and Z or glycol component.
  • PET polyethylene terephthalate
  • PEN polyethylene one 2
  • PBT polyethylene terephthalate
  • PET-D polyethylene terephthalate
  • Polyester B is, for example, based on polyester having terephthalic acid as the acid component and diethylene glycol power as the glycol component, and 5 mol% or more, preferably 6 mol% or more in 100 mol% of the acid component and / or the diol component.
  • a copolymer obtained by copolymerizing different dicarboxylic acid components and Z or glycol components of less than 40 mol% can be used.
  • Specific monomer components include, for example, dicarboxylic acid components such as aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, and orthophthalic acid, and aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid. Acid, and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid.
  • dicarboxylic acid components such as aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, and orthophthalic acid
  • aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid.
  • Acid, and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid.
  • amine component examples include aliphatic diols such as propanediol, butanediol, neopentylglycol, and hexanediol; alicyclic diols such as 1,4-cyclohexanedimethanol, and aromatic diols.
  • Polyester B is preferably composed of terephthalic acid as the acid component and 7 to 35 mol% of neopentyl glycol and Z or 1,4-cyclohexanedimethanol based on polyester having diethylene glycol strength as the glycol component. It is a copolymerized polyesterol.
  • the heat-shrinkable polyester film of the present invention has a structure in which X layers and Y layers are alternately laminated.
  • the number of X layers and Y layers to be laminated the number of X layers and Y layers is More preferably, the total is 500 or more, more preferably 1,000 to 100,000, and most preferably 2,000 to 10,000.
  • the perforation cutting property is particularly excellent.
  • the outermost layer of the heat-shrinkable polyester film may be either the X layer or the Y layer.
  • the X- and Y-layers are dyed separately, and then the film cross-section is observed by TEM.
  • additives for example, organic particles (eg, bridge acrylic particles, crosslinked styrene particles, silicone particles, etc.), inorganic particles (eg, silica, kaolin) Contains phosphorus, clay, calcium carbonate, aluminum oxide, barium sulfate, zinc oxide, zinc sulfide, etc.), lubricant, stabilizer, colorant, antioxidant, antifoaming agent, antistatic agent, UV absorber, etc. May be.
  • organic particles eg, bridge acrylic particles, crosslinked styrene particles, silicone particles, etc.
  • inorganic particles eg, silica, kaolin
  • 1,3-dioxolane is applied slightly inside from one edge of one end of the film, the film is rolled up and the ends are overlapped to form a tube.
  • the film label was covered with a 500mL plastic bottle, heated at 80 ° C for 2.5 seconds, and 10 plastic bottles dropped with a height of lm. In this case, the film label is not damaged due to peeling between the X layer and the Y layer for all the 10 PET bottles.
  • 1,3-dioxolan is applied in a width of 2 ⁇ lmm slightly inward from the edge of one side of the film (application amount: 3.0 ⁇ 0. 3g / m 2).
  • application amount 3.0 ⁇ 0. 3g / m 2.
  • the size of the tube-shaped film label is not limited as long as it can be mounted on a 500 mL plastic bottle without any strain.
  • the folding diameter is 109 mm and the label length is about 90 mm.
  • the label is provided with perforations according to the actual product form. For example, by using a sewing blade, holes with a length of 0.2 to 2. Omm are arranged at intervals of 0.2 to 1. Omm along the direction perpendicular to the main shrinkage direction of the label. Provide one or two perforations of length.
  • the film label breakage due to the peeling between the X layer and the Y layer is, for example, that the label is peeled off due to the delamination between the X layer and the Y layer, particularly in the solvent adhesion portion. It is done.
  • the heat-shrinkable polyester film as described above has a heat shrinkage ratio of 50% or more in the main shrinkage direction after being immersed in warm water at 95 ° C for 5 seconds, and a solvent adhesive strength of 2.0 NZl5 mm or more. Yes, the tear propagation strength is 2. ON or less, and the fracture strength after immersion for 30 minutes in 60 ° C warm water is 20 MPa or more.
  • the problem to be solved by the present invention can be solved by the heat-shrinkable polyester film having such characteristics. I found out.
  • the heat-shrinkable polyester film of the present invention has a hot-water heat shrinkage force when immersed in hot water at 95 ° C ⁇ 0.5 ° C for 10 seconds under no load condition. % Or more. If the heat shrinkage rate is less than 50%, the label may not be properly attached to the container due to insufficient heat shrinkage force.
  • the heat shrinkage rate is preferably 55% or more, more preferably 60% or more. In particular, when the heat shrinkage rate is 60% or more, it is very easy to attach a label even on a difficult part such as a shoulder of a bottle.
  • the upper limit of the thermal shrinkage rate is a technical limit of 98%, preferably 90% or less, more preferably 85% or less. In particular, when the heat shrinkage rate is 85% or less, the occurrence of label jumping due to the excessively large shrinkage force of the label when the bottle is heated and shrunk over the bottle is extremely suppressed.
