WO2023032429A1 - ポリエステル系熱収縮フィルム - Google Patents

ポリエステル系熱収縮フィルム Download PDF

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Publication number
WO2023032429A1
WO2023032429A1 PCT/JP2022/024981 JP2022024981W WO2023032429A1 WO 2023032429 A1 WO2023032429 A1 WO 2023032429A1 JP 2022024981 W JP2022024981 W JP 2022024981W WO 2023032429 A1 WO2023032429 A1 WO 2023032429A1
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Prior art keywords
polyester
heat
polyester resin
shrinkable film
mol
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PCT/JP2022/024981
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English (en)
French (fr)
Japanese (ja)
Inventor
達也 入船
琢磨 金子
裕一郎 勘坂
秀太 弓削
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CI Takiron Corp
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CI Takiron Corp
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Priority to MX2023014561A priority Critical patent/MX2023014561A/es
Priority to DE112022002485.2T priority patent/DE112022002485B4/de
Priority to JP2023504671A priority patent/JP7375258B2/ja
Priority to CN202280040846.0A priority patent/CN117440982A/zh
Priority to KR1020237041821A priority patent/KR20240004952A/ko
Priority to US18/571,342 priority patent/US20240352202A1/en
Publication of WO2023032429A1 publication Critical patent/WO2023032429A1/ja
Priority to JP2023111302A priority patent/JP7411136B2/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B29C61/02—Thermal shrinking
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/253—Preform
    • B29K2105/256—Sheets, plates, blanks or films
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0049—Heat shrinkable
    • 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
    • B29L2007/00—Flat articles, e.g. films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/30—Polymeric waste or recycled polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/30—Polymeric waste or recycled polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a polyester-based heat-shrinkable film (sometimes simply referred to as a polyester heat-shrinkable film or a heat-shrinkable film). More specifically, it relates to a polyester-based heat-shrinkable film that effectively and quantitatively suppresses the blocking phenomenon during recycling while maintaining excellent mountability on PET bottles.
  • PET bottles polyethylene resin (HDPE) bottles and polyester resin (PET) bottles (hereinafter sometimes simply referred to as PET bottles) have been widely used as beverage storage containers, detergent storage containers, and the like.
  • HDPE polyethylene resin
  • PET bottles are widely used worldwide as storage containers for beverages because they are lightweight, durable, and highly convenient.
  • PET bottles are discarded in rivers after use, causing serious environmental problems such as ocean outflow. Therefore, in order to solve such environmental problems, researches are being actively carried out to collect such PET bottles and improve recycling techniques.
  • the PET bottle is covered with a predetermined display label in order to indicate the name of the bottle and various information related to the contents and to improve the decorativeness of the bottle.
  • a method of attaching a paper-based label with an adhesive was often used as a display label, but in recent years, a display label using a heat-shrinkable film has been wrapped around the entire surface of a PET bottle. has become mainstream.
  • the main material of beverage storage containers and the like is basically PET, and since the raw materials are similar, as a heat shrink film, PETG film is melted together with PET bottles and recycled. It can be said that it is highly possible.
  • PETG is basically amorphous, as a thermal property, it basically has no melting point, or only has a melting peak with a small calorific value, and has a thermal shrinkage. In the process of recycling film-wrapped PET bottles, there is a problem that the recycled pellets tend to adhere to each other and cause blocking.
  • Patent Documents 1 and 2 a polyester heat-shrinkable film having a predetermined melting peak (melting point) in differential scanning calorimeter (DSC) measurement by adjusting the thermal properties of a PETG film has been proposed (Patent Documents 1 and 2).
  • the polyester-based heat-shrinkable film disclosed in Patent Document 1 reduces the blending amount of the amorphous polyester resin, for example, crystals derived from the diol component and the dicarboxylic acid component. and a heat treatment of 30% or more in the main shrinkage direction when immersed in hot water at 80°C for 10 seconds, and a melting point measured by DSC of 170°C or more. is characteristic.
  • the polyester-based heat-shrinkable film disclosed in Patent Document 2 also contains (1) 5 to 95% by weight of a crystallizable polyester and (2) an amorphous polyester composition in order to improve the recyclability of PET bottles. 5 to 95% by weight. More specifically, (1) the crystallizable polyester is based on terephthalic acid, and the polyalcohols reacted therewith include predetermined amounts of ethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, and A crystalline polyester heat-shrinkable film containing at least one of diethylene glycol.
  • the amorphous polyester composition has a dicarboxylic acid component of about 70 to about 100 mol % of terephthalic acid residues, and a diol component of about 40 mol % or less of neopentyl glycol residues; 1,4-Cyclohexanedimethanol residue less than mol % and the remainder is ethylene glycol and diethylene glycol residues.
  • a polyester heat-shrinkable film derived from a plurality of polyester resins (at least a first polyester resin and a second polyester resin) having different crystallinities
  • various characteristics such as the exothermic peak time and exothermic peak area due to isothermal crystallization at a predetermined temperature, and the heat shrinkage rate in the main shrinkage direction, not only can good wearability be obtained, but also during recycling. blocking phenomenon can be effectively and quantitatively suppressed. That is, the present invention provides good wearability and excellent wearability even when the PET bottle covered with the polyester-based heat-shrinkable film is recycled together while maintaining excellent wearability on the PET bottle. It is an object of the present invention to provide a polyester-based heat-shrinkable film in which blocking resistance and blocking resistance are well-balanced and quantitatively obtained.
  • a polyester heat shrink derived from a first polyester resin and a second polyester resin as a plurality of polyester resins having different crystallinity which are reaction products of a polyvalent carboxylic acid and a polyalcohol.
  • a polyester-based heat-shrinkable film characterized by satisfying the following properties (A) to (E) is provided, and the above problems can be solved.
  • the polycarboxylic acid contains at least terephthalic acid, and the reaction amount of ethylene glycol is 50 to less than 90 mol% when the total amount of polyalcohol is 100 mol%.
  • the second polyester resin has a crystallinity in which the polycarboxylic acid contains at least terephthalic acid and the reaction amount of ethylene glycol is 90 mol% or more when the total amount of the polyalcohol is 100 mol%. It must be a polyester resin (hereinafter sometimes referred to as a low-crystalline polyester resin).
  • (D) A polyester heat-shrinkable film having a heat quantity corresponding to the exothermic peak area in the range of 5 to 35 J/g when isothermal crystallization measurement at 150°C including a cooling step at a constant temperature is performed by DSC. be.
  • (E) A polyester heat-shrinkable film having a heat shrinkage rate in the main shrinking direction of 20% to 60%, measured under the heat shrink condition of immersion in hot water at 80°C for 10 seconds.
  • the blocking phenomenon can be effectively and quantitatively suppressed.
  • a polyester-based heat-shrinkable film that satisfies the configurations (A) to (C) provides good wearability and excellent blocking resistance in a well-balanced manner and quantitatively. It can be a polyester-based heat-shrinkable film.
  • the weight-based mixing ratio of the first polyester resin/second polyester resin is set to a value within the range of 20/80 to 80/20. .
  • the first polyester resin contains at least 1,4-cyclohexanedimethanol, and the reaction amount of the 1,4-cyclohexanedimethanol is the total amount of the polyalcohol.
  • the amount (reacted amount) is taken as 100 mol %, it is preferable to use the amorphous polyester resin within the range of 1 to less than 35 mol %.
  • the second polyester resin contains ethylene glycol alone or both ethylene glycol and diethylene glycol.