  • the heat-shrinkable polyester film of the present invention has a hot-water heat shrinkage rate in the main shrinkage direction when immersed in hot water at 70 ° C ⁇ 0.5 ° C for 10 seconds under no load!
  • a hot-water heat shrinkage rate in the main shrinkage direction when immersed in hot water at 70 ° C ⁇ 0.5 ° C for 10 seconds under no load!
  • it is preferably 10% or more and 50% or less. If the heat shrinkage rate is less than 10%, the shrinkability is insufficient and the shrinking process needs to be performed at a higher temperature. When the thermal shrinkage rate exceeds 50%, a label jumping phenomenon may occur when the bottle is covered with a bottle and heated and shrunk, because the shrinkage force of the label is too large.
  • the hot water heat shrinkage ratio is measured by measuring the length of the film before and after the dipping treatment, (length before shrinkage, length after shrinkage) Z length before shrinkage) X 100 (%) This is the value obtained from the formula.
  • the main shrinkage direction is a direction in which the hot water heat shrinkage rate is high in the longitudinal direction and the transverse direction.
  • the heat-shrinkable polyester film of the present invention has a characteristic that the solvent adhesive strength is 2.0 NZl 5 mm or more.
  • the solvent adhesive strength is preferably 2.5 to 20 NZl5 mm. 2. 8 to: LON / 15 mm is preferable.
  • the solvent adhesive strength is as follows. This is the value obtained in this way.
  • the heat-shrinkable polyester film of the present invention has a characteristic that the tear propagation strength is 2.0 N or less.
  • the tear propagation strength is preferably 0.2 to 1.9 N, and more preferably 0.5 to 1.8 N.
  • the tear propagation strength is based on JIS K7128-2 (1998).
  • a film that has been shrunk 10% at 85 ° C in advance to 5 lmm x 64 mm is manufactured by Toyo Seiki Seisakusho Co., Ltd. The value obtained by measuring with a light load tear tester.
  • the heat-shrinkable polyester film of the present invention has a characteristic that the breaking strength after immersion for 30 minutes in warm water of 60 ° C ⁇ 1 ° C is 20 MPa or more.
  • the breaking strength is preferably 30 to 200 MPa, more preferably 40 to 150 MPa.
  • the breaking strength is a value obtained as follows.
  • Folded diameter 87.5mm X Label length 120mm film label is put on a 250mL steel can (outer diameter 53mm, height 133mm) and immersed in hot water at 80 ° C for 10 seconds to put the label in the can Wear shrinkage (about 5% shrinkage). Immediately transfer the labeled steel can into warm water of 60 ° C ⁇ 1 ° C and soak for 30 minutes. Cut the sample from the steel can label, and film before heat treatment according to JIS-K-7127 (1999) (test piece is type 2. However, distance between chucks: 20mm, pulling speed: 200mmZ) Conduct a tensile test in the direction perpendicular to the maximum shrinkage direction.
  • the test piece size is 100 mm long (in the direction perpendicular to the maximum film shrinkage direction) and 15 mm wide. mm, temperature 23 ° C, tensile speed 200mmZ.
  • the strength at the time of rupture during the test is the breaking strength.
  • the heat-shrinkable polyester film used in the present invention preferably has a melt specific resistance at a temperature of 275 ° C of 0.70 to 10 8 ⁇ 'cm or less.
  • a melt specific resistance at a temperature of 275 ° C of 0.70 to 10 8 ⁇ 'cm or less.
  • the film melted and extruded by an extruder is cooled by a conductive cooling roll (such as a casting roll), an electrode is disposed between the extruder and the casting roll, and the electrode, the casting roll, A voltage is applied between them (that is, the electrode force also applies electricity to the film), and the film is electrostatically adhered to the roll.
  • a conductive cooling roll such as a casting roll
  • the adhesion between the film and the roll electrostatic adhesion
  • the electrostatic adhesion to the roll is low, the thickness of the cast unstretched film becomes non-uniform, and the thickness non-uniformity is further expanded in the stretched film obtained by stretching the unstretched film.
  • the electrostatic adhesion is sufficiently high, the thickness can be made uniform even in the stretched film.
  • the bonded portions can be easily overlapped even when the film is processed into a tube or the like by solvent bonding.
  • the film can be prevented from becoming wrinkled easily, and the film can be prevented from meandering during running, thereby improving workability (stable workability). it can.
  • the film productivity can be increased as well as the uniformity of the film thickness, and the appearance of the film can also be improved.
  • high electrostatic adhesion improves the stability of film cooling and solidification.
  • the casting speed production speed
  • the electrostatic adhesion is high, the film is incompletely cooled and solidified, and air is locally introduced between the roll and the film, resulting in pinner bubbles (streaky defects) on the film surface. Can be prevented and the film appearance can be enhanced.
  • the melting specific resistance value is preferably 0.65 X 10 8 ⁇ 'cm or less, more preferably 0.60.
  • the melt specific resistance value In order to control the melt specific resistance value within the above range, it is desirable to contain an alkaline earth metal compound and a phosphorus-containing compound in the film.