  • the crystalline polyester resin has a reaction amount of ethylene glycol of 90 mol% or more and a reaction amount of diethylene glycol in the range of 1 to 10 mol%. preferable.
  • the second polyester resin is preferably a homopolyester resin, a post-consumer recycled polyester resin (sometimes referred to as PCRP), or either one.
  • PCRP post-consumer recycled polyester resin
  • the blending amount of the lubricant is 0.01 to 5 parts by weight. is preferably a value within the range of By blending the lubricant and limiting the blending amount in this way, while suppressing the effect on the properties of the polyester heat-shrinkable film, even when it is made into a long roll, the polyester heat-shrinkable It is possible to prevent fusion between films, and in some cases help to further suppress the blocking phenomenon during recycling.
  • the polyester-based heat-shrinkable film of the present invention it is preferable to further satisfy the following property (F).
  • F The thermal shrinkage rate in the direction perpendicular to the main shrinkage direction measured under the thermal contraction conditions of immersion in hot water at 80°C for 10 seconds is a value within the range of -3 to 10%.
  • the polyester-based heat-shrinkable film of the present invention it is preferable to further satisfy the following property (G).
  • G The heat shrinkage stress in the main shrinkage direction measured under the heat shrinkage condition of immersion in hot water at 80°C for 10 seconds is 8 MPa or less.
  • FIGS. 1(a) to 1(c) are diagrams for explaining different forms of the polyester-based heat-shrinkable film.
  • FIGS. 2(a) and 2(b) show the weight-based mixing ratio of the first polyester resin/second polyester resin constituting the polyester-based heat-shrinkable film, evaluation of wearability, and evaluation of blocking resistance. It is a figure where it uses in order to demonstrate the relationship with.
  • FIG. 3 is a diagram for explaining the relationship between the mixing ratio of the first polyester resin/second polyester resin and the thermal shrinkage stress.
  • FIG. 4 is a diagram for explaining the relationship between the mixing ratio of the first polyester resin/second polyester resin and the glass transition temperature.
  • FIG. 5 is a diagram provided for explaining the relationship between the mixing ratio of the first polyester resin/second polyester resin and the peak occurrence time due to isothermal crystallization.
  • FIG. 6 is a diagram for explaining the relationship between the mixing ratio of the first polyester resin/second polyester resin and the thermal shrinkage rate when immersed in hot water at 80° C. for 10 seconds.
  • FIG. 7 is a diagram for explaining the relationship between the peak generation time during isothermal crystallization and the evaluation of blocking resistance.
  • FIGS. 8(a) and 8(b) are provided for explaining DSC charts of polyester heat-shrinkable films (Example 1, Comparative Example 1) obtained by isothermal crystallization including a cooling process at a constant temperature, respectively. It is a diagram.
  • FIG. 9(a) and 9(b) serve to explain the relationship between the amount of heat corresponding to the exothermic peak area due to isothermal crystallization of the polyester-based heat-shrinkable film, and the evaluation of wearability and blocking resistance. It is a diagram.
  • FIG. 10 is a diagram for explaining the relationship between each heat shrink temperature and the heat shrink rate of the polyester-based heat shrink film.
  • FIGS. 11(a) and 11(b) illustrate the relationship between the thermal shrinkage rate of a polyester heat-shrinkable film under the shrinking conditions of immersion in hot water at 80° C. for 10 seconds, and the evaluation of wearability and blocking resistance. It is a figure provided for doing.
  • FIG. 10 is a diagram for explaining the relationship between each heat shrink temperature and the heat shrink rate of the polyester-based heat shrink film.
  • FIGS. 11(a) and 11(b) illustrate the relationship between the thermal shrinkage rate of a polyester heat-shrinkable film under the shrinking conditions of immersion in hot water at 80° C. for 10
  • FIG. 12 is a diagram for explaining a recycling process for PET bottles covered with a polyester-based heat-shrinkable film.
  • FIG. 13(a) is a schematic diagram showing a state in which a blocking phenomenon occurs in the recycling process of a PET bottle covered with a conventional polyester heat-shrinkable film, and
  • FIG. 13(b) shows a state in which the blocking phenomenon does not occur.
  • a schematic diagram of recycled pellets obtained in a PET bottle recycling process is a schematic diagram for recycled pellets obtained in a PET bottle recycling process.
  • a plurality of polyester resins having different crystallinities which are reaction products of polyvalent carboxylic acid and polyalcohol, are first There is provided a polyester heat-shrinkable film derived from the polyester resin and the second polyester resin, wherein the polyester heat-shrinkable film is characterized by satisfying the following properties (A) to (E), and the problems described above can be resolved.
  • the polycarboxylic acid contains at least terephthalic acid, and the reaction amount of ethylene glycol is 50 to less than 90 mol% when the total amount of polyalcohol is 100 mol%.
  • the second polyester resin has a crystallinity in which the polycarboxylic acid contains at least terephthalic acid and the reaction amount of ethylene glycol is 90 mol% or more when the total amount of the polyalcohol is 100 mol%. It must be a polyester resin (sometimes referred to as a low-crystalline polyester resin).
  • (D) A polyester heat-shrinkable film having a heat quantity corresponding to the exothermic peak area in the range of 5 to 35 J/g when isothermal crystallization measurement at 150°C including a cooling step at a constant temperature is performed by DSC. be.
  • (E) A polyester heat-shrinkable film having a heat shrinkage rate in the main shrinking direction of 20% to 60%, measured under the heat shrink condition of immersion in hot water at 80°C for 10 seconds.
  • the polyester-based heat-shrinkable film of the first embodiment will be divided into each component, and will be described in detail with reference to the drawings as appropriate.
  • Polycarboxylic Acid As the polycarboxylic acid, which is one of the polymerization components (raw material components) of the first polyester resin, any compound capable of reacting with polyalcohol to form a polyester structure can be used. Examples include fatty acid dicarboxylic acids such as adipic acid, sebacic acid and azelaic acid; aromatic dicarboxylic acids such as terephthalic acid, naphthalenedicarboxylic acid and isophthalic acid; and 1,4-cyclohexanedicarboxylic acid. or at least one of these ester-forming derivatives.
  • fatty acid dicarboxylic acids such as adipic acid, sebacic acid and azelaic acid
  • aromatic dicarboxylic acids such as terephthalic acid, naphthalenedicarboxylic acid and isophthalic acid
  • 1,4-cyclohexanedicarboxylic acid 1,4-cyclohexanedicarboxylic acid. or at least one of
  • terephthalic acid is preferable because it has good reactivity with polyalcohol, easily forms a polyester structure such as crystallinity, is relatively inexpensive, and is economically advantageous. be. Therefore, when the total amount of the polycarboxylic acid used is 100 mol%, the reaction amount of terephthalic acid is preferably set to a value of 90 mol% or more, and a value within the range of 95 to 100 mol%. is more preferable.
  • the polyalcohol (sometimes referred to as a diol component) as one of the polymerization components of the first polyester resin is characterized by using a mixture containing at least ethylene glycol.
  • diols having an alicyclic structure such as 1,4-cyclohexanedimethanol, diethylene glycol, propanediol, butanediol, neopentyl glycol, and hexane are used as polyalcohols other than ethylene glycol.
  • Aliphatic diols such as diols and at least one other polyalcohol such as aromatic diols are preferably used in combination. This is because by using such a polyalcohol, it is appropriately reacted with the polycarboxylic acid to easily obtain an amorphous polyester resin in which at least the crystallinity/non-crystallinity is controlled.