  • the melting specific resistance value can be lowered by using only the alkaline earth metal compound, but the melting specific resistance value can be remarkably lowered by the presence of the phosphorus-containing compound. It is not clear why the specific resistance of the melt can be significantly lowered by combining the alkaline earth metal compound and the phosphorus-containing compound. It is estimated that the amount of charge carriers can be increased.
  • the content of the alkaline earth metal compound in the film is, for example, 20 ppm (mass basis) or more, preferably 40 ppm (mass basis) or more, based on the alkaline earth metal atom 2 . Preferably it is 50 ppm (mass basis) or more, particularly 60 ppm (mass basis) or more. If the amount of the alkaline earth metal compound is too small, the melting specific resistance value cannot be lowered. Even if the content of the alkaline earth metal compound is excessively increased, the effect of reducing the melt specific resistance value is saturated, and rather adverse effects such as generation of foreign matter and coloring are increased.
  • alkaline earth metal compound based on the alkaline-earth metal atom M 2, for example, 400pp m (by mass) or less, preferably 350 ppm (mass basis) or less, more preferably 300 ppm (mass basis) It is as follows.
  • the content of the phosphorus compound in the film is, for example, 5 ppm (mass standard) or more, preferably 20 ppm (mass standard) or more, more preferably 40 ppm (mass standard) or more, based on the phosphorus atom P. Especially 60ppm (mass basis) or more. If the amount of the phosphorus compound is too small, the melting specific resistance value cannot be lowered sufficiently, and the amount of foreign matter generated cannot be reduced. Even if the content of the phosphorus compound is increased too much, the effect of reducing the melt specific resistance value is saturated. Furthermore, it promotes the production of diethylene glycol, and the force also controls the amount of production.
  • the phosphorus compound content is, for example, 500 ppm (mass basis) or less, preferably 450 ppm (mass basis) or less, more preferably 400 ppm (mass basis) or less, particularly 350 ppm (mass basis), based on the phosphorus atom P. It is as follows.
  • the mass ratio (M 2 ZP) of the alkaline earth metal atom M 2 and phosphorus atom P in the film is 1 It should be 2 or more (preferably 1.3 or more, more preferably 1.4 or more).
  • the mass ratio (M 2 ZP) is 5.0 or less, preferably 4.5 or less, and more preferably 4.0 or less.
  • the melt specific resistance value of the film it is desirable to contain an alkali metal compound in the film in addition to the alkaline earth metal compound and the phosphorus-containing compound.
  • Alkali metal compounds cannot lower the melt resistivity even if they are contained alone in the film, but by adding them to the coexistence system of alkaline earth metal compounds and phosphorus-containing compounds, the melt resistivity can be reduced. Can be significantly reduced. Although the reason for this is not clear, it is presumed that the melting specific resistance value is lowered by forming a complex of the alkali metal compound, the alkaline earth metal compound, and the phosphorus-containing compound.
  • the content of the alkali metal compound in the film based on the alkali metal atom M 1, for example, Oppm (mass basis) or more, preferably 5 ppm (mass basis) or more, more preferably 6 ppm (mass basis) Above, especially 7ppm (mass basis) or more. Even if the content of the alkali metal compound is excessively increased, the effect of reducing the melt specific resistance value is saturated, and further, the amount of foreign matter generated is increased.
  • the alkali metal compound based on the alkali metals atom M 1, for example, LOOppm (mass basis) or less, preferably 90 ppm (mass basis) or less, still more preferably not more than 80 ppm (by weight) .
  • alkaline earth metal compound examples include an alkaline earth metal hydroxide, alkoxide, aliphatic carboxylate (acetate, butyrate, etc., preferably acetate), and aromatic carboxylate (benzoic acid). Acid salt), a salt with a compound having a phenolic hydroxyl group (such as a salt with phenol). Etc.).
  • alkaline earth metal examples include magnesium, calcium, strontium, norium (preferably magnesium).
  • Preferred alkaline earth metal compounds include magnesium hydroxide, magnesium methoxide, magnesium acetate, calcium acetate, strontium acetate, barium acetate and the like, in particular magnesium acetate.
  • the alkaline earth metal compounds can be used alone or in combination of two or more.
  • Examples of the phosphorus compound include phosphoric acids (phosphoric acid, phosphorous acid, hypophosphorous acid, etc.), esters thereof (alkyl esters, aryl esters, etc.), alkyl phosphonic acids, aryl phosphones. Examples thereof include acids and esters thereof (alkyl esters, aryl esters, etc.).
  • Preferred phosphoric acid compounds include phosphoric acid, aliphatic esters of phosphoric acid (alkyl esters of phosphoric acid, etc .; for example, phosphoric acid monomethyl esters, phosphoric acid monoethyl esters, phosphoric acid monobutyl esters, etc. Alkyl ester, dimethyl phosphate
  • Di-C alkyl phosphates such as stealth, jetyl phosphate, dibutyl phosphate
  • ester 1-6 ester, trimethyl phosphate, triethyl ester phosphate, tri-C phosphate ester such as tributyl ester), phosphoric acid aromatic ester (phosphate phosphate)
  • Such as phosphoric acid, tricresyl phosphate, or tri-C aryl ester Such as phosphoric acid, tricresyl phosphate, or tri-C aryl ester.
  • Aliphatic esters of phosphorous acid alkyl esters of phosphorous acid, etc .; for example, phosphorous acid compounds such as trimethyl phosphite, tributyl phosphite, or tri C alkyl ester
  • anorequinolephosphonic acid metal-oxide-semiconductor (methinorephosphonic acid, ethenorephosphonic acid, etc.)
  • alkylphosphonic acid alkyl esters mono- or di-C alkyl ethers of C alkylphosphonic acids such as dimethyl methylphosphonate, dimethyl ethylphosphonate
  • aryl phosphonic acid alkyl esters mono- or di-C alkyl ethers of C allylic phosphonic acids such as dimethyl phosphophosphonate, jetyl phosphophosphonate
  • aryl phosphonic acid aryl ester (mono- or di-C aryl ester of C arylphosphonic acid such as diphosphorus phosphonic acid) etc.
  • the Particularly preferred phosphorus compounds include phosphoric acid and trialkyl phosphates (such as trimethyl phosphate). These phosphorus compounds can be used alone or in combination of two or more.
  • alkali metal compounds include alkali metal hydroxides, carbonates, and aliphatic carbonates. Bonates (acetate, butyrate, etc., preferably acetate), aromatic carboxylates (benzoate), salts with compounds having a phenolic hydroxyl group (such as salts with phenol), etc. It is.
  • alkali metal include lithium, sodium, potassium and the like (preferably sodium).
  • Preferred alkaline earth metal compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium acetate, sodium acetate, potassium acetate and the like, especially sodium acetate.
  • the thickness of the heat-shrinkable polyester film of the present invention,. 5 to: LOO mu m is preferably 20 to 50 111 mosquitoes ⁇ Yori preferably 1 ⁇ 0
  • the heat-shrinkable polyester film of the present invention can be labeled by a conventionally known method.
  • a suitable film is applied to a heat-shrinkable polyester film cut to a desired width, and a film film is manufactured by overlapping and bonding the left and right ends of the film by solvent adhesion or the like.
  • the tube film is cut into an appropriate length to obtain a tube-shaped label.
  • one opening of this tubular label is joined to form a bag-like label.
  • These labels are then perforated by a conventional method, and then covered with a plastic bottle.
  • the plastic bottle is placed on a belt conveyor and the like, and steam is blown into the shrink tunnel (steam tunnel) or hot air.
  • the label is attached to a bottle container such as a plastic bottle by heat shrinking when passing through these tunnels.
  • polyester Le component containing A70 ⁇ 99 wt% polyester and polyester Bl ⁇ 30 wt% M, and polyester B70 ⁇ 99 mass 0 / 0 and polyester component N containing polyester Al ⁇ 30 mass 0/0 melt was poured into separate extruders E and F, respectively, the polyester component by introducing a polyester component M and N of molten state in the stacking device M And the laminate is led from the laminating apparatus to the slit die so that the time from when the laminated body is discharged from the laminating apparatus until it comes into close contact with the cooling roll is 45 seconds to 10 minutes. Extruded into a roll to obtain an unstretched sheet, and the unstretched sheet is stretched at least uniaxially (An example of a production line is shown in Fig. 1).
  • the polyester as a raw material is first dried using a dryer such as a hopper dryer, a paddle dryer, or a vacuum dryer.
  • a dryer such as a hopper dryer, a paddle dryer, or a vacuum dryer.
  • a predetermined amount of polyester A and polyester B are mixed to prepare polyester component M and polyester component N.
  • a method for mixing polyester a chip blend method, a master batch method and the like, which are not particularly limited, can be employed. It is known that even when two or more polyester components are blended, there is a strong tendency to transesterify and copolymerize due to the heat history during melt extrusion.
  • Polyester component M and polyester component N are charged into separate extruders E and F, respectively, and melted.
  • the melting temperature is not particularly limited as long as it does not cause deterioration or alteration for each of the fats and oils.
  • the melting point + 5 ° C to 30 ° C
  • the softening temperature + (20 ° C to 150 ° C) It is preferable.
  • the melted polyester components M and N are guided to the laminating apparatus while being in a molten state, and a stacked body is formed.
  • the laminating apparatus include a feed block, a multi-hold die, and a static mixer. Of these, the stacking of several hundred layers can be easily achieved, so it is more preferable to use a combination of a feed block and a static mixer, which are preferable to use a static mixer.
  • the static mixer in the present invention is an element having a shape in which a horizontally long rectangular plate is twisted and bent so that an angle (torsion angle) between its short sides is 45 degrees to 270 degrees.
  • the in-pipe mixing device arranged alternately so that the short sides of adjacent elements intersect.