  • the melting point, heat shrinkage, heat shrinkage stress, etc. of the polyester resin obtained by reacting with the polycarboxylic acid are This is because it can be more easily adjusted to a value within a predetermined range. Therefore, 1,4-cyclohexanedimethanol and/or diethylene glycol are more preferable as other polyalcohols used in combination with ethylene glycol.
  • reaction amount of polyalcohol When using a mixture containing a predetermined amount of ethylene glycol, at least the reaction amount of ethylene glycol is set to a value of 50 to less than 90 mol %. The reason for this is that if the reaction amount of ethylene glycol is less than 50 mol %, problems such as high melt viscosity, poor fluidity, and difficulty in molding may occur. On the other hand, if the reaction amount of ethylene glycol is 90 mol % or more, an excessively large amount of crystalline portion is generated, and the resulting polyester heat-shrinkable film may have significantly deteriorated wearability and other properties.
  • the reaction amount of each polyalcohol, including ethylene glycol can actually be determined from the residual amount of each alcohol component. can be done.
  • the reaction amount of 1,4-cyclohexanedimethanol and diethylene glycol, or either one be within the range of 1 to 35 mol %.
  • the reason for this is that if the reaction amount of 1,4-cyclohexanedimethanol or the like is less than 1 mol %, the amount of amorphous portion produced is reduced, and conversely, the amount of crystalline portion produced is excessively increased. This is because the properties such as wearability of the polyester-based heat-shrinkable film may be remarkably deteriorated.
  • the total reaction amount of 1,4-cyclohexanedimethanol and the like is more preferably set to a value within the range of 5 to less than 30 mol%, and more preferably set to a value within the range of 10 to 28 mol%. .
  • the molar ratio of 1,4-cyclohexanedimethanol and diethylene glycol it is more preferable to set the molar ratio of 1,4-cyclohexanedimethanol and diethylene glycol to a value within the range of 9:1 to 1:9.
  • other dicarboxylic acids or hydroxycarboxylic acids may be used alone without departing from the object of the present invention. More than seeds may be mixed and used.
  • the first polyester resin is basically amorphous, but as a measure of its amorphousness, for example, in DSC measurement, a predetermined melting peak does not appear, or almost no calorific value is not detected. Similarly, in DSC measurement, it is also possible to judge from the fact that the change point of the specific heat indicating the glass transition temperature is shown in a predetermined temperature range. Furthermore, it can also be judged from the fact that the degree of crystallinity measured according to JIS K 7112 is low.
  • the density gradient tube method of JIS K 7112 the density (d) of a sample of about 3 mm square was measured using an aqueous calcium nitrate solution, and the density (dc) of a known polyethylene terephthalate perfect crystal and polyethylene terephthalate perfect non-crystalline
  • the crystal density (da) the crystallinity of the polyester resin can be calculated, and then the proportion of the amorphous portion can be specifically calculated.
  • the glass transition temperature of the first polyester resin is more preferably in the range of 60 to 85°C, more preferably in the range of 65 to 80°C.
  • the glass transition temperature of the first polyester resin can be measured, for example, in DSC measurement by the following procedure (the same applies hereinafter). 1) As a 1st-Run, the temperature of the first polyester resin as a measurement sample is raised from room temperature to about 300°C at a heating rate of 10°C/min. 2) Then, the temperature is rapidly lowered from 300° C. to room temperature at a rate of about 30° C./min. 3) Next, in the 2nd-run, the temperature is raised from room temperature to about 300°C at a heating rate of 10°C/min. Then, the change point of the specific heat appearing on the DSC chart obtained in the 2nd-run can be taken as the glass transition temperature of the first polyester resin.
  • the melting point When the first polyester resin has a melting point, it is preferable to set the melting point to a value within the range of 190 to 270°C. The reason for this is that if the melting point is less than 190°C, the display label using the polyester heat-shrink film becomes viscous in the drying process when recycling PET bottles, etc., and the flakes, which are recycled pieces, become viscous. This is because it may cause the blocking phenomenon to occur easily. On the other hand, if the melting point exceeds 270° C., the amount of heat required for the extrusion processing and stretching processing of the raw polyester heat-shrinkable film sheet becomes too high, making processing difficult and making it difficult to control the heat shrinkage rate.
  • the melting point is more preferably set to a value within the range of 200 to 270°C, and more preferably set to a value within the range of 210 to 270°C.
  • Tm peak temperature
  • Intrinsic Viscosity Further, it is preferable to set the intrinsic viscosity (IV value) of the first polyester resin to a value within the range of 0.6 to 0.85 dL/g.
  • IV value intrinsic viscosity
  • the melt viscosity is too low, causing problems in extrusion moldability, and furthermore, in recycling, good blocking resistance is obtained. This is because there may not be.
  • the intrinsic viscosity exceeds 0.85 dL/g, the melt viscosity will be too high, causing problems in extrusion moldability, and furthermore, if good wearability cannot be obtained.
  • the first polyester resin may contain antioxidants, weather stabilizers, antistatic agents, antifogging agents, metallic soaps, waxes, antifungal agents, antibacterial agents, and nucleating agents, if necessary. , a flame retardant, a lubricant (slip agent) and the like in a predetermined amount (for example, 0.01 to 10 parts by weight of the total amount).
  • a flame retardant for example, 0.01 to 10 parts by weight of the total amount.
  • the method of adding the additive is not particularly limited, and a known method can be used.
  • an inorganic lubricant such as calcium carbonate-based particles, silica-based particles, or glass-based particles.
  • the type is not particularly limited, and inorganic lubricants and organic lubricants commonly used for films can be used singly or in combination. More specifically, examples of inorganic lubricants include microparticles made of calcium carbonate particles, silica particles, glass particles, zeolite, talc, kaolin, and the like.
  • organic lubricants include fine particles made of crosslinked polymethyl methacrylate, crosslinked polystyrene, silicone rubber, silicone copolymer, polyamide, condensed resin having a triazine ring, and the like. Microparticles made of polymers are preferred.
  • Second polyester resin Polycarboxylic acid
  • the polycarboxylic acid which is one of the polymerization components (raw material components) of the second polyester resin, any compound that can react with polyalcohol to form a polyester structure can be used. Although not particularly limited, it is characterized by containing at least terephthalic acid.
  • terephthalic acid is highly reactive with polyalcohols, readily forms a crystalline polyester structure, is relatively inexpensive, and is economically advantageous. Therefore, when the total amount of the polycarboxylic acid used is 100 mol%, the reaction amount of terephthalic acid is preferably set to a value of 90 mol% or more, and a value within the range of 95 to 100 mol%. is more preferable.
  • polycarboxylic acids other than terephthalic acid such as adipic acid, sebacic acid, and azelaic acid can be used within the scope of the present invention.
  • adipic acid adipic acid
  • sebacic acid azelaic acid
  • azelaic acid a predetermined amount of at least one of fatty acid dicarboxylic acid, naphthalene dicarboxylic acid, aromatic dicarboxylic acid such as isophthalic acid, alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, or an ester-forming derivative thereof. is also preferred.
  • the polyvalent carboxylic acid other than terephthalic acid is isophthalic acid, it is easily mixed uniformly with terephthalic acid, increases the transparency and heat shrinkage of the polyester-based heat-shrinkable film, and further blocks during recycling. The phenomenon can be suppressed more effectively and quantitatively.
  • Type of Polyalcohol The feature is that at least ethylene glycol is used as a polyalcohol (sometimes referred to as a diol component) as one of the polymerization components of the second polyester resin.