  • the LZD (pipe length Z pipe inner diameter) ratio of the static mixer element is preferably in the range of 1.0 to 3.0, more preferably in the range of 1.4 to 2.0. If the L / D ratio is less than 1.0, the efficiency of dividing the resin deteriorates, and if it exceeds 3.0, the residence time of the resin passing through the mixer becomes longer, which is not practical.
  • the torsion angle of the static mixer element shall be 45 degrees or more. This is because if the twist angle is less than 45 degrees, the twist of the resin layer is insufficient.
  • the twist angle is more preferably 90 ° or more, and more preferably 135 ° or more.
  • the upper limit of torsion angle should be 315 degrees. If it exceeds 315 degrees, a uniform laminated structure cannot be obtained due to excessive twisting.
  • the twist angle is preferably 270 degrees or less, more preferably 215 degrees or less. Note that the fact that a uniform laminated structure cannot be obtained means that the laminated structure is disturbed, for example, the laminated layers are wavy.
  • the angle formed by the straight line that follows the joint between the pipe inner wall and the element and the direction of grease movement, that is, the torsional gradient of the element is 27 degrees or more is preferable. If this twist gradient is less than 27 degrees, the LZD ratio must be increased in order to give sufficient twist to the resin with less twisting effect of the resin layer, which is not practical.
  • the torsional gradient is more preferably 38 degrees or more, and more preferably 42 degrees or more. On the other hand, when the torsional gradient exceeds 65 degrees, the turbulent flow of the resin becomes violent and the laminated structure is disturbed.
  • the twist gradient is more preferably 54 degrees or less, and further preferably 50 degrees or less.
  • the preferred shape of the elements of the static mixer can be appropriately selected according to the discharge amount and melting characteristics of the resin, and the shape varies depending on the change of the melting characteristics of the resin passing through the static mixer.
  • a plurality of elements can also be used in combination.
  • the arrangement of the elements of the static mixer is preferably changed alternately so that the twisting directions of the elements are right turn, left turn, and right turn. This is because a uniform laminated structure can be obtained. It is also preferable to arrange adjacent elements so that they intersect at right angles in order to obtain a uniform laminated structure.
  • the number of static mixer elements is preferably 4 or more, more preferably 6 or more. More preferably, it is 8 or more.
  • the film of the present invention has a laminated structure, and the number of layers is particularly preferably 500 or more as will be described later. When the number of elements is 8 or more, a laminated structure of 500 or more layers is ensured. Easy to obtain. On the other hand, if the number of elements becomes too large, the laminated structure tends to be disturbed. Therefore, the number of elements is preferably 24 or less, more preferably 18 or less, and more preferably 14 or less. Is more preferable.
  • the mass ratio of the polyester component is 8Z2 (MZN)
  • the number of elements is preferably 8 to 14, and particularly preferably 10 to 12 forces! / ⁇ .
  • the structure of the static mixer described above is one typical example, and the shape and arrangement can be changed without departing from the object of the present invention, and another apparatus can be arranged before and after the static mixer and between the elements.
  • another apparatus can be arranged before and after the static mixer and between the elements.
  • two or more rows of static mixers smaller in diameter than the resin piping may be arranged in parallel in the piping. It can be obtained by laminating a mixture of the resin component M and the component N of the resin component N by passing through a static mixer and further mixing another resin.
  • the number of stacked feed blocks is preferably within 100 layers.
  • the temperature of the laminating apparatus is as follows: melting point + (5 ° C to 30 ° C) when the composition exhibits crystallinity, softening temperature + Most preferably, it should be set to (20 ° C to 150 ° C).
  • This laminate is extruded through a slit die such as a T-die and is brought into close contact with a cooling tool having a surface temperature of 10 to 40 ° C to obtain an unstretched sheet.
  • a slit die such as a T-die
  • a cooling tool having a surface temperature of 10 to 40 ° C to obtain an unstretched sheet.
  • the laminated body is discharged from the laminating device (the last device that performs laminating when multiple laminating devices are used) until it comes into close contact with the force cooling roll.
  • Time for example, in Fig. 1, the stack is discharged from the static mixer 4 and then extruded from the T die 5 to The time until the laminate adheres to the handle 6) is 45 seconds to 10 minutes, preferably 1 to 8 minutes, and more preferably 1.5 to 5 minutes.
  • the fact that the stacked body is in close contact with the cooling roll means that the laminate is in surface contact with the cooling roll in the entire width direction.
  • the laminated body extruded from the die first comes into surface contact with the cooling roll when the cooling roll rotates as a force that makes contact with the cooling roll in the entire width direction.
  • the starting point of the surface contact appears as a line that is formed when the contact points between the cooling roll and the laminate are continuously arranged in the width direction. Therefore, consider the moment when this line appears as the point of contact with the cooling roll.
  • the stacking device force can be increased by, for example, increasing the flow path to the slit die, or causing the laminate to stay in the path. The method is mentioned.
  • the obtained unstretched sheet is preheated at 50 to 120 ° C, preferably 60 to 100 ° C, if necessary, and then stretched in the transverse direction (direction perpendicular to the extrusion direction) with a tenter. Stretched to 0 times or more, preferably 3.5 times to 15 times.
  • the stretching temperature is 60 ° C or higher and 120 ° C or lower, preferably 70 ° C or higher and 100 ° C or lower.
  • heat treatment is performed at a temperature of 70 to 100 ° C to obtain a heat-shrinkable polyester film.
  • the film may be made into a film roll by winding it according to a conventional method.
  • the stretching method may be biaxial stretching by additionally stretching in the machine direction in addition to transverse monoaxial stretching with a tenter.
  • Such biaxial stretching may be performed by any of the sequential biaxial stretching method and the simultaneous biaxial stretching method, and may be re-stretched in the longitudinal direction or the transverse direction as necessary.
  • the fluctuation range of the surface temperature is a temperature force at each point when the surface temperature of the film is measured at an arbitrary point.
  • the average temperature of the film is within about ⁇ 1 ° C. More preferably, the temperature is within ⁇ 0.6 ° C.
  • the film is stretched through various processes such as a preheating process before stretching, a stretching process, a heat treatment process after stretching, a relaxation process, and a restretching process process. It is preferable to use equipment that can reduce (homogenize) the fluctuation range of the surface temperature of the film partially or entirely. In particular, in order to make the thickness distribution value uniform over the entire length of the film, the fluctuation range of the surface temperature of the film can be reduced in the preheating step and the stretching step (and in the heat treatment step after stretching if necessary). It is preferable to use equipment. In order to make the heat shrinkage rate uniform, it is preferable to use equipment capable of reducing the fluctuation range of the surface temperature of the film in the stretching process.
  • Examples of the equipment that can reduce the fluctuation of the film surface temperature include, for example, equipment equipped with a wind speed control means (such as an inverter) for controlling the supply speed of hot air for heating the film, and stably supplying air.
  • a wind speed control means such as an inverter
  • Examples include equipment equipped with heating means for heating to prepare the hot air [heating means using low-pressure steam of 500 kPa or less (5 kgf Zcm 2 or less) as a heat source].
  • the horizontal direction is practical as the main shrinkage direction, and thus, an example of the film forming method in the case where the main shrinkage direction is the horizontal direction has been shown above.
  • the main shrinkage direction is the longitudinal direction
  • a film can be formed in accordance with the operation of the above method except that the stretching direction in the above method is changed by 90 degrees.
  • the heat-shrinkable polyester film thus obtained has the general characteristics of a heat-shrinkable polyester film such as heat-shrinkability and tensile strength, and also has a perforation cut property and a label wear. It is excellent in the strength of the bonded part and is suitable as a label for a bottle.
  • the label was perforated in a direction perpendicular to the main shrinkage direction of the label. Fold in half Two lmm thick cardboards are placed under the label, and a sewing machine blade (100mm blade with 1mm pitch blades at lmm intervals) is placed on the test sealer (made by Seibu Kikai Co., Ltd.). Attach, press the sewing blade to the label with a gauge pressure of 2kg / cm 2 , and put a perforation parallel to the label edge at 5mm from the edge of the folded label.
  • the label was provided with two perforations with 1 mm long holes arranged at lmm intervals over the entire length of the label, and the interval between the two perforations was 10 mm.
  • the label was attached under the condition (4), and the PET bottle refrigerated at 5 ° C for 12 hours was dust-coated from the height of lm and allowed to fall freely onto the glossy concrete surface. At this time, holding the plastic bottle sideways and letting go of the hand, the bottle dropped on its side force concrete surface. A test was performed on 10 PET bottles, and X was given if even one bonded part was removed.
  • Folded diameter 87.5mm X Label length 120mm film label is placed on a 250mL steel can (outer diameter 53mm, height 133mm) and immersed in 80 ° C hot water for 10 seconds to shrink the label into the can (5% contraction).
  • the steel can with the label was immediately transferred to warm water of 60 ° C ⁇ 1 ° C and immersed for 30 minutes.
  • Also cut out the sample of the steel can label (part without back attachment) and set it to JIS K 7127 (1999) (specimen is type 2; however, distance between chucks: 20 mm, pulling speed: 200 mmZ) According to heat treatment
  • the bow I tension test was conducted in the direction perpendicular to the maximum shrinkage direction of the film before the treatment.
  • the size of the test piece is 100 mm in length (direction perpendicular to the maximum film shrinkage direction), 15 mm in width, and the test conditions are a distance between chucks of 20 mm, a temperature of 23 ° C, and a tensile speed of 200 mmZ.
  • the strength at the time of breaking during the test was defined as the breaking strength.
  • Thermal analysis of the polyester component was performed using a DSC device (model: DSC220) manufactured by Seiko Denshi Kogyo. 10 ⁇ lmg of each chip synthesized in the synthesis example described below is used as a sample. This sample is heated at 300 ° C for 2 minutes, immediately put in liquid nitrogen and rapidly cooled, and then the temperature is increased from 40 ° C to 300 ° C. The temperature was raised at 20 ° CZ and the heat flow rate curve (DSC curve) was measured. The intersection of tangent lines drawn before and after the endothermic start curve in the DSC curve was defined as the glass transition temperature (Tg). The temperature showing the maximum value of the endothermic peak in the DSC curve was defined as the melting temperature (Tm). The integrated value of the endothermic peak of the DSC curve was defined as the heat of fusion (Hm). The results are shown in Table 1.