  • a polyalcohol sometimes referred to as a diol component
  • the crystallinity can be adjusted to the desired range, and the blocking phenomenon can be suppressed more effectively and quantitatively in relation to the first polyester resin.
  • Polyalcohols other than ethylene glycol include aliphatic diols such as diethylene glycol, propanediol, butanediol, neopentyl glycol and hexanediol, or alicyclic diols different from 1,4-cyclohexanedimethanol, It is also preferable to blend at least one aromatic diol or the like. This is because by using such a polyalcohol, it is moderately reacted with the polycarboxylic acid to easily obtain a low-crystalline polyester resin in which at least the crystallinity/non-crystallinity is controlled.
  • diethylene glycol or neopentyl glycol is selected as another polyalcohol, and a combination of ethylene glycol and diethylene glycol or a combination of ethylene glycol and neopentyl glycol is more preferable. That is, by using a linear specific polyalcohol having no branch or a linear chain having a branch, the melting point, heat shrinkage rate, heat shrinkage stress, etc. of the polyester resin obtained by reacting with the polycarboxylic acid are adjusted. This is because it can be more easily adjusted to a value within a predetermined range.
  • reaction amount of polyalcohol is 90 mol% or more when the total amount of polyalcohol used as one of the polymerization components of the second polyester resin is 100 mol%. is preferred.
  • the reason for this is that if the reaction amount of ethylene glycol or the like is less than 90 mol %, the amount of crystals formed is reduced, making it difficult to exhibit good crystallinity when mixed with the first polyester resin. This is because there are cases. That is, it may be difficult to effectively and quantitatively suppress the blocking phenomenon during recycling. Therefore, the reaction amount of ethylene glycol or the like is more preferably set to a value of 95 mol % or more, and more preferably set to a value within the range of 99 to 100 mol %.
  • diols having an alicyclic structure such as diethylene glycol, hydroxycarboxylic acids, etc. may be used alone. may be used, or two or more may be used in combination.
  • polyester resin as shown in (1) to (3) above, a predetermined polycarboxylic acid and a predetermined polyol are subjected to a condensation reaction at a predetermined ratio. It is also preferable to use a homopolyester resin, that is, a polyester resin composed only of terephthalic acid and ethylene glycol. As the second polyester resin, it is also preferable to use a post-consumer recycled polyester resin, that is, a polyester resin obtained by collecting used PET bottles or the like, washing, pulverizing, drying and pelletizing. Furthermore, it is also preferable to use an unused polyester resin together with at least one of a homopolyester resin and a post-consumer recycled polyester resin.
  • the second polyester resin According to such a second polyester resin, it is economically advantageous because it reduces waste, contributes to the reuse of environmental resources, and is inexpensive. Therefore, with a predetermined relationship between the first polyester resin and the second polyester resin, the balance between good wearability and excellent anti-blocking property is further improved and can be obtained quantitatively.
  • the crystallinity of the second polyester resin can be determined from the position of the melting peak (melting point) of the crystal portion by DSC, the heat quantity of the melting peak, etc. can judge. Similarly, the degree of crystallinity measured according to JIS K 7112 can be measured and judged therefrom.
  • the melting point of the second polyester resin is set to a value within the range of 190 to 270.degree.
  • the reason for this is that if the melting point is less than 190°C, the display label using the polyester heat shrinkable film tends to have stickiness in the drying process when recycling the PET bottles with the polyester heat shrinkable film attached. This is because the flakes, which are recycled pieces, may adhere to each other, and the blocking phenomenon may easily occur.
  • the melting point exceeds 270°C, the amount of heat required for the extrusion and stretching of the original sheet of the polyester heat-shrinkable film used for the label becomes too high, making the processing difficult, or This is because the wearability during use may be remarkably deteriorated.
  • the melting point of the polyester resin is more preferably in the range of 200 to 270°C, more preferably in the range of 220 to 270°C.
  • the melting point of the polyester resin can be measured, for example, as the peak temperature (Tm) of the heat of fusion shown as an endothermic reaction in the profile obtained using DSC (the same applies hereinafter).
  • Tm peak temperature
  • the crystallinity of the polyester resin can be estimated from the area, half-value width, etc. of the peak of the heat of fusion.
  • the second polyester resin has a glass transition temperature
  • the glass transition temperature is less than 50°C, the display label using the polyester heat shrinkable film tends to have viscosity in the drying process when recycling the PET bottles with the polyester heat shrinkable film attached. This is because the recycled pieces may stick to each other and the blocking phenomenon may easily occur.
  • the glass transition temperature exceeds 90°C, the amount of heat required for the extrusion processing and stretching processing of the original sheet of the polyester heat-shrinkable film becomes too high, making processing difficult and controlling the heat shrinkage rate.
  • the temperature is more preferably set to a value within the range of 60 to 85°C, and more preferably set to a value within the range of 65 to 80°C. .
  • Intrinsic Viscosity Further, it is preferable to set the intrinsic viscosity (IV value) of the second polyester resin to a value within the range of 0.6 to 0.85 dL/g.
  • IV value intrinsic viscosity
  • the melt viscosity is too low, which may cause problems in extrusion moldability.
  • the intrinsic viscosity exceeds 0.85 dL/g, the melt viscosity is too high, which may cause problems in extrusion moldability. Therefore, it is more preferable to set the intrinsic viscosity to a value within the range of 0.63 to 0.83 dL/g, more preferably to a value within the range of 0.65 to 0.8 dL/g.
  • the second polyester resin may contain antioxidants, weather stabilizers, antistatic agents, antifogging agents, metallic soaps, waxes, antifogging agents, if necessary. It is also preferable to add various additives such as fungicides, antibacterial agents, nucleating agents, flame retardants, and lubricants (slip agents) within a predetermined amount range. Moreover, the method of adding the additive is not particularly limited, and a known method can be used.
  • Polyester-based heat-shrinkable film (1)
  • Mixing ratio of first polyester resin/second polyester resin Weight-based mixing ratio of first polyester resin/second polyester resin (hereinafter, sometimes simply referred to as mixing ratio ) is preferably set to a value within the range of 20/80 to 80/20.
  • mixing ratio is more preferably a value within the range of 25/75 to 75/25, and a value within the range of 30/70 to 70/30. It is more preferable to
  • the mixing ratio of the first polyester resin/second polyester resin is a value within a relatively wide range of 20/80 to 80/20, more preferably 30/70 to It is understood that values within the 70/30 range, respectively, provide relatively good or well acceptable wearability ratings.
  • the horizontal axis represents the mixing ratio of the first polyester resin/second polyester resin constituting the polyester heat-shrinkable film
  • the vertical axis represents the evaluation of blocking resistance ( relative value) is taken and shown. Then, from the characteristic curve in FIG. 2(b), in the mixing ratio range of 100/0 to less than 80/20, the smaller the mixing ratio of the first polyester resin, the better the evaluation of blocking resistance. Tend. Moreover, when the mixing ratio is in the range of 80/20 to 20/80, good anti-blocking evaluation is obtained regardless of the mixing ratio.
  • the polyester-based heat-shrinkable film of the present invention even if the mixing ratio of the first polyester resin/second polyester resin is set to a value within a relatively wide range of at least 20/80 to 80/20, more preferably 30 It is understood that values within the range of /70 to 70/30 also provide good or sufficiently acceptable blocking resistance.
  • FIG. 3 shows the relationship between the mixing ratio of the first polyester resin/second polyester resin and the thermal shrinkage stress (80° C.) of the polyester heat shrinkable film.