  • the number of layers inside the film was determined by observation using a transmission electron microscope.
  • the film was embedded in epoxy resin.
  • epoxy resin As the epoxy resin used, Luabeck 812, Luabeck NMA (manufactured by Nacalai Testa Co., Ltd.) and DMP30 (TAAB Co., Ltd.) were mixed well in a ratio of 100: 89: 3, respectively.
  • TAAB Co., Ltd. TAAB Co., Ltd.
  • the obtained embedding block was attached to Nissan Sangyo Ultracut N, and an ultrathin section was prepared.
  • trimming was performed using a glass knife until the cross section of the part that was desired for film observation appeared on the resin surface.
  • an ultrathin section was cut out using a diamond knife (Sumitomo Electric Sumiknife S K2045). The cut sections were collected on a mesh, stained in ruthenium tetroxide vapor at room temperature for 30 minutes, and then thinly deposited with carbon.
  • JEOL SiiEM—2010 was conducted under the condition of an acceleration voltage of 200 kV. It was. The obtained image was recorded on an imaging plate (FDL UR-V made by Fuji Photo Film). The signal recorded on the imaging plate is read out using digital luminography (PixsysTEM, manufactured by JEOL) and recorded as digital image information on a Windows (registered trademark) PC. We counted the number of layers identified.
  • the number of layers inside the film was determined by observation using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the film was embedded in epoxy resin.
  • As the epoxy resin used Luabeck 812, Luavec NMA (manufactured by Nacalai Testa Co., Ltd.) and DMP30 (TAAB Co.) were mixed well at a ratio (mass) of 100: 89: 3, respectively.
  • the sample film was allowed to stand in an oven adjusted to a temperature of 60 ° C. for 16 hours to cure the resin and obtain an embedded block.
  • the embedded block was cut with a glass knife until the cross section of the film portion appeared on the block surface (surface contact).
  • the embedding block after the surface exposure was placed in a container sealed with ruthenium chloride vapor for 3 days to carry out ruthenium staining.
  • the ruthenium chloride vapor was replaced with fresh vapor every day.
  • the electron microscope was observed using JEOL SiiEM-2010 under an acceleration voltage of 200 kV.
  • the obtained image was recorded on an imaging plate (“FDL UR V” manufactured by Fuji Photo Film Co., Ltd.).
  • the signal recorded on the imaging plate was read out using a digital luminography (“PixsysTEM” manufactured by JEOL Ltd.) and recorded as digital image information on a Windows (registered trademark) PC.
  • the magnification was appropriately selected from the medium power of 5000-20000 times.
  • the shade of the color in the film thickness direction was numerically expressed by the line profile. In particular , Read the shade of 100 pixels wide and 3000 pixels long (number of pixels can be changed arbitrarily), draw a curve with the horizontal axis as the length direction pixel and the vertical axis as the signal intensity (lightness and shade). I was ashamed.
  • the number of layers was counted visually from the TEM image on the ging plate.
  • 1 pixel is 5 nm
  • 1 pixel is 1.25 ⁇ m.
  • This Plot Value format data was read into Microsoft Excel, and the average value (Av) of all data for each pixel of the line parallel to the Y axis was obtained.
  • the judgment value + 1 is given to the pixel, and in other cases, the judgment value 1 is given to the pixel.
  • the judgment value of each pixel is plotted against the pixel (horizontal axis), the resulting graph is a horizontal straight line connecting +1 and +1 (or -1 and -1), and +1 and 1 ( Or the opposite)).
  • the number of diagonal lines was determined as the number of layers.
  • the number of layers obtained by the above method may be less than 2 eta layer or 2 eta + 1 layer obtained theoretically from several elements of the static mixer eta.
  • Polyester constituting the X layer, the resin component ⁇ and the polyester resin component constituting the cocoon layer Although the composition is different from that of the cocoon layer, transesterification occurs at the interface between adjacent layers during the lamination process, and the X layer A polyester with the same composition may be formed near the interface of the cocoon layer.
  • the X layer and the cocoon layer are partly identified as layers of the same polyester composition, and the above dyeing method or layer When the number confirmation method is adopted, it is considered to be less than the theoretical value.
  • esterification reactor 57036 parts by mass of terephthalic acid (TPA), 33244 parts by mass of ethylene glycol (EG), 15733 parts by mass of neopentyl glycol (NPG), 23.2 parts by mass of dianhymonic triacid (Polymerization catalyst), 5.0 parts by weight of sodium acetate (alkali metal compound) and 46.1 parts by weight of trimethyl phosphate (phosphorus compound), and the pressure is adjusted to 0.25 MPa, at a temperature of 220 to 240 ° C. Perform esterification reaction by stirring for 120 minutes It was.