  • the measurement data is limited to the examples in which the heat shrinkage rate at 80°C is within the range of 20 to 60% in Fig. 3.
  • the mixing ratio is set to a value within a relatively wide range of 20/80 to 80/20, more preferably a value within a range of 30/70 to 70/30. It is understood that the heat shrinkage stress value can be controlled to a low value of 8 MPa or less, and effects such as deformation prevention of the wearable object can be exhibited.
  • FIG. 4 shows the relationship between the mixing ratio of the first polyester resin/second polyester resin and the glass transition temperature of the polyester-based heat-shrinkable film. From the characteristic curve in FIG. 4, even if the mixing ratio is a value within a relatively wide range of 20/80 to 80/20, more preferably a value within a range of 30/70 to 70/30, By relatively reducing the blending ratio of the first polyester resin or, conversely, relatively increasing the blending ratio of the second polyester resin, the glass transition temperature can be increased to a higher level with extremely high accuracy and quantitatively. It is understood that the mixing ratio is a value within a relatively wide range of 20/80 to 80/20, more preferably a value within a range of 30/70 to 70/30.
  • FIG. 5 shows the relationship between the mixing ratio of the first polyester resin/second polyester resin and the peak generation time of isothermal crystallization (hereinafter, sometimes simply referred to as the peak generation time), which will be described later.
  • the mixing ratio is set to a value within a relatively wide range of 20/80 to 80/20, more preferably a value within a range of 30/70 to 70/30. It is understood that the peak generation time can be controlled with extremely high accuracy and quantitatively to a value exceeding 5 minutes and within 12 minutes, more preferably within 5.5 minutes and within 9 minutes.
  • FIG. 6 shows the relationship between the mixing ratio of the first polyester resin/second polyester resin and the thermal shrinkage rate when immersed in hot water at 80° C. for 10 seconds.
  • the stretch ratio in the main shrinkage direction may significantly affect the thermal shrinkage rate at 80 ° C.
  • the mixing ratio is set to a value within a relatively wide range of 20/80 to 80/20, more preferably a value within a range of 30/70 to 70/30. It is understood that the thermal shrinkage rate at a predetermined temperature can be controlled quantitatively to a value within the range of 20 to 60%, more preferably within the range of 25 to 50%, with extremely high accuracy.
  • the characteristic (C) is a cooling process at a constant temperature (usually -10 to 10 ° C., 0 ° C. as an example) by DSC. including the cooling step time at a constant temperature (usually 1 to 5 minutes, usually 5 minutes) when performing isothermal crystallization measurements at 150 ° C., and exotherm within 12 minutes from the start It is characterized by being a polyester-based heat-shrinkable film in which a peak appears.
  • isothermal crystallization measurement at 150° C. is performed including a cooling process time (5 minutes) at a constant temperature (0° C.), and 3.8 degrees from the start of heating at 150° C.
  • the reason for this is that the exothermic peak corresponding to crystallization appears in a relatively short time, so that the blocking phenomenon can be effectively and effectively prevented in the drying process when recycling PET bottles with the polyester heat-shrinkable film attached. This is because it can be suppressed quantitatively.
  • isothermal crystallization measurement was performed at 150°C, including a cooling process time (5 minutes) at a constant temperature (0°C), and 12 minutes had passed since the start of heating at 150°C. This is because if the exothermic peak does not appear even later, it is judged that the crystallization under the prescribed conditions is slow. Therefore, in the drying process when recycling PET bottles and the like, the slowness of crystallization of the polyester-based heat-shrinkable film tends to cause a blocking phenomenon in which flakes, which are recycled pieces, adhere to each other. Therefore, as the characteristic (C), the peak generation time is more preferably within 10 minutes, more preferably within 9 minutes, including the cooling process time at a constant temperature.
  • the generation time of the exothermic peak due to isothermal crystallization of the polyester heat-shrinkable film (including the cooling process time at a constant temperature.
  • the peak generation time it may be simply referred to as the peak generation time.
  • the evaluation of blocking resistance that is, in FIG. 7, the horizontal axis represents the peak generation time, and the vertical axis represents the evaluation (relative value) of anti-blocking property. From the characteristic curve in FIG. 7, a good evaluation of blocking resistance can be obtained if the peak generation time is 12 minutes or less, but if the peak generation time exceeds 12 minutes, the evaluation of blocking resistance is poor. A significant downward trend is observed.
  • the blocking phenomenon can be effectively suppressed by setting the peak occurrence time during isothermal crystallization to 12 minutes or less, more preferably exceeding 5 minutes and within 10 minutes. and can be quantitatively suppressed.
  • Heat quantity corresponding to exothermic peak area due to isothermal crystallization As shown in FIG. It is characterized by being a polyester heat-shrinkable film having a heat quantity corresponding to an exothermic peak area of 5 to 35 J/g when subjected to thermal measurement. The reason for this is that it includes a cooling step at a constant temperature, and by isothermal heating at a given temperature, the resin can be This is because crystallization occurs depending on the crystallinity of the. By confirming the appearance of the corresponding exothermic peak, the blocking phenomenon can be effectively and quantitatively suppressed in the drying process when recycling the PET bottles with the polyester heat-shrinkable film attached. .
  • FIGS. 9A and 9B the relationship between the amount of heat corresponding to the exothermic peak area due to isothermal crystallization of the polyester heat-shrinkable film and the evaluation of wearability and blocking resistance is shown.
  • FIG. 9A is a diagram for explaining the relationship between the amount of heat corresponding to the exothermic peak area due to isothermal crystallization and the evaluation of wearability.
  • the amount of heat (J/g) corresponding to the area is taken, and the vertical axis shows the evaluation of wearability (relative value).
  • the wearability evaluation is considered to be significantly affected by the thermal shrinkage rate under predetermined measurement conditions.
  • the description is limited to the data of the measurement and wearability evaluation in Examples in which the heat shrinkage rate at °C is within the range of 20 to 60%. From the characteristic curve in FIG. 9(a), even if the amount of heat corresponding to the exothermic peak area is less than 5 J/g, more than 5 J/g, and less than 35 J/g, the attached A relative value of more than 2 was obtained for the sex evaluation. However, when the amount of heat corresponding to the exothermic peak area exceeds 35 J/g, the wearability evaluation becomes less than 2 and tends to decrease.
  • the amount of heat corresponding to the exothermic peak area is set to a value within a relatively wide range of 8 to 32 J/g, more preferably 11 to 29 J/g. It is understood that good wearability can be obtained effectively and quantitatively by setting the values within the range of .
  • the horizontal axis represents the amount of heat (J/g) corresponding to the exothermic peak area due to isothermal crystallization of the polyester heat-shrinkable film
  • the vertical axis represents the evaluation of blocking resistance ( relative value) is taken and shown. From the characteristic curve in FIG. 9(b), it can be seen that the evaluation of anti-blocking property tends to decrease when the amount of heat corresponding to the exothermic peak area is less than 5 J/g. Also, even if the heat quantity corresponding to the exothermic peak area is 5 to 35 J/g, or even a value higher than that, there is a tendency to obtain good blocking resistance evaluation regardless of the heat quantity.
  • the amount of heat corresponding to the exothermic peak area is set to a value within a relatively wide range of 8 to 32 J/g, more preferably a value within the range of 11 to 29 J/g, both have good wearability and good wearability. , the blocking phenomenon can also be effectively and quantitatively suppressed.
  • the polyester-based heat-shrinkable film is characterized by having the following property (E) with respect to heat shrinkage under predetermined temperature conditions. That is, the thermal shrinkage rate in the main shrinkage direction (usually the TD direction at the time of production) measured under the thermal shrinkage conditions of immersion in hot water at 80 ° C. for 10 seconds (sometimes referred to as the thermal shrinkage rate 1) is 20 to 20. It is characterized by having a value within the range of 60%. The reason for this is that by controlling the thermal contraction rate in the TD direction when thermally shrunk at a predetermined temperature to a value within a predetermined range, wrinkles are less likely to occur and sink marks are less likely to occur. , it is easy to obtain a good appearance.
  • E the thermal shrinkage rate in the main shrinkage direction
  • the thermal shrinkage rate 1 is 20 to 20. It is characterized by having a value within the range of 60%. The reason for this is that by controlling the thermal contraction rate in the TD direction when thermally shrunk at a predetermined temperature to
  • the thermal shrinkage rate in the TD direction is set to a value within the range of 25 to 55%, and more preferably to a value within the range of 30 to 50%.
  • FIG. 10 shows each heat shrink temperature (70 ° C., 80 ° C., 90 ° C., 100 ° C.) in the polyester heat shrinkable films of Examples 1 to 6 and Comparative Examples 1 to 5, and the temperature obtained at that temperature It shows the relationship with the thermal shrinkage rate.
  • the higher the heat shrinkage temperature the larger the value of the heat shrinkage obtained.
  • the value of the heat shrinkage tends to be considerably large.
  • the heat shrinkage temperature exceeds 80°C, particularly in the range of 90°C to 100°C, the value of the heat shrinkage tends to saturate in the range of about 30% to 50%.
  • FIG. 11(a) and 11(b) are diagrams showing the relationship between the heat shrinkage rate of the polyester-based heat-shrinkable film under predetermined shrinkage conditions, and the evaluation of wearability and anti-blocking property. That is, in FIG. 11(a), the horizontal axis indicates the thermal shrinkage rate (%) of the polyester heat-shrinkable film when immersed in hot water at 80° C. for 10 seconds, and the vertical axis indicates the evaluation of wearability ( relative value) is taken and shown. From the characteristic curve in FIG. 11(a), when the thermal shrinkage rate is less than 20%, the wearability evaluation tends to be extremely low.
  • the polyester-based heat-shrinkable film of the present invention by setting the heat shrinkage rate to a value within the range of 20 to 60%, more preferably within the range of 25 to 50%, evaluation of good wearability is stable. It is understood that
  • the horizontal axis shows the thermal shrinkage rate (%) of the polyester heat-shrinkable film when immersed in hot water at 80° C. for 10 seconds, and the vertical axis shows the evaluation of blocking resistance. (relative value) is taken and shown. Further, from the characteristic curve in FIG. 11(a), even if the thermal shrinkage rate is less than 20%, a good evaluation of blocking resistance is obtained. , almost the same, good evaluation of anti-blocking property is obtained. On the other hand, when the heat shrinkage rate exceeds 50% and reaches about 60%, the evaluation of blocking resistance drops significantly, but evaluation of blocking resistance to the extent that it can be used in practice is obtained.
  • the polyester-based heat-shrinkable film of the present invention by setting the heat-shrinkage rate to a value within the range of 20 to 60%, more preferably within the range of 25 to 50%, the blocking phenomenon can be effectively and It is understood that it can be suppressed quantitatively.
  • the thermal shrinkage rate (thermal shrinkage rate 2 ) is preferably set to a value within the range of -3 to 10%. The reason for this is that by controlling the heat shrinkage rate in the MD direction, which is measured under predetermined heat shrink conditions, within a predetermined range, wrinkles are less likely to occur and sink marks are less likely to occur, resulting in a good appearance.
  • the heat shrinkage rate in the MD direction is more preferably set to a value within the range of -2 to 8%, and more preferably set to a value within the range of 0 to 5%.
  • the thermal shrinkage stress in the main shrinkage direction measured under the thermal shrinkage condition of immersion in hot water at 80°C for 10 seconds is preferably 8 MPa or less.
  • the reason for this is that if the heat shrinkage stress exceeds 8 MPa, the same heat shrinkage stress as the polyvinyl chloride heat shrink film cannot be obtained, and as a result, it can be applied to various PET bottles from thin to thick. This is because versatility may not be obtained. Therefore, it is more preferable to set the thermal shrinkage stress to a value within the range of 1 to 7 MPa, and more preferably to a value within the range of 2 to 6 MPa.
  • the heat shrinkage stress at 80 ° C. is measured using a film heat shrinkage tester conforming to ISO 14616-1997, and the heat shrinkage force (N / 15 mm) at 85 ° C. for a long test piece is It can be calculated by dividing by the thickness of the test piece.
  • Thickness and Haze (7)-1 Thickness The thickness of the polyester heat-shrinkable film can be changed according to the shape of various PET bottles, but it is usually within the range of 20 to 100 ⁇ m. preferably. The reason for this is that if the thickness of the polyester heat-shrinkable film is less than 20 ⁇ m, handling becomes difficult and the breaking strength and the like may be significantly reduced. On the other hand, if the thickness of the polyester heat-shrinkable film exceeds 100 ⁇ m, it may not be uniformly heat-shrunk when heated at a predetermined temperature, or the film may not be manufactured to have a uniform thickness.
  • the thickness of the polyester heat-shrinkable film is more preferably in the range of 25-70 ⁇ m, more preferably in the range of 30-50 ⁇ m.
  • the thickness of the polyester-based heat-shrinkable film can be measured using a micrometer (manufactured by Mitutoyo Co., Ltd., product name "Thickness Gauge 547-401") in accordance with ISO4593.
  • the polyester heat-shrinkable film before shrinking has a haze value of 10% or less as measured according to ASTM D1003.
  • the reason for this is that by limiting the haze value to a predetermined value or less, it becomes easy to align the PET bottle and examine the contents, and not only before heat shrinking but also after heat shrinking, the transparency is improved. This is because it is possible to obtain a PET bottle containing a polyester-based heat-shrinkable film that is excellent in appearance, decorativeness, and the like.
  • the haze value exceeds 10%, the alignment with respect to the PET bottle or the like and the recognizability of the contents may be deteriorated, and even if the decorative layer is provided, the coloring property and the like may be significantly deteriorated. be.
  • the haze value is excessively small, the types and blending amounts of the usable polymer components are limited, making it difficult to control the production process, which may excessively reduce the production efficiency. Therefore, the haze value is more preferably in the range of 1-8%, more preferably in the range of 2-5%.
  • the polyester-based heat-shrinkable film may be provided with various functions on its surface or inner surface, if necessary. It is also preferred to have a functional layer.
  • a functional layer examples include a coating layer for imparting surface lubricity, stain resistance, weather resistance, etc., a transfer layer, and a printing layer for imparting design properties.
  • a coating layer using a surfactant is particularly preferable as a functional layer because it greatly contributes to the improvement of antistatic properties and surface lubricity.
  • other resin layers 10a and 10b containing at least one of these various additives are preferably laminated on one or both sides of the polyester-based heat-shrinkable film 10.
  • the resin as the main component constituting the other resin layer may be a polyester resin similar to the polyester heat-shrinkable film, or an acrylic resin, olefin resin, urethane resin, or rubber different from it. It is preferable that it is at least one such as a system resin.
  • the polyester-based heat-shrinkable film is made into a multilayer structure to further improve the hydrolysis prevention effect and mechanical protection, or as shown in FIG. It is also preferable to provide a shrinkage rate adjusting layer 10c on the surface of the polyester-based heat-shrinkable film 10 so that the shrinkage is uniform.