  • TPA terephthalic acid
  • EG ethylene glycol
  • NPG 15733 parts by mass of neopentyl glycol
  • Polymerization catalyst Polymerization catalyst
  • sodium acetate alkali metal compound
  • the reaction vessel was returned to normal pressure, and 3.0 parts by mass of cobalt acetate tetrahydrate and 124.1 parts by mass of magnesium acetate tetrahydrate (alkaline earth metal compound) were added at a temperature of 240 ° C. After stirring for 10 minutes, the pressure was reduced to 0.5 hPa over 75 minutes and the temperature was raised to 280 ° C. Stirring was continued until the melt viscosity reached 4500 boise at a temperature of 280 ° C (about 70 minutes), and then discharged into water as a strand. Polyester chip A was obtained by cutting the discharged material with a strand cutter. The intrinsic viscosity of polyester chip A is 0.75 dlZg.
  • Polyester raw material chips B to D having the chip compositions shown in Table 1 were obtained in the same manner as in Synthesis Example 1.
  • PD is an abbreviation for 1,3 propanediol
  • CHDM is 1,4-cyclohexanedimethanol
  • BD is 1,4 butanediol
  • DEG diethylene glycol.
  • the intrinsic viscosities of each polyester were 0.92 dlZg for chip B, 0.72 dlZg for chip C, and 1.20 dlZg for chip D.
  • the above unstretched sheet was preheated in a tenter at 82 ° C for 24 seconds, subsequently stretched 4.8 times at 77 ° C in the lateral direction, and subsequently heat treated at 70 ° C for 24 seconds. And a heat-shrinkable polyester film having a thickness of 45 m was obtained.
  • Example 1 the change in the surface temperature of the film when the film was continuously produced was changed.
  • the dynamic range was within the range of the average temperature ⁇ 0.6 ° C in the tenter preheating step, the average temperature ⁇ 0.5 ° C in the stretching step, and the average temperature ⁇ 0.5 ° C in the heat treatment step.
  • Example 2 chip A was changed to chip C.
  • Example 3 heat shrinkage was performed in the same manner as in Example 1 except that chip B was changed to chip D and the preheating temperature during transverse stretching was changed to 79 ° C. A conductive polyester film was obtained.
  • Table 1 shows the evaluation results of the films obtained in Examples 1 to 3 and Comparative Example 1.
  • the number of layers in each example was determined by employing the detailed layer number confirmation method described in (8-2) above.
  • Heat shrinkage rate (%) Perforation cutting property Solvent adhesion strength after drop treatment Tear propagation strength Number of layers Horizontal perforation ⁇ La perforation break strength (layer) Breaking from defective rate after shrinkage
  • the heat-shrinkable polyester film of the present invention is suitable for a label for a bottle.

Abstract

Le problème à résoudre dans le cadre de la présente invention est de fournir un film de polyester thermorétractable pouvant être très facilement découpé par perforation et capable de former des étiquettes ayant une excellente résistance de joint. La solution apportée consiste en un film de polyester thermorétractable ayant une structure composée de X couches contenant un polyester M et de Y couches contenant un polyester N, qui sont stratifiées en alternance, caractérisé en ce que, lorsque dix bouteilles de 500 ml en PET obtenues en appliquant du 1,3 dioxolane au niveau d'une marge sur une surface du film de polyester, en enroulant le film et en plaçant la marge en haut de l'autre marge pour former une étiquette en film tubulaire, couvrant ainsi chaque bouteille avec l’étiquette en film, et en chauffant la bouteille couverte à 80 °C pendant 2,5 secondes par application de la chaleur vers le bas depuis une hauteur d'un mètre, aucune bouteille en PET ne cause la rupture de l'étiquette en film en raison du délaminage entre les couches X et Y.
PCT/JP2006/315035 2005-07-29 2006-07-28 Film de polyester thermorétractable et son procédé de fabrication WO2007013618A1 (fr)

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JP2008208270A (ja) * 2007-02-27 2008-09-11 Toyobo Co Ltd 熱収縮性ポリエステル系フィルム、およびその製造方法
JP2019151415A (ja) * 2014-09-09 2019-09-12 東洋紡株式会社 熱収縮性ポリエステル系チューブ状ラベルロール、およびその製造方法
US20220049049A1 (en) * 2018-10-16 2022-02-17 Toyobo Co., Ltd. Polyester resin for heat-shrinkable film, heat-shrinkable film, heat-shrinkable label, and packaged product

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Publication number Priority date Publication date Assignee Title
JP2008208270A (ja) * 2007-02-27 2008-09-11 Toyobo Co Ltd 熱収縮性ポリエステル系フィルム、およびその製造方法
JP2019151415A (ja) * 2014-09-09 2019-09-12 東洋紡株式会社 熱収縮性ポリエステル系チューブ状ラベルロール、およびその製造方法
US20220049049A1 (en) * 2018-10-16 2022-02-17 Toyobo Co., Ltd. Polyester resin for heat-shrinkable film, heat-shrinkable film, heat-shrinkable label, and packaged product

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