  • a shrinkage rate adjusting layer can be laminated as a predetermined layer made of a polyester resin or the like by an adhesive, a coating method, a heat treatment, or the like depending on the shrinkage of the polyester-based heat-shrinkable film.
  • antioxidants are added inside or on the surface of the polyester heat-shrinkable film as necessary.
  • various additives such as agents, nucleating agents, flame retardants, and lubricants (slip agents) in a predetermined amount (for example, a ratio of 0.01 to 10 parts by weight of the total amount), or paint (ink), It is also preferable to apply a wettability improver, an antistatic agent, or the like.
  • an inorganic lubricant inorganic lubricant, an organic lubricant, or either one is added so as to improve the slipperiness of the polyester-based heat-shrinkable film and enable easy winding, etc. when made into a long roll.
  • inorganic lubricants include, for example, at least one fine particle made of calcium carbonate particles, silica particles, glass particles, zeolite, talc, kaolin, or the like.
  • organic lubricants include at least one fine particle made of crosslinked polymethyl methacrylate, crosslinked polystyrene, silicone rubber, silicone copolymer, polyamide, condensed resin having a triazine ring, etc.
  • 2nd Embodiment is a manufacturing method of the polyester-type heat-shrinkable film of 1st Embodiment.
  • a recycling process for PET bottles covered with a polyester-based heat-shrinkable film will also be described. Each step will be described below in detail.
  • Raw Material Preparation and Mixing Process As raw materials, the first polyester resin and the second polyester resin, and if necessary, additives and other additive resins are prepared. Next, it is preferable to put the raw materials into a stirring vessel while weighing them, and to mix and stir them using a stirring device until they become uniform.
  • the obtained raw material is preferably heated to a predetermined temperature (usually -10°C lower than the crystallization temperature) and dried in an absolutely dry state.
  • a predetermined temperature usually -10°C lower than the crystallization temperature
  • polyester-based heat-shrinkable film Next, using a heat-shrinkable film manufacturing device (tenter), the obtained original sheet is heated and pressed while being moved on or between rolls to form a polyester-based heat-shrinkable film. is preferred.
  • a stretching treatment method for expressing such shrinkability it is preferable to employ an inflation method, a roll stretching method, a tenter stretching method, or a combination thereof.
  • sheet molding by cast molding and a combination of roll stretching and tenter stretching are more preferable.
  • the width of the film is basically expanded at a predetermined stretching temperature and draw ratio, and the film is stretched in a predetermined direction while being heated and pressed to form the polyester heat-shrinkable film. It is preferred to crystallize the polyester molecules into a predetermined structure. Then, by solidifying in that state, a heat-shrinkable polyester-based heat-shrinkable film for use as a decoration, label, or the like can be produced.
  • the original film sheet is heated to a temperature equal to or higher than the glass transition temperature of the resin, and the main stretching direction (the original film sheet) It is preferably stretched 3 to 8 times, preferably 4 to 6 times in the width direction (ie, TD direction).
  • polyester heat-shrinkable film having more uniform shrinkability and the like can be provided by measuring the following properties and the like through a predetermined inspection process and confirming that the values fall within a predetermined range.
  • Step of Mounting Polyester Heat-Shrinkable Film It is preferable to carry out the step of mounting the obtained polyester heat-shrinkable film on a PET bottle according to the following procedure. 1) Prepare a PET bottle filled with commercially available drinking water. 2) Next, the widthwise end portions of the polyester-based heat-shrinkable film were welded with an impulse sealer (manufactured by Fuji Impulse Co., Ltd.) to obtain a cylindrical label. 3) Then, the cylindrical PET bottle is covered with the tubular label. 4) As an example, it is placed on a belt conveyor in a steam tunnel maintained at 80°C and moved at a passing speed of 6m/min, and the cylindrical label is heat-shrunk so that it adheres to the cylindrical PET bottle. . An infrared lamp, a warm bath, or the like can be used as other heating jigs instead of or in combination with the steam tunnel.
  • the step represented by S1 is a step of compressing and packing used PET bottles to form a so-called bale.
  • the once-baled used PET bottles are loosened into lumps of several centimeters in length by a debaling device, and PVC bottles, colored bottles, etc. are sorted out and removed. It is a process to do. Through such a process, it is possible to efficiently recycle only the target used PET bottles.
  • the step represented by S3 is a step of washing the used PET bottle to remove contaminants and deposits.
  • the step represented by S4 is a step of crushing the washed PET bottle into flakes having a length of several millimeters using a predetermined crusher. Through such a pulverization process, although the average particle size is several millimeters, the thickness is made into flakes of microns, which makes it easier to handle in the next step.
  • the step represented by S5 is a step of removing the ink layer provided on the heat-shrinkable film.
  • it is a step of removing the ink layer by immersing the flakes obtained in S4 in an ink removing liquid such as hot alkaline water such as sodium hydroxide aqueous solution. That is, it is possible to further reduce the blocking phenomenon caused by the ink layer in the subsequent drying process.
  • the step represented by S6 is a step of separating the ink and the ink remover and washing the separated flakes.
  • the step represented by S7 is then the step of drying the washed flakes obtained in S6. By drying in this way, the handleability in the next step can be further improved.
  • step represented by S8 is a step of heating and melting the flakes obtained in S7 and using a pelletizer or the like to obtain recycled pellets having an average particle size of 1 to 8 mm, for example. Recycling pellets having a uniform average particle diameter in this manner can facilitate reuse in various applications.
  • the polyester-based heat-shrinkable film of the present invention can suppress the blocking phenomenon even when the film is attached to the PET bottle, and efficiently and economically produce recycled pellets.
  • polyester-based heat-shrinkable film of the present invention will be described in more detail below based on examples. However, the scope of rights of the present invention shall not be narrowed by the description of the examples without any particular reason.
  • Amorphous polyester resins and crystalline polyester resins (low-crystalline polyester resins) used in the examples are as follows.
  • Example 1 Preparation of Polyester Heat Shrinkable Film PET1 and PET2 were prepared as a first polyester resin and a second polyester resin, respectively. Next, 700 g of PET1, 300 g of PET2, and 10 g of lubricant which were weighed were put into a stirring container and uniformly mixed to obtain a forming raw material.
  • this forming raw material was extruded using a vented twin-screw extruder at an extrusion temperature of 245° C. to obtain a raw sheet having a thickness of 250 ⁇ m.
  • the preheating temperature is 120 ° C.
  • the stretching temperature is 84 ° C.
  • the heat setting temperature is 86.5 ° C.
  • the stretching ratio MD direction: 1.06 times, TD direction: 4 times
  • polyester heat-shrinkable film (1) Isothermal crystallization peak generation time DSC (manufactured by PerkinElmer, input compensation type double furnace differential scanning calorimeter, product name “DSC8500”, hereinafter the same) was used. The obtained polyester heat-shrinkable film was subjected to heat treatment in the following pre-process, and then subjected to isothermal crystallization measurement. That is, based on the DSC chart obtained in the isothermal crystallization measurement, the time from the start to the occurrence of an exothermic peak due to isothermal crystallization was measured, including a cooling step (5 minutes) at a constant temperature (0 ° C.). .
  • pre-process 1) The measurement sample was held isothermally at 30°C for 1 minute. 2) Then, the temperature was raised from 30°C to 300°C at a temperature elevation rate of 750°C/min. 3) Then, it was kept isothermally at 300° C. for 5 minutes. 4) It was then quenched to 0°C.
  • the heat shrinkage of the obtained polyester heat-shrinkable film was measured according to ASTM D2732-08. That is, it is cut into a square shape having a length of 100 mm along the main shrinkage direction (TD direction) and a length of 100 mm along the direction perpendicular to the main shrinkage direction (MD direction), and is used as a measurement sample. bottom.
  • the measurement samples of the polyester-based heat-shrinkable film were immersed in a constant temperature bath containing hot water of 80° C. for 10 seconds to heat-shrink. Then, at each temperature, from the dimensional changes before and after the heat treatment, the main shrinkage direction and the heat shrinkage rate (%) in the direction orthogonal to the main shrinkage direction were calculated according to the following formula (1).
  • the heat shrinkage force of the obtained polyester heat shrinkable film was measured according to ISO14616-1997. That is, the obtained polyester-based heat-shrinkable film was cut into strips having a length of 90 mm along the main shrinkage direction and a length of 15 mm along the direction perpendicular to the main shrinkage direction, and then tested. cut to pieces.
  • the heat shrinkage force (N/15 mm) of the test piece when immersed in hot water at 80° C. for 10 seconds was measured.
  • the obtained thermal shrinkage force was divided by the thickness (40 ⁇ m) to obtain the thermal shrinkage stress (MPa) at 80°C.
  • the obtained polyester-based heat-shrinkable film was evaluated for blocking resistance by the following procedure in accordance with APR Document Code: PET-S-08.
  • a polyester heat-shrinkable film was attached around the cylindrical bottle, and the inside of the container was emptied and washed.
  • the bottle with the polyester heat-shrinkable film attached thereto was pulverized into flakes having a diameter of 12.5 mm or less.
  • 1 kg of the pulverized flakes was placed in a heat-resistant container and heated in an oven at 210°C. 3) After 90 minutes, the heat-resistant container containing the flakes was taken out from the oven and allowed to cool to room temperature. 4) It was then classified using a 12.5 mm mesh sieve. 5) After that, the mass of aggregates that could not pass through the sieve was measured, and the aggregation rate (%) was calculated from the following formula (2).
  • ⁇ The mass of the aggregate is less than 5%.
  • ⁇ Mass of aggregates is a value of 5% to less than 10%.
  • x Mass of aggregates is a value of 10% or more.
  • the polyester-based heat-shrinkable film obtained was evaluated for wearability to a PET bottle according to the following criteria. That is, 10 cylindrical PET bottles filled with commercially available drinking water were prepared (trade name: Evian, volume: 500 ml). Next, the ends of the polyester heat-shrinkable film in the width direction were welded with an Impulse Sealer (manufactured by Fuji Impulse Co., Ltd.) so as to correspond to the cylindrical PET bottles, and 10 cylindrical labels were produced. Then, ten cylindrical PET bottles were each covered with the obtained ten cylindrical labels to obtain measurement samples.
  • an Impulse Sealer manufactured by Fuji Impulse Co., Ltd.
  • the label was placed on a belt conveyor and moved at a passing speed of 6 m/min, and the cylindrical label was thermally shrunk so as to be in close contact with the cylindrical PET bottle. .
  • the finish of the cylindrical label in a heat-shrunk state that is, the presence or absence of defects such as wrinkles, insufficient shrinkage, label folding, shrinkage whitening, etc., was visually observed. It was evaluated according to the standard.
  • ⁇ No defect at all among 10 measurement samples.
  • Good 1 or more defects on average and 3 or less defects on average in 10 measurement samples.
  • ⁇ An average of 4 or more defects and an average of 5 or less defects in 10 measurement samples.
  • x An average of 6 defects or more in 10 measurement samples.
  • Example 2 In Example 2, as shown in Table 1, a polyester heat-shrinkable film was produced and evaluated in the same manner as in Example 1, except that PET3 was used as the second polyester resin instead of PET2. The results obtained are shown in Table 2.
  • Example 3 In Example 3, as shown in Table 1, a polyester heat-shrinkable film was prepared in the same manner as in Example 1, except that the mixing ratio of the first polyester resin/second polyester resin was 50/50. ,evaluated. The results obtained are shown in Table 2.
  • Example 4 In Example 4, as shown in Table 1, PET3 was used as the second polyester resin instead of PET2, and the mixing ratio of the first polyester resin/second polyester resin was 50/50. A polyester heat-shrinkable film was prepared and evaluated in the same manner as in Example 1. The results obtained are shown in Table 2.
  • Example 5 In Example 5, as shown in Table 1, the mixing ratio of the first polyester resin/second polyester resin was set to 30/70, and the draw ratio in the TD direction was set to 2.5. A polyester heat-shrinkable film was prepared and evaluated in the same manner as in 1. The results obtained are shown in Table 2.
  • Example 6 In Example 6, as shown in Table 1, PET3 was used as the second polyester resin instead of PET2, and the mixing ratio of the first polyester resin/second polyester resin was set to 30/70, and A polyester heat-shrinkable film was prepared and evaluated in the same manner as in Example 1, except that the draw ratio in the TD direction was 2.5. The results obtained are shown in Table 2.
  • Comparative Example 1 In Comparative Example 1, as shown in Table 1, only PET1, which is the first polyester resin, was used, and the mixing ratio of the first polyester resin/second polyester resin was 100/0. Similarly, a polyester heat-shrinkable film was prepared and evaluated. The results obtained are shown in Table 2.
  • Comparative Example 2 In Comparative Example 2, as shown in Table 1, a polyester heat-shrinkable film was prepared in the same manner as in Example 1, except that the mixing ratio of the first polyester resin/second polyester resin was 90/10. ,evaluated. The results obtained are shown in Table 2.
  • Comparative Example 3 In Comparative Example 3, as shown in Table 1, PET3 was used as the second polyester resin instead of PET2, and the mixing ratio of the first polyester resin/second polyester resin was 90/10. A polyester heat-shrinkable film was prepared and evaluated in the same manner as in Example 1. The results obtained are shown in Table 2.
  • Comparative Example 4 In Comparative Example 4, as shown in Table 1, only PET3 was used as the second polyester resin instead of PET2, and the mixing ratio of the first polyester resin/second polyester resin was 0/100. A polyester heat-shrinkable film was prepared and evaluated in the same manner as in Example 1. The results obtained are shown in Table 2.
  • Comparative Example 5 In Comparative Example 5, as shown in Table 1, only PET3 was used as the second polyester resin instead of PET2, the mixing ratio of the first polyester resin/second polyester resin was 30/70, and A polyester-based heat-shrinkable film was produced and evaluated in the same manner as in Example 1, except that the value of the heat-shrinkage rate corresponding to the property (E) was set to less than 20%. The results obtained are shown in Table 2.
  • the polyester heat-shrinkable film of the present invention can be used not only to cover various PET bottles, etc., but also to cover various PET bottles, etc.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • Manufacture Of Macromolecular Shaped Articles (AREA)
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CN117021725B (zh) * 2023-10-10 2024-05-14 河南银金达新材料股份有限公司 一种结晶性易回收聚酯热收缩薄膜及其制备方法
WO2025197668A1 (ja) * 2024-03-22 2025-09-25 タキロンシーアイ株式会社 ポリエステル系熱収縮フィルム、及びポリエステル系樹脂フィルムの製造方法
JP7793256B1 (ja) * 2024-03-22 2026-01-05 タキロンシーアイ株式会社 ポリエステル系熱収縮フィルム、及びポリエステル系樹脂フィルムの製造方法

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